Name: 119-80-2|2,2'-Dithiodibenzoic acid|96%
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SKU: A249546
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1
[ 67-56-1 ]
[ 119-80-2 ]
[ 5459-63-2 ]

Yield	Reaction Conditions	Operation in experiment
100%	With triethylamine for 18h;
92%	Stage #1: 2,2'-dithiobenzoic acid With thionyl chloride for 2h; Reflux; Stage #2: methanol With triethylamine for 2h; Reflux;
91%	With sulfuric acid for 24h; Reflux;	4.2.1.1. Synthesis of dimethyl 2,2'-disulfanediyldibenzoate (4). Route 1. General procedure: To a solution of thiosalicylic acid 1 (15.4 g, 100 mmol) in 95% ethanol (800 mL) at room temperature 400 mL of a saturated slurry of I2 (38.1 g, 150 mmol) prepared by suspending neat I2 (100 g, 390.0 mmol) in 95% ethanol (1000 mL) were added dropwise. The solution was stirred at room temperature until a persistent yellow color formed (30 min). A colorless precipitate slowly formed, was filtered, collected and dried under vacuum (11.3 g,37%). The mother liquor was evaporated in vacuo and purified by flash chromatography (CH2Cl2/AcOEt/CH3COOH 98:2:0.1) to give another portion of 2,2'-disulfanediyldibenzoic acid (2) (17.1 g, 56%). ESI-MS (m/z): 329 [M+Na].+. The other chemical and analytical data were identical to those of the already described compound 2. To a solution of disulfide 2 (17.1 g, 56.0 mmol) in methanol (600 mL) neat 98% H2SO4 (10 mL) was added and the reaction mixture was heated at reflux for 24 h (TLC inn-hexanes/AcOEt 9:1), poured into a cold K2CO3/H2O mixture (300 g, 600 mL) and the organics were extracted in CHCl3 (3 x 500 mL), dried over anhydrous Na2SO4, filtered and evaporated to dryness in vacuo to give the title compound 4 as a colorless solid (17.0 g, 91%). The mother liquor was acidified to pH 2 by diluted HCl (as needed) and extracted with CHCl3 to recover the starting compound 2 (1.71 g, 10%).

82%	With sulfuric acid for 72h; Heating / reflux;	6 Example 6 Compounds of formula I Syeitlzesis of 102. 5-Fluoro-3-(2-piperidin-1-ylmethyl-phenylsulfanyl)-1H-indole; 6 mL conc. H2SO4 was added to 2, 2'-dithiodibenzoic acid (20 g, 65.3 mmol) in 150 mL methanol. The reaction mixture was refluxed for three days, cooled to room temperature and neutralized with sat. aqueous NaHC03. Methanol was removed in vacuo. The residue was extracted with ethyl acetate. The organic phase was washed with brine, dried with MgS04 and concentrated in vaclJo to give 17.8 g dimethyl 2,2'-dithiodibenzoic acid ester (53. 2 mmol, 82%). 1.20 mL Sulfurylchloride (15 mmol) was added to 5.00 g dimethyl 2, 2'- dithiodibenzoic acid ester (15 mmol) in 40 mL dry 1, 2-dichloroethane under Ar at 0°C. The reaction mixture was stirred 15 min at room temperature and added to 4. 10 g fluoro-1H- indole (30. 3 mmol) in 50 mL dry THF under Ar. The reaction mixture was stirred for 2 hours at room temperature and then quenched by addition of sat. aqueous NaHCO3. Ethyl acetate was added, the two phases were separated and the organic phase was washed with brine, dried with MgSO4 and concentrated in vacuum. 8.30 g 2- (5-Fluoro-IH-indol-3- ylsulfanyl) -benzoic acid methyl ester (27. 5 mmol, 92%) was isolated after flash chromatography on silica gel. 4.15 g 2- (5-Fluoro-lH-indol-3-ylsulfanyl)-benzoic acid methyl ester (13. 8 mmol) in 50 mL dry THF was added dropwise to 0.58g LiAIH4 (15. 4 mmol) in 20 mL dry diethyl ether at 0°C. 150 mL dry THF was added and the reaction mixture was stirred 16 hours at room temperature. The raction was quenched with 1 mL water and 1 mL 2N NaOH. The reaction mixture was stirred for 1 hour, then 2. 5 mL water was added and stirring was continued for another hour. The mixture was filtered, dried with MgS04 and concentrated in vactio to give 3.00 g 2-(5-fluoro-lH-indol-3-ylsulfanyl)- phenyl] -methanol (11. 0 mmol, 80%). 0. 275gp-Toluenesulfonylchloride (1. 44 mmol) was added to 0.375g 2- (5-fluoro-lH-indol-3-ylsulfanyl)-phenyl]-methanol (1. 37 mmol) in 5 mL dry THF at 0°C. The reaction mixture was stirred 2 hours at 0°C and then added to 2.75 mmol piperidine in 10 mL dry THF and stirred 16 hours at room temperature. Water and ethyl acetate were added to the reaction mixture. The two phases were separated and the organic phase was washed with brine, dried with MgSO4 and concentrated in vacua. 5- Fluoro-3-(2-piperidin-1-ylmethyl-phenylsulfanyl)-1H-indole was isolated after flash chromatography.
82%	With sulfuric acid In water for 72h; Heating / reflux;	13.18 Example 13; Synthesis of methyl 2-[[2-(methoxycarbonyl)phenyl]dithio]benzoate (Method 18.) 6 mL Sulphuric acid is added to ‘2,2’-dithiodibenzoic acid (20 g, 65.3 mmol) in 150 mL methanol. The reaction mixture is refluxed 3 days. The reaction mixture is cooled to room temperature and saturated aqueous NaHCO3 is added. Methanol is removed in vacuo. The resulting heterogeneous mixture is extracted with ethyl acetate. The organic phase is washed with brine, dried with MgSO4 and concentrated in vacuo to give 17.8 g (82%) of the title compound as a solid, which is used without further purification.
82%	In water for 72h; Reflux;	3.2 R²=2-COOCH₃; 2-COOC₂H₅ General procedure: 1.5 mL concentrated H2SO4 was added to a solution of 2,2'-dithiosalicylic acid (5 g, 16.3 mmol) in 37.5 mL anhydrous methanol, and then heated under reflux for 72 h until the solution was clarified, cooled to room temperature. After that excess methanol was removed under vacuum and the concentrated solution was neutralized with saturated sodium bicarbonate to PH=8-9, extracted with ethyl acetate, washed with brine. The ethyl acetate layer was dried with anhydrous sodium sulfate overnight. After the ethyl acetate was removed under vacuum to give claybank solid methyl 2,2'-dithiosalicylate (4.5 g, 82% yield).
49%	With sulfuric acid for 5h; Reflux;
37%	With dmap; dicyclohexyl-carbodiimide In acetonitrile at 20℃;
	With hydrogenchloride
	With sulfuric acid
	With sulfuric acid

Reference： [1]Domagala, John M.; Bader, John P.; Gogliotti, Rocco D.; Sanchez, Joseph P.; Stier, Michael A.; Song, Yuntao; Vara Prasad; Tummino, Peter J.; Scholten, Jeffrey; Harvey, Patricia; Holler, Tod; Gracheck, Steve; Hupe, Donald; Rice, William G.; Schultz, Robert [Bioorganic and Medicinal Chemistry, 1997, vol. 5, # 3, p. 569 - 579]
[2]Mampuys, Pieter; Zhu, Yanping; Sergeyev, Sergey; Ruijter, Eelco; Orru, Romano V. A.; Van Doorslaer, Sabine; Maes, Bert U. W. [Organic Letters, 2016, vol. 18, # 12, p. 2808 - 2811]
[3]Viani, Fiorenza; Rossi, Bianca; Panzeri, Walter; Merlini, Luca; Martorana, Alessandra M.; Polissi, Alessandra; Galante, Yves M. [Tetrahedron, 2017, vol. 73, # 13, p. 1745 - 1761]
[4]Current Patent Assignee: H. LUNDBECK A/S - WO2005/61455, 2005, A1 Location in patent: Page/Page column 69
[5]Current Patent Assignee: H. LUNDBECK A/S - US2006/287386, 2006, A1 Location in patent: Page/Page column 18
[6]Li, Zai-Shun; Wang, Wei-Min; Lu, Wei; Niu, Cong-Wei; Li, Yong-Hong; Li, Zheng-Ming; Wang, Jian-Guo [Bioorganic and Medicinal Chemistry Letters, 2013, vol. 23, # 13, p. 3723 - 3727]
[7]Location in patent: experimental part Nyoni, Dubekile; Lobb, Kevin A.; Kaye, Perry T.; Caira, Mino R. [ARKIVOC, 2012, vol. 2012, # 6, p. 245 - 252]
[8]Dallinger, Doris; Kappe, C. Oliver; Zlatković, Dragan [Organic and Biomolecular Chemistry, 2020, vol. 18, # 41, p. 8371 - 8375]
[9]Gattermann [Chemische Berichte, 1899, vol. 32, p. 1156] Aulich [Dissertation <Genf 1893>]
[10]Overman,L.E. et al. [Journal of the American Chemical Society, 1974, vol. 96, # 19, p. 6081 - 6089]
[11]Current Patent Assignee: MAUMEE DEV - US2705242, 1953, A

2
[ 1677-27-6 ]
[ 141-52-6 ]
[ 119-80-2 ]

Reference： [1]Journal of the Chemical Society,1922,vol. 121,p. 90

3
[ 1677-27-6 ]
[ 119-80-2 ]

Reference： [1]Journal of the Chemical Society,1922,vol. 121,p. 90

4
[ 13993-58-3 ]
[ 64-17-5 ]
[ 141-52-6 ]
[ 147-93-3 ]
[ 7153-08-4 ]
4-ethoxy-3,5-diiodopyridine [ No CAS ]
[ 119-80-2 ]
2-(3,5-diiodo-[4]pyridylmercapto)-benzoic acid [ No CAS ]

Reference： [1]Journal of the American Pharmaceutical Association (1912),1951,vol. 40,p. 143,144, 149

5
[ 64-17-5 ]
[ 119-80-2 ]
[ 54481-26-4 ]

Yield	Reaction Conditions	Operation in experiment
46%	With dmap; dicyclohexyl-carbodiimide In acetonitrile at 20℃;
	With toluene-4-sulfonic acid
	In water for 72h; Reflux;	3.2 R²=2-COOCH₃; 2-COOC₂H₅ General procedure: 1.5 mL concentrated H2SO4 was added to a solution of 2,2'-dithiosalicylic acid (5 g, 16.3 mmol) in 37.5 mL anhydrous methanol, and then heated under reflux for 72 h until the solution was clarified, cooled to room temperature. After that excess methanol was removed under vacuum and the concentrated solution was neutralized with saturated sodium bicarbonate to PH=8-9, extracted with ethyl acetate, washed with brine. The ethyl acetate layer was dried with anhydrous sodium sulfate overnight. After the ethyl acetate was removed under vacuum to give claybank solid methyl 2,2'-dithiosalicylate (4.5 g, 82% yield).

Reference： [1]Dallinger, Doris; Kappe, C. Oliver; Zlatković, Dragan [Organic and Biomolecular Chemistry, 2020, vol. 18, # 41, p. 8371 - 8375]
[2]Pierson et al. [Journal of Polymer Science, 1955, vol. 17, p. 221,233]
[3]Li, Zai-Shun; Wang, Wei-Min; Lu, Wei; Niu, Cong-Wei; Li, Yong-Hong; Li, Zheng-Ming; Wang, Jian-Guo [Bioorganic and Medicinal Chemistry Letters, 2013, vol. 23, # 13, p. 3723 - 3727]

6
[ 505-73-7 ]
[ 119-80-2 ]
[ 108085-49-0 ]

Yield	Reaction Conditions	Operation in experiment
	With sulfuric acid at 30℃;

Reference： [1]Smiles; McClelland [Journal of the Chemical Society, 1922, vol. 121, p. 90]

7
[ 119-80-2 ]
[ 19602-82-5 ]

Yield	Reaction Conditions	Operation in experiment
97%	With thionyl chloride In N,N-dimethyl-formamide; toluene at 82℃; for 20h;	9 2,2'-dithiosalicylic acid (421 g) is dissolved in toluene (1.7 L) and thionyl chloride (212 mL) and DMF (7 ml_) are added, and the mixture is agitated for 20 hours at 820C. The mixture is then cooled to 7O0C and hexanes (2 L) are added. Further cooling to 100C provides a solid precipitate. The solids are filtered, washed with hexanes (2 x 250 mL), and dried in a vacuum oven for 24 hours (550C and 25 mm Hg) to provide 390 g of 2.2' -dithiosalicylic acid dichloride (97% yield with a purity of 80% by 1H NMR/DMSO).
95%	With thionyl chloride In N,N-dimethyl-formamide for 4h; Reflux;
91.3%	With thionyl chloride; N,N-dimethyl-formamide In toluene at 82℃; for 20h;	1 2,2'-Dithiosalicylic acid (421g) is dissolved in toluene (1.7L),Add thionyl chloride (212ml) and DMF (7ml),The mixture was stirred at 82°C for 20 hours.Then the mixture was cooled to 70°C and hexane (2L) was added.It was further cooled to 10°C to obtain a solid precipitate.Filter the solid and rinse with hexane (2×250ml),Dry in a vacuum drying oven for 24 hours (55°C and 25mm Hg) to obtain 2.2'-dithiosalicylic acid dichloride,The yield is 91.3%, and the HPLC purity is 78.95%.

90%	With thionyl chloride; N,N-dimethyl-formamide In toluene at 70℃; for 4h;	1.1 1) Chlorination reaction: Mix 421 g (1.37 mol) of 2,2'-dithiodibenzoic acid, 1.15 L (10.83 mol) of toluene, 212 mL (3 mol) of thionyl chloride, and 10.6 mL (0.14 mol) of DMF, and carry out acid chloride at 70°C Reaction for 4 hours,Add 2L n-hexane (15mol), lower the temperature to 10°C, crystallize, filter, wash the filter cake twice with 250mL n-hexane, and dry to obtain 2,2'-dithiodibenzoyl chloride 425g (1.24mol) , The yield is 90%.
89%	With thionyl chloride In N,N-dimethyl-formamide; toluene at 80℃;	1f Step If. 2,2Dithiosalicylic acid dichloride (Compound 108)2,2'-dithiosalicylic acid 107 (3.22 g, 10.5 mmol) was dissolved in toluene (30 niL) and thionyl chloride (2 rnL) and DMF (0.2 rnL) were added. The mixture was stirred at 80 0C overnight. Solvents were evaporated to obtain compound 108 as a yellow solid (3.2 g, 89% yield).
89%	With oxalyl dichloride; N,N-dimethyl-formamide In dichloromethane at 20 - 50℃; for 42h;	58 Production of 2,2’-dithiosalicylic dichloride Oxalyl chloride (25 mL, 291.5 mmol) and N,N-dimethylformamide (150 mL, 1.94 mmol) were added to a solutionof 2,2’-dithiosalicylic acid (25.0 g, 81.6 mmol) in dichloromethane (220 mL), and stirred at room temperature for 18 hours.The resulting solution was further stirred at 50°C for 24 hours, and then the solvent was distilled away under a reducedpressure. The resulting solid was washed with hexane at 0°C and dried to obtain the title compound (24.9 g, 89%) asa pale yellow solid.1H NMR (400 MHz, CDCl3) δ 8.40 (2H, dd, J = 8.0, 1.4 Hz), 7.77 (2H, dd, J = 8.0, 1.1 Hz), 7.55 (2H, td, J = 8.0, 1.4 Hz),7.24 (2H, td, J = 8.0, 1.1 Hz)
89%	Stage #1: 2,2'-dithiobenzoic acid With N,N-dimethyl-formamide In 1,2-dichloro-ethane at 30 - 40℃; for 0.5h; Stage #2: With trichloromethyl chloroformate In 1,2-dichloro-ethane	15 Add o-dithiodibenzoic acid (61.3g, 0.20mol), 150mL of dichloroethane and a catalytic amount of N,N-dimethylformamide into the reaction flask, increase the temperature to 30-40°C, and continue to stir 0.5 hThen, add dropwise a solution prepared by trichloromethyl chloroformate (43.5g, 0.22mol) and 130mL dichloroethane, keep the reaction warm, after all the raw materials are converted (about 2~3h), cool down, concentrate under reduced pressure, and crystallize , Vacuum drying, 61.1g o-dithiodibenzoyl chloride, yield 89%.
84%	With thionyl chloride for 24h; Heating;
83%	With thionyl chloride; N,N-dimethyl-formamide In toluene at 35 - 75℃; for 16h; Large scale;
80%	With thionyl chloride for 48h; Reflux;	Preparation of compound 1. The known compound 1 was prepared using a published protocol.1 A mixture of 2,2'-dithio-dibenzoic acid (3.0 g, 9.8 mmol) and SOCl2 (25 mL) was heated under reflux for 48 h, and the solvent was removed by distillation followed by evaporation in vacuo. The residue was triturated with hexanes, quickly filtered, and washed with hexanes and dried under vacuum to afford compound 1 (2.69 g, 80%) as a yellow solid: 1H NMR (400 MHz, CDCl3, Fig. S1, which matches the lit.1) δ8.37 (d, J = 7.6 Hz, 2H), 7.75 (d, J = 8.4 Hz, 2H), 7.53 (t, J = 7.6 Hz, 2H), 7.36 (t, J = 7.6 Hz,2H).
80%	With thionyl chloride Reflux;	4.2.1. Preparation of ebsulfurs 1a-o following procedure A General procedure: 2-(Chlorosulfanyl)benzoyl chloride (b) has been obtained by 2,2′-disulfanediyldibenzoic acid (a) react with SOCl2 according to the procedure described [22]. To a stirred and ice-cooled mixture of primary amine (3mmol) and 75 Et3N (0.45mL, 3.2mmol) in anhydrous CH2Cl2 (40mL), 2, 2′-dithiobenzoyl chloride (b, 0.50g, 1.5mmol) in anhydrous CH2Cl2 (20mL) was added dropwise over 20min. The reaction mixture was warmed-up to RT, stirred for 12h, and washed with aq. sat. NaHCO3 (30mL) and H2O (30mL). The organic layer was dried over anhydrous Na2SO4, concentrated in vacuo, and the resulting residue was purified by flash column chromatography (SiO2, EtOAc:hexane/1:2) to afford the final compounds 1a-o [25].
78%	With thionyl chloride Reflux;
71%	With thionyl chloride In N,N-dimethyl-formamide; toluene at 75℃; for 18h;
70%	With thionyl chloride; N,N-dimethyl-formamide In toluene at 0 - 75℃; for 18h; Inert atmosphere;
68%	With thionyl chloride for 14h; Heating;
68%	With thionyl chloride for 12h; Heating / reflux;	A Example A; Synthesis of bis-[2-(2-oxazolyl)-phenyl]-disulfide (2OPD); A mixture of 20 g of 2,2'-dithio-bis-(benzoic acid) (65 mmol) in 28.6 mL thionylchloride (390 mmol) was refluxed for 12 hours and then filtered. The filtrate was dried using a rotary evaporator and 15.0 g of 2,2'-dithio-bis-(benzoyl chloride) powder (44 mmol) was collected. Yield for this reaction was 68%.
68%	With thionyl chloride at 80℃; for 0.166667h; Microwave irradiation;	Microwave-assisted Method 2,2'-Dithiodibenzoic acid (1.0000 g,3.26 mmol) and thionyl chloride (1.6000 g, 13.50 mmol) was takenin a round bottom flask in StartSYNTH-Microwave Synthesis Labstationsystem.(MW, E1000 W, 80 C, 10 min, yield [68%). M.p.75e76 C; FT-IR (g cm1) 746, 786, 1109, 1160, 1242, 1350, 1450,1560, 1600, 1725, 3080; 1HNMR (CDCl3, 100 MHz) d 7.30e7.60 (m,4H), 7.75 (d, 2H, J 8.0 Hz), 8.40 (d, 2H, J 8.0 Hz). LS-MS (m/z) 342(M), 340, 338, 303, 233, 201, 179, 169, 167, 148, 133, 118, 102, 94
68%	With thionyl chloride for 1h; Microwave irradiation; Reflux;	2.2.1. 2,2’-Dithiodibenzoyl dichloride (A) The synthesis of 2,20-dithiodibenzoyl dichloride was carriedout according to the literature (Abd El-Hady et al., 2013;Bruening et al., 1991; Calisir & Cicek, 2017; Seyedi et al.,2005). 7.00 g (22.85 mmol) of 2,20-dithiodibenzoic acid wastaken into a 100 mL reaction flask. It was heated with microwavesynthesis device (1000 W) under reflux for 1 hour byadding 25 mL of thionyl chloride. Reaction was followed byTLC. Excess thionyl chloride was removed under low temperatureby evaporator. Brown solid product was obtained. Itwas used directly in the next step without further purification(M.P.: 75-76 C, yield: 68%). FT-IR (c cm1): 3071 CH(sp2) stretch, 1717OC-Cl stretch, 1580 asymmetric strain ofbenzene ring, 1554 benzene ring symmetric strain, 1435-1320-1294-1263-1208-1194-1134-1039872 C-Cl bends,689 C-Cl bends.
68%	With thionyl chloride for 1h; Microwave irradiation; Reflux;	2.2.1. 2,2’-Dithiodibenzoyl dichloride (A) The synthesis of 2,20-dithiodibenzoyl dichloride was carriedout according to the literature (Abd El-Hady et al., 2013;Bruening et al., 1991; Calisir & Cicek, 2017; Seyedi et al.,2005). 7.00 g (22.85 mmol) of 2,20-dithiodibenzoic acid wastaken into a 100 mL reaction flask. It was heated with microwavesynthesis device (1000 W) under reflux for 1 hour byadding 25 mL of thionyl chloride. Reaction was followed byTLC. Excess thionyl chloride was removed under low temperatureby evaporator. Brown solid product was obtained. Itwas used directly in the next step without further purification(M.P.: 75-76 C, yield: 68%). FT-IR (c cm1): 3071 CH(sp2) stretch, 1717OC-Cl stretch, 1580 asymmetric strain ofbenzene ring, 1554 benzene ring symmetric strain, 1435-1320-1294-1263-1208-1194-1134-1039872 C-Cl bends,689 C-Cl bends.
67%	With thionyl chloride for 24h; Heating;
47%	With thionyl chloride; N,N-dimethyl-formamide for 0.5h; Heating;
42%	With thionyl chloride In benzene Heating;
	With phosphorus pentachloride
	With thionyl chloride
	With thionyl chloride
	With pyridine; thionyl chloride In benzene Heating;
	With pyridine; thionyl chloride In toluene Heating;
	With thionyl chloride Heating;
	With thionyl chloride; N,N-dimethyl-formamide In toluene at 75 - 80℃;
	With oxalyl dichloride
	With thionyl chloride Heating;
	With thionyl chloride for 1.5h; Heating;
	With thionyl chloride at 80℃;
	With thionyl chloride for 18h; Heating;
	With thionyl chloride for 1h; Heating;
	With thionyl chloride In benzene for 3h; Heating;
		7 Example 7 Compounds of formula I Synthesis of 128. 2-(5-Fluoro-1H-indol-3-ylsulfanyl)-benzylamine; 4.50 g NaBH4 (119 mmol) was added in portions to 7.50 g allyl bromide (62. 0 mmol) and 8.35 g 2,2'-dithiodibenzamide (27.4 mmol, prepared from 2, 2'-dithiodibenzoic acid via 2,2'- dithiodibenzoic acid chloride) in 80 mL methanol at 0°C. The reaction mixture was stirred 1 hour at room temperature. 50 mL 1N HC1 was added and stirring was continued 1 hour. Methanol was removed in vacuo. The residue was extracted with ethyl acetate. The organic phase was washed with brine, dried with MgSO4 and concentrated in i) actio to give 10.0 g 2- allylsulfanyl-benzamide (51.7 mmol, 94%). 2.1 g LiAlH4 (55 mmol) was added to 6.0 g 2- allylsulfanyl-benzamide (31 mmol) in 50 mL dry THF at 0°C. The reaction mixture was stirred for 16 hours at room temperature. The reaction was quenched with 4 mL water and 3 mL 2N NaOH. The reaction mixture was stirred for 1 hour, then 9 mL water was added and stirring was continued for another hour. The mixture was filtered, dried with MgSO4 and concentrated ift vaczto to give 5.05 g 2-allylsulfanyl-benzylamine (28. 2 mmol, 91%). 2.05 g Di-tert-butyl dicarbonate (9.37 mmol) was added to 1.40 g 2-allylsulfanyl-benzylamine (7. 81 mmol) and a catalytic amount of N, N-dimethyl-4-amino pyridine in 20 mL THF. The reaction mixture was stirred for 15 minutes at room temperature. 10 mL 20% citric acid was added and the reaction mixture was stirred for 30 minutes. The reaction mixture was extracted with ethyl acetate, the two phases were separated and the organic phase was washed with brine, dried with MgSO4 and concentrated ira vaczro to give (2-allylsulfanyl- benzyl) -carbamic acid te} t-butyl ester in quantitative yield. 0.70g NaIO4 (3.3 mmol) in 20 mL water was added to 0. 75 g (2-allylsulfanyl-benzyl)-carbamic acid te) t-butyl ester (2, 7 mmol) in 20 mL methanol and stirred for 2 hours at room temperature. The reaction mixture was filtered and methanol was removed in vaciso. The residue was extracted with ethyl acetate. The organic phase was washed with brine, dried with MgSO4 and concentrated il7 vaczso. The residue was redissolved in 5 mL THF and added to 0. 50 g fluoro-lH-indole (3.7 mmol) and 0.65 g trichlor acetic acid (4.0 mmol) in 5 mL THF and stirred for 16 hours at 50°C. Sat. aqueous NaHCO3 and ethyl acetate was added, the two phases were separated and the organic phase was washed with brine, dried with MgSO4 and concentrated ill vaczso. The residue was purified by flash chromatography and 0.157g [2- (5-fluoro-lH-indol-3- ylsulfanyl) -benzyl] -carbamic acid tert-butyl ester (0. 42 mmol, 16%) was isolated after recrystallization from ethyl acetate/heptane. 8 mL diethyl ether saturated with HCl was added to 0.157g [2- (5-fluoro-lH-indol-3-ylsulfanyl)-benzyl]-carbamic acid test-butyl ester (0.42 mmol) in 8 mL methanol and stirred 16 hours. The reaction was neutralized with 2N NaOH and extracted with ethyl acetate. The organic phase was washed with brine, dried with MgSO4 and concentrated in vaczto to give 0. 112 g 2- (5-fluoro-lH-indol-3-ylsulfanyl)- benzylamine (98%).
	With thionyl chloride In <i>N</i>-methyl-acetamide; toluene	R.7.1 Reference example 7 (1) 12.5 ml of thionylchloride are added dropwise to a solution of 25.0 g of 2,2'-dithiodibenzoic acid in a mixture of 120 ml of toluene and 0.5 ml of dimethylformamide at a room temperature. The mixture is warmed to a temperature of 70° to 80° C. and then stirred at the same temperature overnight. After 20 hours, the crystals are collected by filtration to obtain 14.9 g of 2,2'-dithiodibenzoyl chloride as colorless crystal. m.p.:140°-141° C.
	In thionyl chloride; hexane	A 2,2'-Dithiobisbenzoyl chloride PREPARATION A 2,2'-Dithiobisbenzoyl chloride A mixture of 2,2'-dithiobisbenzoic acid (25 g, 81.6 mmol) in 350 mL of thionyl chloride was heated at reflux for 18 hours. The resulting solution was cooled to about 30° C. and excess thionyl chloride was removed in vacuo. The crude solid was slurried in hexane and the title compound was recovered by filtration to yield 21.2 g. This compound was used without further purification, mp 150°-151° C.; NMR (CDCl3): δ8.4 (m, 2H), 7.7 (d, 2H), 7.5 (m, 2H), 7.3-7.4 (m, 2H).
	In thionyl chloride; hexane	1 2,2'-Dithiobisbenzoyl chloride PREPARATION 1 2,2'-Dithiobisbenzoyl chloride A mixture of 2,2'-dithiobisbenzoic acid (25 g, 81.6 mmol) in 350 mL of thionyl chloride was heated at reflux for 18 hours. The resulting solution was cooled and excess thionyl chloride was removed in vacuo. The crude solid was slurried in hexane and the title compound was recovered by filtration to yield 21.2 g mp 150°-151° C. This compound was used without further purification.
1619 g (71%)	With thionyl chloride In N,N-dimethyl-formamide; toluene	1 1,2-Benzisothiazol-3(2H)-one (Method 1) EXAMPLE 1 1,2-Benzisothiazol-3(2H)-one (Method 1) A slurry of 2,2'-dithiosalicylic acid (2017 g, 6.584 moles), thionyl chloride (1645 g, 13.826 moles), toluene (10 liter) and N,N-dimethylformamide (40 mL) was heated at about 75° for 18 hours. At this point all solid had dissolved and the resulting dark solution was cooled to 8°. The reaction product crystallized and was isolated by filtration and washed on the filter with about 1 liter of cold Skelly F. Drying yielded 1619 g (71%) of 2,2'-dithio-bis-benzoyl chloride, m.p. 154°-156° (Lit. m.p. 155°-156°; cf: I. R. Douglass and B. S. Farrah, J. Org. Chem., 26, 351-354 (1961)).
	With thionyl chloride; N,N-dimethyl-formamide for 3h; Heating / reflux;	1.1.1 1.1 : Dithiodibenzoic acid - dimethylester 25 g (81.6 mmol) of dithiodibenzoic acid is refluxed in 60 ml of SOCI2 and 1.5 ml of dimethylformamide (DMF) for 3 hrs. Then the excess of SOCI2 is distilled off, and the residue is dissolved in CHCI3 and added dropwise to a solution of methanol (50 ml) and triethylamine (0.204 mol) in CHCI3 (300 I). After standing over night the reaction mixture is shaked with water and saturated K2CO3 solution. After drying the organic layer the solvent is evaporated and methanol is added to the residue (oil). 13.6 g (50%) of solid product is obtained.
	With thionyl chloride for 3h; Heating / reflux;
	With oxalyl dichloride; N,N-dimethyl-formamide In dichloromethane
	With thionyl chloride for 8h; Reflux;
	With oxalyl dichloride In N,N-dimethyl-formamide at 0℃;	4.2.1. Synthesis of para- and ortho-substituted aromatic ethylene glycol disulfide polymers⁵⁷ (general procedure using polymer 20 as an example) General procedure: 4,4'-Dithiobenzoic acid (11) [23], [58] and [59] (0.213 g, 0.696 mmol) was dissolved in 4 mL of THF, and then DMF (10 μL) was added. The solution was cooled to 0 °C, and oxalyl chloride (13) (0.883 g, 6.96 mmol) was slowly added into the solution via syringe. The solution was stirred for 3 h and then reduced under vacuum to give a yellow oil. The yellow oil was dissolved in 6 mL of CH2Cl2 and then transferred to a flask containing triethylene glycol disulfide (17) (0.981 g, 2.98 mmol), Et3N (0.77 mL, 5.57 mmol), and 46 mL of CH2Cl2 at 0 °C. The reaction mixture was stirred at 0 °C for 30 min and gradually warmed to room temperature, and then stirring continued overnight. The reaction mixture was dissolved in 50 mL of CH2Cl2 and then washed with 50 mL of 0.1 N HCl. The organic layer was then washed with water (2 × 50 mL), dried (MgSO4), filtered, and reduced under vacuum to provide 0.81 g of polymer 20.
	With thionyl chloride for 24h; Reflux;
	With thionyl chloride Reflux;
	With thionyl chloride at 80℃; for 24h; Reflux;	Typical experimental procedure Various benzisothiazolones (1.1 to 1.31) were synthesized starting from commercially available dithiodibenzoic acid (2). Dithiodibenzoic acid (2 g) was refluxed with thionyl chloride (10 mL) for 24 h at 80 oC. Excess thionyl chloride was removed by distillation and chased-up with dry benzene to get dithiodibenzoyl chloride as a pale brown solid 2.2 g (crude). To a stirred solution of dithiodibenzoyl chloride (2.2 g, 6.41 mmol) in dry DCM (20 mL) was added bromine (0.66 mL, 12.8 mmol) and the mixture was refluxed for 12 h. Dichloromethane and excess bromine were distilled off and the residue was chased with dry benzene (2 x 5 mL) to get 3.2 g of 2-bromosulfenylbenzoyl chloride (3) as a brown solid which was directly subjected to next step without further purification.
	With oxalyl dichloride In dichloromethane for 3h; Inert atmosphere; Cooling with ice;	1 Preparation of a compound formula 1 Under argon atmosphere, 2,2'-dithiodibenzoic acid (1.53 g, 5 mmol) and oxalyl chloride (2.96 g, 23.3 mmol) were reacted in 100 ml of methylene chloride under ice-cooling for 3 hours. The solvent was evaporated to dryness stand-by. Under ice-water bath, the cyanine fluorophore (500mg, 1.08mmol) was dissolved in methylene chloride, and then 2,2'-dithiodibenzoyl chloride was added dropwise. After reacting for 1 hour in ice bath, The mixture was then extracted with dichloromethane (100ml X 3). After evaporation of the solvent, the crude product was dissolved in 50ml of ethanol and sodium borohydride (g, mol) was added dropwise in ice-water bath. The reaction was continued for 15 minutes with dilute hydrochloric acid (10%) To neutrality, then extracted with dichloromethane (100 ml X 3), dried over sodium sulfate, and the solvent was evaporated to dryness. The residue was separated by silica gel column chromatography (200-300 mesh). The eluent was dichloromethane and petroleum ether (1: 1 / V / V). The yellow component was collected and the product was evaporated to dryness to yield 0.51 g. Yield: 75%.
	With phosphorus pentachloride
	With thionyl chloride In N,N-dimethyl-formamide for 4h; Reflux;	Procedure for synthesis of compound 11 After 2,2’-dithiosalicylic acid 10 (1.1 g, 3 mmol, 1 equiv) was dissolved in thionylchloride (0.7 mL, 9.6 mmol, 3 equiv), DMF (10 mL) was added to the reaction mixture. The reaction mixture was stirred at refluxing for 4 h, then cooled down to room temperature, concentrated in a vacuum, and then recrystallized in n-hexane. The solid residue was filtered and dried in a vacuum to provide 2,2’-dithiosalicylic aciddichloride 10a. To a solution of the intermediate 10a (654.8 mg, 2 mmol, 1 equiv) in THF (2 mL) was added 8-Aminoquinoline (576.7 mg, 4 mmol, 2 equiv) at 0 °C for over 1 h until the PH value was stable between 9 and 10. The reaction mixture was then allowed to stir at room temperature for another 10 h. The reaction mixture was poured into water and the slurry was filtered. The white solid was obtained after washing with water and dried in a vacuum to provide 10b. The intermediate 10b (1.4 g, 2 mmol, 1 equiv) was dissolved in THF (4 mL). After the solution was cooled down to 0 °C, sodium borohydride (302.6 mg, 8 mmol, 4 equiv) was added in potions over 4 h. In this period, the temperature was controlled below 30 °C. After the reaction was complete, water and acetic acid were added to quench the reaction. Then ethyl acetate (4x500mL) was used to extract the product. The organic phase was combined, dried over anhydrous Na2SO4, and concentrated. The residue was purified by flash chromatography (eluent: petroleum ether :ethylacetate = 4 : 1) to afford the final product 11 as a yellow solid (343.3 mg, 61%).
	With oxalyl dichloride; N,N-dimethyl-formamide In dichloromethane for 4h; Reflux;
	With oxalyl dichloride; N,N-dimethyl-formamide In dichloromethane at 20℃; for 3h;
	With oxalyl dichloride In N,N-dimethyl-formamide at 0 - 20℃; for 3.5h;	4 DMF (0.15 ml, cat.) was added to a suspension of bis(2-carboxyphenyl) disulfide (2.94 g, 9.6 mmol, 1.0 eq.) in THF (60 ml). Oxalyl chloride (8.23 ml, 12.19 g, 96.0 mmol, 10.0 eq.) was added dropwise to the reaction mixture at 0° C. and the mixture was stirred at this temperature for 30 min. The resulting yellow solution was then stirred at RT for a further 3 h. The solvent and excess oxalyl chloride were then distilled off. A yellow solid was isolated that was used for the next synthesis step without further analysis or purification (on account of its reactivity).

Reference： [1]Current Patent Assignee: PFIZER INC - WO2006/48745, 2006, A1 Location in patent: Page/Page column 27
[2]Zhai, Li-Hai; Guo, Li-Hong; Luo, Yang-Hui; Ling, Yang; Sun, Bai-Wang [Organic Process Research and Development, 2015, vol. 19, # 7, p. 849 - 857]
[3]Current Patent Assignee: LUNAN PHARMACEUTICAL GROUP CO LTD - CN112209861, 2021, A Location in patent: Paragraph 0075-0076
[4]Current Patent Assignee: DALIAN CHEMPHY CHEMICAL CO., LTD. - CN111440102, 2020, A Location in patent: Paragraph 0061-0065
[5]Current Patent Assignee: CURIS INC - WO2009/36066, 2009, A1 Location in patent: Page/Page column 54
[6]Current Patent Assignee: SENJU PHARMACEUTICAL CO.,LTD. - EP3127900, 2017, A1 Location in patent: Paragraph 0244; 0245
[7]Current Patent Assignee: DALIAN BIO CHEM SHARE - CN111574472, 2020, A Location in patent: Paragraph 0074-0076
[8]Domagala, John M.; Bader, John P.; Gogliotti, Rocco D.; Sanchez, Joseph P.; Stier, Michael A.; Song, Yuntao; Vara Prasad; Tummino, Peter J.; Scholten, Jeffrey; Harvey, Patricia; Holler, Tod; Gracheck, Steve; Hupe, Donald; Rice, William G.; Schultz, Robert [Bioorganic and Medicinal Chemistry, 1997, vol. 5, # 3, p. 569 - 579]
[9]Fiore, Phillip J.; Puls, Timothy P.; Walker, Jonathan C. [Organic Process Research and Development, 1998, vol. 2, # 3, p. 151 - 156]
[10]Ngo, Huy X.; Shrestha, Sanjib K.; Green, Keith D.; Garneau-Tsodikova, Sylvie [Bioorganic and Medicinal Chemistry, 2016, vol. 24, # 24, p. S1 - S53]
[11]Su, Jianpeng; Liu, Jiayun; Chen, Cheng; Zhang, Yuejuan; Yang, Kewu [Bioorganic Chemistry, 2019, vol. 84, p. 192 - 201]
[12]Location in patent: scheme or table Pietka-Ottlik, Magdalena; Potaczek, Piotr; Piasecki, Egbert; Mlochowski, Jacek [Molecules, 2010, vol. 15, # 11, p. 8214 - 8228]
[13]Yevich, Joseph P.; New, James S.; Smith, David W.; Lobeck, Walter G.; Catt, John D.; et al. [Journal of Medicinal Chemistry, 1986, vol. 29, # 3, p. 359 - 369]
[14]Castelli, Riccardo; Scalvini, Laura; Vacondio, Federica; Lodola, Alessio; Anselmi, Mattia; Vezzosi, Stefano; Carmi, Caterina; Bassi, Michele; Ferlenghi, Francesca; Rivara, Silvia; Møller, Ingvar R.; Rand, Kasper D.; Daglian, Jennifer; Wei, Don; Dotsey, Emmanuel Y.; Ahmed, Faizy; Jung, Kwang-Mook; Stella, Nephi; Singh, Simar; Mor, Marco; Piomelli, Daniele [Journal of Medicinal Chemistry, 2020, vol. 63, # 3, p. 1261 - 1280]
[15]Seyedi, Seyed Mohammad; Shadkam; Ziafati [Phosphorus, Sulfur and Silicon and the Related Elements, 2005, vol. 180, # 8, p. 1953 - 1960]
[16]Current Patent Assignee: BRIDGESTONE CORPORATION - EP1803713, 2007, A2 Location in patent: Page/Page column 14
[17]Calisir, Umit; Çiçek, Baki [Journal of Molecular Structure, 2017, vol. 1148, p. 505 - 511]
[18]Akkemik, Ebru; Camadan, Yasemin; Çalışır, Ümit; Çiçek, Baki; Adem, Şevki; Eyüpoğlu, Volkan [Journal of Biomolecular Structure and Dynamics, 2021]
[19]Akkemik, Ebru; Camadan, Yasemin; Çalışır, Ümit; Çiçek, Baki; Adem, Şevki; Eyüpoğlu, Volkan [Journal of Biomolecular Structure and Dynamics, 2021]
[20]Ranganathan, Subramania; Muraleedharan; Bharadwaj, Parimal; Chatterji, Dipankar; Karle, Isabella [Tetrahedron, 2002, vol. 58, # 14, p. 2861 - 2874]
[21]Collman, James P.; Groh, Susan E. [Journal of the American Chemical Society, 1982, vol. 104, # 5, p. 1391 - 1403]
[22]Jammal, Tamim El; Guiliano, Michel; Fourneron, Jean Dominique; Mille, Gilbert [Phosphorus and Sulfur and the Related Elements, 1983, vol. 16, p. 313 - 324]
[23]List; Stein [Chemische Berichte, 1898, vol. 31, p. 1668]
[24]Hilditch [Journal of the Chemical Society, 1911, vol. 99, p. 1099] Okachi, Ryo; Niino, Hideki; Kitaura, Kozo; Mineura, Kazuyuki; Nakamizo, Yoshinobu; et al. [Journal of Medicinal Chemistry, 1985, vol. 28, # 12, p. 1772 - 1779] Gryff-Keller, Adam; Szczecinski, Przemyslaw [Magnetic Resonance in Chemistry, 1985, vol. 23, # 8, p. 655 - 658]
[25]Douglass,I.B.; Farah,B.S. [Journal of Organic Chemistry, 1961, vol. 26, p. 351 - 354] xxx [Indian Journal of Chemistry - Section B Organic and Medicinal Chemistry, 2000, vol. 39, # 11, p. 842 - 846] Bhowon, Minu G.; Laulloo, B. S. Jhaumeer [Indian Journal of Chemistry, Section A: Inorganic, Physical, Theoretical and Analytical, 2004, vol. 43, # 5, p. 1131 - 1133]
[26]Miura, Yozo [Journal of Organic Chemistry, 1988, vol. 53, # 12, p. 2850 - 2852]
[27]Yamada; Niino; Hashimoto; Shuto; Nakamizo; Kubo; Ono; Nakamizo; Murayama [Chemical and Pharmaceutical Bulletin, 1985, vol. 33, # 3, p. 1214 - 1220]
[28]Bordi; Catellani; Morini; Plazzi; Silva; Barocelli; Chiavarini [Il Farmaco, 1989, vol. 44, # 9, p. 795 - 807] Aiello, Francesca; Brizzi, Antonella; Garofalo, Antonio; Grande, Fedora; Ragno, Gaetano; Dayam, Raveendra; Neamati, Nouri [Bioorganic and medicinal chemistry, 2004, vol. 12, # 16, p. 4459 - 4466]
[29]Norman; Kelley; Hollingsworth [Journal of Medicinal Chemistry, 1993, vol. 36, # 22, p. 3417 - 3423]
[30]Elworthy, Todd R.; Ford, Anthony P. D. W.; Bantle, Gary W.; Morgans Jr., David J.; Ozer, Rachel S.; Palmer, Wylie S.; Repke, David B.; Romero, Magarita; Sandoval, Leticia; Sjogren, Eric B.; Talamás, Francisco X.; Vazquez, Alfredo; Wu, Helen; Arredondo, Nicolas F.; Blue Jr., David R.; DeSousa, Andrea; Gross, Lisa M.; Kava, M. Shannon; Lesnick, John D.; Vimont, Rachel L.; Williams, Timothy J.; Zhu, Quan-Ming; Pfister, Jürg R.; Clarke, David E. [Journal of Medicinal Chemistry, 1997, vol. 40, # 17, p. 2674 - 2687]
[31]Gebbink, Robertus J. M. Klein; Klink, Stephen I.; Feiters, Martinus C.; Nolte, Roeland J. M. [European Journal of Inorganic Chemistry, 2000, # 2, p. 253 - 264]
[32]Neamati, Nouri; Turpin, Jim A.; Winslow, Heather E.; Christensen, John L.; Williamson, Karen; Orr, Ann; Rice, William G.; Pommier, Yves; Garofalo, Antonio; Brizzi, Antonella; Campiani, Giuseppe; Fiorini, Isabella; Nacci, Vito [Journal of Medicinal Chemistry, 1999, vol. 42, # 17, p. 3334 - 3341]
[33]Song, Yongsheng; Goel, Atul; Basrur, Venkatesha; Roberts, Paula E.A; Mikovits, Judy A; Inman, John K; Turpin, Jim A; Rice, William G; Appella, Ettore [Bioorganic and Medicinal Chemistry, 2002, vol. 10, # 5, p. 1263 - 1273]
[34]Roehr, Holger; Trieflinger, Christian; Rurack, Knut; Daub, Joerg [Chemistry - A European Journal, 2006, vol. 12, # 3, p. 689 - 700]
[35]Nagy, Peter; Csampai, Antal; Szabo, Denes; Varga, Jeno; Harmat, Veronika; Ruff, Ferenc; Kucsman, Arpad [Journal of the Chemical Society. Perkin Transactions 2 (2001), 2001, # 3, p. 339 - 349]
[36]Neamati, Nouri; Lin, Zhaiwei; Karki, Rajeshri G.; Orr, Ann; Cowansage, Kiriana; Strumberg, Dirk; Pais, Godwin C. G.; Voigt, Johannes H.; Nicklaus, Marc C.; Winslow, Heather E.; Zhao, He; Turpin, Jim A.; Yi, Jizu; Skalka, Anna Marie; Burke Jr., Terrence R.; Pommier, Yves [Journal of Medicinal Chemistry, 2002, vol. 45, # 26, p. 5661 - 5670]
[37]Current Patent Assignee: H. LUNDBECK A/S - WO2005/61455, 2005, A1 Location in patent: Page/Page column 70-71
[38]Current Patent Assignee: MITSUBISHI CHEMICAL HOLDINGS CORPORATION - US5442055, 1995, A
[39]Current Patent Assignee: PFIZER INC - US5463122, 1995, A
[40]Current Patent Assignee: PFIZER INC - US5620997, 1997, A
[41]Current Patent Assignee: BRISTOL-MYERS SQUIBB CO - US4590196, 1986, A
[42]Current Patent Assignee: BASF SE - WO2007/3507, 2007, A1 Location in patent: Page/Page column 69; 11
[43]Current Patent Assignee: BIOAGENCY AG - WO2005/82873, 2005, A2 Location in patent: Page/Page column 13
[44]Location in patent: experimental part Shockravi, Abbas; Sadeghpour, Mahdieh; Zakeri, Masoomeh; Abouzari-Lotf, Ebrahim; Olyaei, Abolfazl [Phosphorus, Sulfur and Silicon and the Related Elements, 2010, vol. 185, # 4, p. 808 - 815]
[45]Henke, Adam; Srogl, Jiri [Chemical Communications, 2010, vol. 46, # 36, p. 6819 - 6821]
[46]Location in patent: experimental part Patel, Amar S.; Lees, Watson J. [Bioorganic and Medicinal Chemistry, 2012, vol. 20, # 2, p. 1020 - 1028]
[47]Gopinath, Pushparathinam; Ramalingam, Krishnan; Muraleedharan, Kannoth Manheri; Karunagaran, Devarajan [MedChemComm, 2013, vol. 4, # 4, p. 749 - 752]
[48]Liebeskind, Lanny S.; Gangireddy, Pavankumar; Lindale, Matthew G. [Journal of the American Chemical Society, 2016, vol. 138, # 21, p. 6715 - 6718]
[49]Gopinath; Yadav; Shukla; Srivastava; Puri; Muraleedharan [Bioorganic and Medicinal Chemistry Letters, 2017, vol. 27, # 5, p. 1291 - 1295]
[50]Current Patent Assignee: CHINESE ACADEMY OF SCIENCES - CN105017128, 2017, B Location in patent: Paragraph 0050; 0052; 0053
[51]Current Patent Assignee: Basler Chem. Fabr. - DE80713, 1800, C [Fortschr. Teerfarbenfabr. Verw. Industriezweige, vol. 4, p. 1266][Fortschr. Teerfarbenfabr. Verw. Industriezweige, vol. 4, p. 1266]
[52]Li, Jian-Ye; Huang, Jun; Zhang, Shi-Jin; Yao, Chunna; Sun, Wen-Wu; Liu, Bin; Zhou, Yingbi; Wu, Bin [Tetrahedron Letters, 2019, vol. 60, # 13, p. 895 - 899]
[53]Dent, Matthew R.; Milbauer, Michael W.; Hunt, Andrew P.; Aristov, Michael M.; Guzei, Ilia A.; Lehnert, Nicolai; Burstyn, Judith N. [Inorganic Chemistry, 2019, vol. 58, # 23, p. 16011 - 16027]
[54]Jin, Wen Bin; Xu, Chen; Cheung, Qipeng; Gao, Wei; Zeng, Ping; Liu, Jun; Chan, Edward W.C.; Leung, Yun-Chung; Chan, Tak Hang; Wong, Kwok-Yin; Chen, Sheng; Chan, Kin-Fai [Bioorganic Chemistry, 2020, vol. 100]
[55]Current Patent Assignee: CONTINENTAL AG - US10858499, 2020, B1 Location in patent: Page/Page column 17-18

8
[ 119-80-2 ]
[ 1677-27-6 ]

Reference： [1]Journal of the Chemical Society,1922,vol. 121,p. 90
[2]Il Farmaco,2003,vol. 58,p. 995 - 998

9
[ 119-80-2 ]
[ 3354-42-5 ]

Yield	Reaction Conditions	Operation in experiment
93%	With tetraphosphorus decasulfide In 1,4-dioxane for 48h; Inert atmosphere; Reflux;
71%	With tetraphosphorus decasulfide In 5,5-dimethyl-1,3-cyclohexadiene at 145℃;	1.1 Step (1): accurately weigh the raw material 2,2'-dithiodibenzoic acid (919mg, 3.0mmol) into a round bottom flask, add 5mL xylene to dissolve it, add phosphorus pentasulfide (1133mg, 5.1mmol) under stirring, The reaction temperature is raised to 145°C and the reaction is detected by TLC (Thin Layer Chromatography). After the raw material has been reacted, it is filtered while hot, and the filtrate is concentrated under reduced pressure to obtain a crude product. The crude product is recrystallized from absolute ethanol to obtain 788 mg of pure product 3H-benzo [1,2] Disulfide-3-thione, compound 1, yield 71%, red needle-like crystals.
	With phosphorous (V) sulfide; xylene

	With Lawessons reagent In benzene Heating; Yield given;
	With tetraphosphorus decasulfide In pyridine for 1h; Heating;
	With pyridine; tetraphosphorus decasulfide

Reference： [1]Shukla, Rahul; Dhaka, Arun; Aubert, Emmanuel; Vijayakumar-Syamala, Vishnu; Jeannin, Olivier; Fourmigué, Marc; Espinosa, Enrique [Crystal Growth and Design, 2020, vol. 20, # 12, p. 7704 - 7725]
[2]Current Patent Assignee: XIHUA UNIVERSITY - CN113444067, 2021, A Location in patent: Paragraph 0037-0041
[3]Fowkes; McClelland [Journal of the Chemical Society, 1941, p. 187,190]
[4]El-Barbary, A. A.; Clausen, K.; Lawesson, S.-O. [Tetrahedron, 1980, vol. 36, p. 3309 - 3316]
[5]Borgna; Vicarini; Carmellino; Pagani [Farmaco, Edizione Scientifica, 1983, vol. 38, # 10, p. 801 - 810]
[6]Salvetti, Raul; Martinetti, Giovanni; Ubiali, Daniela; Pregnolato, Massimo; Pagani, Giuseppe [Il Farmaco, 2003, vol. 58, # 9, p. 995 - 998]

10
[ 119-80-2 ]
[ 147-93-3 ]

Yield	Reaction Conditions	Operation in experiment
85%	With hydrogenchloride; hydrogen iodide; hypophosphorous acid for 3h; Heating;
73%	With hydrogenchloride; diphenylphosphinopolystyrene In tetrahydrofuran for 7h; Heating;
	With tin; acetic acid weiteres Reagens: konz. Salzsaeure;

	With acetic acid; zinc weiteres Reagens: konz. Salzsaeure;
	With sodium hydroxide; D-glucose
	With phosphorus; hydrogen iodide at 115 - 120℃; im geschlossenen Rohr;
	With sodium dithionite; water; sodium carbonate
	Multi-step reaction with 2 steps 1: concentrated sulfuric acid 2: zinc dust; glacial acetic acid
	With hydrogenchloride; zinc In water Inert atmosphere; Cooling with ice;

Reference： [1]Bhatt, M. Vivekananda; El Ashry, Shaker H.; Somayaji, Vishwanatha [Indian Journal of Chemistry - Section B Organic and Medicinal Chemistry, 1980, vol. 19, # 6, p. 473 - 486]
[2]Amos, Richard A.; Fawcett, Shayne M. [Journal of Organic Chemistry, 1984, vol. 49, # 14, p. 2637 - 2639]
[3]Hinsberg [Chemische Berichte, 1910, vol. 43, p. 652]
[4]Hinsberg [Chemische Berichte, 1910, vol. 43, p. 652]
[5]Claasz [Chemische Berichte, 1912, vol. 45, p. 2427]
[6]Organic Syntheses [12 <New York 1932>, S. 77]
[7]Aulich [Dissertation <Genf 1893>] Anlich zit. bei List; Stein [Chemische Berichte, 1898, vol. 31, p. 1666]
[8]Katz et al. [Journal of Organic Chemistry, 18 <1953 1380, 1387]
[9]Smiles; McClelland [Journal of the Chemical Society, 1922, vol. 121, p. 90]
[10]Location in patent: experimental part Xu, Hua-Jian; Liang, Yu-Feng; Cai, Zhen-Ya; Qi, Hong-Xia; Yang, Chun-Yan; Feng, Yi-Si [Journal of Organic Chemistry, 2011, vol. 76, # 7, p. 2296 - 2300]

11
[ 118-92-3 ]
[ 119-80-2 ]

Yield	Reaction Conditions	Operation in experiment
	With potassium iodide; sodium nitrite In water	2 EXAMPLE 2 EXAMPLE 2 137.5 g of anthranilic acid were dissolved in 500 g of water and 134 g of 30% strength hydrochloric acid, and the solution was cooled to 5° C. 241 g of a 30% strength NaNO2 solution were added to the stirred solution in such a manner that the internal temperature did not exceed 5° C. 6 g of a 50% strength aqueous solution of Cu(II) Cl2.2H2 O and 1.6 g of potassium iodide in 100 g of water were initially taken in a stirred vessel, and the previously prepared solution of the diazonium salt of the anthranilic acid was pumped, in the course of one hour, into the decomposition vessel. From the beginning of the addition of diazonium solution, a stream of 184 g/hour of SO2 was passed into the decomposition vessel, whose internal temperature was kept at 30° C. from the beginning, by cooling. After all the diazonium salt solution had been introduced (a procedure which took 60 minutes), the SO2 stream was reduced to 130 g/hour, and after 90 minutes (from the beginning) the passage of SO2 was discontinued. The mixture was then heated to the reflux temperature (99° C.) in the course of 30 minutes. The residence time (from the beginning of the reaction) was 1.7 hours in total in the 1st stage, and 0.7 hour in the 2nd stage. The mixture was kept at 99° C. for 20 minutes, cooled to 40° C. in the course of 20 minutes, and then filtered. 143.8 g (94% of theory) of o,o'-dithiodibenzoic acid of melting point 286°-288° C. were obtained.
	Stage #1: anthranilic acid With hydrogenchloride; sodium nitrite In water at 0 - 5℃; Stage #2: With potassium borohydride; sulfur; sodium hydroxide In water at 60℃; for 5h;	15 50 mL aqueous solution of 12 g KBH4 is slowly added dropwise to 400 mL aqueous solution of 64 g selenium powder in room temperature, and then 64 g selenium powder is added, and stirred in room temperature for 2 h, and then 75 mL 9 mol/L NaOH solution is added, and stirred for 3 h to obtain the alkaline solution of Se ion. [0107] 240 g o-aminobenzoic acid is added into 500 mL water and 400 mL concentrated HCl, completely dissolved, and put still in 0° C.5° C. ice water bath. 12 g NaNO2 is added into 50 mL water and stirred to dissolve, and then added dropwise into o-aminobenzoic acid solution, and the temperature is controlled between 0° C.5° C., [0108] Potassium iodide-starch test paper is used to determine the end of reaction (drip one drop of reaction liquid onto potassium iodide-starch test paper, the test paper turning blue indicates complete reaction) to obtain diazonium salt solution. [0109] The diazonium salt solution is added dropwise to the prepared alkaline solution of Se ion, after dripping, the temperature is raised to 60° C., reacted for 5 h. pH of the reaction liquid is adjusted with concentrated hydrochloric acid to less than 3, and yellow precipitate is obtained, filtered and washed with water. Then NaHCO3 is added, dissolved, boiled and filtered, and the filtrate is acidized by diluted hydrochloric acid and pH is adjusted to less than 3, and yellow precipitate is obtained, filtered and white-like or light yellow filter cake is obtained, and dried under 100° C. to obtain benzoic acid 2,2′-diselenide.
	Stage #1: anthranilic acid With hydrogenchloride; sodium nitrite In water at 5℃; for 0.333333h; Stage #2: With sodiumsulfide nonahydrate; sulfur; sodium hydroxide In water at 0 - 20℃; for 2h;

Reference： [1]Organic Syntheses [12 <New York 1932>, S. 76]
[2]Current Patent Assignee: BASF SE - US4493802, 1985, A
[3]Current Patent Assignee: YANTAI DONGCHENG PHARMACEUTICAL CO., LTD. - US2013/211097, 2013, A1 Location in patent: Paragraph 0106; 0107; 0108; 0109; 0222
[4]Luo, Li; Li, Yan; Qiang, Xiaoming; Cao, Zhongcheng; Xu, Rui; Yang, Xia; Xiao, Ganyuan; Song, Qing; Tan, Zhenghuai; Deng, Yong [Bioorganic and Medicinal Chemistry, 2017, vol. 25, # 6, p. 1997 - 2009]

12
[ 119-80-2 ]
[ 106-48-9 ]
[ 59803-22-4 ]

Yield	Reaction Conditions	Operation in experiment
99%	With sulfuric acid at -5 - 70℃; for 21h;	1 2,2'-dithiosalicylic acid (84.4 g, 0.27 mol) was added to sulfuric acid (18M) (300 mL). The suspension was cooled to -5°C and 4-chlorophenol ( 120.2 g, 0.94 mol) was added and the mixture was slowly brought to room temperature. The reaction mixture was heated to 60°C and allowed to stir for 15 hours and another 6 hours at 70°C. After reaction, the reaction mixture was poured into a mixture of ice (500 g) and distilled water (200 ml). The crude 1-chloro-4-hydroxy-hioxanthen-9-one precipitated from the medium and was isolated by filtration. The crude 1-chloro-4-hydroxy- hioxanthen-9-one was dissolved in water, using an aqueous solution of potassium hydroxide (1.5 N) (3,5L). The mixture was acidified to pH = 2.4 with an aqueous solution of hydrochloric acid (12M). 1-chloro-4-hydroxy- hioxanthen-9-one was isolated by filtration and dried to yield 140 g (99%) of 1 -Chloro-4-hydroxy-hioxanthen-9-one.
77.9%	Stage #1: 2,2'-dithiobenzoic acid With sulfuric acid In water for 0.5h; Stage #2: 4-chloro-phenol In water at 40 - 100℃; for 5h;	1.1 To a 250ml round-bottomed flask was charged 98% sulphuric acid (275.4g) and to this water (6.Ig) was added to reduce the acid strength to 96%. To this was added dithiobisbenzoic acid (30.6g; O.lOg mole) and the mixture stirred for 30 minutes. p-Chlorophenol (58.1g; 0.45g mole) was then added gradually over 1.5 hours, the temperature being maintained at 40-450C. A 60-minute workout at this temperature yielded a mobile orange/red slurry. This was warmed slowly to 80-850C and held for 2 hours, steady sulphur dioxide evolution occurring during this period. The mixture was finally warmed to 1000C and held for 30 minutes before then cooling the resultant deep red solution. This solution was poured slowly into water (269ml) at 5O0C, allowing the temperature to rise to 880C. After self-cooling to 5O0C the mixture was filtered and the filter cake washed three times with water (100ml) . A buff coloured solid was obtained that was then oven-dried to constant weight.Weight obtained = 40.9g (77.9% yield from DTBBA)
69.7%	In sulfuric acid	1 1-Chloro-4-Hydroxythioxanthone EXAMPLE 1 1-Chloro-4-Hydroxythioxanthone 2,2'-Dithiobisbenzoic acid (15.3 g; 0.05 mol) was stirred in concentrated sulphuric acid (150 ml) and 4-chlorophenol (38.5; 0.3) added over two hours at 10°-20° C. After stirring for a further hour the temperature was raised to 70°-80° for 2 hours. The mixture was cooled and quenched on to water (500 ml) and the resulting slurry cooled. The solid was filtered off, washed well with cold water and dried at 60° to give the title compound (18.3 g; 69.7%) of mp 260°-265° C.

	With sulfuric acid
	With sulfuric acid
	With sulfuric acid at 10 - 80℃; for 5h;	1 EXAMPLE 1 1-Chloro-4-hydroxythioxanthone was prepared as described in U.S. Patent No. 5,414,092 (1995). 2,2'-Dithiobisbenzoic acid (15.3 g, 0.05 mol) was stirred in concentrated sulfuric acid (150 mL) at 10-20º C and 4-chlorophenol (38.5 g, 0.3 mol) was added over 2 h. After stirring for an additional 1 h, the reaction was raised to 70-80ºC and stirred for 2 h. The mixture was cooled to room temperature and poured into ice water (500 mL). An orange solid was formed, filtered off, washed well with cold water and dried overnight under vacuum to give 1-chloro-4-hydroxythioxanthone (18.3g, 70 %) with mp 260-265º C. The identity of this compound was shown by 1H NMR to have the following structure:
	With sulfuric acid at -5 - 70℃; for 21h;	1 2,2'-dithiosalicylic acid (84.4 g, 0.27 mol) was added to sulfuric acid (18M) (300 mL). The suspension was cooled to -5°C and 4-chlorophenol (120.2 g, 0.94 mol) was added and the mixture was slowly brought to room temperature. The reaction mixture was heated to 60°C and allowed to stir for 15 hours and another 6 hours at 70°C. After reaction, the reaction mixture was poured into a mixture of ice (500 g) and distilled water (200 ml). The crude 1-chloro-4-hydroxy-hioxanthen-9-one precipitated from the medium and was isolated by filtration. The crude 1-chloro-4-hydroxy-hioxanthen-9-one was dissolved in water, using an aqueous solution of potassium hydroxide (1.5 N) (3,5L). The mixture was acidified to pH = 2.4 with an aqueous solution of hydrochloric acid (12M). 1-chloro-4-hydroxy-hioxanthen-9-one was isolated by filtration and dried to yield 140 g (99) of 1-Chloro-4-hydroxy-hioxanthen-9-one.

Reference： [1]Current Patent Assignee: AGFA-GEVAERT - WO2012/52288, 2012, A1 Location in patent: Page/Page column 43-44
[2]Current Patent Assignee: ARKEMA - WO2009/60235, 2009, A1 Location in patent: Page/Page column 9-10
[3]Current Patent Assignee: ARKEMA - US5414092, 1995, A
[4]Marsden; Smiles [Journal of the Chemical Society, 1911, vol. 99, p. 1356]
[5]Mancini, M. L.; Honek, J. F. [Synthetic Communications, 1986, vol. 16, # 9, p. 1109 - 1118]
[6]Current Patent Assignee: HENKEL AG & CO. KGAA - EP1538149, 2005, A2 Location in patent: Page/Page column 14
[7]Current Patent Assignee: AGFA-GEVAERT - EP2447259, 2012, A1 Location in patent: Page/Page column 27-28

13
[ 147-93-3 ]
[ 119-80-2 ]

Yield	Reaction Conditions	Operation in experiment
99%	With xenon difluoride In dichloromethane at 25℃;
99%	With 1-oxa-2-azaspiro<2.5>octane In toluene
99%	With polyvinylpolypyrrolidonium tribromide In ethanol at 20℃; for 1.5h; Green chemistry;	General procedure: A 25 mL round-bottom flask was charged with thiol (1 mmol), polyvinylpolypyrrolidoniume tribromide (1.2 gr), and EtOH(5 mL) as solvent. The reaction mixture was stirred at room temperature, and the progressof the reaction was monitored by TLC. After completion of the reaction, corresponding disulfides easily obtained by passing of reaction mixture through a short column using dichlromethane and acetone (95:5) as eluent.

99%	With dihydrogen peroxide In ethanol at 20℃; for 2h;
99%	With dihydrogen peroxide In ethanol at 20℃; for 1h; Green chemistry; chemoselective reaction;	2.5. General procedure for the oxidative coupling of thiols into disulfides using H2O2 in the presence of M-Salen-MNPs General procedure: M-Salen-MNPs (0.01 g) was added to a mixture of thiol (1 mmol) and H2O2 (0.4 mL) in ethanol (5 mL). Then the mixture was stirred for the appropriate time at room temperature. The progress was monitored by TLC. After completion of the reaction, the catalyst was separated by an external magnet and the mixture was washed with ethyl acetate. The product was extracted with ethylacetate. The organic layer was dried over anhydrous Na2SO4 (1.5 g). In some cases, the product was recrystallized from ethanol for further purification and products were obtained in good to high yield.
98%	for 0.333333h; microwave irradiation, max temp.: 180 deg C;
98%	With 3,6-di(2'-pyridyl)-1,2,4,5-tetrazine In ethanol; lithium hydroxide monohydrate at 40℃; for 0.0833333h;
98%	With dihydrogen peroxide In dichloromethane at 20℃; for 1.75h;
98%	With dihydrogen peroxide at 20℃; for 0.15h;
98%	With dihydrogen peroxide In ethanol at 20℃; for 0.25h; Green chemistry;
98%	With dihydrogen peroxide In ethanol; lithium hydroxide monohydrate at 20℃; for 1h; Green chemistry;	General procedure for the oxidative coupling of thiols into disulfides General procedure: Fe3O4MCM-41Ni-P2C (10 mg) was added to a mixture of thiol (1 mmol) and 33% H2O2 (0.4 mL) in ethanol (3 mL). The resulting reaction mixture was stirred for the specified time at room temperature (the progress of reaction was monitored by TLC). After completion of the reaction, the catalyst was separated by an external magnet and the product was washed with ethyl acetate. Then organic layer was dried over anhydrous Na2SO4 (1.5 g). Finally, the organic solvent was removed by simple evaporation and disulfides were obtained in very high isolated yields.
98%	With dihydrogen peroxide In ethanol at 20℃; for 1.16667h;	General procedure for the oxidative coupling of thiols General procedure: To the mixture of the thiol (1 mmol) and Fe3O4*MCM-41Zn-Arg (15 mg) in ethanol (3 mL), H2O2 (0.4 mL) was added and stirred at room temperature. After completion ofthe reaction (monitored by TLC), the catalyst was separated from the mixture by an external magnet and the product was extracted with ethyl acetate and the solvent was removed by simple evaporation to give pure disulfides.
98%	With dihydrogen peroxide In ethanol at 20℃; for 0.25h; Green chemistry;	General process for the synthesis of symmetrical disulfides General procedure: CoFe2O4/Trp/La was added (8 mg) to a mixture of thiol (1 mmol), H2O2(0.8 mL), and EtOH (3 ml) at room temperature. At the end of the reaction (checked by TLC),the CoFe2O4/Trp/La was filtrated and rinsed with distilled water and EtOAc. Then the product was rinsed using distilled water and dried over anhydrous Na2SO4.
97%	With iodine In lithium hydroxide monohydrate; acetonitrile at 20℃;
97%	With dihydrogen peroxide In ethanol at 20℃; for 2h; Green chemistry;
97%	With dihydrogen peroxide In ethanol at 20℃; for 2h;
97%	With dihydrogen peroxide In ethyl acetate at 20℃; for 0.666667h;	General procedure for the oxidative coupling of thiols General procedure: Boehmite-SSA (0.002 g) was added to a mixture of thiol(1 mmol) and H2O2 (0.4 mL) in ethyl acetate (2 mL). Then,the mixture was stirred for the appropriate time at room temperature. The progress of reaction was monitored byTLC. After completion of the reaction, the catalyst was separated by filtration and the mixture was washed with ethyl acetate. The product was extracted with ethyl acetate.The organic layer was dried over anhydrous Na2SO4(1.5 g). The products were obtained in good to high yield.
97%	With dihydrogen peroxide In ethanol at 20℃; for 0.0833333h;	2.5 General Procedure for the Oxidation of Thiolsto Disulfides General procedure: General experimental procedure for the oxidative couplingof thiols is as following: MCM-41(at)Tryptophan-M (Cd orHg) (0.005) was added to a mixture of thiol (1 mmol) andH2O2(0.5 mL) in ethanol (3 mL). Then the mixture wasmagnetically stirred for the appropriate time at room temperature.The progress of reaction was monitored by TLC.After completion of the reaction, the catalyst was removedby filtration and the mixture was washed with ethyl acetate.The product was extracted with ethyl acetate. After the evaporationof ethyl acetate, the pure product was obtained bycrystallization from ethanol (Scheme 3).
97%	With manganese dihydrogen carbonate; 3,4,5-trihydroxybenzoic acid; oxygen; anhydrous sodium carbonate In lithium hydroxide monohydrate at 80℃; for 4h; Schlenk technique; Green chemistry;
97%	With dihydrogen peroxide In ethanol at 20℃; for 0.0833333h; Green chemistry;
96%	With dihydrogen peroxide In acetonitrile at 20℃; for 0.416667h; Green chemistry;
96%	With dihydrogen peroxide at 20℃; for 0.0833333h; Green chemistry;	2.6. Typical procedures for the oxidative coupling of thiols General procedure: Typically, thiol (1 mmol), H2O2 (0.5 mL) and 0.005 g of catalystwas mixed with stirring. Upon completion of the reaction (monitoredby TLC), the catalyst was collected by simple filtration andthe resulting product was extracted, washed and the solvent evaporatedover anhydrous Na2SO4 (Scheme 1a).
96%	With dihydrogen peroxide In ethanol; lithium hydroxide monohydrate at 20℃; for 0.833333h;	General procedure for the oxidative coupling of thiols into disulfides General procedure: A mixture of thiol (1 mmol), 33 % H2O2 (0.4 mL) and Fe3O4MCM-41VO-SPATB (10 mg) in ethanol (3 mL) was stirred for the specified time at ambient temperature (the progress of reaction was monitored by TLC). After completion of the reaction, the catalyst was separated by applying an external magnet and the product was washed with ethyl acetate, and then dried over anhydrous Na2SO4 (1.5 g). Finally, Evaporation of the solvent gave the disulfides invery high isolated yields
96%	With dihydrogen peroxide In neat (no solvent, solid phase) at 20℃; for 1.58333h; Green chemistry;	General procedure for the oxidation reactions General procedure: To a stirred suspension of Fe3O4(at)Tryptophan-La in H2O2(0.5 mL) at room temperature, sulfide or thiol (1.0 mmol) was added under solvent-free condition. After the completion of reaction (monitored by TLC), the catalyst was separated using a magnet and the reaction mixture was concentrated to get pure sulfoxide or disulfide derivatives.
96%	With dihydrogen peroxide at 20℃; for 0.166667h;	2.4 General Procedure for the Oxidative Coupling of Thiols General procedure: In the typical procedure for oxidative coupling of thiols,0.01g Fe3O4(at)SiO2(at)DOP-BenPyr-M(II) (M=Ni or Cu) as catalyst was added to a mixture of thiol (1mmol), 0.4 mL H2O2 and PEG and stirred at room temperature. The progress was monitored by TLC. After the completion of the reaction, the catalyst was separated by an external magnet,then product extracted with CH2Cl2 (4 × 5mL). Anhydrous Na2SO4 was used for drying of the organic layer, then, the mixture was filtered and solvent was evaporated to obtain the disulfide product.
95%	With hydrogenchloride; copper(II) sulphate In lithium hydroxide monohydrate for 1h;
95%	With poly(4-vinylpyridinium nitrate) I; silica supported sulfuric acid In ethyl acetate at 20℃; for 1.33333h;
95%	With guanidinium nitrate In dichloromethane at 20℃; for 0.166667h; chemoselective reaction;
95%	With aluminum(III) oxide In neat (no solvent) for 0.5h; Milling; chemoselective reaction;
95%	With Cu(NO<SUB>3</SUB>)<SUB>2</SUB>3H<SUB>2</SUB>O In lithium hydroxide monohydrate; ethyl acetate at 20℃; for 0.75h; Green chemistry;
95%	With formic acid; 5-ethyl-10-(2-hydroxylethyl)-3,7,8-trimethylisoalloxazin-5-ium triflate; oxygen; triethylamine In acetonitrile at 60℃; for 4h;
95%	With dihydrogen peroxide In ethanol at 20℃; for 2h; Green chemistry;	General procedure for oxidative coupling of thiols General procedure: Dopamine sulfamic acid-functionalized magnetic Fe3O4 nanoparticles (DSA(at)MNPs) (0.004 g) were added to solution of thiol (1 mmol) and H2O2 33 % (0.5 mL) in ethanol (10 mL). The reaction mixture was stirred at room temperature, and the progress of the reaction was monitored by TLC. After completion of the reaction, the catalyst was separated using an external magnet, and the product was extracted with CH2Cl2 and dried over anhydrous Na2SO4. Finally, the solvent was removed by simple evaporation to give the corresponding pure disulfides.
95%	With urea hydrogen peroxide addition compound In ethanol at 20℃; for 0.35h;	Typical procedure for the synthesis of disulfides catalyzed by Co(at)MCM-41 or Fe(at)MCM-41: as a typical procedure General procedure: A mixture of thiols (1 mmol), UHP (5 mmol), and Co orFeMCM-41 (20 mg) was stirred at room temperature inethanol and the progress of the reaction was monitored by TLC.After completion of the reaction, the catalyst was removed andthe products were extracted with CH2Cl2 (3 × 10 mL). Theresults are shown in Table 7.
95%	With dihydrogen peroxide In ethanol at 20℃; for 0.333333h; Green chemistry;	General procedure for the oxidative coupling of thiols to the disulfides General procedure: A mixture of thiol (1 mmol), hydrogen peroxide (0.5 mL) and the catalyst (0.005 g) in ethanol (2 mL) was stirred at ambient temperature. Reaction progress was monitored by TLC (acetone: n-hexane, 2:8). After completion of the reaction, catalyst was separated by an external magnet and washed with ethyl acetate; next, the product was extracted with ethyl acetate (5 mL 9 4). The organic layer was dried over anhydrous Na2SO4 (1.5 g). Finally, the organic solvents were evaporated, and the corresponding disulfides were obtained in high to excellent yields (88-98%).
95%	With dihydrogen peroxide In ethanol; lithium hydroxide monohydrate at 20℃; for 0.0833333h; Green chemistry;	General procedure for the oxidative coupling of thiols General procedure: In a typical procedure, a solution of thiol (1 mmol) and Fe3O4/AMPD/Ni (0.005 g) was added to a round-bottomed flask containing H2O2 (0.5 mL) and 2 mL of ethanol and stirred at room temperature for an appropriate time. After completion of the addition, Fe3O4/AMPD/Ni catalyst was easily separated by a simple magnet, and then the product was extracted with ethyl acetate and dried over anhydrous Na2SO4 to give the pure disulfides.
95%	With dihydrogen peroxide In lithium hydroxide monohydrate; ethyl acetate at 20℃; for 0.333333h; Green chemistry;	General procedure for the oxidation of thiols to disulfides General procedure: In another study, a mixture of the VO-AMPD(at)SBA-15 (0.004 g), thiol (1 mmol) and H2O2 (0.4 mL) was stirred at room temperature in ethyl acetate (2 mL). The progress was monitored by TLC. After completion of the reaction, VO-AMPD(at)SBA-15 catalyst was separated from the mixture by filtration. Then products were extracted with ethyl acetate and dried, and the solvent was removed to give the pure disulfides.
95%	With dihydrogen peroxide In ethanol at 25℃; for 0.0833333h; Sonication; chemoselective reaction;	2.5. General procedure for oxidation of sulfides and thiols General procedure: For the fabrication of sulfoxide, 1 mmol sulfide, 0.6 ml H2O2 (33%) and 0.005 g nanocatalyst were stirred at room temperature. Also, for producing disulfides, 1 mmol thiols and 0.4 ml H2O2 (33%) with 0.008 g nanocatalyst in ethanol as a green solvent were mixed at 25 °C. After completion of the reaction, the catalyst was removed by a magnet and the product was extracted with ethyl acetate and dried using a vacuum dryer.
94%	With 1,3-dibromo-5,5-dimethylhydantoin In dichloromethane at 20℃; for 5h;
94%	With hydrogen bromide; dimethyl sulfoxide In chloroform at 20℃; for 10h; Inert atmosphere; Schlenk technique;	General procedure for the synthesis of symmetrical disulfides: General procedure: A mixture of thiols(1.0 mmol) and HX (0.2 mmol) in DMSO-CHCl3 (5 mL, 1:1, v/v) was stirred atroom temperature for respective time (Table 3). After the completion of thereaction, as monitored by TLC, the reaction mixture was diluted with 10 mL ofwater and extracted with CHCl3 (3 15 mL). The combined organic layerswere washed with brine (2 10 mL), dried over anhydrous Na2SO4, andevaporated in a rotary evaporator under reduced pressure. A reasonably pureproduct obtained was further purified by recrystallization using hexane-CHCl3mixture. The purity of the compound was confirmed by melting point andNMR measurements.
94%	With urea hydrogen peroxide addition compound In ethanol at 20℃; for 0.266667h;	General procedure for oxidative coupling of thiols to disulfides with UHP catalyzed by Cr-MCM-41 and Mn-MCM-41 General procedure: Thiols ((1 mmol), 5 mmol UHP, and 4 mL acetone as solvent along with 25 mg catalyst were added to a 10-mL two-necked flask equipped with a stirrer. The progress of the reaction was monitored by TLC. After completion of the reaction, the catalyst was removed and the pure products were extracted with CH2Cl2(3 9 10 mL). The results are presented in Table 6.
94%	With dihydrogen peroxide In ethanol at 20℃; for 0.416667h; Green chemistry;
93%	With iodine In ethanol at 20℃; for 0.5h;	4.2.1.1. Synthesis of dimethyl 2,2'-disulfanediyldibenzoate (4). Route 1. General procedure: To a solution of thiosalicylic acid 1 (15.4 g, 100 mmol) in 95% ethanol (800 mL) at room temperature 400 mL of a saturated slurry of I2 (38.1 g, 150 mmol) prepared by suspending neat I2 (100 g, 390.0 mmol) in 95% ethanol (1000 mL) were added dropwise. The solution was stirred at room temperature until a persistent yellow color formed (30 min). A colorless precipitate slowly formed, was filtered, collected and dried under vacuum (11.3 g,37%). The mother liquor was evaporated in vacuo and purified by flash chromatography (CH2Cl2/AcOEt/CH3COOH 98:2:0.1) to give another portion of 2,2'-disulfanediyldibenzoic acid (2) (17.1 g, 56%). ESI-MS (m/z): 329 [M+Na].+. The other chemical and analytical data were identical to those of the already described compound 2. To a solution of disulfide 2 (17.1 g, 56.0 mmol) in methanol (600 mL) neat 98% H2SO4 (10 mL) was added and the reaction mixture was heated at reflux for 24 h (TLC inn-hexanes/AcOEt 9:1), poured into a cold K2CO3/H2O mixture (300 g, 600 mL) and the organics were extracted in CHCl3 (3 x 500 mL), dried over anhydrous Na2SO4, filtered and evaporated to dryness in vacuo to give the title compound 4 as a colorless solid (17.0 g, 91%). The mother liquor was acidified to pH 2 by diluted HCl (as needed) and extracted with CHCl3 to recover the starting compound 2 (1.71 g, 10%).
93%	With dihydrogen peroxide In ethanol at 20℃; for 0.5h;	General procedure for the oxidative coupling of thiols to thedisulfdes: General procedure: A mixture of thiol (1 mmol), hydrogen peroxide (0.5 mL)and Fe3O4 MNPs-DETA/Benzyl-Br3 (12.5 × 10-3 mol%) inethanol (2 mL) was stirred at ambient temperature. Reactionprogress was monitored by TLC (acetone: n-hexane, 2:8). Aftercompletion of the reaction, catalyst was separated by externalmagnet and washed with ethyl acetate, and next, the productwas extracted with ethyl acetate (4 × 5 mL). The organic layerwas dried over anhydrous Na2SO4 (1.5 g). Finally, the organic solvents were evaporated, and the corresponding disulfdeswere obtained in high to excellent yields (89-98%).All the products are known compounds and were characterized by comparison of their IR and NMR spectraldata and physical properties with those reported in theliterature.
93%	With dihydrogen peroxide In ethanol at 20℃; for 0.666667h; Green chemistry; chemoselective reaction;
93%	With dihydrogen peroxide In ethanol at 20℃; for 1.25h; Green chemistry;
93%	With Bromotrichloromethane In tetrahydrofuran at 20℃; Schlenk technique; Irradiation;	13 Example 13 Add 61.6mg (0.4mmol) o-carboxythiophenol and 237.9mg (1.2mmol) chlorobromomethane into a 10mL Schlenk container, then add 10mL tetrahydrofuran with a syringe, and react for 24h under the irradiation of a 50W energy-saving lamp at room temperature. After the reaction is complete After concentrating to remove the solvent, the crude product was separated by silica gel column chromatography (eluent: petroleum ether) to obtain a white solid: 57.0 mg, yield: 93%.
92%	With dihydrogen peroxide at 20℃; for 1.33333h;	2.3. General procedure for the oxidation reactions General procedure: To a stirred suspension of Fe3O4Nd in H2O at room temperature,sulfide or thiol (1 mmol) was added under solvent-free condition. After the completion of reaction (monitored by TLC) in appropriatetime, the separated catalyst (using by magnetic) washedwith ethyl acetate to obtained pure sulfoxide or disulfidederivatives.
91%	With ethylenebis(N-methylimidazolium) chlorochromate In acetonitrile at 20℃; for 0.0833333h;
91%	With salen complex of Cu(II) immobilized on Fe₃O₄ nanoparticles; dihydrogen peroxide In ethanol at 20℃; for 2h;	2.6 General procedure for the oxidative coupling of thiols General procedure: A 25mL round-bottom flask was charged with thiol (1mmol), H2O2 33% (0.5mL), and catalyst (0.01g) in ethanol as solvent. The reaction mixture was stirred at room temperature, and the progress of the reaction was monitored by TLC. After completion of the reaction, the catalyst was separated by an external magnet and the product was extracted with CH2Cl2. The combined organics were washed with water (5mL) and dried over anhydrous Na2SO4. Finally, the solvent was removed to give the corresponding pure disulfides
91%	With oxygen In ethanol at 20℃; for 0.583333h; Green chemistry;
91%	With dihydrogen peroxide In ethanol at 20℃; for 1h; Green chemistry;
90%	In dimethyl sulfoxide at 20℃; for 0.5h;
90%	With (Bu₄N)₂S₂O₈ at 20℃; for 0.0833333h;
90%	With silicium tetrachloride; ammonium dichromate; mesoporous silica at 80℃; for 0.0333333h;
90%	With N-bromophthalimide In lithium hydroxide monohydrate; propan-2-one for 0.2h; microwave irradiation;
90%	With tungstate sulfuric acid; NaNO₂ In dichloromethane at 20℃; for 0.833333h;
90%	With poly(N-bromobenzene-1,3-disulfonylamide) In dichloromethane at 20℃; for 72h;
90%	With N-(tert-butyl)-N-chloro-cyanamide; sodium bromide In propan-2-one at 20℃;
90%	With N,N′-bis(salicylidene)ethylenediaminocobalt(II) In ethanol at 50℃; for 1h;
90%	With urea hydrogen peroxide addition compound In acetonitrile at 20℃; for 0.416667h;
90%	With dihydrogen peroxide In neat (no solvent) at 20℃; for 0.283333h; chemoselective reaction;
90%	With dihydrogen peroxide In ethanol at 20℃; for 1.5h; Green chemistry;	2.2 General procedure for the synthesis of disulfides General procedure: A mixture of thiol (1mmol) and H2O2 (37%) was stirred in solvent-free conditions at room temperature in presence of 0.006g of Fe3O4(at)L-aspartic-Gd as catalyst. Progress of the reaction was monitored by TLC. After completion, the catalyst was separated by magnetic field and crystallized to obtain pure product
90%	With dihydrogen peroxide In lithium hydroxide monohydrate at 20℃; for 0.333333h; Green chemistry;	The typical procedure for oxidative couplingof thiols to disulfides with H2O2 General procedure: 1 mmol thiol, 20 mg of γ-Fe2O3 /CuHPECGs, and H2O2(0.4 mL, 3.92 mmol) were stirred at room temperaturein 2 mL of H2Ofor the specified time shown in Table 1.The reaction progress was monitored by TLC (n-hexane/ethyl acetate: 1:4). After completion of the reaction, the heterogeneous catalyst was magnetically separated from themixture and the product was extracted using ethyl acetate.The obtained products dried over anhydrous Na2SO4andorganic solvent evaporation were afforded pure product.
89%	With dihydrogen peroxide In neat (no solvent) at 20℃; for 0.666667h; Green chemistry;
89%	With dihydrogen peroxide In neat (no solvent) at 20℃; for 0.666667h;	2.4. General procedure for the oxidative coupling of thiols to thedisulfides General procedure: 0.005 g Fe3O4-AMPD-Pd was added to a mixture including1 mmol thiol, 0.4 mL H2O2 33% and free solvent were stirred atroom temperature. The reaction was followed by TLC after completion.The nanocatalyst was isolated by a simple magnet.
88%	With dihydrogen peroxide In ethanol at 25℃; for 0.75h;
87%	With dihydrogen peroxide In neat (no solvent) at 20℃; for 1.5h; Green chemistry;
86.5%	With nickel(IV) oxide In diethyl ether at 30℃; for 2h;
86%	With anhydrous sodium perchlorate In lithium hydroxide monohydrate at 0 - 5℃; for 0.25h;
86%	With benzyltriphenylphosphonium dichromate for 0.25h;
86%	With silica sulfuric acid; potassium iodide at 20℃; for 1h; chemoselective reaction;	General procedure for the oxidative coupling of thiols using PVPP-H2O2/SiO2-OSO3H/KI General procedure: To a suspension of polyvinylpolypyrrolidone-supported hydrogen peroxide (0.175 g),silica sulfuric acid (0.1 g) and potassium iodide (0.02 mmol) in dichloromethane or ethylacetate (5 mL) was added a thiol (1 mmol), and the mixture was stirred at room temperaturefor the specified time (Table I). The progress of the reaction was monitored by TLC. Aftercompletion of the reaction, the reaction mixture was filtered and the residue washed withCH2Cl2 (20 mL), (the residue of entry 5 was washed with ethanol). Finally, the organicsolvent was evaporated and pure product was obtained as judged by TLC and 1H-NMRspectroscopy.
86%	With tert.-butylnitrite; oxygen In acetonitrile at 50℃; for 3h; Sealed tube; Green chemistry;	Typical procedure for disulfides (2a) General procedure: A sealed tube (90 mL) equipped with a magnetic stirring bar and an O2 balloon was charged with dichloroethane (DCE, 20 mL), thiophenol (1a, 4 mmol, 0.44 g) and TBN (0.16 mmol, 4 mol%, 19.2 mL). Then the tube was placed in an oil bath, which was preheated to 50°C. The mixture was stirred for 1 h until starting material was completely consumed as monitored by GC and TLC. After removing the solvent, the residue was purified by column chromatography on silica gel to give the desired diphenyl disulfide (2a, 90%, 0.394 g) as a white solid.
85%	With dihydrogen peroxide In ethanol at 20℃; for 1.33333h;
84%	With dihydrogen peroxide In neat (no solvent) at 25℃; for 0.6h; Green chemistry;
84%	With urea hydrogen peroxide addition compound at 25℃; for 2h;	2.1 General procedure for the preparation of symmetrical diorganoyl disulfides General procedure: Thiol (1.0 mmol) and the oxidant UHP (1.0 mmol) were placed in a test-tube, followed by polysorbate-80 (0.25 mL). The mixture was stirred at room temperature and the progress of the reaction was monitored by TLC. When the reaction was complete, the product was extracted with hexane or diethyl ether, and the mixture was stirred using a vortex. The extraction process is monitored by TLC until complete removal of the product from the polysorbate phase (aprox. 10×1 mL). The organic layer is subsequently completely removed under vacuum. The crude product was purified by column chromatography over silica gel with hexane or a mixture of ethyl acetate/hexane to afford the desired disulfide.
82%	With ammonium dichromate; magnesium hydrogen sulfate; mesoporous silica In hexane at 20℃; for 0.5h;
80%	With sodium hydroxide; dihydrogen peroxide In lithium hydroxide monohydrate at 0 - 60℃;
75%	With 2,6-dicarboxypyridinium hydrobromide perbromide at 20℃; for 0.416667h; Neat (no solvent);
69%	With oxone; mesoporous silica In acetonitrile at 20℃;
68%	With magnetic ion exchanged Montmorillonite-k10 In tetrahydrofuran at 50℃; for 1h; Green chemistry;
65.3%	With self-assembled mesoporous ZSM-5 zeolite nanocrystal; air In lithium hydroxide monohydrate at 69.84℃; for 6h;
65%	With dihydrogen peroxide In ethyl acetate at 20℃; for 1.25h;	General procedure for the oxidative couplingof thiols to disulfides General procedure: A solution of thiol (1 mmol), H2O2(30%) and Cu immobilizedon Fe3O4SiO2l-Arginine (0.005 g, 4.1 mol%) inethyl acetate was stirred at room temperature. The reactionprogress was monitored by TLC in the mixture of n-hexaneand acetone (8:2). Then, the catalyst was separated using amagnetic field. Then, water (15 mL) was added to the reactionmixture and the product was extracted in the organicphase. Finally, the excess of solvent was removed underreduced pressure to give the corresponding pure disulfideswith excellent yield.
62%	With lithium hydroxide monohydrate; dihydrogen peroxide In various solvent(s) at 20℃; for 0.166667h;
60%	With iodine In ethanol for 0.5h;
58%	With Porcine Pancreas Lipase In lithium hydroxide monohydrate at 20℃; for 30h; Green chemistry; Enzymatic reaction;
40%	With barium manganate In chloroform for 10h; Ambient temperature;
30%	With air; Me₄ (dibenzo[b,i]-1,4,8,11-tetraaza[14]annulene) cobalt(II) In chloroform at 25℃; for 3h;
25%	With ethyl 2-hydroxypropionate at 60℃; for 16h;
	beim Stehen an der Luft;
	With [7-(dimethylamino)phenothiazin-3-ylidene]dimethylazanium chloride In methanol; lithium hydroxide monohydrate at 30℃; different concentrations, with or without KCl or H₂SO₄, diferent pH, different dielectric constants of the solution;
	also with additives;
	With lead tetraacetate
	With hydrogenchloride; iron(III) chloride
	With iodine
	With sulfuric acid
	With NBS
	With alkali
	With ferric alum
	With anhydrous sodium perchlorate In tetrahydrofuran at 10℃; for 0.166667h;
	With sulfuric acid; [7-(dimethylamino)phenothiazin-3-ylidene]dimethylazanium chloride; copper atom In ethanol; lithium hydroxide monohydrate at 35℃;

Reference： [1]Patrick, Timothy B.; Khazaeli, Sadegh; Nadji, Sourena; Hering-Smith, Katy; Reif, Dirk [Journal of Organic Chemistry, 1993, vol. 58, # 3, p. 705 - 708]
[2]Andreae, Siegfried [Journal fur Praktische Chemie - Chemiker-Zeitung, 1997, vol. 339, # 2, p. 152 - 158]
[3]Ghorbani-Choghamarani, Arash; Azadi, Gouhar; Tahmasbi, Bahman; Hadizadeh-Hafshejani, Mojtaba; Abdi, Zainab [Phosphorus, Sulfur and Silicon and the Related Elements, 2014, vol. 189, # 4, p. 433 - 439]
[4]Ghorbani-Choghamarani, Arash; Darvishnejad, Zahra; Norouzi, Masoomeh [Applied Organometallic Chemistry, 2014, vol. 29, # 3, p. 170 - 175]
[5]Ghorbani-Choghamarani, Arash; Darvishnejad, Zahra; Tahmasbi, Bahman [Inorganica Chimica Acta, 2015, vol. 435, p. 223 - 231]
[6]Sainte-Marie, Laurent; Guibe-Jampel, Eryka; Therisod, Michel [Tetrahedron Letters, 1998, vol. 39, # 52, p. 9661 - 9662]
[7]Samanta, Suvendu; Ray, Shounak; Ghosh, Abhisek Brata; Biswas, Papu [RSC Advances, 2016, vol. 6, # 45, p. 39356 - 39363]
[8]Rezaei, Somaieh; Ghorbani-Choghamarani, Arash; Badri, Rashid; Nikseresht, Ahmad [Applied Organometallic Chemistry, 2018, vol. 32, # 1]
[9]Hajjami, Maryam; Sharifirad, Fatemeh; Gholamian, Fatemeh [Applied Organometallic Chemistry, 2017, vol. 31, # 12]
[10]Moeini, Nazanin; Tamoradi, Taiebeh; Ghadermazi, Mohammad; Ghorbani-Choghamarani, Arash [Applied Organometallic Chemistry, 2018, vol. 32, # 9]
[11]Nikoorazm, Mohsen; Ghorbani, Farshid; Ghorbani-Choghamarani, Arash; Erfani, Zahra [Phosphorus, Sulfur and Silicon and the Related Elements, 2018, vol. 193, # 9, p. 552 - 561]
[12]Nikoorazm, Mohsen; Erfani, Zahra [Inorganic and Nano-Metal Chemistry, 2020, vol. 51, # 5, p. 642 - 655]
[13]Molaei, Somayeh; Ghadermazi, Mohammad; Moeini, Nazanin [Research on Chemical Intermediates, 2022, vol. 48, # 2, p. 771 - 793]
[14]Zeynizadeh, Behzad [Journal of Chemical Research - Part S, 2002, # 11, p. 564 - 566]
[15]Ghorbani-Choghamarani, Arash; Tahmasbi, Bahman; Arghand, Fatemeh; Faryadi, Sara [RSC Advances, 2015, vol. 5, # 112, p. 92174 - 92183]
[16]Hajjami, Maryam; Ghorbani-Choghamarani, Arash; Ghafouri-Nejad, Raziyeh; Tahmasbi, Bahman [New Journal of Chemistry, 2016, vol. 40, # 4, p. 3066 - 3074]
[17]Ghorbani-Choghamarani, Arash; Hajjami, Maryam; Tahmasbi, Bahman; Noori, Nourolah [Journal of the Iranian Chemical Society, 2016, vol. 13, # 12, p. 2193 - 2202]
[18]Molaei, Somayeh; Tamoradi, Taiebeh; Ghadermazi, Mohammad; Ghorbani-Choghamarani, Arash [Catalysis Letters, 2018, vol. 148, # 7, p. 1834 - 1847]
[19]Song, Lijuan; Li, Wenhao; Duan, Wenxue; An, Jichao; Tang, Shanyu; Li, Longjia; Yang, Guanyu [Green Chemistry, 2019, vol. 21, # 6, p. 1432 - 1438]
[20]Molaei, Somayeh; Ghadermazi, Mohammad [Applied Organometallic Chemistry, 2019, vol. 33, # 7]
[21]Shiri, Lotfi; Narimani, Hojatollah; Kazemi, Mosstafa [Applied Organometallic Chemistry, 2018, vol. 32, # 1]
[22]Molaei, Somayeh; Tamoradi, Taiebeh; Ghadermazi, Mohammad; Ghorbani-Choghamarani, Arash [Polyhedron, 2018, vol. 156, p. 35 - 47]
[23]Nikoorazm, Mohsen; Ghorbani, Farshid; Ghorbani-Choghamarani, Arash; Erfani, Zahra [Journal of the Iranian Chemical Society, 2019, vol. 16, # 3, p. 553 - 562]
[24]Tamoradi, Taiebeh; Irandoust, Asrin; Ghadermazi, Mohammad [Journal of the Iranian Chemical Society, 2019, vol. 16, # 8, p. 1723 - 1733]
[25]Hajjami, Maryam; Sheikhaei, Shiva; Gholamian, Fatemeh; Yousofvand, Zakieh [Catalysis Letters, 2021, vol. 151, # 8, p. 2420 - 2435]
[26]Subrahmanyan, T. [Journal of the Indian Chemical Society, 1986, vol. 63, p. 1068 - 1069]
[27]Location in patent: experimental part Ghorbani-Choghamarani, Arash; Sardari, Sara [Journal of Sulfur Chemistry, 2011, vol. 32, # 1, p. 63 - 69]
[28]Location in patent: experimental part Ghorbani-Choghamarani, Arash; Nikoorazm, Mohsen; Goudarziafshar, Hamid; Shokr, Alireza; Almasi, Hosein [Journal of Chemical Sciences, 2011, vol. 123, # 4, p. 453 - 457]
[29]Chatterjee, Tanmay; Ranu, Brindaban C. [RSC Advances, 2013, vol. 3, # 27, p. 10680 - 10686]
[30]Soleiman-Beigi, Mohammad; Taherinia, Zahra [Monatshefte fur Chemie, 2014, vol. 145, # 7, p. 1151 - 1154]
[31]Murahashi, Shun-Ichi; Zhang, Dazhi; Iida, Hiroki; Miyawaki, Toshio; Uenaka, Masaaki; Murano, Kenji; Meguro, Kanji [Chemical Communications, 2014, vol. 50, # 71, p. 10295 - 10298]
[32]Ghorbani-Choghamarani, Arash; Rabiei, Hossein; Tahmasbi, Bahman; Ghasemi, Banoo; Mardi, Farideh [Research on Chemical Intermediates, 2016, vol. 42, # 6, p. 5723 - 5737]
[33]Noori, Nourolah; Nikoorazm, Mohsen; Ghorbani-Choghamarani, Arash [Phosphorus, Sulfur and Silicon and the Related Elements, 2016, vol. 191, # 10, p. 1388 - 1395]
[34]Shiri, Lotfi; Ghorbani-Choghamarani, Arash; Kazemi, Mosstafa [Research on Chemical Intermediates, 2017, vol. 43, # 5, p. 2707 - 2724]
[35]Tamoradi, Taiebeh; Mehraban-Esfandiari, Bita; Ghadermazi, Mohammad; Ghorbani-Choghamarani, Arash [Research on Chemical Intermediates, 2018, vol. 44, # 2, p. 1363 - 1380]
[36]Tamoradi, Taiebeh; Ghadermazi, Mohammad; Ghorbani-Choghamarani, Arash; Molaei, Somayeh [Research on Chemical Intermediates, 2018, vol. 44, # 7, p. 4259 - 4276]
[37]Moeini, Nazanin; Ghadermazi, Mohammad; Ghorbani-Choghamarani, Arash [Polyhedron, 2019, vol. 170, p. 278 - 286]
[38]Khazaei, Ardeshir; Zolfigol, Mohammad Ali; Rostami, Amin [Synthesis, 2004, # 18, p. 2959 - 2961]
[39]Natarajan, Palani; Sharma, Himani; Kaur, Mandeep; Sharma, Pooja [Tetrahedron Letters, 2015, vol. 56, # 41, p. 5578 - 5582]
[40]Nikoorazm, Mohsen; Ghorbani-Choghamarani, Arash; Noori, Nourolah [Research on Chemical Intermediates, 2016, vol. 42, # 5, p. 4621 - 4640]
[41]Shiri, Lotfi; Ghorbani-Choghamarani, Arash; Kazemi, Mosstafa [Applied Organometallic Chemistry, 2017, vol. 31, # 5]
[42]Viani, Fiorenza; Rossi, Bianca; Panzeri, Walter; Merlini, Luca; Martorana, Alessandra M.; Polissi, Alessandra; Galante, Yves M. [Tetrahedron, 2017, vol. 73, # 13, p. 1745 - 1761]
[43]Shiri, Lotfi; Kazemi, Mosstafa [Phosphorus, Sulfur and Silicon and the Related Elements, 2017, vol. 192, # 11, p. 1171 - 1176]
[44]Tamoradi, Taiebeh; Ghadermazi, Mohammad; Ghorbani-Choghamarani, Arash [New Journal of Chemistry, 2018, vol. 42, # 7, p. 5479 - 5488]
[45]Veisi, Hojat; Tamoradi, Taibeh; Karmakar, Bikash [New Journal of Chemistry, 2019, vol. 43, # 26, p. 10343 - 10351]
[46]Current Patent Assignee: NANJING TECH UNIVERSITY - CN113666854, 2021, A Location in patent: Paragraph 0020; 0078-0080
[47]Ghadermazi, Mohammad; Taherabadi, Samira; Tamoradi, Taiebeh [Polyhedron, 2019, vol. 171, p. 305 - 311]
[48]Hosseinzadeh, Rahman; Tajbakhsh, Mahmood; Khaledi, Hamid; Ghodrati, Keivan [Monatshefte fur Chemie, 2007, vol. 138, # 9, p. 871 - 873]
[49]Ghorbani-Choghamarani, Arash; Ghasemi, Banoo; Safari, Zohre; Azadi, Gouhar [Catalysis Communications, 2015, vol. 60, p. 70 - 75]
[50]Molaei, Somayeh; Ghadermazi, Mohammad [Applied Organometallic Chemistry, 2020, vol. 34, # 2]
[51]Nikoorazm, Mohsen; Khanmoradi, Maryam [Journal of the Chinese Chemical Society, 2020, vol. 67, # 8, p. 1477 - 1489]
[52]Sanz, Roberto; Aguado, Rafael; Pedrosa, María R.; Arnáiz, Francisco J. [Synthesis, 2002, # 7, p. 856 - 858]
[53]Chen, Fen-Er; Lu, Yun-Wen; He, Yan-Ping; Luo, You-Fu; Yan, Ming-Guo [Synthetic Communications, 2002, vol. 32, # 22, p. 3487 - 3492]
[54]Shirini, Farhad; Zolfigol, Mohammad A.; Khaleghi, Mahroo [Mendeleev Communications, 2004, vol. 14, # 1, p. 34 - 35]
[55]Khazaei, Ardeshir; Manesh, Abbas Amini; Rostami, Amin [Journal of Chemical Research, 2005, # 6, p. 391 - 393]
[56]Karami, Bahador; Montazerozohori, Morteza; Habibi, Mohammad Hossein [Phosphorus, Sulfur and Silicon and the Related Elements, 2006, vol. 181, # 12, p. 2825 - 2831]
[57]Ghorbani-Vaghei, Ramin; Zolfigol, Mohammad Ali; Moshfeghifar, Nasrin; Koukabi, Nadiya; Chehardoli, Gholamabbas [Journal of the Chinese Chemical Society, 2007, vol. 54, # 3, p. 791 - 794]
[58]Location in patent: experimental part Kumar, Vinod; Kaushik, Mahabir Parshad [Bulletin of the Chemical Society of Japan, 2008, vol. 81, # 1, p. 160 - 162]
[59]Location in patent: experimental part Tan, Cheng-Xia; Pan, Li-Yan; Zhang, Guo-Fu; Li, Yong-Shu [Phosphorus, Sulfur and Silicon and the Related Elements, 2012, vol. 187, # 1, p. 16 - 21]
[60]Nikoorazm, Mohsen; Ghorbani-Choghamarani, Arash; Noori, Nourolah [Applied Organometallic Chemistry, 2015, vol. 29, # 5, p. 328 - 333]
[61]Tabrizian, Elham; Amoozadeh, Ali; Rahmani, Salman [RSC Advances, 2016, vol. 6, # 26, p. 21854 - 21864]
[62]Nemati, Mohammad; Tamoradi, Taiebeh; Veisi, Hojat [Polyhedron, 2019, vol. 167, p. 75 - 84]
[63]Yarmohammadi, Nasrin; Ghadermazi, Mohammad; Derikvand, Zohreh; Mozafari, Roya [Chemical Papers, 2022, vol. 76, # 7, p. 4289 - 4307]
[64]Tamoradi, Taiebeh; Ghorbani-Choghamarani, Arash; Ghadermazi, Mohammad [Applied Organometallic Chemistry, 2018, vol. 32, # 5]
[65]Tamoradi, Taiebeh; Moeini, Nazanin; Ghadermazi, Mohammad; Ghorbani-Choghamarani, Arash [Polyhedron, 2018, vol. 153, p. 104 - 109]
[66]Yarmohammadi, Nasrin; Ghadermazi, Mohammad; Mozafari, Roya [RSC Advances, 2021, vol. 11, # 16, p. 9366 - 9380]
[67]Tamoradi, Taiebeh; Ghadermazi, Mohammad; Ghorbani-Choghamarani, Arash [Applied Organometallic Chemistry, 2018, vol. 32, # 1]
[68]Nakagawa, K.; Shiba, S.; Horikawa, M.; Sato, K.; Nakamura, H.; et al. [Synthetic Communications, 1980, vol. 10, # 4, p. 305 - 310]
[69]Ramadas; Srinivasan [Synthetic Communications, 1995, vol. 25, # 2, p. 227 - 234]
[70]Hajipour, Abdol Reza; Mallakpour, Shadpour E. [Journal of Chemical Research, 2000, vol. 2000, # 1, p. 32 - 33]
[71]Ghorbani-Choghamarani, Arash; Nikoorazm, Mohsen; Azadi, Gouhar [Journal of the Serbian Chemical Society, 2013, vol. 78, # 2, p. 173 - 178]
[72]Yi, Shan-Li; Li, Mei-Chao; Hu, Xin-Quan; Mo, Wei-Min; Shen, Zhen-Lu [Chinese Chemical Letters, 2016, vol. 27, # 9, p. 1505 - 1508]
[73]Ghorbani-Choghamarani, Arash; Moradi, Parisa; Tahmasbi, Bahman [RSC Advances, 2016, vol. 6, # 61, p. 56458 - 56466]
[74]Zohrevandi, Mina; Mozafari, Roya; Ghadermazi, Mohammad [RSC Advances, 2021, vol. 11, # 24, p. 14717 - 14729]
[75]Azeredo, Juliano Braun; Godoi, Marcelo; Keller, Mateus Henrique; Roehrs, Juliano Alex; Thedy, Maria Eduarda Candido; de Souza, Bruno Silveira [Tetrahedron Letters, 2022, vol. 100]
[76]Shirini, Farhad; Zolfigol, Mohammad Ali; Mallakpour, Bahareh; Moha-mmadpour-Baltork, Iraj; Mallakpour; Hajipour [Journal of Chemical Research - Part S, 2003, # 1, p. 28 - 29]
[77]Gebbink, Robertus J. M. Klein; Klink, Stephen I.; Feiters, Martinus C.; Nolte, Roeland J. M. [European Journal of Inorganic Chemistry, 2000, # 2, p. 253 - 264]
[78]Location in patent: experimental part Lakouraj, Moslem M.; Ghodrati, Keivan [Phosphorus, Sulfur and Silicon and the Related Elements, 2008, vol. 183, # 6, p. 1432 - 1439]
[79]Movassagh; Lakouraj; Ghodrati [Synthetic Communications, 1999, vol. 29, # 20, p. 3597 - 3603]
[80]Masnabadi, Nasrin; Ghasemi, Mohammad Hadi; Beyki, Mostafa Hossein; Sadeghinia, Mohammad [Research on Chemical Intermediates, 2017, vol. 43, # 3, p. 1609 - 1618]
[81]Patra, Astam K.; Dutta, Arghya; Pramanik, Malay; Nandi, Mahasweta; Uyama, Hiroshi; Bhaumik, Asim [ChemCatChem, 2014, vol. 6, # 1, p. 220 - 229]
[82]Nikoorazm, Mohsen; Moradi, Parisa; Noori, Nourolah; Azadi, Gouhar [Journal of the Iranian Chemical Society, 2021, vol. 18, # 2, p. 467 - 478]
[83]Kesavan, Venkitasamy; Bonnet-Delpon, Daniele; Begue, Jean-Pierre [Synthesis, 2000, # 2, p. 223 - 225]
[84]Sengar, Raghvendra S.; Miller, Jonathan J.; Basu, Partha [Dalton Transactions, 2008, # 19, p. 2569 - 2577]
[85]Saima; Soni, Isha; Lavekar, Aditya G.; Shukla, Manjulika; Equbal, Danish; Sinha, Arun K.; Chopra, Sidharth [Drug Development Research, 2019, vol. 80, # 1, p. 171 - 178]
[86]Srivastava, Ram Gopal; Venkataramani, Pudukkottai S. [Indian Journal of Chemistry - Section B Organic and Medicinal Chemistry, 1981, vol. 20, # 11, p. 996]
[87]Singh, Randhir; Kumar, Pankaj [Indian Journal of Chemistry, Section A: Inorganic, Physical, Theoretical and Analytical, 2002, vol. 41, # 4, p. 756 - 757]
[88]Groendyke, Brian J.; Modak, Atanu; Cook, Silas P. [Journal of Organic Chemistry, 2019, vol. 84, # 20, p. 13073 - 13091]
[89]List; Stein [Chemische Berichte, 1898, vol. 31, p. 1668]
[90]Mishra, K. K.; Bhargava, R. [Phosphorus, Sulfur and Silicon and the Related Elements, 1990, vol. 54, # 1/4, p. 39 - 47]
[91]Perez-Barrales; Caraballo; Rabasco [Pharmazie, 1997, vol. 52, # 6, p. 453 - 455]
[92]Field; Lawson [Journal of the American Chemical Society, 1958, vol. 80, p. 838,840]
[93]List; Stein [Chemische Berichte, 1898, vol. 31, p. 1668] Prescott; Smiles [Journal of the Chemical Society, 1911, vol. 99, p. 645]
[94]Wang; Cohen [Journal of the American Chemical Society, 1959, vol. 81, p. 3005,3008]
[95]Archer; Suter [Journal of the American Chemical Society, 1952, vol. 74, p. 4296,4301]
[96]Abdel-Wahab; Barakat [Monatshefte fur Chemie, 1957, vol. 88, p. 692,697]
[97]List; Stein [Chemische Berichte, 1898, vol. 31, p. 1668] Jones [American Chemical Journal, 1894, vol. 16, p. 366] Delisle [Chemische Berichte, 1889, vol. 22, p. 2206]
[98]Mishra, K. K.; Bhargava, R. [Phosphorus, Sulfur and Silicon and the Related Elements, 1990, vol. 54, # 1/4, p. 39 - 47]
[99]Ramadas; Srinivasan; Janarthanan; Pritha [Organic Preparations and Procedures International, 1996, vol. 28, # 3, p. 352 - 354]
[100]Gupta; Chaturvedi; Mishra [Indian Journal of Chemistry, Section A: Inorganic, Physical, Theoretical and Analytical, 2006, vol. 45, # 11, p. 2431 - 2434]

14
[ 119-80-2 ]
[ 3950-02-5 ]

Yield	Reaction Conditions	Operation in experiment
99%	With chlorine; sulfur In 1,1,2,2-tetrachloroethylene at 70℃;	1-4 Example 4 30.6 grams of dithiosalicylic acid, 4.8 grams of sulfur, add 200ml of tetrachloroethylene, heat up to 70°C and pass 23.2 grams of chlorine, the solution becomes clear, and the solvent is removed under reduced pressure to obtain 43.5 grams of CTBC, yield 99%, content 98 %.
93%	Stage #1: 2,2'-dithiobenzoic acid With thionyl chloride at 80℃; Heating / reflux; Stage #2: With sulfuryl dichloride at 50℃; for 0.5h;	1 Example 1; 2-chlorothiobenzoyl chloride (CTBC) Example 1 ; 2-Chlorothiobenzoyl Chloride (CTBC) 100 g 2,2"-dithiodibenzoic acid (assay 95%) and 1.0 g 1-methyl-2-pyrrolidone are added to 260 g thionyl chloride.The stirred slurry is heated slowly to reflux at 80° C., until a clear solution has been achieved and HCl evolution has been ceased.The mixture was cooled to 50° C. and 48.6 g sulfuryl chloride are slowly introduced.Stirring is continued for 30 min, after which volatiles were evaporated a rotary evaporator leaving 140.0 g crude CTBC as a light brown solid.The product is vacuum distilled through a short Vigreux column at 165-170° C., 10 mm Hg, affording 119.5 g CTBC (yield: 93% of theory; purity: 98.5%) as a light yellow crystalline product.The purity is estimated by derivatization of CTBC with ammonia to 1,2-benzisothiazolin-3-one and analyzing the solution by HPLC.
46%	Stage #1: 2,2'-dithiobenzoic acid With thionyl chloride; N,N-dimethyl-formamide at 80℃; for 3h; Inert atmosphere; Stage #2: With sulfuryl dichloride In 1,2-dichloro-ethane at 40℃; for 2h; Inert atmosphere;

	With thionyl chloride; chlorine; N,N-dimethyl-formamide 1.) 1,2-dichloroethane, reflux, 1 h, 2.) 10 deg C, 20 min; Multistep reaction;
	With thionyl chloride; chlorine 1.) reflux; 2.) CCl₄; Multistep reaction;
	With thionyl chloride; chlorine In tetrachloromethane
	Multi-step reaction with 2 steps 1: SOCl₂ / Heating 2: Cl₂ / CCl₄ / Ambient temperature
	Multi-step reaction with 2 steps 1: 71 percent / SOCl₂ / dimethylformamide; toluene / 18 h / 75 °C 2: Cl₂ / CH₂Cl₂
	Multi-step reaction with 2 steps 1: thionyl chloride / Reflux 2: chlorine / tetrachloromethane / 20 °C
	Stage #1: 2,2'-dithiobenzoic acid With thionyl chloride at 80℃; for 3h; Stage #2: With sulfuryl dichloride at 50℃; for 0.5h;
	With thionyl chloride at 80℃; for 3h;	15 150 g benzoic acid 2,2′-diselenide is added to 650 mL SOCl2 solution, refluxed under 80° C. for 3 h, and the solvent is removed through reduced pressure distillation, and the residue is added to 400 mL petroleum ether, heated up and refluxed for 30 min. The reaction liquid is filtered when hot, and the filtrate is put still in room temperature to crystallize, and yellow solid is obtained, and filtered, and the filter cake is dried in room temperature with good ventilation and 2-o-seleniumchloroylbenzoyl chloride is obtained.
	Multi-step reaction with 2 steps 1: thionyl chloride; N,N-dimethyl-formamide / toluene / 18 h / 0 - 75 °C / Inert atmosphere 2: chlorine / dichloromethane / 0 °C / Inert atmosphere
	With thionyl chloride for 5h; Reflux;

Reference： [1]Current Patent Assignee: ZHEJIANG YANGFAN NEW MAT - CN111253335, 2020, A Location in patent: Paragraph 0030; 0033-0040
[2]Current Patent Assignee: PROM - US2003/229233, 2003, A1 Location in patent: Page 3
[3]Alaoui-Jamali, Moulay A.; Amzil, Hind; Bijian, Krikor; Lim, Felicia Phei Lin; Miron, Caitlin E.; Moitessier, Nicolas; Nivedha, Anita K.; Su, Jie; Wernic, Dominik [Journal of Medicinal Chemistry, 2022, vol. 65, # 4, p. 3134 - 3150]
[4]Honek, John F.; Manchini, Michael L.; Belleau, Bernard [Synthetic Communications, 1983, vol. 13, # 12, p. 977 - 984]
[5]Plazzi; Bordi; Vitali; et al. [Farmaco, Edizione Scientifica, 1984, vol. 39, # 9, p. 788 - 796]
[6]Maggiali; Mingiardi; Lugari Mangia; et al. [Farmaco, Edizione Scientifica, 1982, vol. 37, # 5, p. 319 - 327]
[7]Bordi; Catellani; Morini; Plazzi; Silva; Barocelli; Chiavarini [Il Farmaco, 1989, vol. 44, # 9, p. 795 - 807]
[8]Yevich, Joseph P.; New, James S.; Smith, David W.; Lobeck, Walter G.; Catt, John D.; et al. [Journal of Medicinal Chemistry, 1986, vol. 29, # 3, p. 359 - 369]
[9]Pietka-Ottlik, Magdalena; Potaczek, Piotr; Piasecki, Egbert; Mlochowski, Jacek [Molecules, 2010, vol. 15, # 11, p. 8214 - 8228]
[10]He, Jie; Li, Dongdong; Xiong, Kun; Ge, Yongjie; Jin, Hongwei; Zhang, Guozhou; Hong, Mengshi; Tian, Yongliang; Yin, Jin; Zeng, Huihui [Bioorganic and Medicinal Chemistry, 2012, vol. 20, # 12, p. 3816 - 3827]
[11]Current Patent Assignee: YANTAI DONGCHENG PHARMACEUTICAL CO., LTD. - US2013/211097, 2013, A1 Location in patent: Paragraph 0110; 0221; 0222
[12]Castelli, Riccardo; Scalvini, Laura; Vacondio, Federica; Lodola, Alessio; Anselmi, Mattia; Vezzosi, Stefano; Carmi, Caterina; Bassi, Michele; Ferlenghi, Francesca; Rivara, Silvia; Møller, Ingvar R.; Rand, Kasper D.; Daglian, Jennifer; Wei, Don; Dotsey, Emmanuel Y.; Ahmed, Faizy; Jung, Kwang-Mook; Stella, Nephi; Singh, Simar; Mor, Marco; Piomelli, Daniele [Journal of Medicinal Chemistry, 2020, vol. 63, # 3, p. 1261 - 1280]
[13]Cao, Hongxuan; Chen, Han; Han, Xinya; Huang, Yunyuan; Liu, Jiaqi; Peng, Chao; Rao, Li; Ren, Yanliang; Sheng, Chunquan; Su, Chen; Tu, Jie; Wan, Chen; Wan, Jian; Wen, Wuqiang [Journal of Medicinal Chemistry, 2022, vol. 65, # 3, p. 2656 - 2674]

15
[ 119-80-2 ]
[ 79-11-8 ]
[ 135-13-7 ]

Yield	Reaction Conditions	Operation in experiment
71%	Stage #1: 2,2'-dithiobenzoic acid With sodium dithionite; sodium carbonate In water for 0.5h; Reflux; Stage #2: chloroacetic acid With sodium carbonate In water for 1h; Reflux;
71%	Stage #1: 2,2'-dithiobenzoic acid With sodium dithionite; sodium carbonate In water for 0.5h; Reflux; Stage #2: chloroacetic acid With sodium carbonate In water for 1h; Reflux;
69%	Stage #1: 2,2'-dithiobenzoic acid With sodium dithionite; sodium carbonate In water for 0.5h; Reflux; Stage #2: chloroacetic acid With sodium carbonate In water for 1h; Reflux;	10 2-((Carboxymethyl)thio)benzoic acid (XXVIa): To a solution of 20 g of anhydrous sodium carbonate (189 mmol, 6.0 eq.) in 150 mL of waterwere added lOg (32,6 mmol, 1.0 eq.) of 2,2-dithiodisalicylic acid and 14.2 g (82.1 mmol, 2.5eq.) of sodium dithionite. The mixture was heated at reflux for 30 mm. A solution of 15 g(163 mmol, 5.0 eq.) of chloroacetic acid was neutralized with sodium carbonate and thenadded. The mixture was then heated at reflux for a further 1 h. The mixture was allowed tocool to room temperature and acidified to pH 3 with concentrated hydrochloric acid. The resulting yellow precipitate was collected by filtration and recrystallized from water, removing insoluble material by hot filtration, to provide 12 g (69%) of 2- ((carboxymethyl)thio)benzoic acid (XXVIa). ‘HNMR (400 IVIFIz, DMSO-d6): ö 13.00 (s,2H), 7.91-7.89 (q, 1H), 7.54-7.50 (m, 1H), 7.37-7.35 (d, 1H), 7.25-7.21 (m, 1H), 3.8 (s, 2H).

	With sodium hydroxide In water for 4h; Heating;
	With sodium hydroxide

Reference： [1]Varedian, Miranda; Langer, Vratislav; Bergquist, Jonas; Gogoll, Adolf [Tetrahedron Letters, 2008, vol. 49, # 42, p. 6033 - 6035]
[2]Location in patent: experimental part Erdelyi, Mate; Varedian, Miranda; Skoeld, Christian; Niklasson, Ida B.; Nurbo, Johanna; Persson, Asa; Bergquist, Jonas; Gogoll, Adolf [Organic and Biomolecular Chemistry, 2008, vol. 6, # 23, p. 4356 - 4373]
[3]Current Patent Assignee: ARBUTUS BIOPHARMA CORP - WO2018/172852, 2018, A1 Location in patent: Page/Page column 232
[4]Irie, Masahiro; Kato, Masatoshi [Journal of the American Chemical Society, 1985, vol. 107, # 4, p. 1024 - 1028]
[5]Saika, Tetsuyuki; Iyoda, Tomokazu; Honda, Kenichi; Shimidzu, Takeo [Journal of the Chemical Society. Chemical communications, 1992, # 8, p. 591 - 592]

16
[ 119-80-2 ]
[ 35190-71-7 ]

Yield	Reaction Conditions	Operation in experiment
75%	With borane-THF; boron trifluoride diethyl etherate In tetrahydrofuran at 20℃; for 18h;
	With sodium bis(2-methoxyethoxy)aluminium dihydride In benzene

Reference： [1]Chen; Iakovleva; Kesten; Magano; Rodriguez; Sexton; Zhang; Lee [Organic Preparations and Procedures International, 2002, vol. 34, # 6, p. 665 - 670]
[2]Smrz,R. et al. [Collection of Czechoslovak Chemical Communications, 1976, vol. 41, p. 2771 - 2787]

17
[ 7647-01-0 ]
[ 19934-09-9 ]
[ 1677-27-6 ]
[ 119-80-2 ]

Reference： [1]Journal of the Chemical Society,1936,p. 1143,1147

18
[ 3749-51-7 ]
[ 119-80-2 ]
2-(4-hydroxy-6-methyl-2-oxo-1,2-dihydro-pyridin-3-ylsulfanyl)-benzoic acid [ No CAS ]

Reference： [1]Journal of Heterocyclic Chemistry,2000,vol. 37,p. 911 - 919

19
[ 6066-82-6 ]
[ 119-80-2 ]
[ 497262-13-2 ]

Yield	Reaction Conditions	Operation in experiment
89%	With diisopropyl-carbodiimide In tetrahydrofuran; isopropyl alcohol at 20℃; for 4h;
89%	With diisopropyl-carbodiimide In tetrahydrofuran; isopropyl alcohol at 25℃; for 4h;
	With diisopropyl-carbodiimide In tetrahydrofuran; isopropyl alcohol at 25℃;

Reference： [1]Song, Yongsheng; Goel, Atul; Basrur, Venkatesha; Roberts, Paula E.A; Mikovits, Judy A; Inman, John K; Turpin, Jim A; Rice, William G; Appella, Ettore [Bioorganic and Medicinal Chemistry, 2002, vol. 10, # 5, p. 1263 - 1273]
[2]Srivastava, Pratibha; Schito, Marco; Fattah, Rasem J.; Hara, Toshiaki; Hartman, Tracy; Buckheit Jr., Robert W.; Turpin, Jim A.; Inman, John K.; Appella, Ettore [Bioorganic and Medicinal Chemistry, 2004, vol. 12, # 24, p. 6437 - 6450]
[3]Goel, Atul; Mazur, Sharlyn J.; Fattah, Rasem J.; Hartman, Tracy L.; Turpin, Jim A.; Huang, Mingjun; Rice, William G.; Appella, Ettore; Inman, John K. [Bioorganic and Medicinal Chemistry Letters, 2002, vol. 12, # 5, p. 767 - 770]

20
[ 119-80-2 ]
[ 7716-66-7 ]

Reference： [1]Journal of Medicinal Chemistry,1986,vol. 29,p. 359 - 369

21
[ 98-82-8 ]
[ 119-80-2 ]
[ 5495-84-1 ]

Reference： [1]Patent: EP1211252,2002,A1 .Location in patent: Page 6

22
[ 119-80-2 ]
[ 122-59-8 ]
[ 84434-05-9 ]

Yield	Reaction Conditions	Operation in experiment
76%	With sulfuric acid at 0 - 25℃; for 1h;	1 Example 1; Preparation of 2-carboxymethoxythioxanthone from dithiobisbenzoic acid Concentrated sulphuric acid (500g) and dithiobisbenzoic acid (30.6g) were charged to a reactor and phenoxyacetic acid (60.8g) was added over 1 hour keeping the temperature at 0-25°C. After stirring for 1 hour, water (470mls) was added. The solid product was filtered and washed with water (2x50mls). The solid was then stirred in 50% aqueous acetone (200mls) and heated to reflux for 0.5 hours. After cooling to ambient temperature the solid was filtered, washed with water and dried. 2-Carboxymethoxythioxanthone (43.4g) was obtained in 76% yield. This was a dull yellow solid, melting point 207 - 212°C. Assay by HPLC >97%. A single isomer was obtained.

Reference： [1]Current Patent Assignee: LANXESS AG - EP1380580, 2004, A1 Location in patent: Page 4

23
[ 119-80-2 ]
[ 13335-73-4 ]
1,2-dimethyl-4-carboxymethoxythioxanthone [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
54%	With sulfuric acid at 10 - 40℃; for 4 - 5h;	3 Example 3; Preparation of 1,2-dimethyl-4-carboxymethoxythioxanthone Concentrated sulphuric acid (115 cm3) and dithiobisbenzoic acid (12.2 g) were charged to a reactor and 3,4-dimethylphenoxyacetic acid (25.2 g) was added over 1 to 2 hours at 10° to 15°C with cooling. After stirring for a further 1 hour at 10° to 20°C, then at 30° to 40°C for 2 hours a bright red solution was obtained. This reaction mixture was then quenched onto water (230 mls) whilst allowing the temperature to rise to ∼80°C. The quenched mixture was stirred for a further 25 minutes at ∼80°C then cooled to 30°C. The resulting precipitate was filtered, washed with water and dried. The resulting crude product was slurried in a mixture of water (80 mls), acetic acid (25 mls), and 2-butanone (45 mls) at reflux for 30 minutes, cooled to ambient temperature and filtered. The damp product cake was washed with a mixture of water and 2-butanone followed by water, then dried. 1,2-Dimethyl-4-carboxymethoxythioxanthone (13.7g) was obtained in 54.4% yield. This was a bright yellow solid, melting point 226° to 229°C. Assay by hplc >98%.
	With sulfuric acid at 20℃; for 2h;

Reference： [1]Current Patent Assignee: LANXESS AG - EP1380580, 2004, A1 Location in patent: Page 5
[2]Turner, Keith [Organic Process Research and Development, 2006, vol. 10, # 3, p. 682 - 682]

24
[ 122-88-3 ]
[ 119-80-2 ]
(1-chloro-9-oxo-9H-thioxanthen-4-yloxy)-acetic acid [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
99.5%		<strong>[122-88-3]4-chlorophenoxyacetic acid</strong> was condensed with dithiobisbenzoic acid to yield the carboxymethoxy intermediate as the acid which was precipitated in water and isolated in a first filtration. This was then purified, in a second filtration, from a hot mixed solvent system before being used in the next stage of the process. The first filtration was reasonably quick but after the reslurry in the mixed solvent system it was extremely slow and a very low solids content cake was obtained. Consequently, a high proportion of materials in the liquor is dried back onto the filter cake. The yield at this point was 99.5%.
73.8%	With sulfuric acid; at 10 - 40℃; for 4 - 5h;	Concentrated sulphuric acid (120 mls) and dithiobisbenzoic acid (12.2 g) were charged to a reactor and <strong>[122-88-3]4-chlorophenoxyacetic acid</strong> (26.1 g) was added over 1 to 2 hours at 10 to 15C with cooling. After stirring for a further 1 hour at 10 to 20C, then at 30 to 40C for 2 hours a deep red solution was obtained. This reaction mixture was then quenched onto water (250 mls) whilst allowing the temperature to rise to ?80C. The quenched mixture was stirred for a further 25 minutes at ?80C then cooled to 30C. The resulting precipitate was filtered, washed with water and dried. The resulting crude product was slurried in a mixture of water (80 mls), acetic acid (25 mls), and 2-butanone (45 mls) at reflux for 30 minutes, cooled to ambient temperature and filtered. The damp product cake was washed with a mixture of water and 2-butanone followed by water, then dried. 1-Chloro-4-carboxymethoxythioxanthone (18.9g) was obtained in 73.8% yield. This was a pale dull yellow solid, melting point 230 to 232C.
53.8%	With sulfuric acid; at -5 - 50℃; for 58h;	Sulfuric acid (18M) (1620 ml_) was cooled to -5C and 2,2'-dithiosalicylic acid (165.4 g, 0.54 mol) was added, followed by the addition of 4- chlorophenoxyacetic acid ( 352.7 g, 1.89 mol) over 3 hours, which resulted in the formation of thick yellow/green suspension. This suspension was stirred for 1 hour at 0C. The reaction mixture was heated at 50C and allowed to stir for 54 hours. After reaction, the reaction mixture was poured into ice (1300 g). After stirring for 1 hour at room temperature, the crude (1-chloro-9-oxo-9H-thioxanthen-4-yloxy)-acetic acid was isolated by filtration. The crude (1-chloro-9-oxo-9H-thioxanthen-4-yloxy)-acetic acid was recrystallized from acetonitrile (3000 ml_). (1-chloro-9-oxo-9H- thioxanthen-4-yloxy)-acetic acid was isolated by filtration, yielding 186.3 g (53.8%) (1-chloro-9-oxo-9H-thioxanthen-4-yloxy)-acetic acid.

With sulfuric acid; at -5 - 50℃; for 58h;

Sulfuric acid (18M) (1620 mL) was cooled to -5C and 2,2'-dithiosalicylic acid (165.4 g, 0.54 mol) was added, followed by the addition of <strong>[122-88-3]4-chlorophenoxyacetic acid</strong> (352.7 g, 1.89 mol) over 3 hours, which resulted in the formation of thick yellow/green suspension. This suspension was stirred for 1 hour at 0C. The reaction mixture was heated at 50C and allowed to stir for 54 hours. After reaction, the reaction mixture was poured into ice (1300 g). After stirring for 1 hour at room temperature, the crude (1-chloro-9-oxo-9H-thioxanthen-4-yloxy)-acetic acid was isolated by filtration. The crude (1-chloro-9-oxo-9H-thioxanthen-4-yloxy)-acetic acid was recrystallized from acetonitrile (3000 mL). (1-chloro-9-oxo-9H-thioxanthen-4-yloxy)-acetic acid was isolated by filtration, yielding 186.3 g (53.8) (1-chloro-9-oxo-9H-thioxanthen-4-yloxy)-acetic acid.

Reference： [1]Patent: WO2009/60235,2009,A1 .Location in patent: Page/Page column 15-16
[2]Patent: EP1380580,2004,A1 .Location in patent: Page 5
[3]Patent: WO2012/52288,2012,A1 .Location in patent: Page/Page column 40
[4]Patent: EP2447259,2012,A1 .Location in patent: Page/Page column 25-26
[5]Organic Process Research and Development,2006,vol. 10,p. 682 - 682

25
[ 940-31-8 ]
[ 119-80-2 ]
2[(9-oxo-9H-thioxanthen-2-yl)oxy]-propionic acid [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
56.37%	With sulfuric acid at 10 - 40℃; for 4 - 5h;	7 Example 7; Preparation of 2-(2-methyl)-carboxymethoxythioxanthone Concentrated sulphuric acid (120 mls) and dithiobisbenzoic acid (12.2 g) were charged to a reactor and 2-phenoxypropionic acid (23.3 g) was added over 1 to 2 hours at 10° to 15°C with cooling. After stirring for a further 1 hour at 10° to 20°C, then at 30° to 40°C for 2 hours a deep red solution was obtained. This reaction mixture was then quenched onto water (250 mls) whilst allowing the temperature to rise to ∼80°C. The quenched mixture was stirred for a further 25 minutes at ∼80°C then cooled to 30°C. The product precipitated as an oily mass which was slurried in a mixture of water (80 mls), acetic acid (30 mls), and 2-butanone (40 mls) at reflux for 30 minutes, cooled to ambient temperature and filtered. The damp product cake was washed with a mixture of water and 2-butanone followed by water, then dried. 2-(2-Methyl)-carboxymethoxythioxanthone (13.6g) was obtained in 56.37% yield. This was a green powder, melting point = 174° to 177°C.

Reference： [1]Current Patent Assignee: LANXESS AG - EP1380580, 2004, A1 Location in patent: Page 7

26
[ 1877-75-4 ]
[ 119-80-2 ]
1-carboxymethoxy-4-methoxythioxanthone [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
66.4%	With sulfuric acid at 10 - 40℃; for 4 - 5h;	5 Example 5; Preparation of 1-carboxymethoxy-4-methoxythioxanthone Concentrated sulphuric acid (120 mls) and dithiobisbenzoic acid (12.2 g) were charged to a reactor and 4-methoxyphenoxyacetic acid (25.5 g) was added over 1 to 2 hours at 10° to 15°C with cooling. After stirring for a further 1 hour at 10° to 20°C, then at 30° to 40°C for 2 hours a deep red solution was obtained. This reaction mixture was then quenched onto water (250 mls) whilst allowing the temperature to rise to ∼80°C. The quenched mixture was stirred for a further 25 minutes at ∼80°C then cooled to 40°C. The resulting precipitate was filtered and then washed with water. The resulting crude product was slurried in a mixture of water (80 mls), acetic acid (25 mls), and 2-butanone (45 mls) at reflux for 30 minutes, cooled to ambient temperature and filtered. The damp product cake was washed with a mixture of water and 2-butanone followed by water, then dried. 1-Carboxymethoxy-4-methoxythioxanthone (16.8g) was obtained in 66.4% yield. This was an orange / yellow powder, melting point 223° to 225°C.
	With sulfuric acid at 20℃; for 2h;

Reference： [1]Current Patent Assignee: LANXESS AG - EP1380580, 2004, A1 Location in patent: Page 5
[2]Turner, Keith [Organic Process Research and Development, 2006, vol. 10, # 3, p. 682 - 682]

27
[ 940-64-7 ]
[ 119-80-2 ]
1-methyl-4-carboxymethoxythioxanthone [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
58.3%	With sulfuric acid at 10 - 40℃; for 4 - 5h;	6 Example 6; Preparation of 1-methyl-4-carboxymethoxythioxanthone Concentrated sulphuric acid (120 mls) and dithiobisbenzoic acid (12.2 g) were charged to a reactor and 4-methylphenoxyacetic acid (19.9 g) was added over 1 to 2 hours at 10° to 15°C with cooling. After stirring for a further 1 hour at 10° to 20°C, then at 30° to 40°C for 2 hours a deep red solution was obtained. This reaction mixture was then quenched onto water (250 mls) whilst allowing the temperature to rise to ∼80°C. The quenched mixture was stirred for a further 25 minutes at ∼80°C then cooled to 30°C. The resulting precipitate was filtered and then washed with water and dried. The resulting crude product was slurried in a mixture of water (60 mls), acetic acid (20 mls), and 2-butanone (30 mls) at reflux for 30 minutes, cooled to ambient temperature and filtered. The damp product cake was washed with a mixture of water and 2-butanone followed by water, then dried. 1-Methyl-4-carboxymethoxythioxanthone (14.0g) was obtained in 58.3% yield. This was a pale yellow powder, melting point 198° to 235°C.
	With sulfuric acid at 20℃; for 2h;

Reference： [1]Current Patent Assignee: LANXESS AG - EP1380580, 2004, A1 Location in patent: Page 6
[2]Turner, Keith [Organic Process Research and Development, 2006, vol. 10, # 3, p. 682 - 682]

28
[ 4661-46-5 ]
[ 119-80-2 ]
[ 147-93-3 ]

Yield	Reaction Conditions	Operation in experiment
	With sodium sulfide; sodium hydroxide; sulfur In water at 5 - 60℃; for 4h;	1 EXAMPLE 1 13.7 g (0.1 mole) of anthranilic acid, 41.1 g of water, and 20.86 g (0.2 mole) of 35% hydrochloric acid were charged into a 100-ml glass flask equipped with agitator and thermometer. The charged materials were cooled to a temperature of 5° C. while agitation was employed. Next, an aqueous solution prepared by dissolving 7.25 g (0.105 mole) of sodium nitrite in 13.5 g of water was dropped into the thus obtained reactant liquid using a dropping funnel over 30 min. with the temperature maintained at 5° C. or below and the same temperature level was maintained for another 30 min. [0023] Charged into a 200-ml glass flask equipped with agitator, thermometer, and reflux condenser, separate from the aforesaid glass flask, were 21.6 g (0.09 mole) of sodium sulfide 9 hydrate, 0.64 g (0.02 mole) of sulfur, 24 g of water, and 12.5 g (0.15 mole) of 48% aqueous solution of sodium hydroxide, which were thereupon cooled to a temperature of 5° C. while agitation was employed throughout. Next, the aforesaid diazotized aqueous solution was dropped into the thus obtained reactant liquid using a dropping funnel over 1 hr with the temperature maintained at 5° C. or below and the reaction was allowed to progress for further 1 hr at room temperature and for further 2 hr at a temperature of 60° C., respectively, whereupon the reaction was terminated. [0024] Upon termination of the reaction the reaction mixture was cooled down and added to 84 g of 10% hydrochloric acid for crystallizing thiosalicylic acid. The precipitated crystalline matters were filtered out and dried into 15.5 g of crystalline matters. Liquid chromatography analysis of the obtained crystalline matters revealed that the components comprised 83.2% of thiosalicylic acid and 2.6% of dithiosalicylic acid. The yield of thiosalicylic acid was 83.7%. Pertinent test results are summarized in Table 1

Reference： [1]Current Patent Assignee: AIR WATER INC - US2004/116734, 2004, A1 Location in patent: Page 3

29
[ 119-80-2 ]
[ 1941-30-6 ]
[ 142051-76-1 ]

Yield	Reaction Conditions	Operation in experiment
	With hydrogenchloride; sodium hydroxide; In water;	EXAMPLE 8 30.6 g of 2,2'-dithiodibenzoic acid (0.10 mol) are introduced into and dissolved in a solution of 8.00 g of sodium hydroxide (0.20 mol) in 800 ml of water at room temperature, while stirring. A solution of 26.6 g of <strong>[1941-30-6]tetrapropylammonium bromide</strong> (0.10 mol) in 300 ml of water is added to this solution. A solution of 3.65 g of hydrogen chloride (0.10 mol) in 100 ml of water is then slowly added dropwise, during which the product precipitates. The reaction mixture is subsequently stirred for 15 hours. The precipitate is then filtered off with suction, washed with water and dried in a through-circulation drying cabinet at 120 C. Yield: 48.3 g (98.2% of theory) of 2,2'-dithiodibenzoic acid mono(tetrapropylammonium) salt of the formula shown in Example 5.

Reference： [1]Patent: US5274184,1993,A

30
[ 119-80-2 ]
[ 19602-82-5 ]
1-(2,4,6-trichlorophenyl)-3-(2-chloro-5-tetradecanamido)-4-[2-(2,4-di-t-amylphenoxy)-butylcarbamoyl]-phenylthio}-5-pyrazolone [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
80%	With thionyl chloride In n-heptane	1 Preparation of 1-(2,4,6-trichlorophenyl)-3-(2-chloro-5-tetradecanamido)-4-[2-(2,4-di-t-amylphenoxy)-butylcarbamoyl]-phenylthio}-5-pyrazolone (Coupler V-1) EXAMPLE 1 Preparation of 1-(2,4,6-trichlorophenyl)-3-(2-chloro-5-tetradecanamido)-4-[2-(2,4-di-t-amylphenoxy)-butylcarbamoyl]-phenylthio}-5-pyrazolone (Coupler V-1) 45 g of 2.2'-dithiodibenzoic acid were added to 64.33 ml of thionyl chloride. Under stirring, the solution was refluxed for 3 hours and, after evaporation of half the total volume of the solvent, 120 ml of dry heptane were added. A pale yellow-brown solid was collected by filtration and dried overnight under vacuum to obtain 2,2'-dithiodibenzoyl chloride in 80% yield.

Reference： [1]Current Patent Assignee: FERRANIA TECHNOLOGIES SPA - US5646297, 1997, A

31
[ 1273-82-1 ]
[ 119-80-2 ]
2,2'-dithiobis(N-ferrocenylbenzamide)*0.8H₂O [ No CAS ]

Reference： [1]Journal of Organometallic Chemistry,2007,vol. 692,p. 248 - 256

32
6-amino-N-(pyridin-3-yl)hexanamide dihydrochloride [ No CAS ]
[ 119-80-2 ]
[ 1141277-35-1 ]

Yield	Reaction Conditions	Operation in experiment
27%	With benzotriazol-1-ol; 1-ethyl-(3-(3-dimethylamino)propyl)-carbodiimide hydrochloride; N-ethyl-N,N-diisopropylamine In N,N-dimethyl-formamide at 20℃;	3 Step 3: 2, 2 ' -Dlthlo-bls {N- [5- (pyrldln-3- ylcarbamoyl) pentyl] benz amide (6); :035H4QNgO4S2 MoI. Wt.: 684.87Scheme 5To a mixture 2-thiobenzoic acid disulfide (5, 0.765 g, 2.5 mmole) , HOBt (0.665 g, 4.9 mmole) , EDC. HCl (2 g, 10 mmole) in DMF (40 mL) was added the amine derivative 4 (1.5 g, 5 mmole) followed by DIPEA (3.5 mL, 20 mmole) . The mixture was stirred at room temperature overnight. It was then poured into water and extracted with ethyl acetate (5 x 30 mL) . The combined organic layers were washed with brine, dried over anhydrous sodium sulfate, filtered and concentrated. The crude residue was purified by column chromatography using 2 to 5% methanol in methylene chloride to elute the required product 6 (1 g,27%) as a colorless solid. 1H NMR (DMSO-d6) δ 10.01 (br s, 2H), 8.67. (s, 2H), 8.21 (d, 2H), 7.98 (m, 4H), 7.83 (d, 2H), 7.65 (t, 2H), 7.42 (t, 2H), 7.30 (m, 2H), 3.81 (t, 4H), 2.30 (t, 4H), 1.46 (m, 4H), 1.30 (m, 4H).

Reference： [1]Current Patent Assignee: LIXTE BIOTECHNOLOGY - WO2009/45440, 2009, A1 Location in patent: Page/Page column 61-62

33
[ 119-80-2 ]
[ 88-73-3 ]
[ 19806-43-0 ]

Yield	Reaction Conditions	Operation in experiment
	Stage #1: 2,2'-dithiobenzoic acid With sodium hydroxide; zinc In water at 40℃; for 1h; Stage #2: 2-Chloronitrobenzene In water for 6h;	1.a EXAMPLE 1; a) Production of 2-(2-nitrophenylthio)benzoic acid; 2,2'-dithiosalicylic acid (45.7 g, 0.15 mol) and sodium hydroxide (24.5 g, 0.61 mol) were put in a 0.5 L reactor having an agitator and a reflux device, and dissolved in 160 M of water. Zinc (9.8 g) was added thereto, and a reaction was conducted at 40 °C for 1 hour, l-chloro-2-nitrobenzene (48.2 g, 0.31 mol) was added thereto, and the resulting mixture was refluxed for 6 hours and extracted with toluene (200 mi X 2) to remove unreacted l-chloro-2-nitrobenzene so as to produce a 2-(2-rntrophenylthio)benzoic acid aqueous solution.

Reference： [1]Current Patent Assignee: SK INC - WO2006/1619, 2006, A1 Location in patent: Page/Page column 13

34
[ 119-80-2 ]
[ 4299-07-4 ]

Reference： [1]Molecules,2010,vol. 15,p. 8214 - 8228

35
[ 119-80-2 ]
[ 2527-66-4 ]

Reference： [1]Molecules,2010,vol. 15,p. 8214 - 8228
[2]Bioorganic Chemistry,2019,vol. 84,p. 192 - 201

36
[ 88-65-3 ]
[ 119-80-2 ]

Yield	Reaction Conditions	Operation in experiment
82%	With indium(III) oxide; ammonia; water; sulfur In ethanol at 60℃; Green chemistry;	Synthesis of disulfide, 2a-2v; general procedure General procedure: A mixture of alkyl/aryl halide, 1 (1.2 mmol), ammonium hydroxide (1 mmol) and nanosulfur powder (3 mmol, 96 mg) was stirred in 5mL of solvent (ethanol/water (2:1)) at 60 °C. Under this stirring condition indium oxide nanoparticles (3 mol-%) were added to it and the reaction was stirred for a period of 10 min to 1 h at 60 °C. After completion of the reaction as indicated by thin layer chromatography (TLC), the reaction mixture was cooled to room temperature and a 2:1 mixture of ethyl acetate/water (15 mL) was added and indium oxide was removed by centrifuge. The combined organic extracts were dried with anhydrous sodium sulfate and concentrated to give desired product in high purity.
	With copper(l) iodide; tetra(n-butyl)ammonium hydroxide; sulfur In water at 80℃; for 48h; Inert atmosphere; Sealed tube; chemoselective reaction;

Reference： [1]Devi, Namita; Hazarika, Sukanya; Gogoi, Prasanta; Barman, Pranjit [Synthetic Communications, 2018, vol. 48, # 15, p. 1927 - 1938]
[2]Xu, Hua-Jian; Liang, Yu-Feng; Cai, Zhen-Ya; Qi, Hong-Xia; Yang, Chun-Yan; Feng, Yi-Si [Journal of Organic Chemistry, 2011, vol. 76, # 7, p. 2296 - 2300]

37
[ 119-80-2 ]
[ 13515-97-4 ]
2,2'-dithiodibenzoyl bis-alanine methyl ester [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
76%		To a solution of dithiosalicylic acid (1.53 g; 5 mmol) in 10 mL THF and 6 mL DMF was added dropwise a suspension of carbonyl diimidazole (1.70 g; 10 mmol) in 10 mL THF. The reaction mixture was stirred at room temperature for 20 min and refluxed for 20 min. After the reaction was cooled to room temperature, (dl) alanine methyl ester hydrochloride (1.40 g; 10 mmol) and triethylamine (1.5 mL; 12 mmol) were added. The resulting reaction mixture was stirred at room temperature for 2 days. The solvent was removed and the residue was taken up in ethyl acetate (50 mL) and water (20 mL). The layers were separated and the organic layer was washed with 5% HCl (3 × 30 mL), saturated NaHCO3 (3 × 30 mL) and brine (30 mL). The organic layer was dried over anhydrous sodium sulfate. The drying agent was filtered off and the solvent evaporated, leaving an intermediate (1.8 g; 76% yield) which was used directly in the next step. To a chilled solution of this intermediate (1.8 g; 3.78 mmol) in 25 mL methylene chloride was added bromine (0.60 g; 3.78 mmol). The reaction mixture was stirred for 30 min and then treated with triethylamine (0.77 g; 7.5 mmol). The reaction mixture was allowed to warm to room temperature and then refluxed for 30 min. The solution was cooled to room temperature and washed with brine (2 × 15 mL). The organic layer was dried over anhydrous sodium sulfate, filtered, and the solvent was evaporated under vacuum, leaving compound 1 as a yellow oil (1.8 g; 100% yield).

Reference： [1]Bioorganic and Medicinal Chemistry,2011,vol. 19,p. 5782 - 5787

38
[ 2314-97-8 ]
[ 147-93-3 ]
[ 119-80-2 ]

Yield	Reaction Conditions	Operation in experiment
	Stage #1: Thiosalicylic acid With sodium hydride In N,N-dimethyl-formamide at 20℃; Inert atmosphere; Stage #2: iodotrifluoromethane In N,N-dimethyl-formamide at 20℃; for 14h; Stage #3: With hydrogenchloride In water; N,N-dimethyl-formamide at 20℃;	Typical procedure: Sodium-hydride (1.20 g, 28.5 mmol, 57% dispersion in oil) is washed free from the oil with pentane (3 × 10 ml) and is suspended in 25 ml of DMF. The thiol (25 mmol) is added in small portions under nitrogen atmosphere and the mixture is stirred at 20 °C for 15 min. A pre-weighed rubber balloon is charged with CF3I (6.5-7.0 g, 33-35 mmol, 1.3-1.4 equivalent) at ambient temperature and is fixed to the neck of the flask. The mixture immediately turns yellow and is stirred overnight at room temperature. To the end of stirring a white precipitate is formed, the slurry is poured to 200 ml of water and the mixture is set for distillation. The product is isolated with steam distillation, the organic layer is separated from the aqueous one, this latter is extracted with ether (2 × 15 ml), the united organic phases are washed with water (3 × 10 ml), and with brine (10 ml) and dried (Na2SO4). Upon filtration, the evaporation of ether under reduced pressure (∼16 mmHg) leaves the pure product. Analytically pure samples are obtained by vacuum-distillation. Comment: For 1k, 1q, and 1r double amount of NaH was used. Finally, the reaction mixtures were acidified with 6 N HCl and worked up. The formation of the corresponding disulfide was indicated by TLC and NMR analysis.

Reference： [1]Location in patent: experimental part Harsányi, Antal; Dorkó, Éva; Csapó, Ágnes; Bakó, Tibor; Peltz, Csaba; Rábai, József [Journal of Fluorine Chemistry, 2011, vol. 132, # 12, p. 1241 - 1246]

39
[ 122-88-3 ]
[ 119-80-2 ]
[ 1372490-05-5 ]

Reference： [1]Patent: WO2012/52288,2012,A1
[2]Patent: EP2447259,2012,A1

40
[ 119-80-2 ]
[ 405-79-8 ]
[ 1372490-34-0 ]

Yield	Reaction Conditions	Operation in experiment
38.9%	With sulfuric acid; at -5 - 60℃; for 6h;	To 60 ml_ sulfuric acid (18M), cooled to -5C, 2,2'-dithiosalicylic acid (6.1 g, 0.02 mol) was added in portions, followed by the addition of 4- fluorophenoxyacetic acid ( 11.9 g, 0.07 mol), which resulted in the formation of thick yellow suspension. The reaction mixture is heated to 60C and allowed to stir for 6 hours. After the reaction, the reaction mixture was poured into ice (300 g) and distilled water (100 ml_). The crude (1-fluoro-9-oxo-9H-thioxanthen-4-yloxy)-acetic acid was isolated by filtration. The crude (1-fluoro-9-oxo-9H-thioxanthen-4-yloxy)-acetic acid was recrystallized from 250 ml_ acetonitrile. (1-fluoro-9-oxo-9H- thioxanthen-4-yloxy)-acetic acid was isolated by filtration and dried yielding 4.5 g (38.9%) of (1-fluoro-9-oxo-9H-thioxanthen-4-yloxy)-acetic acid.
38.9%	With sulfuric acid; at -5 - 60℃; for 6h;	To 60 mL sulfuric acid (18M), cooled to -5C, 2,2'-dithiosalicylic acid (6.1 g, 0.02 mol) was added in portions, followed by the addition of 4-fluorophenoxyacetic acid (11.9 g, 0.07 mol), which resulted in the formation of thick yellow suspension. The reaction mixture is heated to 60C and allowed to stir for 6 hours. After the reaction, the reaction mixture was poured into ice (300 g) and distilled water (100 mL). The crude (1-fluoro-9-oxo-9H-thioxanthen-4-yloxy)-acetic acid was isolated by filtration. The crude (1-fluoro-9-oxo-9H-thioxanthen-4-yloxy)-acetic acid was recrystallized from 250 mL acetonitrile. (1-fluoro-9-oxo-9H-thioxanthen-4-yloxy)-acetic acid was isolated by filtration and dried yielding 4.5 g (38.9%) of (1-fluoro-9-oxo-9H-thioxanthen-4-yloxy)-acetic acid.

Reference： [1]Patent: WO2012/52288,2012,A1 .Location in patent: Page/Page column 51-52
[2]Patent: EP2447259,2012,A1 .Location in patent: Page/Page column 33

41
[ 119-80-2 ]
[ 530-62-1 ]
2,2'-dithiodibenzoyl bis-alanine methyl ester [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	With triethylamine In tetrahydrofuran; N,N-dimethyl-formamide at 20℃; for 0.666667h; Reflux;	2.3 4.2.3 2,2′-Dithiodibenzoyl bis-alanine methyl ester (3a) General procedure: Compound 3a was prepared as described previously.33 Briefly, a solution of 2,2′-dithiodibenzoic acid (1.53 g; 5 mmol) in 10 mL THF and 6 mL DMF was added dropwise a suspension of 1,1′-carbonyl diimidazole (1.70 g; 10 mmol) in 10 mL THF. The reaction mixture was stirred at room temperature for 20 min and refluxed for 20 min. The reaction mixture was allowed to cool to room temperature and (DL) alanine methyl ester hydrochloride (1.40 g; 10 mmol) and triethylamine (1.5 mL; 12 mmol) were added. The reaction mixture was stirred at room temperature overnight and concentrated. The residue was taken up in ethyl acetate (40 mL) and water (30 mL). The organic layer was washed with 5% HCl (3 × 30 mL), saturated NaHCO3 (3 × 30 mL) and brine (30 mL). The organic layer was dried over anhydrous sodium sulfate, filtered, and concentrated, leaving behind 3a as an yellow solid (1.8 g; 76% yield).

Reference： [1]Lai, Huiguo; Dou, Dengfeng; Aravapalli, Sridhar; Teramoto, Tadahisa; Lushington, Gerald H.; Mwania, Tom M.; Alliston, Kevin R.; Eichhorn, David M.; Padmanabhan, Radhakrishnan; Groutas, William C. [Bioorganic and Medicinal Chemistry, 2013, vol. 21, # 1, p. 102 - 113]

42
[ 553-26-4 ]
cobalt(II) sulphate heptahydrate [ No CAS ]
[ 119-80-2 ]
[ 7732-18-5 ]
2C₁₀H₈N₂*Co⁽²⁺⁾*2H₂O*2C₁₄H₉O₄S₂^(1-) [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
6%	With sodium 1,3-dicarboxybenzene-5-sulphonate In N,N-dimethyl-formamide at 20℃;	4.2 Synthesis of complex 1, [[Co (C₁₀H₈N₂)₂(H₂O)₂]·2(C₁₄H₉O₄S₂)]_n Cobalt sulfate heptahydrate (0.06 g, 0.20 mmol) was dissolved in water (10 ml), and the solution was mixed with a dimethylformamide solution (10 ml) of 4,4′-bipyridine (0.04 g, 0.30 mmol), sodium 5-sulphoisophthalate (0.05 g, 0.20 mmol) and 2,2′-dithiosalicylic acid (0.06 g, 0.20 mmol) at room temperature. The reaction mixture was filtered and the filtrate was left to stand for about four weeks, until single crystals were obtained. Three kinds of single crystals with different color were obtained in this system, and complex 1 was brown crystal. The crystal data of complex 1 were not very good, and there still a labile hydrogen atom was not positioned. The block crystals were collected, washed with distilled water and dried in air (yield: 6%, based on 2,2′-dithiosalicylic acid). IR(KBr pellet, cm-1): 3193(m), 2364(m), 1701(s), 1600(vs), 1389(m), 1355(s), 1276(vs), 1145(vs), 1063(m), 822(m), 788(m), 704(w), 628(s), 540(m).

Reference： [1]Chen, Lu; Xiao, Hong-Ping; Li, Xin-Hua [Journal of Molecular Structure, 2013, vol. 1037, p. 283 - 287]

43
[ 119-80-2 ]
[ 6265-93-6 ]
[ 1478061-65-2 ]

Yield	Reaction Conditions	Operation in experiment
68%	With dmap; 1-ethyl-(3-(3-dimethylamino)propyl)-carbodiimide hydrochloride In dichloromethane at 20℃;	2.2. Synthesis of probe 1 and 2 HMBT was synthesized according to the method we reportedpreviously [40]. To a suspension of 2,2'-dithiodipropionbenzoic acid (0.153 g, 0.5 mmol) in anhydrous dichloromethane (10 mL)was added 1-(3-dimethylaminopropyl)-3 -ethylcarbodiimide hydrochloride (EDC, 0.21 g, 1.1 mmol), 4-dimethylaminopyridine(DMAP, 5 mg) and HMBT (0.257 g, 1.0 mmol). The mixture was stirred at room temperature overnight and then the solvent wasremoved under reduced pressure. The resulting residue was purifiedby silica gel column chromatography (petroleum ether/ethylacetate, 1:1, v/v) to give the target compound 1 as off-white solids (0.27 g, 68%) (Scheme 1). IR (ATR, cm-1), 2937, 1729, 1583, 1470,1268, 1184, 1088, 1028, 897, 740. 1H NMR (400 MHz, CDCl3): 8.52 (d,J 7.6 Hz, 2H), 7.98 (q, J 7.7 Hz, 4H), 7.91 (d, J 8.4 Hz, 2H), 7.84(d, J 8.0 Hz, 2H), 7.507-7.409 (m, 6H), 7.36 (q, J 6.9 Hz, 4H), 7.16 (d, J 8.0 Hz, 2H), 3.91 (s, 6H). 13C NMR (100 MHz, CDCl3): 164.00,162.26, 152.90, 152.15, 141.92, 138.09, 135.56, 133.84, 132.84, 127.67,127.10, 126.68, 126.36, 126.26, 125.86, 125.40, 123.46, 121.51, 121.48,114.31, 56.55. HRMS (ESI) [M+H] m/z 785.0975, [M+Na] m/z807.0802, calcd for C42H29N2O6S4 785.0908; C42H28N2O6S4Na 807.0728.

Reference： [1]Huang, Qian; Yang, Xiao-Feng; Li, Hua [Dyes and Pigments, 2013, vol. 99, # 3, p. 871 - 877]

44
[ 120-72-9 ]
[ 119-80-2 ]
[ 81471-22-9 ]

Yield	Reaction Conditions	Operation in experiment
95%	With sodium hydroxide In water; isopropyl alcohol at 130℃; for 48h; Green chemistry;
46%	Stage #1: 2,2'-dithiobenzoic acid With ammonium peroxydisulfate In methanol at 70℃; for 3h; Stage #2: indole In methanol at 20 - 70℃;

Reference： [1]Zhou, Xiaofei; Li, Xinhua [RSC Advances, 2014, vol. 4, # 3, p. 1241 - 1245]
[2]Prasad, Ch. Durga; Kumar, Shailesh; Sattar, Moh.; Adhikary, Amit; Kumar, Sangit [Organic and Biomolecular Chemistry, 2013, vol. 11, # 46, p. 8036 - 8040]

45
[ 387-44-0 ]
[ 119-80-2 ]
C₁₅H₁₀FNO₂S [ No CAS ]

Reference： [1]RSC Advances,2014,vol. 4,p. 1241 - 1245

46
[ 108-78-1 ]
copper(II) nitrate trihydrate [ No CAS ]
[ 119-80-2 ]
silver nitrate [ No CAS ]
[Cu₆(cyanuricacid)2(H₂O)] [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
51%	In water at 180℃; for 72h;	Synthesesof[Cu6(CA)2(H2O)]n (3) Replacementof2,4-diamino-6-phenyl-1,3,5-triazine,3-nitro-phthalic acidandAgNO3 of 1 by melamine(0.063g,0.5mmol),2,2′-dithiodibenzoic acid(0.153g,1mmol)andCu(NO3)2 3H2O(0.241g,1mmol),violetblockcrystalsof 3 wereobtained(Yield0.176g,54.1%basedonmelamine).Anal.Calc.for(%):C6H2Cu6N6O7: C11.12,H0.31,N12.97;Found:C11.38,H0.78,N12.94.IR(KBrpellet,cm1): 1689,1649,1608,1472,1413,1392,1091,851,771,711,613,564.

Reference： [1]Xiao, Changyu; Li, Yamin; Lun, Huijie; Cui, Caiyan; Xu, Yanqing [Journal of Solid State Chemistry, 2013, vol. 208, p. 127 - 133]

47
[ 119-80-2 ]
[ 3196-73-4 ]
C₂₂H₂₄N₂O₆S₂ [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	Stage #1: 2,2'-dithiobenzoic acid With 1,1'-carbonyldiimidazole In tetrahydrofuran; N,N-dimethyl-formamide for 0.333333h; Inert atmosphere; Reflux; Stage #2: methyl 3-aminopropanoate hydrochloride With triethylamine In tetrahydrofuran; N,N-dimethyl-formamide at 20℃; for 48h; Inert atmosphere;	1 3-(4-Fluoro-3-oxobenzo[d]isothiazol-2(3H)-yl)propanoic acid (7b) General procedure: A solution of 6,6'-disulfanediylbis(2-fluorobenzoic acid) (4b) (2.23 g, 6.5 m Mol) in a mixture of THF (10 mL) and DMF (6 mL) was added to a stirred suspension of carbonyldiimidazole (CDI) (2.21 g, 13.6 m Mol) in THF (15 mL). The resulting reaction mixture was refluxed for 20 min until it became limpid. Then it was cooled to ambient temperature and β-alanine methylester hydrogen chloride (2.00 g, 14.3 m Mol) and NEt3 (4.50 mL, 32.3 m Mol) were added and the resulting mixture was stirred for 48 h at ambient temperature. Then the reaction mixture was evaporated to dryness and water (80 mL) was added. The resulting mixture was stirred for 10 min., filtered and washed on the filter with water (2 * 40 mL) and t-butylmethylether (20 mL). The drying of the resulting solid in air for 16 h and under the vacuum (0.5 Torr) for 3 h provided intermediate dimethyl 3,3'-((2,2'-disulfanediylbis(6-fluorobenzoyl))bis(azanediyl))dipropionate (5b) (3.00 g, 90%).A solution of Br2 (1.88 g, 11.8 m Mol) in CH2Cl2 (15 mL) wasadded to a solution of 5b (3.00 g, 5.9 m Mol) in CH2Cl2 (65 mL)and the reaction mixture was stirred for 30 min at ambient temperature.Then, NEt3 (1.65 mL, 11.8 m Mol) was added and theresulting reaction mixture was refluxed for 30 min. The reactionmixture was cooled to ambient temperature and washed with asolution of Na2SO3 (0.2 g) in 1 M aqueous solution of NaH2PO4(pH 4.5). The organic phase was additionally washed with water(2 20 mL), brine (20 mL), dried over anhydr. Na2SO4, filteredand evaporated to yield methyl 3-(4-fluoro-3-oxobenzo[d]isothiazol-2(3H)-yl)propanoate (6b) (2.13 g, 71%) as yellowish foam.An aqueous 1 M solution of LiOH (16.0 mL, 16.0 m Mol) wascooled to 5-7 C and then added to a cooled (7-10 C) suspensionof 6b (2.13 g, 8.3 m Mol) in dioxane (17 mL). The reaction mixturewas stirred for 1 h at 2-5 C (the temperature at which the mixturedoes not freeze yet) until complete dissolution of the precipitate.An aqueous 10% solution of HCl (10 mL) was added. The resultingsuspension was additionally diluted with water (150 mL) and filtered.The precipitate was washed on the filter with water(2 20 mL), Et2O (20 mL) and dried in air for 16 h. This providedthe target compound 7b (1.51 g, 75%; 48% over 3 steps) as a colorlesscrystalline powder.

Reference： [1]Zhulenkovs, Dmitrijs; Rudevica, Zhanna; Jaudzems, Kristaps; Turks, Maris; Leonchiks, Ainars [Bioorganic and Medicinal Chemistry, 2014, vol. 22, # 21, p. 5988 - 6003]

48
[ 119-80-2 ]
[ 319460-85-0 ]

Reference： [1]Organic Process Research and Development,2015,vol. 19,p. 849 - 857

49
[ 88-67-5 ]
[ 119-80-2 ]

Yield	Reaction Conditions	Operation in experiment
96%	With nickel(II) chloride hexahydrate; morpholinium morpholine-1-carbodithioate; potassium hydroxide In water; ethylene glycol; N,N-dimethyl-formamide at 130℃;
95%	With potassium sulfide; nickel(II) chloride hexahydrate; acetylacetone; potassium hydroxide In water; N,N-dimethyl-formamide at 110℃; for 24h;	General procedure for the synthesis of diaryl(dialkyl) disulfides General procedure: To a stirred mixture of aryl (primary alkyl) halide (2.0 mmol), 0.33 g potassium sulfide (3.0 mmol) and acac (20 mol%) in 2 cm3 DMF (containing a few drops water),NiCl2.6H2O (10 mol%) and then 1.0 g KOH (18.0 mmol) were added and the whole reaction mixture was heated at 110 °C under atmospheric conditions until completion. The progress of the reaction was monitored by TLC. Upon completion of the reaction, the mixture was cooled to room temperature. Then, the pH of mixture was adjusted to 7 with 5 % HCl and filtered. The filtrate was evaporated under vacuum, 20 cm3 ethyl acetate was added and the mixture was washed with H2O (2 x 15 cm3). The combined organic layer was dried over Na2SO4 and filtered to afford the crude diaryldisulfide and dialkyldisulfide, which was purified by preparative chromatography (silica gel, n-hexane:ethyl acetate 20:1; in the case of Table 3, entries 12-15 was 4:1).

Reference： [1]Soleiman-Beigi, Mohammad; Arzehgar, Zeinab [Heteroatom Chemistry, 2015, vol. 26, # 5, p. 355 - 360]
[2]Soleiman-Beigi, Mohammad; Arzehgar, Zeinab [Monatshefte fur Chemie, 2016, vol. 147, # 10, p. 1759 - 1763]

50
[ 147-93-3 ]
hexamethylene-1,6-bis(thiosulfate)disodium salt [ No CAS ]
[ 119-80-2 ]
C₂₆H₃₄O₄S₆ [ No CAS ]
C₂₀H₂₂O₄S₄ [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	Stage #1: Thiosalicylic acid; hexamethylene-1,6-bis(thiosulfate)disodium salt With formaldehyd; sodium hydroxide In water at 5℃; for 1h; Inert atmosphere; Stage #2: With hydrogenchloride In water at 5℃; for 1h; Inert atmosphere; Overall yield = 233 g;	2 EXAMPLE 2 (0126) Apparatus: 4000 ml four-necked flask with thermometer, dropping funnel with pressure equalization, reflux condenser with gas-outlet attachment (bubble counter), and tubing, stirrer, gas-inlet tube, Dulcometer (0127) Initial charge: 198.0 g (0.5 mol) of Duralink HTS disodium hexamethylene 1,6-bisthiosulfate dihydrate from Flexsys (98.59%) (0128) 1200 ml of demineralized water (0129) 82.3 g (1.0 mol) of formaldehyde solution, about 36.5% (0130) Feed: 157.4 g (1.0 mol) of 2-mercaptobenzoic acid (98%), dissolved under nitrogen in 1000 ml of water via addition of 60 g of NaOH (0131) Auxiliaries: 292 g (0.4 mol) of 5% HCl (metering by way of Dulcometer) 108.4 g (1.1 mol) of 37% HCl (0132) Duralink HTS and water were used as initial charge in the nitrogen-flushed apparatus. Formaldehyde was added with stirring. 2-Mercaptobenzoic acid solution was then added dropwise at a temperature of 5° C. with nitrogen blanketing within about 90 min. The pH of the reaction mixture was kept at from 9.5 to 10.5 during the addition of the 2-mercaptobenzoic acid solution via dropwise addition of 5% HCl. After addition had ended, stirring was continued at 5° C. for 1 h, and then the 37% hydrochloric acid was added dropwise within 1 h with nitrogen blanketing at 5° C. Stirring was continued for one hour, and the solid was then isolated by suction filtration, by using a D4 frit. The product was then washed with portions of in each case 600 ml of water, until the conductivity of the wash water was <0.3 mS/cm, and was then dried at 50° C. in a vacuum drying oven. (0133) Yield: 233 g (102.5%) of a mixture of polysulfides of the formula (I) where m=0, 1, and 2, where K1+ and K2═H+: [table-us-00002-en] Elemental analysis: C: 52.4% H: 5.1% O: 14.3% S: 27.7% Cl: 130 ppm (0134) The percentage data relating to the compounds of the formula (I) resulted from the area percentage proportions from the HPLC measurement, using UV detector. (0135) 3% of compound where m=0; 96% of compound where m=1; 1% of compound where m=2.

Reference： [1]Current Patent Assignee: LANXESS AG - US2015/274655, 2015, A1 Location in patent: Paragraph 0126-0135

51
[ 132-65-0 ]
[ 119-80-2 ]

Yield	Reaction Conditions	Operation in experiment
14%	With ozone; acetic acid at 16.84℃;	General procedure: The oxidation of hetarenes I-VI was carried out in a temperature controlled reactor made as a glass column of a 0.1 dm3 volume equipped with a finely porous separating wall for dispersing an ozone-air mixture and a reflux condenser. The reactor was charged with 0.05 dm3 of glacial acetic acid and a calculated amount of hetarene; then, the ozone-air mixture was supplied at a rate of 3.3 × 10-3 dm3/s. The amount of the reactant hetarenes in solution was determined by GLC using an LKhM80 chromatograph with FID on a 2m column packed with polymethyl phenylsiloxane (PMPS6)coated ChromatonNAW. Peroxides were determined by iodometry afterthe reactor with air to remove ozone residue accordingto the published procedure [6]. The concentration ofcarboxylic acids was determined by alkalimetric titration with a 0.05 N sodium hydroxide solution after solvent evaporation. The IR spectra were recorded on aUR20 spectrophotometer in KBr disks.

Reference： [1]Andreev [Petroleum Chemistry, 2015, vol. 55, # 6, p. 497 - 502][Neftekhimiya, 2015, vol. 55, # 4, p. 347 - 352,6]

52
[ 95-15-8 ]
[ 119-80-2 ]

Yield	Reaction Conditions	Operation in experiment
26.7%	With ozone; acetic acid at 16.84℃;	General procedure: The oxidation of hetarenes I-VI was carried out in a temperature controlled reactor made as a glass column of a 0.1 dm3 volume equipped with a finely porous separating wall for dispersing an ozone-air mixture and a reflux condenser. The reactor was charged with 0.05 dm3 of glacial acetic acid and a calculated amount of hetarene; then, the ozone-air mixture was supplied at a rate of 3.3 × 10-3 dm3/s. The amount of the reactant hetarenes in solution was determined by GLC using an LKhM80 chromatograph with FID on a 2m column packed with polymethyl phenylsiloxane (PMPS6)coated ChromatonNAW. Peroxides were determined by iodometry afterthe reactor with air to remove ozone residue accordingto the published procedure [6]. The concentration ofcarboxylic acids was determined by alkalimetric titration with a 0.05 N sodium hydroxide solution after solvent evaporation. The IR spectra were recorded on aUR20 spectrophotometer in KBr disks.

Reference： [1]Andreev [Petroleum Chemistry, 2015, vol. 55, # 6, p. 497 - 502][Neftekhimiya, 2015, vol. 55, # 4, p. 347 - 352,6]

53
[ 119-80-2 ]
[ 17672-21-8 ]
dimethyl 2,2’-((2,2’-disulfanediylbis(benzoyl))bis(azanediyl))bis(3-hydroxybenzoate) [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
33%		2,2?-Dithiodibenzoic acid (0.100g,0.326 mmol) and 1-1?-carbonyldiimidazole (0.127g, 0.782 mmol) weredissolved in THF (3mL) and stirred for 30 minutes under inert atmosphere.Methyl 3-hydroxyanthranilate (0.109g, 0.652 mmol) was added and the reactionmixture was refluxed for 21 hours. The reaction mixture was cooled to roomtemperature and transferred to a separatory funnel along with 30mL H2Oand extracted with EtOAc (3x30mL). Combined organic phases were washed with H2O(2x50mL) and brine (1x50mL), dried with MgSO4, and concentrated underreduced pressure to give a light brown solid. Crude product was purified viaflash chromatography (5% EtOAc in CH2Cl2) to give 0.0640gdesired compound as a yellow-orange solid (33% yield). 1H NMR(400MHz, CDCl3) d11.92 (1H, s), d 9.51(1H, s), d 7.90 (2H, d, J= 11.0Hz), d 7.68(1H, d, J= 7.4Hz), d7.46 (1H, t, J= 7.8Hz), d 7.35(2H, m), d 7.21 (1H, m), d 3.94 (3H, s).

Reference： [1]Bioorganic and Medicinal Chemistry Letters,2016,vol. 26,p. 1196 - 1199

54
[ 119-80-2 ]
[ 536-74-3 ]
1-phenyl-2-[(2-carboxyphenyl)thio]ethene [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
65%	With potassium hydroxide In water for 48h; Heating; Green chemistry; stereoselective reaction;	General procedure for the phenylacetylene hydrothiolation with 2,2’-dithiosalicylic acid A solution of DTSA (1.5mmol, 0.4595 g), phenylacetylene (2.0mmol, 0.22 mL), and 40% KOH aqueous solution (0.2 mL) in 2 mL H2O was heated at 130 °C for 48 h on an oil bath. The reaction was monitored by TLC. After the completion of the reaction, the reaction mixture was cooled to room temperature naturally and extracted with 20 mL ethyl acetate and 2 mL saturated sodium chloride aqueous solution. The organic layer was separated, washed with a saturated NaCl solution thrice, and dried over anhydrous magnesium sulfate. The solvent was evaporated using arotary evaporator to afford the crude product. The crude product was purifiedby column chromatography as follows: First, PE with a boiling point range of 60-90 °C was used to wash the column. Then, the crude sample was loaded, and the column was eluted with amixture of PE/ethyl acetate (10:1, v/v). The eluate with an Rf value of 0.3 was collected, and the solvent was evaporated using a rotary evaporator to afford 1-phenyl-2-[2-carboxyphenyl)thio]ethene. The E/Z was determinedby 1H NMR spectroscopy. 1-Phenyl-2-[(2-carboxyphenyl)thio]ethene (3a) 65% yield (Z:E > 97:3). White solid, mp 121.7-122.8 °C. 1HNMR (500 MHz, CDCl3): δ 6.52 (d, J= 10.5 Hz, 1H, Z form), 6.87 (d, J = 10.5 Hz, 1H, Z form), 7.27-7.30 (m, 2H, Zform), 7.39 (dd, J1 = J2 = 7.5 Hz, 2H, Z form), 7.51-7.55 (m, 2H, Z form), 7.64 (d, J = 8.0 Hz, 2H, Z form),8.12 (d, J = 8.0 Hz, 1H, Z form). 13C NMR (126 MHz, CDCl3,for major isomer): δ 123.35, 125.45, 127.38, 127.72, 128.39, 128.85, 129.17,132.10, 132.52, 133.41, 135.98, 141.43, 171.61. HRMS calcd for C15H12O2S[M + H]+: 257.0631; Found: 257.0631. Anal. calcd for C15H12O2S (%): C, 70.29; H, 4.72; S,12.51; Found: C, 70.26; H, 4.70; S, 12.61.

Reference： [1]Ye, Yanyan; Huang, Chengcheng; Zhao, Caixia; Ren, Baodong; Xiao, Hongping; Li, Xinhua [Synthetic Communications, 2016, vol. 46, # 19, p. 1634 - 1641]

55
[ 119-80-2 ]
[ 536-74-3 ]
1-phenyl-2-[(2-carboxyphenyl)thio]ethene [ No CAS ]
1-phenyl-2-[(2-carboxyphenyl)thio]ethene [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
34 % de	With potassium <i>tert</i>-butylate In N,N-dimethyl-formamide for 48h; Heating; Overall yield = 77 %;
14 % de	In N,N-dimethyl-formamide for 48h; Heating; Overall yield = 77 %;
72 % de	With tetra(n-butyl)ammonium hydroxide In water; N,N-dimethyl-formamide at 130℃; for 48h; Overall yield = 97 %;	1 To the reaction tube was added 1.5 mL (0.4595 g) of 2,2'-dithiosalicylic acid and 2 mmol (0.22 mL) of phenylacetylene. 0.2 mL of 40% aqueous solution of tetra-n-butylammonium hydroxide was added, followed by 2 mL of DMF. Heating dissolved, 130 ° C oil bath, the reaction. The TLC follow-up reaction was complete for 48 hours. The mixture was allowed to cool to room temperature and extracted with 20 mL of ethyl acetate and 2 mL of saturated brine, and the organic layer was taken. After extraction three times, the extract was washed with saturated brine, dried over anhydrous magnesium sulfate, and evaporated to dryness to obtain a crude product. Wash the column with petroleum ether at a boiling point of 60-90 ° C. The crude product was loaded and washed with a 10: 1 by volume mixture of petroleum ether and ethyl acetate at a boiling range of 60-90 ° C. (Ε: Z, 14: 86) was obtained by column elution with the Rf value of 0.3 and the eluent was evaporated to dryness by rotary evaporation. The yield of 1-phenyl-2-benzoic acid was 97% (E: Z, 14: 86). White solid

Reference： [1]Ye, Yanyan; Huang, Chengcheng; Zhao, Caixia; Ren, Baodong; Xiao, Hongping; Li, Xinhua [Synthetic Communications, 2016, vol. 46, # 19, p. 1634 - 1641]
[2]Ye, Yanyan; Huang, Chengcheng; Zhao, Caixia; Ren, Baodong; Xiao, Hongping; Li, Xinhua [Synthetic Communications, 2016, vol. 46, # 19, p. 1634 - 1641]
[3]Current Patent Assignee: WENZHOU UNIVERSITY - CN104387304, 2016, B Location in patent: Paragraph 0057

56
[ 766-83-6 ]
[ 119-80-2 ]
1-(3-chlorophenyl)-2-[(2-carboxyphenyl)thio]ethene [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
58%	With potassium hydroxide In water for 48h; Heating; Green chemistry; stereoselective reaction;	General procedure for the phenylacetylene hydrothiolation with 2,2’-dithiosalicylic acid General procedure: A solution of DTSA (1.5mmol, 0.4595 g), phenylacetylene (2.0mmol, 0.22 mL), and 40% KOH aqueous solution (0.2 mL) in 2 mL H2O was heated at 130 °C for 48 h on an oil bath. The reaction was monitored by TLC. After the completion of the reaction, the reaction mixture was cooled to room temperature naturally and extracted with 20 mL ethyl acetate and 2 mL saturated sodium chloride aqueous solution. The organic layer was separated, washed with a saturated NaCl solution thrice, and dried over anhydrous magnesium sulfate. The solvent was evaporated using arotary evaporator to afford the crude product. The crude product was purifiedby column chromatography as follows: First, PE with a boiling point range of 60-90 °C was used to wash the column. Then, the crude sample was loaded, and the column was eluted with amixture of PE/ethyl acetate (10:1, v/v). The eluate with an Rf value of 0.3 was collected, and the solvent was evaporated using a rotary evaporator to afford 1-phenyl-2-[2-carboxyphenyl)thio]ethene. The E/Z was determinedby 1H NMR spectroscopy.

Reference： [1]Ye, Yanyan; Huang, Chengcheng; Zhao, Caixia; Ren, Baodong; Xiao, Hongping; Li, Xinhua [Synthetic Communications, 2016, vol. 46, # 19, p. 1634 - 1641]

57
[ 119-80-2 ]
[ 766-49-4 ]
1-(2-fluorophenyl)-2-[(2-carboxyphenyl)thio]ethene [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
53%	With potassium hydroxide In water for 48h; Heating; Green chemistry; stereoselective reaction;	General procedure for the phenylacetylene hydrothiolation with 2,2’-dithiosalicylic acid General procedure: A solution of DTSA (1.5mmol, 0.4595 g), phenylacetylene (2.0mmol, 0.22 mL), and 40% KOH aqueous solution (0.2 mL) in 2 mL H2O was heated at 130 °C for 48 h on an oil bath. The reaction was monitored by TLC. After the completion of the reaction, the reaction mixture was cooled to room temperature naturally and extracted with 20 mL ethyl acetate and 2 mL saturated sodium chloride aqueous solution. The organic layer was separated, washed with a saturated NaCl solution thrice, and dried over anhydrous magnesium sulfate. The solvent was evaporated using arotary evaporator to afford the crude product. The crude product was purifiedby column chromatography as follows: First, PE with a boiling point range of 60-90 °C was used to wash the column. Then, the crude sample was loaded, and the column was eluted with amixture of PE/ethyl acetate (10:1, v/v). The eluate with an Rf value of 0.3 was collected, and the solvent was evaporated using a rotary evaporator to afford 1-phenyl-2-[2-carboxyphenyl)thio]ethene. The E/Z was determinedby 1H NMR spectroscopy.

Reference： [1]Ye, Yanyan; Huang, Chengcheng; Zhao, Caixia; Ren, Baodong; Xiao, Hongping; Li, Xinhua [Synthetic Communications, 2016, vol. 46, # 19, p. 1634 - 1641]

58
[ 100-42-5 ]
[ 119-80-2 ]
1-phenyl-2-[(2-carboxyphenyl)thio]ethene [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
25%	With potassium hydroxide In N,N-dimethyl-formamide at 130℃; for 48h;	6 To the reaction tube was added 1.5 mmol (0.4595 g) of 2,2'-dithiosalicylic acid and 1.5 mmol (0.16 mL) of styrene block, 2 mmol (0.1122 g) of potassium hydroxide was added, and 2 mL of DMF , Heating dissolved, 130 ° C oil bath under the reaction. The TLC follow-up reaction was complete for 48 hours. The mixture was allowed to cool to room temperature and extracted with 20 mL of ethyl acetate and 2 mL of saturated brine, and the organic layer was taken. After extraction three times, the extract was washed with saturated brine, dried over anhydrous magnesium sulfate, and evaporated to dryness to obtain a crude product. Wash the column with petroleum ether at a boiling point of 60-90 ° C. The crude product was loaded and washed with a 10: 1 by volume mixture of petroleum ether and ethyl acetate at a boiling range of 60-90 ° C. The yield of the 1-phenyl-2 (2-thiosalicyl) ethylene-ethylene was 25% after the elution was carried out by rotary evaporation of the eluant. White solid.

Reference： [1]Current Patent Assignee: WENZHOU UNIVERSITY - CN104387304, 2016, B Location in patent: Paragraph 0068

59
[ 108-73-6 ]
[ 119-80-2 ]
[ 402564-19-6 ]

Yield	Reaction Conditions	Operation in experiment
46.4%	With methanesulfonic acid; phosphorus pentoxide at 90℃; for 1.5h; Inert atmosphere;	4.1.2. Synthesis of 1,3-dihydroxy-9H-thioxanthen-9-one (2) A mixture of phosphorous pentoxide (4.13 g, 29.1 mmol) andmethanesulfonic acid (30 mL) was heated to 90 C and stirred for0.5 h under an argon atmosphere until a clear solution (Eaton’sreagent) was obtained. Anhydrous phloroglucinol (1.11 g,8.79 mmol) and 2,20-disulfanediyldibenzoic acid (1, 1.14 g,3.63 mmol) were then added in one portion. The reaction mixturewas stirred at 90 C for 1.5 h. After cooling to room temperature,the reaction mixture was poured into ice-water and stirred for1 h at room temperature. The resulting solid was collected by filtration,washed with water to adjust the pH to approximately 6,and dried at 70 C to give 2 as a reddish brown solid. The crude productwas purified by silica gel column chromatography using petroleumether/ethyl acetate (12:1, v/v) as eluent to obtain compound 2 (1.03 g, 46.4%) as a yellow solid. 1H NMR (400 MHz,DMSO-d6) d 14.37 (s, 1H), 11.10 (s, 1H), 8.43 (d, J = 7.6 Hz, 1H),7.80-7.72 (m, 2H), 7.60-7.54 (m, 1H), 6.65 (s, 1H), 6.32 (s, 1H).

Reference： [1]Luo, Li; Li, Yan; Qiang, Xiaoming; Cao, Zhongcheng; Xu, Rui; Yang, Xia; Xiao, Ganyuan; Song, Qing; Tan, Zhenghuai; Deng, Yong [Bioorganic and Medicinal Chemistry, 2017, vol. 25, # 6, p. 1997 - 2009]

60
[ 119-80-2 ]
Docetaxel [ No CAS ]
C₁₀₀H₁₁₂N₂O₃₀S₂ [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	Stage #1: 2,2'-dithiobenzoic acid With O-(1H-benzotriazol-1-yl)-N,N,N',N'-tetramethyluronium hexafluorophosphate; N-ethyl-N,N-diisopropylamine In dichloromethane for 0.333333h; Cooling with ice; Stage #2: Docetaxel In dichloromethane at 20℃; for 20h; Inert atmosphere; Darkness;	2 Example 2 According to the synthetic route, 20 mg of 2,2'-dithiodibenzoic acid and 60 mg of HBTU were dissolved in 6 ml of dichloromethane, and 60 L of DIPEA was slowly added dropwise under ice bath. After 20 minutes of reaction, 90 mg of docetaxel was added, protected with nitrogen, protected from light, stirred at room temperature for 20 hours, and subjected to thin layer chromatography to monitor the reaction (TLC: chloroform: methanol = 15: 1). 55 ml of methylene chloride was added to the reaction solution, washed with 10 mL of a 5% aqueous solution of sodium hydrogencarbonate, 10 mL of 5% glacial acetic acid, 10 mL of water. The organic layer was dried over anhydrous sodium sulfate, filtered and concentrated under reduced pressure to give the crude product. The purified docetaxel prodrug PTX-SS-PTX was purified by silica gel column chromatography with chloroform: methanol = 100: 1.

Reference： [1]Current Patent Assignee: NANJING MEDICAL UNIVERSITY - CN106083769, 2016, A Location in patent: Paragraph 0027; 0028

61
[ 119-80-2 ]
3,3',5,5'-tetraphenyl-ms-aza-2,2'-dipyrrolylmethene difluoroborate [ No CAS ]
C₆₀H₃₈BF₂N₃O₈S₄ [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
30%	With dmap; 1-ethyl-(3-(3-dimethylamino)propyl)-carbodiimide hydrochloride In dichloromethane at 20℃; for 24h; Inert atmosphere;	1 Preparation of a compound of formula 1 Under argon protection, BODIPY fluorophores (52.9 mg, 0.1 mmol) and sulphur phthalic acid (67.4 mg, 0.22 mmol), DMAP (24.4 mg, 0.2 mmol) EDCI (19.2 mg, 0.1 mmol) was dissolved in a 50 ml flask containing 20 ml of dry DCM, Stirring at room temperature for 24 h, TLC tracks the progress of the reaction. The crude product was neutralized by hydrobromic acid and washed from saturated solution of NaBr to neutral, Dichloromethane extraction, The organic layer was dried with sodium sulfate and steamed. The product was separated by column chromatography (200-300 mesh) The eluent is methanol. Collect green components, After evaporation of the solvent, 33 mg of the compound represented by Formula 1 was obtained, Yield: 30%.

Reference： [1]Current Patent Assignee: CHINESE ACADEMY OF SCIENCES - CN105017297, 2017, B Location in patent: Paragraph 0047; 0048; 0049; 0050

62
[ 119-80-2 ]
C₅₄H₄₄BF₂N₃OP⁽¹⁺⁾ [ No CAS ]
C₆₈H₅₂BF₂N₃O₅PS₂⁽¹⁺⁾ [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
24%	With dmap; 1-ethyl-(3-(3-dimethylamino)propyl)-carbodiimide hydrochloride In dichloromethane at 20℃; for 24h; Inert atmosphere;	1 Preparation of a compound of formula 2 Under argon protection, A fluorophore with a triphenylphosphine group (84.6 mg, 0.1 mmol) And thiophthalic acid (33.7 mg, 0.11 mmol) DMAP (12.2 mg, 0.1 mmol), EDCI (9.6 mg, 0.05 mmol) in 20 ml of dry Dichloromethane in a 50 ml flask, Stirring at room temperature for 24h, TLC tracks the progress of the reaction. After the crude product is neutralized by hydrobromic acid, Washed with saturated solution of NaBr to neutral, Dichloromethane extraction, The organic layer was dried with sodium sulfate and steamed. The resulting solid was dissolved in DCM, And separated by silica gel column chromatography (200-300 mesh). The eluent was eluted with ethyl acetate and methanol (2: 1-0: 1 /V / v), Collect green components, After evaporation of the solvent, 27.2 mg of the compound represented by formula (2) Yield: 24%.

Reference： [1]Current Patent Assignee: CHINESE ACADEMY OF SCIENCES - CN105017297, 2017, B Location in patent: Paragraph 0051; 0052; 0053; 0054

63
[ 119-80-2 ]
C₃₉H₃₅BF₂N₄O₂ [ No CAS ]
C₅₃H₄₃BF₂N₄O₆S₂ [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
26%	With dmap; 1-ethyl-(3-(3-dimethylamino)propyl)-carbodiimide hydrochloride In dichloromethane at 20℃; for 24h; Inert atmosphere;	1 Preparation of a compound of formula 3 A fluorophore (84.6 mg, 0.1 mmol) of the prepared mitochondrial localization group was prepared, And thiophthalic acid (33.7 mg, 0.11 mmol) 4-dimethylaminopyridine DMAP (12.2 mg, 0.1 mmol), 1-ethyl-(3-dimethylaminopropyl) carbodiimide hydrochloride EDCI (9.6mg, 0.05mmol) was dissolved in 20ml filled with dried flask 50ml of dichloromethane, Stirring at room temperature for 24 h, TLC tracks the progress of the reaction. The crude product was neutralized by hydrobromic acid and washed with a saturated solution of NaBr To neutral, Dichloromethane extraction, The organic layer was dried with sodium sulfate and steamed. The product was separated by column chromatography, The eluent was eluted with a gradient of ethyl acetate and methanol (2: 1-0: 1 / v / v). Collect green components, After evaporation of the solvent, 24.5 mg of the compound represented by formula 3 was obtained, Yield: 26%.

Reference： [1]Current Patent Assignee: CHINESE ACADEMY OF SCIENCES - CN105017297, 2017, B Location in patent: Paragraph 0055; 0056; 0057; 0058

64
[ 119-80-2 ]
[ 506-59-2 ]
[ 1240-22-8 ]

Yield	Reaction Conditions	Operation in experiment
62%	Stage #1: 2,2'-dithiobenzoic acid With thionyl chloride; N,N-dimethyl-formamide In toluene at 90℃; for 16h; Stage #2: N,N-dimethylammonium chloride With N-ethyl-N,N-diisopropylamine In tetrahydrofuran; toluene at 20℃;	a (a) 2,2'-Disulfanediylbis(N,N-dimethylbenzamide) 1-58 2,2'-Dithiobenzoic acid 1-55 (500 mg, 1.6 mmol) was suspended in anhydrous toluene (5 mL) and DMF (31 μΙ_). Thionyl chloride (310 μΙ_, 4.3 mmol) was added and the reaction mixture stirred at 90°C for 16 h. Dimethylamine hydrochloride (1 .3 g, 16.3 mmol), DIPEA (5.7 mL, 32.6 mmol) and THF (10 mL) were then added and stirred at rt O/N. The reaction mixture was evaporated to dryness, suspended in DCM and washed sequentially with water, 10% aqueous K2C03 and saturated aqueous citric acid. The organic layer was passed through a phase separator cartridge (Biotage) and concentrated in vacuo. The residue was purified by column chromatography (Biotage, Isolera 4, 25 g KP-Sil, eluting with EtOAc) to afford the title compound as a yellow solid (360 mg, 1.0 mmol, 62%).
5.1 g	Stage #1: 2,2'-dithiobenzoic acid With oxalyl dichloride In tetrahydrofuran; N,N-dimethyl-formamide at 0 - 5℃; Stage #2: N,N-dimethylammonium chloride With potassium carbonate In dichloromethane; water at 0 - 10℃;	2 Preparation Example 2:Preparation of compound of formula X-3-a Formula IX compound (5.00g, 16.32mmol), tetrahydrofuran (50mL),N,N-Dimethylformamide (2mL) was cooled to 0-5°C, stirred, and oxalyl chloride (20.72g, 163.24mmol) was added dropwise. After the reaction was complete, the solvent was evaporated.Add dichloromethane (10 mL) to dissolve for later use.Purified water (30mL), potassium carbonate (13.54g, 97.97mmol), dimethylamine hydrochloride (5.60g, 68.68mmol) were cooled and stirred, and the above standby solution was dropped at 0-10°C. After the reaction was completed,Separate the organic phase, extract the aqueous phase with dichloromethane, combine the organic phases,Wash with saturated sodium chloride aqueous solution, evaporate the solvent, and separate by column chromatography.The compound of formula X-3-a (light yellow oil, 5.10 g) was prepared.

Reference： [1]Current Patent Assignee: AUSPHERIX LTD - WO2017/93543, 2017, A2 Location in patent: Page/Page column 104
[2]Current Patent Assignee: BEIJING SIHUAN PHARM; BEIJING AOHE DRUG INST; JILIN SIHUAN PHARMA - CN112300120, 2021, A Location in patent: Paragraph 0200-0203

65
[ 119-80-2 ]
[ 62-53-3 ]
[ 2527-63-1 ]
[ 2527-03-9 ]

Yield	Reaction Conditions	Operation in experiment
1: 43% 2: 34%	Stage #1: 2,2'-dithiobenzoic acid With thionyl chloride Reflux; Stage #2: aniline With triethylamine In tetrahydrofuran at 0℃;	2-Phenylbenzo [d] isothiazol-3(2H)-one In a flame-dried round bottom flask, 2,2'-disulfanediyldibenzoic acid (5 g, 16.3 mmol) was added to 12.3 mL of thionyl chloride. The reaction was heated to reflux and stirred overnight. Excess thionyl chloride was removed under vacuum. The resulting solid was taken up in 10 mL of dry THF and added dropwise to a solution of aniline (2.85 g, 30.8 mmol) and triethylamine (4.27 mL, 30.8 mmol) in 80 mL of THF at 0 °C. After completion of the reaction as monitored by Si02 TLC (by treating a small portion of the reaction mixture with methanol), the reaction was concentrated to dryness. The solid residue was triturated with sat'd. NaHC03 (50 mL), filtered and washed with CH2C12 (100 mL) to leave behind 2,2'-disulfanediylbis(N-phenylbenzamide) as a white solid (2.89 g, 43% yield). The NaHC03/CH2C12 filtrate was separated and the aqueous layer extracted with CH2C12 (100 mL and 50 mL). The combined CH2C12 layers were back-washed with aqueous sat'd. NaCl (50 mL), dried over anhydrous Na2S04, filtered, and concentrated in vacuum. The crude product was purified by Si02 column chromatography using ethyl acetate and hexanes as an eluent to provide 2- phenylbenzo[d]isothiazol-3(2H)-one (Id) as an off-white solid (2.25 g 34% yield).

Reference： [1]Current Patent Assignee: EMORY UNIVERSITY - WO2017/70157, 2017, A1 Location in patent: Page/Page column 60

66
[ 93-35-6 ]
[ 119-80-2 ]
C₃₂H₁₈O₈S₂ [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
75%	With dmap; 1-ethyl-(3-(3-dimethylamino)propyl)-carbodiimide hydrochloride In dichloromethane at 20℃;	2.2 Preparation and Characterization of the YQ-1 Synthesis of probe (YQ-1) is summarized in Scheme 1. 2,2′-Dithiosalicylic acid (210mg, 1.0mmol), 4-dimethylaminopyridine (40mg, 0.3mmol), 1-(3-dimethylaminopropyl)-3-ethylcarbodiimidehydrochloride (EDC, 400mg, 2.1mmol) and 7-hydroxycoumarin (370mg, 2.1mmol) were mixed in 30mL anhydrous dichloromethane. The mixture was stirred at room temperature overnight. The solvent was removed under reduced pressure. The resulting residue was further purified by column chromatography on silica gel using petroleum: dichloromethane: ethyl acetate (5:1:1, v/v/v) as eluent to give the target as off-white solids (445mg, 75%). 1H NMR (DMSO-d6, 600MHz): δ (ppm): 8.36 (d, J=7.7Hz, 2H), 8.13 (d, J=9.4Hz, 2H), 7.87 (d, J=8.0Hz, 2H), 7.77 (t, J=8.9Hz, 2H), 7.74 (d, J=7.7Hz, 2H), 7.56 (s, 2H), 7.51 (s, 2H), 7.41 (d, J=8.3Hz, 2H), 6.53 (d, J=9.6Hz, 2H). 13C NMR (DMSO-d6, 150MHz): δ (ppm): 163.2, 159.1, 153.5, 152.0, 143.2, 139.1, 134.0, 131.9, 128.9, 126.0, 125.2, 124.9, 118.2, 116.4, 115.2, 109.8 (Fig. S1). ESI-MS m/z: [probe +H]+ Calcd. For 595.0443, Found 595.0542 (Fig. S2).

Reference： [1]Zhao, Qi; Kang, Jin; Wen, Ying; Huo, Fangjun; Zhang, Yongbin; Yin, Caixia [Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy, 2018, vol. 189, p. 8 - 12]

67
[ 119-80-2 ]
[ 4499-86-9 ]
[ 142051-76-1 ]

Yield	Reaction Conditions	Operation in experiment
	In ethanol; water; at 20℃; for 0.5h;	General procedure: DTSA (98%, A. R.) was purchased from Alfa Company and tetraalkylammonium hydroxides(25% aqueous solution, A. R.) were from Aladdin company. DTSA and the correspondingtetraalkylammonium hydroxides were dissolved in small quantities of water/ethanol(100/50 v/v) with a 1: 2 molar ratio. The mixtures were stirred for about half an hour andset aside to crystallize, finally yielding yellow block crystals suitable for single crystal X-raydiffraction after 15 days.

Reference： [1]Molecular Crystals and Liquid Crystals,2017,vol. 658,p. 165 - 176

68
[ 707-74-4 ]
[ 119-80-2 ]
[ 19602-82-5 ]
[ 938-18-1 ]

Yield	Reaction Conditions	Operation in experiment
1: 15.4 g 2: 15.6 g	With iron(III) chloride In toluene at 100℃; Inert atmosphere;	6 Example 6 300 ml of dry toluene, 24.1 g of 1,3,5-trimethyl-2-(trichloromethyl)-benzene, 90mg anhydrous ferric chloride, and 15.3 g dithiosalicylic acid were successively added to the flask under nitrogen atmosphere, the system was heated to about 100 degrees Celsius and the reaction was stirred untill TLC Thin Layer Chromatography detected nearly disappearance of raw materials (approximately 2 hours, the dry hydrochloric acid released by the reaction was absorbed by a dilute alkaline solution), the residual chlorine or hydrogen chloride gas in the system was removed by nitrogen bubbling. The solvent was recovered under reduced pressure in a reaction system, and the residue was distilled in vacuo to give 15.6 g of 2,4,6-trimethyl benzoyl chloride and 15.4 g of 2,2’-dithiosalicyloyl chloride successively.

Reference： [1]Current Patent Assignee: SHENZHEN YOUWEI CHEMICAL TECH - CN107540580, 2018, A Location in patent: Paragraph 0016

69
[ 707-74-4 ]
[ 119-80-2 ]
[ 3950-02-5 ]
[ 938-18-1 ]

Yield	Reaction Conditions	Operation in experiment
1: 17.4 g 2: 15.2 g	Stage #1: (trichloromethyl)mesitylene; 2,2'-dithiobenzoic acid With iron(III) chloride In chlorobenzene at 100℃; Inert atmosphere; Stage #2: With chlorine at 60℃; for 1h; Inert atmosphere;	2 300 ml of dry chlorobenzene, 24.0 g of 1,3,5-trimethyl-2-(trichloromethyl)-benzene, 85 mg of anhydrous ferric chloride along with 15.3 g of dithiosalicylic acid were successively added to the flask under a nitrogen atmosphere, the system was heated to about 100 degrees Celsius and the reaction was stirred untill TLC Thin Layer Chromatography detected nearly disappearance of raw materials (approximately 2 hours, the dry hydrochloric acid released by the reaction was absorbed by a dilute alkaline solution),after the system was cooled to room temperature, under effective stirring within 1 hour, 8.5 to 10.0 grams of chlorine was slowly passed into the above reaction phase, the reaction was gradually heated to 60 ° C and then stirred for 1 hour, the residual chlorine or hydrogen chloride gas in the system was removed by nitrogen bubbling. The solvent was recovered under reduced pressure in a reaction system, and the residue was distilled under vacuum to obtain 15.2 g of 2,4,6-trimethylbenzoyl chloride (colorless liquid) and 17.4 g of o-chlorothiobenzoyl chloride (pure yellow solid).

Reference： [1]Current Patent Assignee: SHENZHEN YOUWEI CHEMICAL TECH - CN107540580, 2018, A Location in patent: Paragraph 0012

70
[ 98-82-8 ]
[ 119-80-2 ]
[ 98-07-7 ]
4-isopropylthioxanthone [ No CAS ]
[ 5495-84-1 ]
3-isopropylthioxanthone [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
		350 ml of dry chlorobenzene, 1.1 g of trichloromethylbenzene, 92 mg anhydrous ferric chloride, and 22.2 g dithiosalicylic acid were successively added to the flask under a nitrogen atmosphere, , the system was heated to about 100 degrees Celsius and the reaction was stirred untill TLC Thin Layer Chromatography detected nearly disappearance of raw materials, the residual chlorine or hydrogen chloride gas in the system was removed by nitrogen bubbling.The solvent was recovered under reduced pressure in the reaction system, and the residue was distilled under reduced pressure to obtain 20.5 g of benzoyl chloride, the remaining o-chlorothiobenzoyl chloride intermediate in the flask was directly mixed with 19.1 grams of cumene and 200 milliliters of dichloroethane,the above liquid was gradually added dropwise to 150 ml of dichloroethane containing 25.3 g of anhydrous aluminum trichloride powder over a period of half an hour under efficient stirring, after maintaining the reaction temperature at 20 degrees Celsius for half an hour with stirring, slowly pour the reaction mixture into an equal volume of ice-water mixture with rapid mechanical stirring, the organic phase was washed with water and dilute sodium hydroxide,and the solvent was evaporated to dryness and the resulting oil was distilled under high vacuum at about 60 Pa to give 32.8 g of 2/4/3-isopropylthioxanthone ITX (82/11/7 mass ratio).

Reference： [1]Patent: CN107540580,2018,A .Location in patent: Paragraph 0017

71
[ 141-93-5 ]
[ 119-80-2 ]
[ 98-07-7 ]
[ 82799-44-8 ]

Yield	Reaction Conditions	Operation in experiment
28.6 g		300 ml of dry toluene, 28.6 g of trichloromethylbenzene, 86 mg of anhydrous ferric chloride, and 20.4 g of dithiosalicylic acid were sequentially added under the nitrogen atmosphere, the system was heated to about 100 degrees Celsius and the reaction was stirred untill TLC Thin Layer Chromatography detected nearly disappearance of raw materials, the residual chlorine or hydrogen chloride gas in the system was removed by nitrogen bubbling.The solvent was recovered under reduced pressure in the reaction system, and the residue was distilled under reduced pressure to obtain 17.6 g of benzoyl chloride, the remaining o-chlorothiobenzoyl chloride intermediate in the flask was directly mixed with 20.3 g of diethylbenzene and 200 milliliters of dichloroethane,the above liquid was gradually added dropwise to 150 ml of dichloroethane containing 23.3 g of anhydrous aluminum trichloride powder over a period of half an hour under efficient stirring, after maintaining the reaction temperature at 20 degrees Celsius for half an hour with stirring, slowly pour the reaction mixture into an equal volume of ice-water mixture with rapid mechanical stirring, the organic phase was washed with water and dilute sodium hydroxide, and the solvent was evaporated to dryness to give an oil which was recovered and recrystallized from methanol while hot to obtain 28.6 g of 2,4-diethylthioxanthone DETX.

Reference： [1]Patent: CN107540580,2018,A .Location in patent: Paragraph 0018

72
[ 119-80-2 ]
[ 98-07-7 ]
[ 19602-82-5 ]
[ 98-88-4 ]

Yield	Reaction Conditions	Operation in experiment
1: 16.4 g 2: 12.9 g	With iron(III) chloride In toluene at 100℃; Inert atmosphere;	5 Example 5 300 ml of dry toluene, 19.5 g of trichloromethylbenzene, 80 mg anhydrous ferric chloride, and 15.3 g dithiosalicylic acid were successively added to the flask under nitrogen atmosphere, the system was heated to about 100 degrees Celsius and the reaction was stirred untill TLC Thin Layer Chromatography detected nearly disappearance of raw materials (approximately 2 hours, the dry hydrochloric acid released by the reaction was absorbed by a dilute alkaline solution), the residual chlorine or hydrogen chloride gas in the system was removed by nitrogen bubbling. The solvent was recovered under reduced pressure in a reaction system, and the residue was distilled in vacuo to give 12.9 g of benzoyl chloride and 16.4 g of 2,2’- dithiosalicyloyl chloride successively (pale yellow solid, melting point 146-148 degrees Celsius).

Reference： [1]Current Patent Assignee: SHENZHEN YOUWEI CHEMICAL TECH - CN107540580, 2018, A Location in patent: Paragraph 0015

73
[ 119-80-2 ]
[ 98-07-7 ]
[ 3950-02-5 ]
[ 98-88-4 ]

Yield	Reaction Conditions	Operation in experiment
1: 18.9 g 2: 12.6 g	Stage #1: 2,2'-dithiobenzoic acid; Benzotrichlorid With iron(III) chloride In chlorobenzene at 100℃; Inert atmosphere; Stage #2: With chlorine at 60℃; for 1h; Inert atmosphere;	1 300 ml of dry chlorobenzene , 19.5 g of trichloromethylbenzene, 80 mg anhydrous ferric chloride along with 15.3 g of dithiosalicylic acid were successively added to the flask under a nitrogen atmosphere, the system was heated to about 100 degrees Celsius and the reaction was stirred untill TLC Thin Layer Chromatography detected nearly disappearance of raw materials (approximately 2 hours, the dry hydrochloric acid released by the reaction was absorbed by a dilute alkaline solution),after the system was cooled to room temperature, under effective stirring within 1 hour, 8.5 to 10.0 grams of chlorine was slowly passed into the above reaction phase, the reaction was gradually heated to 60 ° C and then stirred for 1 hour, the residual chlorine or hydrogen chloride gas in the system was removed by nitrogen bubbling. The solvent was recovered under reduced pressure in a reaction system, and the residue was distilled under vacuum to give 12.6 g of benzoyl chloride (colorless liquid) and 18.9 g of o-chlorothiobenzoyl chloride (pale yellow solid, melting point 65-67 degrees Celsius).

Reference： [1]Current Patent Assignee: SHENZHEN YOUWEI CHEMICAL TECH - CN107540580, 2018, A Location in patent: Paragraph 0011

74
[ 119-80-2 ]
[ 2632-13-5 ]
C₃₂H₂₆O₈S₂ [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	Stage #1: 2,2'-dithiobenzoic acid With N-ethyl-N,N-diisopropylamine In N,N-dimethyl-formamide at 21℃; for 0.333333h; Stage #2: 2-Bromo-4'-methoxyacetophenone In N,N-dimethyl-formamide at 21℃; for 16h;	2a. Preparation of bisphenacylester 5b Disulfanediyldibenzoic acid 4 (306 mg, 1 mmol) was dissolved in DMF (3.5 ml) andDIPEA (350 μl, 2 mmol) was added. Reaction mixture was stirred for 20 min at rt. Then 4-methoxy-2-bromo-1-phenylethan-1-one (456 mg, 2 mmol) was added and the reactionmixture was stirred at rt for 16 hours. After the completion of the reaction, the brown solution was poured into the mixture of ice and 10% NaHCO3 (4 ml). Brown solid 5b was precipitated,filtered and washed with 10% NaHCO3 and water. The compound was used in a next stepwithout further purification.

Reference： [1]Trapani, Patricia; Kvapil, Lubomír; Hradil, Pavel; Soural, Miroslav [Synlett, 2018, vol. 29, # 6, p. 810 - 814]

75
[ 20201-29-0 ]
[ 119-80-2 ]
C₁₆H₈⁽²⁾H₆OS [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
15.4%	With sulfuric acid at 20℃; for 3h;	5.D D. Synthesis of stable isotope labeled ITX-D6 Connect the condensation return pipe (dried pipe with anhydrous calcium chloride) on the flask,Dithiosalicylic acid (DTSA) and stable isotopically labeled cumene-D6 were added in succession.The molar ratio of dithiosalicylic acid to cumene-D6 is 2:1.Under stirring,Concentrated sulfuric acid (1:1 molar ratio to DTSA) was added and stirred at 20° C. for 3 h.Water quenching reaction, toluene extraction, washing, anhydrousNa2SO4 is dried and the initial product is obtained.Purification by column chromatography (hexane:ethyl acetate=150:1),A yellow sticky solid was obtained, which was recrystallized from methanol to give a pale yellow solid, namely 2-isopropylthioxanthone-D6 (ITX-D6) in a yield of 15.4% (calculated as input cumene-D6). ,The product was found to have a purity of 99.0% by liquid phase and an abundance of 98.2 atom% by LC-MS.

Reference： [1]Current Patent Assignee: SHANGHAI HUAYI (GROUP) COMPANY - CN105085470, 2018, B Location in patent: Paragraph 0053; 0103; 0104; 0113; 0114; 0123; 0124

76
[ 119-80-2 ]
C₃⁽¹³⁾C₆H₁₂ [ No CAS ]
C₁₀⁽¹³⁾C₆H₁₄OS [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
15.3%	With sulfuric acid at 10℃; for 4h;	7.C C. Synthesis of stable isotope labeled ITX-13C6 Connect the condensation return pipe (dried pipe with anhydrous calcium chloride) on the flask,Dithiosalicylic acid (DTSA) and stable isotopically labeled cumene-13C6 were added in succession.The molar ratio of dithiosalicylic acid to cumene-13C6 is 1:1.Under stirring, concentrated sulfuric acid (1:1 molar ratio with DTSA) was added and stirred at 10° C. for 4 h.Water quenching, toluene extraction, washing, drying over anhydrous Na2SO4 yielded the initial product.Purification by column chromatography (hexane:ethyl acetate=150:1),Yellow sticky solid,Recrystallization from methanol to give a pale yellow solid is 2-isopropylthioxanthone-13C6 (ITX-13C6).The yield is 15.3% (in terms of input cumene-13C6),The purity of the product was 99.1% by liquid-phase quantitative detection and 98.6% by LC-MS.

Reference： [1]Current Patent Assignee: SHANGHAI HUAYI (GROUP) COMPANY - CN105085470, 2018, B Location in patent: Paragraph 0057; 0131; 0132; 0139; 0140; 0147; 0148

77
[ 119-80-2 ]
C₆⁽¹³⁾C₃H₁₂ [ No CAS ]
C₁₃⁽¹³⁾C₃H₁₄OS [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
15.4%	With sulfuric acid at 20℃; for 3h;	11.D D. Synthesis of stable isotope labeled ITX-13C3 Connect the condensation return pipe (dried pipe with anhydrous calcium chloride) on the flask,Add dithiosalicylic acid (DTSA) and stable isotopically labeled cumene-13C3 in succession.The molar ratio of dithiosalicylic acid to cumene-13C3 is 2:1.Under stirring,Add concentrated sulfuric acid (1:1 molar ratio with DTSA),Stirred for 3 h at 20°C.Water quenching, toluene extraction, washing, drying over anhydrous Na2SO4 yielded the initial product.Purification by column chromatography (hexane:ethyl acetate=150:1),Yellow sticky solid,After recrystallization from methanol, the pale yellow solid is 2-isopropylthioxanthone-13C3ITX-13C3).The yield is 15.4% (input cumene-13C3),The product was tested for 99.0% purity by liquid phase and 98.2% detected by LC-MS.

Reference： [1]Current Patent Assignee: SHANGHAI HUAYI (GROUP) COMPANY - CN105085470, 2018, B Location in patent: Paragraph 0060; 0157; 0158; 0167; 0168; 0177; 0178

78
[ 119-80-2 ]
⁽¹³⁾C₉H₁₂ [ No CAS ]
C₇⁽¹³⁾C₉H₁₄OS [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	With hydrogenchloride; sulfuric acid at 100℃; for 1h;	18.6 (6) The molar ratio of the isomeric cumene to dithiosalicylic acid labeled with a stable isotope 13C is 1:3.Add dithiosalicylic acid,Then add Catalyst B,At 5MPa, 100 °C, the reaction can be 1h.

Reference： [1]Current Patent Assignee: SHANGHAI HUAYI (GROUP) COMPANY - CN105085470, 2018, B Location in patent: Paragraph 0063; 0231; 0232

79
[ 119-80-2 ]
[ 97095-85-7 ]
C₁₆H₁₁⁽²⁾H₃OS [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
15.3%	With sulfuric acid at 10℃; for 4h;	1.C C. Synthesis of stable isotope labeled ITX-D3 Connect the condensation return pipe (dried pipe with anhydrous calcium chloride) on the flask,In turn add dithiosalicylic acid (DTSA) and stable isotopically labeled cumene-D5,The molar ratio of dithiosalicylic acid to cumene-D5 is 1:1.While stirring, add concentrated sulfuric acid (1:1 molar ratio with DTSA),Stir 4h at 10°C.Water quenching, toluene extraction, washing, drying over anhydrous Na2SO4 yielded the initial product. Purification by column chromatography (hexane:ethyl acetate=150:1),A yellow sticky solid is obtained, which is recrystallized from methanol to give a pale yellow solid, namely 2-isopropyl thioxanthone-D3 (ITX-D3).The yield is 15.3% (input cumene-D5),The purity of the product was 99.1% by liquid-phase quantitative detection and 98.6 atom% D by LC-MS.

Reference： [1]Current Patent Assignee: SHANGHAI HUAYI (GROUP) COMPANY - CN105085470, 2018, B Location in patent: Paragraph 0051; 0077; 0078; 0085; 0086; 0093; 0094

80
[ 119-80-2 ]
[ 22219-00-7 ]
Cu*BF₄*(x)H₂O [ No CAS ]
[ 7732-18-5 ]
[ 33513-42-7 ]
C₁₄H₈O₄S^(2-)*3C₃H₇NO*2Cu⁽²⁺⁾*C₁₄H₈O₆S^(2-)*H₂O [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
65%	In methanol at 20℃; for 0.166667h;	2.2.2. Synthesis of [Cu2(tdb)(sdb)(dmf)(H2O)]2(dmf)}n (2) Cu(BF4)2xH2O (0.0237 g, 0.01 mmol) was dissolved in the 6 mLCH3OH and stirred at room temperature until complete dissolution.The resulting mixture was added to the H2dtdb (0.0612 g,0.01 mmol) separately dissolved in the 2 mL dmf and stirred untilcomplete dissolution for 10 min, at room temperature. Theobtained solution was stirring for more 2 min. From transparentgreen-yellow solution green crystals of needle habitus precipitatedafter two months. Yield: 65% (based on Cu).

Reference： [1]Gorobet, Anastasia; Vitiu, Aliona; Petuhov, Oleg; Croitor, Lilia [Polyhedron, 2018, vol. 151, p. 51 - 57]

81
[ 119-80-2 ]
Cu*BF₄*(x)H₂O [ No CAS ]
[ 33513-42-7 ]
C₁₄H₈O₄S^(2-)*2C₃H₇NO*Cu⁽²⁺⁾ [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
60%	In methanol at 20℃; for 0.5h; Sonication;	2.2.1. Synthesis of [Cu(tdb)(dmf)](dmf)}n (1) Cu(BF4)2xH2O (0.0237 g, 0.01 mmol) and H2dtdb (0.0306 g,0.01 mmol) were dissolved in 8 mL mixture of CH3OH:dmf (5:3)and ultrasonicated for 30 min at room temperature. The resultingtransparent light yellow solution was filtered off and green crystalsof prism habitus were precipitated after six months. Yield: 60%(based on Cu).

Reference： [1]Gorobet, Anastasia; Vitiu, Aliona; Petuhov, Oleg; Croitor, Lilia [Polyhedron, 2018, vol. 151, p. 51 - 57]

82
[ 119-80-2 ]
[ 1066-45-1 ]
[(Me₃Sn)₂(O₂CC₆H₄S)₂]_n [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
45%	Stage #1: 2,2'-dithiobenzoic acid With potassium hydroxide In methanol for 0.5h; Inert atmosphere; Schlenk technique; Stage #2: trimethyltin(IV)chloride In methanol at 45℃; for 12h; Schlenk technique; Inert atmosphere;	4.3.1 [(Me₃Sn)₂(O₂CC₅H₃NS)₂]_n (1) General procedure: The reaction was carried out under nitrogen atmosphere by use of standard Schlenk techniques. H2L1 (0.308g, 1mmol) was added to the solution of methanol (30ml) together with potassium hydroxide (0.112g, 2mmol), and the mixture was stirred for 0.5h. Trimethyltin chloride (0.398g, 2mmol) was then added to the mixture, and the reaction was allowed to continue at 45°C for another 12h. After cooling down to room temperature, the solution was filtered. The solvent was gradually removed by evaporation under vacuum until a solid product was obtained. The solid was then recrystallized from diethyl ether, and colorless crystals of complex 1 were recovered.

Reference： [1]Yan, Fei-fei; Zhu, Qi; Li, Qian-Li; Zhang, Ru-Fen; Ma, Chun-Lin [Journal of Organometallic Chemistry, 2019, vol. 880, p. 156 - 162]

83
[ 119-80-2 ]
[ 1461-22-9 ]
[(n-Bu₃Sn)₂(O₂CC₆H₄S)₂]_n [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
38%	Stage #1: 2,2'-dithiobenzoic acid With potassium hydroxide In methanol for 0.5h; Inert atmosphere; Schlenk technique; Stage #2: tributyltin chloride In methanol at 45℃; for 12h; Schlenk technique; Inert atmosphere;	4.3.1 [(Me₃Sn)₂(O₂CC₅H₃NS)₂]_n (1) General procedure: The reaction was carried out under nitrogen atmosphere by use of standard Schlenk techniques. H2L1 (0.308g, 1mmol) was added to the solution of methanol (30ml) together with potassium hydroxide (0.112g, 2mmol), and the mixture was stirred for 0.5h. Trimethyltin chloride (0.398g, 2mmol) was then added to the mixture, and the reaction was allowed to continue at 45°C for another 12h. After cooling down to room temperature, the solution was filtered. The solvent was gradually removed by evaporation under vacuum until a solid product was obtained. The solid was then recrystallized from diethyl ether, and colorless crystals of complex 1 were recovered.

Reference： [1]Yan, Fei-fei; Zhu, Qi; Li, Qian-Li; Zhang, Ru-Fen; Ma, Chun-Lin [Journal of Organometallic Chemistry, 2019, vol. 880, p. 156 - 162]

84
[ 119-80-2 ]
[ 7732-18-5 ]
[ 6080-56-4 ]
N,N′-bis(4-methylenepyridin-4-yl)-1,4-benzenedicarboxamide [ No CAS ]
[Pb₂(N,N'-bis(4-methylenepyridin-4-yl)-1,4-benzenedicarboxamide)_0.5(DTSA)₂] [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
34%	With sodium hydroxide at 120℃; for 96h; High pressure; Autoclave;	2.2.1. Synthesis of CP1 General procedure: Zn(NO3)26H2O (0.060 g, 0.2 mmol), L (0.035 g, 0.1 mmol), H2-DTSA (0.062 g, 0.2 mmol), H2O (6 mL) and NaOH (4 mL, 0.1 mmol)were sealed in a 25 mL Teflon-lined stainless steel and heated to120 C for 4 d. Gradually cooled to room temperature, colorlessblock-shaped crystals were obtained and dried in air. Yield 15%(based on Zn).

Reference： [1]Liu, Guo-Cheng; Li, Yan; Lu, Zhen-Jie; Wang, Xiu-Li; Wang, Xiang; Chen, Xing-Xing [Polyhedron, 2019, vol. 170, p. 294 - 302]

85
[ 141-93-5 ]
[ 119-80-2 ]
[ 82799-44-8 ]

Yield	Reaction Conditions	Operation in experiment
90.2%	With sulfuric acid; at 0 - 65℃; for 6h;	Add 40 ml of concentrated sulfuric acid to a 500 ml four-neck reaction flask.100 grams of dithiosalicylic acid,8 grams of polyphosphate,With stirring in an ice-salt bath to cool below 0 C, 100 g of 1,3-diethylbenzene was added dropwise to control the reaction temperature not to exceed 5 C.After the addition was completed, the ice-salt bath was removed, the temperature was naturally raised to room temperature, and the reaction was continued for 1 hour.The oil bath was replaced, the temperature was slowly raised to 65 C, and the reaction was performed at 65 C for 5 hours. The reaction was followed by HPLC until the dithiosalicylic acid reaction was completed.The reaction product was cooled, 90 g of 1,3-diethylbenzene and 60 g of water were added, and the mixture was stirred for half an hour, and the phases were separated. The organic phase was washed with alkali, washed with water, concentrated, and then cooled to 5 C.Overnight, the next day was filtered, the filter cake was washed with a small amount of ice ethanol, and dried in vacuum.150 g of bright yellow crystalline powder, namely DETX finished product,Yield 90.2%,Melting point 71 72 ,The purity of the product by HPLC was 99.6%.

Reference： [1]Patent: CN110845471,2020,A .Location in patent: Paragraph 0008; 0027-0030

86
[ 1122-58-3 ]
[ 119-80-2 ]
2C₇H₁₀N₂*C₁₄H₁₀O₄S₂*H₂O [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
71.39%	With methanol In methanol	f. (4-dimethylaminopyridine) 2 : (2,2 -dithiodibenzoic acid) : (H 2 O) [(HDMAP + ) 2 •(dtdba 2 -) •(H 2 O), dtdba 2- = 2,2 -dithiodibenzoate] (6)) 4-dimethylaminopyridine (12.2 mg, 0.10 mmol) was dissolved in 3 mL methanol. To this solution was added 2,2 -dithiodibenzoicacid (30.6 mg, 0.1 mmol) in 15 mL methanol. Colorless prisms were afforded after 18 days of slow evaporation of the solvent (yield: 40.6 mg, 71.39% based on 4 - dimethylaminopyridine). mp 210.3-212.8 °C. Elem. Anal.: Calc. for C 28 H 32 N 4 O 5 S 2 (568.70): C, 59.08; H, 5.63; N, 9.85; S, 11.25. Found: C, 58.97; H, 5.55; N, 9.79; S, 11.14. Infrared spectrum (KBr disc, cm -1 ): 3640s( (OH)), 3454s( as (NH)), 3366s( s (NH)), 3246m, 3150m, 3077m, 2959m, 2875m, 1600s( as (COO -)), 1556m, 1512m, 1470m, 1427m, 1485m

Reference： [1]Chen, Bin; Chen, Xinlei; Chen, Zhuoran; Gao, Xingjun; He, Li; Jin, Shouwen; Wang, Daqi; Wu, Ronghui [Journal of Molecular Structure, 2021, vol. 1246]

87
[ 119-80-2 ]
[ 109127-21-1 ]
2,2'-disulfanediylbis(N-(7-oxo-7-(phenylamino)heptyl)benzamide) [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
10%	With dmap; 1-ethyl-(3-(3-dimethylamino)propyl)-carbodiimide hydrochloride; triethylamine In dichloromethane at 20℃; for 2h; Inert atmosphere; Cooling with ice;	10 General procedure: (4) Mix 7-amino-N-phenylheptanamide (1 mmol), 2-(methylamino)benzoic acid (1.2 mmol), 1-ethyl-(3-dimethylaminopropyl)carbodiimide hydrochloride The salt (EDCl, 1.2 mmol) and 4-dimethylaminopyridine (DMAP, 0.1 mmol) were placed in a 10 ml round bottom flask and replaced with argon. After adding 5 ml of dry dichloromethane as solvent, put it in an ice bath and stir, and add triethylamine (1.2 mmol) dropwise, then move to room temperature and react for 2 h. After the completion of the reaction was monitored by TLC, the solvent was evaporated by rotary evaporation, and column chromatography was separated to obtain the product 2-(methylamino)-N-(7-oxo-7-(phenylamino)heptyl)benzamide (Compound X2, Formula I, n=6, R1=NHCH3), the yield is 80%.
10%	With dmap; 1-ethyl-(3-(3-dimethylamino)propyl)-carbodiimide hydrochloride; triethylamine In dichloromethane at 20℃; for 2h; Inert atmosphere; Cooling with ice;	10 General procedure: (4) Mix 7-amino-N-phenylheptanamide (1 mmol), 2-(methylamino)benzoic acid (1.2 mmol), 1-ethyl-(3-dimethylaminopropyl)carbodiimide hydrochloride The salt (EDCl, 1.2 mmol) and 4-dimethylaminopyridine (DMAP, 0.1 mmol) were placed in a 10 ml round bottom flask and replaced with argon. After adding 5 ml of dry dichloromethane as solvent, put it in an ice bath and stir, and add triethylamine (1.2 mmol) dropwise, then move to room temperature and react for 2 h. After the completion of the reaction was monitored by TLC, the solvent was evaporated by rotary evaporation, and column chromatography was separated to obtain the product 2-(methylamino)-N-(7-oxo-7-(phenylamino)heptyl)benzamide (Compound X2, Formula I, n=6, R1=NHCH3), the yield is 80%.

Reference： [1]Current Patent Assignee: UNIVERSITY OF SOUTH CHINA - CN113200885, 2021, A Location in patent: Paragraph 0022; 0025; 0028
[2]Current Patent Assignee: UNIVERSITY OF SOUTH CHINA - CN113200885, 2021, A Location in patent: Paragraph 0022; 0025; 0028

88
[ 88-67-5 ]
[ 119-80-2 ]
[ 22219-02-9 ]

Yield	Reaction Conditions	Operation in experiment
89%	With potassium carbonate In water at 100℃; for 2h; Green chemistry;	4.6 General Procedure for Synthesis of DiarylSulfides andSelenides Via C-S andC-SeCross-coupling Reactions Catalyzed byFe3O4SiO2/2-amino Pyridine-Pd(II) General procedure: A mixture of aryl halide (1mmol), diaryl disulfide ordiselenide (0.5mmol), K2CO3(1mmol) and Fe3O4SiO2-/2-amino pyridine-Pd(II) (0.8mol%) in H2O/PEG(1:1, 2mL) was stirred at 100°C for the time indicatedin Tables2 and 3. The reaction progress was followed byTLC (eluent:ether/ethyl acetate, 5:1). At the end of thereaction, the mixture was cooled to room temperature,ethyl acetate (10mL) was added and the catalyst wasseparated by an eternal magnet. The organic phase waswashed with water (2 × 10mL) and dried over anhydrousMgSO4.The solvent was evaporated and the resultingcrude material was purified by recrystallization fromether and ethyl acetate (5:1) to afford the pure product.

Reference： [1]Lu, Lu; Luo, Jia; Wang, Weiqi; Xu, Xiaoqing; Zhang, Jingzheng [Catalysis Letters, 2022]

Purity	Size	Price	VIP Price	USA Stock *0-1 Day	Global Stock *5-7 Days	Quantity
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CAS No. :	119-80-2	MDL No. :	MFCD00002465
Formula :	C₁₄H₁₀O₄S₂	Boiling Point :	-
Linear Structure Formula :	-	InChI Key :	LBEMXJWGHIEXRA-UHFFFAOYSA-N
M.W :	306.36	Pubchem ID :	8409
Synonyms :

Signal Word:	Warning	Class:	N/A
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Hazard Statements:	H315-H319-H335	Packing Group:	N/A
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P332	IF SKIN irritation occurs:
P333	If skin irritation or rash occurs:
P334	Immerse in cool water/wrap n wet bandages.
P335	Brush off loose particles from skin.
P336	Thaw frosted parts with lukewarm water. Do not rub affected area.
P337	If eye irritation persists:
P338	Remove contact lenses, if present and easy to do. Continue rinsing.
P340	Remove victim to fresh air and keep at rest in a position comfortable for breathing.
P341	If breathing is difficult, remove victim to fresh air and keep at rest in a position comfortable for breathing.
P342	If experiencing respiratory symptoms:
P350	Gently wash with plenty of soap and water.
P351	Rinse cautiously with water for several minutes.
P352	Wash with plenty of soap and water.
P353	Rinse skin with water/shower.
P360	Rinse immediately contaminated clothing and skin with plenty of water before removing clothes.
P361	Remove/Take off immediately all contaminated clothing.
P362	Take off contaminated clothing and wash before reuse.
P363	Wash contaminated clothing before reuse.
P370	In case of fire:
P371	In case of major fire and large quantities:
P372	Explosion risk in case of fire.
P373	DO NOT fight fire when fire reaches explosives.
P374	Fight fire with normal precautions from a reasonable distance.
P376	Stop leak if safe to do so. Oxidising gases (section 2.4) 1
P377	Leaking gas fire: Do not extinguish, unless leak can be stopped safely.
P378
P380	Evacuate area.
P381	Eliminate all ignition sources if safe to do so.
P390	Absorb spillage to prevent material damage.
P391	Collect spillage. Hazardous to the aquatic environment
P301 + P310	IF SWALLOWED: Immediately call a POISON CENTER or doctor/physician.
P301 + P312	IF SWALLOWED: call a POISON CENTER or doctor/physician IF you feel unwell.
P301 + P330 + P331	IF SWALLOWED: Rinse mouth. Do NOT induce vomiting.
P302 + P334	IF ON SKIN: Immerse in cool water/wrap in wet bandages.
P302 + P350	IF ON SKIN: Gently wash with plenty of soap and water.
P303 + P361 + P353	IF ON SKIN (or hair): Remove/Take off Immediately all contaminated clothing. Rinse SKIN with water/shower.
P304 + P312	IF INHALED: Call a POISON CENTER or doctor/physician if you feel unwell.
P304 + P340	IF INHALED: Remove victim to fresh air and Keep at rest in a position comfortable for breathing.
P304 + P341	IF INHALED: If breathing is difficult, remove victim to fresh air and keep at rest in a position comfortable for breathing.
P305 + P351 + P338	IF IN EYES: Rinse cautiously with water for several minutes. Remove contact lenses, if present and easy to do. Continue rinsing.
P306 + P360	IF ON CLOTHING: Rinse Immediately contaminated CLOTHING and SKIN with plenty of water before removing clothes.
P307 + P311	IF exposed: call a POISON CENTER or doctor/physician.
P308 + P313	IF exposed or concerned: Get medical advice/attention.
P309 + P311	IF exposed or if you feel unwell: call a POISON CENTER or doctor/physician.
P332 + P313	IF SKIN irritation occurs: Get medical advice/attention.
P333 + P313	IF SKIN irritation or rash occurs: Get medical advice/attention.
P335 + P334	Brush off loose particles from skin. Immerse in cool water/wrap in wet bandages.
P337 + P313	IF eye irritation persists: Get medical advice/attention.
P342 + P311	IF experiencing respiratory symptoms: call a POISON CENTER or doctor/physician.
P370 + P376	In case of fire: Stop leak if safe to Do so.
P370 + P378	In case of fire:
P370 + P380	In case of fire: Evacuate area.
P370 + P380 + P375	In case of fire: Evacuate area. Fight fire remotely due to the risk of explosion.
P371 + P380 + P375	In case of major fire and large quantities: Evacuate area. Fight fire remotely due to the risk of explosion.
Storage
Code	Phrase
P401
P402	Store in a dry place.
P403	Store in a well-ventilated place.
P404	Store in a closed container.
P405	Store locked up.
P406	Store in corrosive resistant/ container with a resistant inner liner.
P407	Maintain air gap between stacks/pallets.
P410	Protect from sunlight.
P411
P412	Do not expose to temperatures exceeding 50 oC/ 122 oF.
P413
P420	Store away from other materials.
P422
P402 + P404	Store in a dry place. Store in a closed container.
P403 + P233	Store in a well-ventilated place. Keep container tightly closed.
P403 + P235	Store in a well-ventilated place. Keep cool.
P410 + P403	Protect from sunlight. Store in a well-ventilated place.
P410 + P412	Protect from sunlight. Do not expose to temperatures exceeding 50 oC/122oF.
P411 + P235	Keep cool.
Disposal
Code	Phrase
P501	Dispose of contents/container to ...
P502	Refer to manufacturer/supplier for information on recovery/recycling

Physical hazards
Code	Phrase
H200	Unstable explosive
H201	Explosive; mass explosion hazard
H202	Explosive; severe projection hazard
H203	Explosive; fire, blast or projection hazard
H204	Fire or projection hazard
H205	May mass explode in fire
H220	Extremely flammable gas
H221	Flammable gas
H222	Extremely flammable aerosol
H223	Flammable aerosol
H224	Extremely flammable liquid and vapour
H225	Highly flammable liquid and vapour
H226	Flammable liquid and vapour
H227	Combustible liquid
H228	Flammable solid
H229	Pressurized container: may burst if heated
H230	May react explosively even in the absence of air
H231	May react explosively even in the absence of air at elevated pressure and/or temperature
H240	Heating may cause an explosion
H241	Heating may cause a fire or explosion
H242	Heating may cause a fire
H250	Catches fire spontaneously if exposed to air
H251	Self-heating; may catch fire
H252	Self-heating in large quantities; may catch fire
H260	In contact with water releases flammable gases which may ignite spontaneously
H261	In contact with water releases flammable gas
H270	May cause or intensify fire; oxidizer
H271	May cause fire or explosion; strong oxidizer
H272	May intensify fire; oxidizer
H280	Contains gas under pressure; may explode if heated
H281	Contains refrigerated gas; may cause cryogenic burns or injury
H290	May be corrosive to metals
Health hazards
Code	Phrase
H300	Fatal if swallowed
H301	Toxic if swallowed
H302	Harmful if swallowed
H303	May be harmful if swallowed
H304	May be fatal if swallowed and enters airways
H305	May be harmful if swallowed and enters airways
H310	Fatal in contact with skin
H311	Toxic in contact with skin
H312	Harmful in contact with skin
H313	May be harmful in contact with skin
H314	Causes severe skin burns and eye damage
H315	Causes skin irritation
H316	Causes mild skin irritation
H317	May cause an allergic skin reaction
H318	Causes serious eye damage
H319	Causes serious eye irritation
H320	Causes eye irritation
H330	Fatal if inhaled
H331	Toxic if inhaled
H332	Harmful if inhaled
H333	May be harmful if inhaled
H334	May cause allergy or asthma symptoms or breathing difficulties if inhaled
H335	May cause respiratory irritation
H336	May cause drowsiness or dizziness
H340	May cause genetic defects
H341	Suspected of causing genetic defects
H350	May cause cancer
H351	Suspected of causing cancer
H360	May damage fertility or the unborn child
H361	Suspected of damaging fertility or the unborn child
H361d	Suspected of damaging the unborn child
H362	May cause harm to breast-fed children
H370	Causes damage to organs
H371	May cause damage to organs
H372	Causes damage to organs through prolonged or repeated exposure
H373	May cause damage to organs through prolonged or repeated exposure
Environmental hazards
Code	Phrase
H400	Very toxic to aquatic life
H401	Toxic to aquatic life
H402	Harmful to aquatic life
H410	Very toxic to aquatic life with long-lasting effects
H411	Toxic to aquatic life with long-lasting effects
H412	Harmful to aquatic life with long-lasting effects
H413	May cause long-lasting harmful effects to aquatic life
H420	Harms public health and the environment by destroying ozone in the upper atmosphere

[ CAS No. 119-80-2 ] {[proInfo.proName]}

Quality Control of [ 119-80-2 ]

Related Doc. of [ 119-80-2 ]

Product Details of [ 119-80-2 ]

Safety of [ 119-80-2 ]

Application In Synthesis of [ 119-80-2 ]

[ 119-80-2 ] Synthesis Path-Upstream 1~6

[ 119-80-2 ] Synthesis Path-Downstream 1~88

Related Functional Groups of
[ 119-80-2 ]

Aryls

Carboxylic Acids

Sulfides

Precautionary Statements-General

Prevention

Response

Storage

Disposal

Physical hazards

Health hazards

Environmental hazards

Inquiry

[ CAS No. 119-80-2 ] {[proInfo.proName]}

Quality Control of [ 119-80-2 ]

Related Doc. of [ 119-80-2 ]

Product Details of [ 119-80-2 ]

Safety of [ 119-80-2 ]

Application In Synthesis of [ 119-80-2 ]

[ 119-80-2 ] Synthesis Path-Upstream 1~6

[ 119-80-2 ] Synthesis Path-Downstream 1~88

Related Functional Groups of [ 119-80-2 ]

Aryls

Carboxylic Acids

Sulfides

Precautionary Statements-General

Prevention

Response

Storage

Disposal

Physical hazards

Health hazards

Environmental hazards

Inquiry

Related Functional Groups of
[ 119-80-2 ]