Name: 6320-03-2|2-chlorothiophenol|98%
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1
[ 6320-03-2 ]
[ 57616-74-7 ]
4-[3-(2-chloro-phenylsulfanyl)-propyl]-morpholine [ No CAS ]

Reference： [1]Journal of the American Chemical Society,1958,vol. 80,p. 162

2
[ 6320-03-2 ]
[ 14575-10-1 ]

Yield	Reaction Conditions	Operation in experiment
	With Carbon tetrachloride; chlorine
	With chlorine
	In Carbon tetrachloride; hexane	13 o-Chlorobenzenesulfenyl Chloride EXAMPLE 13 o-Chlorobenzenesulfenyl Chloride Under nitrogen, N-chlorosuccinimide (5.34 g., 40 mmoles) was slurried in 50 ml. of carbon tetrachloride and the stirred mixture cooled in an ice-water bath. o-Chlorothiophenol (5.76 g., 40 mmoles), dissolved in 25 ml. of carbon tetrachloride, was added dropwise. The ice-water bath was removed and the reaction mixture stirred at room temperature for approximately 16 hours. The reaction was filtered, evaporated to an oil, taken up in hexane, refiltered and reconcentrated to yield o-chlorobenzenesulfenyl chloride (6.8 g., oil).

	In Carbon tetrachloride; hexane	7 o-Chlorobenzenesulfenyl Chloride PREPARATION 7 o-Chlorobenzenesulfenyl Chloride Under nitrogen, N-chlorosuccinimide (5.34 g., 40 mmoles) was slurried in 50 ml. of carbon tetrachloride and the stirred mixture cooled in an ice-water bath. o-Chlorothiophenol (5.76 g., 40 mmoles), dissolved in 25 ml. of carbon tetrachloride, was added dropwise. The ice-water bath was removed and the reaction mixture stirred at room temperature for approximately 16 hours. The reaction was filtered, evaporated to an oil, taken up in hexane, refiltered and reconcentrated to yield o-chlorobenzenesulfenyl chloride (6.8 g., oil).
	With chlorine In n-Pentane at 0℃;	5.1.23 N-(4-chlorophenylthio)-phthalimide (28) General procedure: To a stirred solution of 4-chlorobenzenethiol (6.9mmol) in n-pentane (15mL), chlorine gas was added at 0°C until the solution turned red orange to obtain the sulfenyl chloride. The sulfenyl chloride solution was added dropwise to a stirred solution of phthalimide (6.9mmol) and TEA (9.0mmol) in DMF (15mL). The mixture was stirred for 30min, transferred to a large beaker, and then cold water was added. The suspension was filtered to give compound 28 as a solid (967mg, 48.4% yield).
	With N-chloro-succinimide In dichloromethane at 20℃; for 0.0833333h;	General procedure for the synthesis of chlorothiolated adducts of alkynes: General procedure: To a solution of aryl/heteroaryl thiols (0.55 mmol) in CH2Cl2 (4 mL) was added N-chlorosuccinimde(0.55 mmol) and the reaction mixture was allowed to stir for 5 minutes to form sulphenylchlorides as yellow colored solution. To this stirred solution of sulphenylchloride was added internal alkynoate (0.5mmol) and the reaction mixture was again stirred for 2-5 h. After completion of the reaction (monitored by TLC) water (10 mL) was added to the reaction mixture and extracted with CH2Cl2 (3 x 10 mL). The combined organic layers were washed with brine (10 mL) and dried over anh. sodium sulphate. The organic layer was concentrated using a rotary evaporator and chromatographed on silica gel (100-200 mesh) using 1:9 ethyl acetate-hexane as the eluent to give pure chloroalkenyl sulphides (4a-4n).
	With sulfuryl dichloride In dichloromethane at 0℃; for 1h;	4.2.44 2-((4-fluorophenyl)disulfaneyl)thiazole (4c) General procedure: General procedure for compounds 4c-d, 4g-m, and 4p-q [42]. Sulfuryl chloride (0.63g, 5mmol) was added dropwise to a solution of substituted phenthiol (5mmol) in 20mL dichloromethane at 0°C. The reaction mixture was stirred for 1hat the same temperature, then concentrated under vacuum to give yellow liquid phenylsulfenyl chlorine, which was used immediately in the next step. A solution of freshly prepared phenylsulfenyl chlorine in 5mL anhydrous ethyl ether was added dropwise to a solution of 2-mercaptothiazole, 2-mercapto-1,3,4-thiadiazol, or substituted2-mercapto-1,3,4-thiadiazol (5mmol) in 5mL anhydrous ethyl ether at room temperature. The reaction mixture was stirred for 12hat the same temperature to give a precipitate. The product was filtered, washed with anhydrous ethyl ether and further purified by silica gel column chromatography to afford pure target compounds.
	With trichloroisocyanuric acid In acetonitrile at 20℃; for 0.166667h;	Typical procedure for the preparation of phosphites General procedure: A mixture of thiol 1 (1 mmol) and TCCA (0.35 mmol) in MeCN (2 mL) was stirred for 10 min at room temperature under air atmosphere. Then phosphite 2 (1.2 mmol) was added to the above reaction mixture, and the reaction solution was stirred for another 10 min. The resulting solution was directly filtered through a pad of silica gel. After removal of the volatiles under vacuum, the crude product was purified by column chromatography on silica gel with petroleum ether/ethyl acetate to give the corresponding product. The characterization data and NMR spectra (1H,13C, 31P and 19F) for the products 3 were contained in the Supplemental Materials (Figures S1 - S79).
	With sulfuryl dichloride; triethylamine In Carbon tetrachloride at 0℃; for 0.5h;

Reference： [1]Montanari [Gazzetta Chimica Italiana, 1956, vol. 86, p. 428,431, 755]
[2]Babushkina,T.A.; Kalinkin,M.I. [Bulletin of the Academy of Sciences of the USSR Division of Chemical Science, 1969, p. 147 - 149][Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, 1969, # 1, p. 157 - 158] Welch, C. J.; Bazin, H.; Chattopadhyaya, J. [Acta chemica Scandinavica. Series B: Organic chemistry and biochemistry, 1986, vol. 40, # 5, p. 343 - 357]
[3]Current Patent Assignee: PFIZER INC - US4282242, 1981, A
[4]Current Patent Assignee: PFIZER INC - US4282246, 1981, A
[5]Wu, Puhua; Zhang, Jiong; Meng, Qingqing; Nare, Bakela; Jacobs, Robert T.; Zhou, Huchen [European Journal of Medicinal Chemistry, 2014, vol. 81, p. 59 - 75]
[6]Surineni, Naresh; Buragohain, Pori; Saikia, Bishwajit; Barua, Nabin C.; Baruah, Rajani K. [Tetrahedron Letters, 2015, vol. 56, # 50, p. 6965 - 6969]
[7]Xu, Yi-xiang; Huang, Yun-yuan; Song, Rong-rong; Ren, Yan-liang; Chen, Xin; Zhang, Chao; Mao, Fei; Li, Xiao-kang; Zhu, Jin; Ni, Shuai-shuai; Wan, Jian; Li, Jian [European Journal of Medicinal Chemistry, 2020, vol. 203]
[8]Chen, Yingying; Li, Meichao; Gong, Zhangshui; Shen, Zhenlu [Phosphorus, Sulfur and Silicon and the Related Elements, 2020, vol. 196, # 1, p. 19 - 27]
[9]Cao, Yilin; Engle, Keary M.; Kang, Taeho; Li, Zi-Qi [Journal of the American Chemical Society, 2022, vol. 144, # 16, p. 7189 - 7197]

3
[ 6320-03-2 ]
[ 31121-19-4 ]

Yield	Reaction Conditions	Operation in experiment
99%	With aluminum(III) oxide; sodium periodate In hexane at 20℃; for 0.5h;
98%	With oxygen In dichloromethane at 0℃; for 0.166667h;
98%	With 1-n-butyl-3-methylimidazolium methylselenite at 60℃; for 4h;	General procedure for the oxidation of thiols with [bmim][SeO₂(OCH₃)]: Method A: In a Schlenk tube under open atmosphere and at room temperature, the corresponding thiol (1.0 mmol) was added to [bmim][SeO2(OCH3)]10 (1.0 mL). The reaction mixture was allowed to stir at 60 °C for the time indicated in Table 1. The progress of the reaction was monitored by TLC. Method B: In a 10 mL glass vial equipped with a small magnetic stirring bar, containing 1.0 mL of [bmim][SeO2(OCH3)] was added the thiol (1.0 mmol). The vial was tightly sealed with an aluminum/Teflon crimp top. The mixture was then irradiated in a microwave reactor (CEM Explorer) for the time indicated in Table 2 at 30 °C (temperature was measured with an IR sensor on the outer surface of the reaction vial), using an irradiation power of 100 W and pressure of 150 psi. After the reaction was complete, the product was extracted by successive washings with petroleum ether (3 × 5 mL), dried over MgSO4, and concentrated in vacuum. The residue was purified by column chromatography on silica gel using ethyl acetate/hexanes as the eluent.

96%	With sodium perborate In methanol; lithium hydroxide monohydrate for 2h; Ambient temperature;
96%	With potassium fluoride on basic alumina for 0.025h; microwave irradiation;
96%	With Co(salophen) In ethanol at 60℃; for 3h;
96%	With tert.-butylnitrite; oxygen In 1,2-dichloro-ethane at 50℃; for 2h; 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.
95%	With potassium bromate; hexaammonium heptamolybdate tetrahydrate In lithium hydroxide monohydrate; acetonitrile at 20℃; for 0.0833333h;	Typical Procedure General procedure: 4-chlorothiophenol (0.145 g, 1 mmol) was added to a heterogeneous mixture of KBrO3 (0.167 g, 1 mmol), (NH4)6Mo7O24·4H2O (0.124 g, 10 mmol%), and CH3CN/H2O (7:3) (5 mL) and the mixture was stirred under a hood for 4 min at ambient atmosphere and room temperature. The progress of the reaction was monitored by TLC (eluent: EtOAc/n-C6H14, 1/13). After completion, CH2Cl2 (20 mL) was added and the reaction mixture was filtered. The filtrate was washed with 5% NaOH, water, and dried over anhydrous MgSO4. Finally, evaporation of the solvent gave the product with sufficient purity formost purposes
94%	In dimethyl sulfoxide at 20℃; for 0.166667h;
94%	With urea hydrogen peroxide addition compound at 25℃; for 0.0833333h;	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.
93%	With potassium permanganate In dichloromethane at 20℃; for 0.666667h;
92%	With aluminum(III) oxide; dimethyl sulfoxide at 50℃; for 0.5h;
92%	With air In hexane at 30℃; for 2.5h;
92%	With silica-supported 1,1,3,3-tetramethylguanidine/Br₂ complex In lithium hydroxide monohydrate; acetonitrile at 20℃; for 0.0833333h;
92%	With oxygen; anhydrous sodium carbonate; 1-n-butyl-3-methylimidazolium tetrafluoroborate at 20℃; for 0.5h;
91%	With dihydrogen peroxide In dichloromethane; 2,2,2-trifluoroethanol at 20℃;	B.A Method A: General procedure: The phenyl sulfide (6,2 mmol, 1 eq) was dissolved in DCM (1 mL). CF3CI-120H (3 mL) and H202 solution (0.66 mL, 6.8 mmol, 1.1 eq) was added. The reaction mixture was stirred at room temperature overnight under vigorous stirring. The white precipitate was filtered and dried under reduced pressure to deliver the desired disulfide.
91%	With 2,2,2-trifluoroethanol; dihydrogen peroxide In dichloromethane at 20℃;	B Method A General procedure: The phenyl sulfide (6.2 mmol, 1 eq) was dissolved in DCM (1 mL). CF3CH2OH (3 mL) and H202 solution (0.66 mL, 6.8 mmol, 1.1 eq) was added. The reaction mixture was stirred at room temperature overnight under vigorous stirring. The white precipitate was filtered and dried under reduced pressure to deliver the desired disulfide.
91%	With Bromotrichloromethane In tetrahydrofuran at 20℃; for 12h; Schlenk technique; Irradiation;	5 Example 5 Add 57.8mg (0.4mmol) o-chlorobenzenethiol and 237.9mg (1.2mmol) bromotrichloromethane into a 10mL Schlenk container, then add 2mL tetrahydrofuran with a syringe, and react for 12h under the irradiation of a 23W 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: 51 mg, yield: 91%.
90%	With barium manganate In chloroform for 10h; Ambient temperature;
89%	With 10 wtpercent cubic Ag₂O nanoparticle incorporated mesoporous silica; air In lithium hydroxide monohydrate for 5h; Reflux; Green chemistry; chemoselective reaction;
83%	With bis(trichloromethyl) carbonate; triethylamine; Triphenylphosphine oxide In chloroform for 4h; Heating;
83%	With air In ethanol at 20℃; for 4h;	Thiol coupling reactions for the synthesis of disulfides General procedure: General procedure (1mM scale): In a 25 mL round bottom flask, a thiol(1; 1.0 mmol) was dissolved in EtOH (1 mL) and the mixture was stirredin the open atmosphere for 4 h (completion of reaction was confirmedby TLC). Then the mixture in the flask was evaporated in vacuo. Theresidue was either directly dried to give pure products 2a-i or subjectedto silica gel column chromatography using petroleum ether as eluent togive pure products 2j-l (see Table 2).
83%	With magnetic ion exchanged Montmorillonite-k10 In tetrahydrofuran at 50℃; for 1h; Green chemistry;
82.9%	Stage #1: 2-chlorobenzenethiol With Sodium hydrogenocarbonate In dichloromethane at 20℃; for 0.25h; Stage #2: With iodine In dichloromethane for 0.5h;	Synthesis of compound 1 General procedure: Thiophenol (440 mg, 4 mmol) was added to a flask and dissolved in anhydrous dichloromethane (DCM, 50 mL),sodium bicarbonate (420 mg, 5 mmol) was added to the flask with vigorous stirring at room temperature. After stirring for 15 min, iodine(1.5 g, 6 mmol) was added to the reaction mixture slowly and stirred for an additional 30 min vigorously. Then, add saturated aqueous Na2S2O3 to the reaction mixture to remove excess iodine, until the solution turns colorless. The resulting mixture was extracted with DCM. The organic phase was dried over anhydrous MgSO4, filtered, evaporated under reduced pressure and purified with column chromatography by using petroleum ether/ethyl acetate as eluent to give the desired product.
80%	With potassium-t-butoxide In tetrahydrofuran at 25℃;
76%	With sodium lauryl sulfate In lithium hydroxide monohydrate at 5℃; for 0.05h;
63%	With [bis(acetoxy)iodo]benzene In acetonitrile at 20℃; for 0.5h;	General procedure for the synthesis of disulfide from thiols: General procedure: To a solution of thiols (1m-x) (1.0 mmol) in acetonitrile (2 ml), diacetoxyiodo benzene (DIB) (0.5 mmol) was added. The reaction mixture was stirred for 30 min at room temperature. After completion of the reaction (monitored by TLC), the solvent was evaporated under reduced pressure. The solid obtained was collected, and washed with water. It was dried and recrystallized from ethanol to give disulfides (2m-x).
57%	With oxygen at 60℃; for 12h; Green chemistry;
	With bromine; glacial acetic acid
	With iodine
	With manganese(IV) oxide; molecular sieve In hexane for 1h; Heating; Yield given;
	With 1-benzyl-1-aza-4-azoniabicyclo<2.2.2>octane periodate In acetonitrile Heating;
	Multi-step reaction with 2 steps 1: aq. NaOH / 2 h 2: K₂CO₃ / ethanol; H₂O / 90 °C
	With dimethyl sulfoxide; 1,1,1,3,3,3-hexamethyl-disilazane In acetonitrile at 20℃; for 2h;	18.i l.,1 '-dithiobis(2-chlorobenzene)Hexamethyldisilazane (4.4 ml) was added to a stirred solution of 2-chlorobenzenethiol (2.0 20 ml) and DMSO (3.7 ml) in dry acetonitrile at room temperature. After 2 h the white precipitate was filtered and washed (cold acetonitrile) to give the sub-title compound as a white solid (2.27 g). 1H NMR CDCl3: δ 7.56 (2H, dd), 7.36 (2H, dd), 7.26-7.14 (4H, m).
	With N-chloro-succinimide In dichloromethane at 20℃; for 0.5h;	General procedure for the preparation of diaryldisulfides General procedure: To the stirred solution of thiols (5 mmol) in dichloromethane (10 mL),NCS (0.5 eq.) was added. The mixture was then stirred for 30 min. The progressof the reaction was monitored by TLC. After completion of the reaction, CH2Cl2(10 mL) was added and the mixture was washed successively with water (2×20mL).The organic layer was separated and dried by adding anhydrous Na2SO4.Evaporation of the solvent under reduced pressure gave almost pure product.Further purication was achieved by column chromatography on silica gel (ethyl acetate:hexane (1:30)) to give pure product in good to excellent yield.
	With N-chloro-succinimide In dichloromethane at 20℃; for 0.5h;
	With iodine; dimethyl sulfoxide
	With potassium carbonate In acetonitrile at 20℃; for 1h;

Reference： [1]Hirano, Masao; Yakabe, Sigetaka; Ando, Ken-Ichiro; Morimoto, Takashi [Journal of Chemical Research - Part S, 1998, # 12, p. 816 - 817]
[2]Sathe, Manisha; Ghorpade, Ramarao; Kaushik, Mahabir Parshad [Chemistry Letters, 2006, vol. 35, # 9, p. 1048 - 1049]
[3]Location in patent: experimental part Thurow, Samuel; Pereira, Vanda A.; Martinez, Débora M.; Alves, Diego; Perin, Gelson; Jacob, Raquel G.; Lenardão, Eder J. [Tetrahedron Letters, 2011, vol. 52, # 5, p. 640 - 643]
[4]McKillop; Koyuncu; Krief; Dumont; Renier; Trabelsi [Tetrahedron Letters, 1990, vol. 31, # 35, p. 5007 - 5010]
[5]Lenardão, Eder J.; Lara, Renata G.; Silva, Márcio S.; Jacob, Raquel G.; Perin, Gelson [Tetrahedron Letters, 2007, vol. 48, # 43, p. 7668 - 7670]
[6]Location in patent: experimental part Chai, Pin Ji; Li, Yong Shu; Tan, Cheng Xia [Chinese Chemical Letters, 2011, vol. 22, # 12, p. 1403 - 1406]
[7]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]
[8]Bayraq, Samad Shoghpour; Nikseresht, Ahmad; Khosravi, Iman [Phosphorus, Sulfur and Silicon and the Related Elements, 2013, vol. 188, # 9, p. 1236 - 1243]
[9]Sanz, Roberto; Aguado, Rafael; Pedrosa, María R.; Arnáiz, Francisco J. [Synthesis, 2002, # 7, p. 856 - 858]
[10]Azeredo, Juliano Braun; Godoi, Marcelo; Keller, Mateus Henrique; Roehrs, Juliano Alex; Thedy, Maria Eduarda Candido; de Souza, Bruno Silveira [Tetrahedron Letters, 2022, vol. 100]
[11]Shaabani, Ahmad; Tavasoli-Rad, Farahnaz; Lee, Donald G. [Synthetic Communications, 2005, vol. 35, # 4, p. 571 - 580]
[12]Hirano, Masao; Yakabe, Sigetaka; Monobe, Hiroyuki; Morimoto, Takashi [Journal of Chemical Research - Part S, 1998, # 8, p. 472 - 473]
[13]Hirano, Masao; Monobe, Hiroyuki; Yakabe, Sigetaka; Morimoto, Takashi [Journal of Chemical Research - Part S, 1999, # 6, p. 374 - 375]
[14]Location in patent: experimental part Shaabani, Ahmad; Farhangi, Elham; Rahmati, Abbas [Phosphorus, Sulfur and Silicon and the Related Elements, 2010, vol. 185, # 2, p. 463 - 468]
[15]Location in patent: experimental part Singh, Devender; Galetto, Fabio Z.; Soares, Letiere C.; Rodrigues, Oscar E. Dorneles; Braga, Antonio Luiz [European Journal of Organic Chemistry, 2010, # 14, p. 2661 - 2665]
[16]Current Patent Assignee: SPERMATECH; GOLDING LOUISE - WO2018/211276, 2018, A1 Location in patent: Page/Page column 31; 32
[17]Current Patent Assignee: ARCTIC PHARMA - WO2018/211277, 2018, A1 Location in patent: Page/Page column 45-46
[18]Current Patent Assignee: NANJING TECH UNIVERSITY - CN113666854, 2021, A Location in patent: Paragraph 0020; 0054-0056
[19]Srivastava, Ram Gopal; Venkataramani, Pudukkottai S. [Indian Journal of Chemistry - Section B Organic and Medicinal Chemistry, 1981, vol. 20, # 11, p. 996]
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4
[ 39876-88-5 ]
[ 6320-03-2 ]
[ 65023-98-5 ]

Reference： [1]Indian Journal of Chemistry - Section B Organic and Medicinal Chemistry,1977,vol. 15,p. 485 - 487

5
[ 39786-40-8 ]
[ 6320-03-2 ]
[ 68217-88-9 ]

Reference： [1]Indian Journal of Chemistry - Section B Organic and Medicinal Chemistry,1978,vol. 16,p. 627 - 629

6
[ 3034-57-9 ]
[ 6320-03-2 ]
[ 17119-33-4 ]

Reference： [1]Canadian Journal of Chemistry,1967,vol. 45,p. 1807 - 1811

7
[ 6320-03-2 ]
[ 3034-48-8 ]
[ 53316-68-0 ]

Reference： [1]Journal fur praktische Chemie (Leipzig 1954),1974,vol. 316,p. 349 - 352

8
[ 6320-03-2 ]
[ 627-42-9 ]
[ 117341-26-1 ]

Reference： [1]Journal of the American Chemical Society,1989,vol. 111,p. 258 - 268

9
[ 6320-03-2 ]
[ 638-07-3 ]
ethyl 4-(2-chlorophenylthio)-3-oxobutanoate [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
68%	With triethylamine In dichloromethane at 0℃; for 0.5h;	2 General procedure for the synthesis of Ethyl 4-(thioaryloxy)acetoacetates (4a-l) General procedure: A solution of 4-chloroacetoacetate (500 mg, 3.28 mmol, 1 eq.), NEt3 (348 mg, 3.44 mmol, 1.05 eq.) and appropriate thiophenols 3a-l (1.03 eq.) in CH2Cl2 (6.5 mL) was stirred at 0 °C for 30 min. The reaction mixture was diluted with EtOAc and washed with an aqueous solution of NaOH (1 M), hydrochloric acid (1 M) and brine. The combined organic layers were dried (Na2SO4), filtered and the solvent was removed under reduced pressure. The residue was purified by flash chromatography (silica gel, hexane/EtOAc 9:1).
	With triethylamine for 4h;
0.96 g	With triethylamine In dichloromethane at 0℃; for 0.5h;	4.1.18. 5-((2-Chlorophenylthio)methyl)-1H-pyrazol-3(2H)-one (14) General procedure: 4-Chlorothiophenol (1.1 g, 7.61 mmol) was mixed with ethyl 4-chloroacetoacetate (0.95 mL, 7.00 mmol) in CH2Cl2 (100 mL) at 0 °C. Triethylamine (1.5 mL, 10.8 mmol) was then added dropwise. After the resulting suspension was stirred at 0 °C for another 30 min, the reaction mixture was poured into water, and the aqueous layer was extracted with EtOAc. The combined organic layer was washed with saturated NaHCO3, HCl (0.25 N), brine, concentrated in vacuo, and purified by flash column chromatography (ethyl acetate/hexanes = 1/9) to afford 23 as a light yellow oil, which was not very stable. Therefore, 23 was used directly for the next step immediately after the flash column chromatography purification.Compound 23 (0.48 g, 1.76 mmol) was stirred in EtOH (5 mL), and an ethanolic solution of NH2NH2 (2 N, 0.88 mL, 1.76 mmol) was added. The resulting solution was stirred overnight at room temperature, during which time a precipitate formed. The precipitate was filtered, washed with cold EtOH, and dried in vacuo to afford 5 (0.31 g, 69%, two steps) as a white solid.

Reference： [1]Peduto, Antonella; Krauth, Verena; Collarile, Selene; Dehm, Fiederike; Ambruosi, Marika; Belardo, Carmela; Guida, Francesca; Massa, Antonio; Esposito, Veronica; Maione, Sabatino; De Rosa, Mario; Werz, Oliver; Filosa, Rosanna [European Journal of Medicinal Chemistry, 2016, vol. 108, p. 466 - 475]
[2]Sircar; Gregor; Anderson; Haleen; Shih; Weishaar; Steffen; Pugsley; Taylor [Journal of Medicinal Chemistry, 1991, vol. 34, # 7, p. 2248 - 2260]
[3]Location in patent: experimental part Chen, Tian; Benmohamed, Radhia; Arvanites, Anthony C.; Ranaivo, Hantamalala Ralay; Morimoto, Richard I.; Ferrante, Robert J.; Watterson, D. Martin; Kirsch, Donald R.; Silverman, Richard B. [Bioorganic and Medicinal Chemistry, 2011, vol. 19, # 1, p. 613 - 622]

10
[ 6320-03-2 ]
[ 13420-63-8 ]
[ 125091-44-3 ]

Reference： [1]Journal of Heterocyclic Chemistry,1989,vol. 26,p. 635 - 637

11
[ 95-50-1 ]
[ 75-08-1 ]
[ 188290-36-0 ]
[ 90407-14-0 ]
[ 6320-03-2 ]
[ 5097-95-0 ]
[ 108-90-7 ]
[ 71-43-2 ]

Reference： [1]Journal of Organic Chemistry USSR (English Translation),1986,vol. 22,p. 755 - 760
Zhurnal Organicheskoi Khimii,1986,vol. 22,p. 846 - 850

12
[ 6320-03-2 ]
[ 74-88-4 ]
[ 17733-22-1 ]

Yield	Reaction Conditions	Operation in experiment
89%	With sodium hydroxide; tetra-(n-butyl)ammonium iodide In benzene for 24h; Ambient temperature;
85%	With sodium methylate In methanol at 20℃; for 24h;
85%	Stage #1: 2-chlorothiphenol With methanol; sodium at 20℃; for 24h; Stage #2: methyl iodide	Preparation of o-Chlorophenyl Methyl Sulphide Sodium metal (0.80 g, 34 mmol) was dissolved in methanol (80 ml) and a solution of o-chlorothiophenol (5.1 g, 35 mmol) in methanol (10 ml) added. The reaction mixture was cooled with an ice/water bath and a solution of methyl iodide (5.0 g, 35 mmol) in methanol (10 ml) was added dropwise. The reaction mixture was stirred at ambient temperature for 24 h. Water (100 ml) was added and the resultant mixture extracted with chloroform (three-100 ml aliquots). The organic layers were combined, dried (MgSO4) and the solvent evaporated. The residue was distilled at reduced pressure yielding o-chlorophenyl methyl sulphide (4.7 g, 29.7 mmol, 85%), b.p. 80-86° C./3.0 Torr. 1H n.m.r. (270 MHz) δ7.33, d, 1H; 7.22, t, 1H; 7.12, d, 1H; 7.07, t, 1H; 2.47, s, 3H. 13C n.m.r. δ137.70, 131.75 129.69, 129.34, 127.18, 125.46, 15.13. m/z 160 (33%),158 (100%, M+), 145 (24%), 143 (66%).

With sodium hydride 1.) THF, RT, 10 min, 2.) THF, RT, 3 h; Multistep reaction;

Reference： [1]Imboden, Christoph; Renaud, Philippe [Tetrahedron Asymmetry, 1999, vol. 10, # 6, p. 1051 - 1060]
[2]Baerlocher, Felix Jakob; Baerlocher, Mark Otto; Langler, Richard Francis; MacQuarrie, Stephanie Lee; Marchand, Maurice Emile [Australian Journal of Chemistry, 2000, vol. 53, # 1, p. 1 - 5]
[3]Current Patent Assignee: UNIVERSITY HEALTH NETWORK - US2003/220524, 2003, A1 Location in patent: Page/Page column 25
[4]Gadwood, Robert C.; Mallick, Ishwar M.; DeWinter, Amy J. [Journal of Organic Chemistry, 1987, vol. 52, # 5, p. 774 - 782]

13
[ 499214-11-8 ]
[ 6320-03-2 ]
6-formylpyridine-2-carbothionic acid-S-2-chlorophenyl ester [ No CAS ]

Reference： [1]Bioorganic and Medicinal Chemistry Letters,2003,vol. 13,p. 609 - 612

14
[ 6320-03-2 ]
[ 4163-60-4 ]
2-chlorophenyl 2,3,4,6-tetra-O-acetyl-1-thio-β-D-galactopyranoside [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
85%	With tin(IV) chloride In dichloromethane at 20℃; for 4h;

Reference： [1]Li, Zhitao; Gildersleeve, Jeffrey C. [Journal of the American Chemical Society, 2006, vol. 128, # 35, p. 11612 - 11619]

15
[ 6320-03-2 ]
[ 5979-85-1 ]
[ 897781-06-5 ]

Yield	Reaction Conditions	Operation in experiment
95%	With potassium carbonate; potassium iodide In acetone for 24h; Reflux;	4.10. General procedure for the synthesis of substituted 2-(2-phenylsulfanylacetylamido)benzoic acids 14a-f, (Method I) General procedure: A mixture of substituted benzenethiol (38 mmol), K2CO3 (2.0 g) and KI (200 mg) in acetone (100 mL) was stirred for 15 min. 2-(2-Bromoacetylamido)-benzoic acid (13) (38 mmol) was added to the reaction mixture and refluxed for 24 h. The reaction was allowed to cool to rt and acetone was removed on rotary evaporator. The residue obtained was dissolved in water (200 mL) and 10% HCl (100 mL) was added. The resulting white precipitate was filtered, washed with H2O (2 × 100 mL) and dried to give the desired compounds 14a-f in good to excellent yields. These intermediates were used as such for the next step without further purification.
	With potassium carbonate; potassium iodide In acetone for 24h; Heating / reflux;	Compound 2a: A mixture of crude product 1 (10 gm, 38.75 mmol), 2-chlorobenzene-thiol (5.6 gm, 38.75 mmol), acetone (100 ml), K2CO3 (2.0 gm) and KI (200 mg) was refluxed for one day, cooled to room temperature and acetone was removed on a rotary vapor. The colorless precipitate was dissolved in water (200 ml) and 10% aqueous hydrochloric acid (100 ml) was added and solids were separated by filtration. The solid was washed with water (2x100 ml) and dried to give compound 2a as a colorless solid (8 gm). Compounds 2b and 2c were similarly prepared. 1H NMR: (CD3OD): ? 3.90 (s, 2H), 7.00-7.08 (m, 1H), 7.12-7.18 (m, 1H), 7.20-7.23 (m, 1H), 7.30-7.32 (m, 1H), 7.33-7.40 (m, 1H), 7.46-7.52 (dd, 1H, J=1.5, 6.3 Hz), 8.00-8.04 (dd, 1H, J=1.5, 6.3 Hz), 8.38-8.44 (d, 1H, J=8.1 Hz). (2b) 1H NMR: (CD3OD): ? 3.80 (s, 2H), 7.00-7.08 (m, 1H), 7.14-7.18 (m, 1H), 7.22-7.28 (t, 1H, J=7.8 Hz), 7.30-7.38 (m, 2H), 7.44 (t, 1H, J=2.1 Hz), 7.88-8.04 (dd, 1H, J=1.5, 6.0 Hz), 8.40-8.44 (dd, 1H, J=0.9, 7.5 Hz). (2c) 1H NMR (CD3OD): ? 3.90 (s, 2H), 7.10-7.16 (m, 1H), 7.24-7.30 (m, 2H), 7.38-7.44 (m, 2H), 7.48 (m, 1H), 8.02-8.04 (dd, 1H, J=1.5, 6.6 Hz), 8.50-8.56 (dd, 1H, J=0.9, 7.8 Hz).

Reference： [1]Location in patent: experimental part Boateng, Comfort A.; Eyunni, Suresh V.K.; Zhu, Xue Y.; Etukala, Jagan R.; Bricker, Barbara A.; Ashfaq; Jacob, Melissa R.; Khan, Shabana I.; Walker, Larry A.; Ablordeppey, Seth Y. [Bioorganic and Medicinal Chemistry, 2011, vol. 19, # 1, p. 458 - 470]
[2]Current Patent Assignee: STATE UNIVERSITY SYSTEM OF FLORIDA - US2007/232640, 2007, A1 Location in patent: Page/Page column 10; 11

16
[ 6320-03-2 ]
[ 29823-21-0 ]
8-(2-chloro-phenylsulfanyl)-octanoic acid [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
88%	Stage #1: 2-chlorothiphenol; Ethyl 8-bromooctanoate With potassium hydroxide In ethanol at 20℃; for 1h; Stage #2: With ethanol; water at 20 - 45℃; for 99.5h; Stage #3: With hydrogenchloride; water at 4℃; for 0.75h;	30 Example 30 -- Preparation of 8-(2-Chloro-phenylsulfanyl)-octanoic acid (Compound 30); [123] To a mini-tube equipped with a magnetic stir bar, was added 2-chlorobenzene thiol (1.0 mL, 8.2 mmol), ethyl 8-bromooctanoate (1.8 mL, 8.2 mmol), and 45 mL ethyl alcohol. Potassium hydroxide (1.5 g, 26 mmol) was added at room temperature and the reaction was allowed to stir at room temperature for 1 hr under a nitrogen atmosphere. Water (10 mL) was added and the stirring continued for 3 hours. The reaction was heated to 45°C for 0.5 hr, cooled to room temperature and stirred for an additional 96 hours. Solvent was removed under reduced pressure and the resulting solution was acidified to pH 1 with aqueous 1 N hydrochloric acid and cooled to 40C for 45 min. Product (2.24 g, 88%) was isolated as a white powder by filtration. IH NMR (d-DMSO): δ 11.96, broad s, IH (COOH); δ 7.42, dd, IH (aryl H); δ 7.33, multiplet,SUBSTITUTE SHEET (RULE 26) 2H (aryl H); δ 7.16, dt, IH (aryl H); δ 2,97, t, 2H (CH2 α to S); δ 2.17, t, (CH2 α to COOH); δ 1.6-1.25, complex, 1OH (rest of CH25S).

Reference： [1]Current Patent Assignee: NOVO NORDISK A/S - WO2008/14430, 2008, A1 Location in patent: Page/Page column 47-48

17
[ 6320-03-2 ]
[ 1835-65-0 ]
4,5-bis(2-chlorophenylthio)-3,6-difluorophthalonitrile [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	With potassium fluoride; butanone; at 0 - 35℃; for 1.66667h;	Referential Example 3; Synthesis of 4,5-bis(2-chloro phenylthio)-3-fluoro-6-(2,6-dimethylphenoxy)phthalocyanine; Into a four-neck flask of glass provided with a stirrer, a thermometer, a water separation tube, and a cooling tube and having an inner volume of 100 ml, 30 gr of 2-butanone, 10 gr (0.05 mol) of <strong>[1835-65-0]tetrafluorophthalonitrile</strong>, and 7.26 gr (0.125 mol) of potassium fluoride were placed and the flask was dipped in a water bath. 15.2 g (0.105 mol) of 2-chlorobenzene thiol was added to the reaction mixture with stirred at room temperature over about 40 minutes. The reaction temperature rose to the maximum of about 35° C. When the reaction was continued for additional one hour after the completion of this addition, the conversion of <strong>[1835-65-0]tetrafluorophthalonitrile</strong> reached 99.2percent. The content of the bisthiol moiety, 4,5-bis(2-chloro phenylthio)-3,6-difluorophthalonitrile, a determined by liquid chromatography, was 92.5percent. Then, 7.33 gr (0.06 mol) of 2,6-xylenol, 4.35 gr (0.075 mol) of potassium fluoride and and 6 gr of 2-butanone were added to the reaction mixture in the reaction vessel and the resultant mixture was heated to a temperature in the range of 83-86° C., and then left reacting under reflux for 30 hours. The conversion of 4,5-bis(2-chloro phenylthio)-3,6-difluorophthalonitrile after the completion of the reaction was determined by liquid chromatography, to find to be 99.8percent and the content of the target product, 4,5-bis(2-chloro phenylthio)-3-fluoro-6-(2,6-dimethylphenoxy)phthalonitrile, as determined by liquid chromatography, was 70percent. The reaction slurry was cooled to room temperature and filtered to separate a solid component. The filtrate consequently formed was separated. The resultant cake was washed with about 200 ml of chloroform. By evaporating the washing under a reduced pressure at 50° C., 18.0 g (0.0326 mol, yield: 65.2 mol percent based on tetrafluoronitrile) of 4,5-bis(2-chloro phenylthio)-3-(2,6-dimethylphenoxy)-6-fluorophthalonitrile was obtained.

Reference： [1]Patent: US2005/203293,2005,A1 .Location in patent: Page/Page column 19-20

18
[ 6320-03-2 ]
[ 53595-65-6 ]
[ 63031-97-0 ]

Yield	Reaction Conditions	Operation in experiment
	With sodium hydroxide; In water; N,N-dimethyl-formamide; at 130 - 150℃; for 0.416667h;Microwave irradiation;	EXAMPLE 19; This example illustrates the preparation of N-({5-[(2-chlorophenyl)thio]-2- thienyl}sulfonyl)-2-(3-methyl-1-phenyl-1H-pyrazol-5-yl)acetamide. EPO <DP n="65"/>To a solution of 2-chlorothiophenol (87 mg) and 5-bromothiophene-2-sulfonamide (121 mg) in DMF (1 mL) was added 2 N aqueous sodium hydroxide (100μL) and water (1 mL). The reaction mixture was heated in a CEM Discover microwave at 130 C for 5 min, then 150 C for 20 min. The mixture was partitioned between diethyl ether and water, and the organic phase was dried over sodium sulfate, filtered, and concentrated in vacuo. The resultant oil was purified by RPHPLC (Xterra, 5% to 95% acetonitrile in TFA (0.2% aq.)> to give a small amount of 5-[(2-chlorophenyl)thio]thiophene-2-sulfonamide (22 mg) that was dissolved in DCM (2 mL). To this solution was added Intermediate 2 (15 mg), EDCI (17 mg) and DMAP (3 mg). The reaction mixture was stirred for 3 h, then concentrated in vacuo and the residue purified by RPHPLC (Xterra, 5% to 95% acetonitrile in TFA (0.2% aq.)) to give the title compound N-( {5-[(2-chlorophenyl)thio]-2-thienyl} sulfonyl)-2-(3 - methyl- 1 -phenyl-1H-pyrazol-5-yl)acetamide (17 mg). 1H NMR (300 MHz, DMSQ) δ 7.70 (d, 1H), 7.59 (dd, 1H), 7.46 (d, 1H), 7.41 - 7.25 (m, 7H), 7.16 (d, 1H), 6.08 (s, 1H), 3.73 (s, 2H), 2.17 (s, 3H); APCI-MS: m/z 502, 504 [M- H]-.

Reference： [1]Patent: WO2006/75955,2006,A1 .Location in patent: Page/Page column 63-64

19
[ 58832-36-3 ]
[ 6320-03-2 ]
[ 1317-39-1 ]
5-(2-chlorophenylthio)furan-3-carboxylic acid [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	With sodium hydroxide; acetic acid; In N-methyl-acetamide; water; ethyl acetate;	EXAMPLE 16 5-(2-Chlorophenylthio)furan-3-carboxylic Acid o-Chlorothiophenol (4.5 g., 31 mmoles) and cuprous oxide (2.2 g., 15.5 mmoles) in 100 ml. of dimethylformamide were heated in an oil bath at 170-175 C. for 1.5 hours, during which time a precipitate formed. 5-Bromofuran-3-carboxylic acid (3 g., 15.7 mmoles) was added and heating continued for 2.5 hours. The reaction mixture was cooled to room temperature, filtered, diluted with 500 ml. of water, acidified with conc. hydrochloric acid and product extracted into 250 ml. of ethyl acetate. The ethyl acetate was back-washed with 150 ml. of water and insolubles removed by filtration. Product was extracted from the ethyl acetate into 150 ml. of 1 N sodium hydroxide, the aqueous phase acidified with conc. hydrochloric acid and product reextracted into 150 ml. of fresh ethyl acetate. The ethyl acetate was back-washed with water and concentrated to an oil (3.5 g.). Recrystallization from ether/hexane gave partially purified product in two crops (575 mg., 403 mg.). These were combined and chromatographed on approximately 150 ml. of silica gel with hexane/5% acetic acid as eluant. Middle fractions afforded purified 5-(2-chlorophenylthio)furan-3-carboxylic acid (490 mg., m.p. 146-148 C., m/e 254). Analysis: Calcd. for C11 H7 O3 SCl: C, 51.87; H, 2.77. Found: C, 51.81; H, 2.91.

Reference： [1]Patent: US4282246,1981,A

20
[ 6320-03-2 ]
[ 15726-38-2 ]
4,6-dichloro-5-(2-chlorophenylsulfanyl)-pyrimidine [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	In N-methyl-acetamide;	Example 18 Production of 4,6-dichloro-5-(2-chlorophenylsulfanyl)-pyrimidine In 5 ml of dimethylformamide was suspended 249 mg of sodium hydride (a 60% oil dispersion). Thereto was added 628 mg of 2-chlorothiophenol. The resulting mixture was stirred at room temperature for 1 hour to obtain solution 1. On the other hand, 1.0 g of 5-bromopyrimidine-4,6-diol was dissolved in 5 ml of dimethylformamide to obtain solution 2. Solution 1 was added dropwise to solution 2. The resulting mixture was heated under reflux for 8 hours, cooled to room temperature, and then poured into ice water. The crystals precipitated were collected by filtration, washed with water and then dried. Subsequently, the crystals were dissolved in 3 ml of phosphorus oxycloride and the resulting solution was heated under reflux for 2 hours. The reaction solution was cooled to room temperature and then poured into ice water. The resulting mixture was made basic with aqueous ammonia and extracted with toluene. The organic layer was washed with water and then dried over anhydrous magnesium sulfate. The drying agent was removed and the solvent was distilled off under reduced pressure to obtain 453 mg of 4,6-dichloro-5-(2-chlorophenyl)sulfanylpyrimidine as yellow crystals.

Reference： [1]Patent: EP826674,1998,A1

21
[ 6320-03-2 ]
[ 860625-21-4 ]
5-[(2-chlorophenyl)thio]-3-[1-(ethylsulfonyl)-4-piperidinyl]-1H-indole-7-carboxamide [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
26%	With potassium carbonate; ethylene glycol In isopropyl alcohol at 180℃; for 1h; Microwave irradiation;	37 To a solution of 5-bromo-3-[1-(ethanesulfonyl)-4-piperidinyl]-1 H-indole-7-carboxamide (66 mg, 0.159 mmol) in isopropanol (2 mL) was added chlorothiophenol (46 mg, 0.30 mmol), ethylene glycol (18 μl_, 0.32 mmol), copper iodide (4 mg, 0.016 mmol) and potassium carbonate (45 mg, .032 mmol). The reaction was heated in a microwave at 180 0C for 1 h. The solvent was evaporated, and EtOAc and H2O were added. The layers were separated, and the aqueous layer was extracted with EtOAc. The combined organic layers were dried, concentrated, and purified by Gilson Prepatory HPLC to give 15 mg (26%) of the title compound.LC/MS = m/z 478 [M+H] Rt 2.27 min

Reference： [1]Current Patent Assignee: GLAXOSMITHKLINE PLC - WO2007/62318, 2007, A2 Location in patent: Page/Page column 69

22
[ 6320-03-2 ]
[ 854755-94-5 ]
[ 76-05-1 ]
12'-(2-chlorophenylsulfanyl)vincristine trifluoroacetate [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
35%	Stage #1: 2-chlorothiphenol; 12'-iodovincristine With triethylamine In 1-methyl-pyrrolidin-2-one at 60℃; Stage #2: trifluoroacetic acid	56 Preparation of 12'- (2-Chlorophenylsulfanyl) vincristine Trifluoroacetate [00113] A solution of 12'-iodovincristine (60 mg, 0.05 mmol) in NMP (1.5 mL) was deoxygenated with argon for 10 minutes. The reaction vessel was charged with 1, 1'-bis (diphenylphosphino) ferrocene (20 mg, 0.035 mmol), tris (dibenzylideneacetone) dipalladium (0) (9 mg, 0.009 mmol) and Et3N (13 mg, 0.13 mmol). The mixture was stirred for 20 min at room temperature, 2-chlorobenzene- thiol (15 mg, 0.105 mmol) was added and then stirred at 60 °C overnight. The mixture was cooled to room temperature, diluted with ethyl acetate (100 mL) and washed with saturated aqueous NH4Cl (3 x 10 mL) and brine (3 x 10 mL). The organic layer was dried (Na2SO4), filtered and concentrated. The residue was purified by flash chromatography (silica, 10: 1 CH2Cl2/MeOH) and then by reverse phase chromatography (C-18, acetonitrile/water, 0.05% trifluoroacetic acid) to give 11'-(2- chlorophenylsulfanyl) vincristine (18 mg, 35%) trifluoroacetate

Reference： [1]Current Patent Assignee: CURIA INC - WO2005/55939, 2005, A2 Location in patent: Page/Page column 67

23
[ 6320-03-2 ]
[ 2032-35-1 ]
[ 936902-05-5 ]

Yield	Reaction Conditions	Operation in experiment
100%	With potassium carbonate In acetone for 24h; Heating / reflux;	80.A EXAMPLE 80[4-(7-Chloro-benzo[b]thiophen-2-yl)-pyrimidin-2-yl]-[3-(4-methyl-piperazin-1-yl)-propyl]-amine(A). Preparation of 7-chloro-benzo[b]thiophene; Into a 2 L round bottomed flask is added 2-chlorobenzenethiol (50.0 g, 346 mmol), potassium carbonate (52.7 g, 381 mmol) and acetone (1 L). 2-Bromo-1,1-diethoxyethane (71.5 g, 363 mmol) is added and the mixture is heated to reflux for 24 hours. The cooled mixture is filtered and concentrated under reduced pressure to yield crude 2-chlorophenyl-(2,2-diethoxyethyl)sulfane as a pale pink oil (101.8 g, quantitative). A 2 L, 3-necked round-bottomed flask, fitted with a mechanical stirrer, condenser and addition funnel is charged with chlorobenzene (1 L) and polyphosphoric acid (200 g) and the mixture is heated to reflux. At reflux the crude (2-chlorophenyl)(2,2-diethoxyethyl)sulfane is added dropwise over 1.5 hours and the mixture is refluxed for a further 24 hours. The cooled organic layer is decanted and concentrated under reduced pressure. The crude material is subjected to chromatography on silica (hexane) to provide the title compound as a brown oil (54.4 g, 93% yield).
97%	With potassium carbonate In acetone for 3.5h; Reflux;	Intermediate 1: 7-chlorobenzo[b]thiophene To a solution of 2-chlorobenzenethiol (1.53 g, 10.58 mmol, 1.0 eq.) and 2-bromo-1,1-diethoxyethane (2.4 mL, 15.87 mmol, 1.5 eq.) in acetone (10 ml) was added potassium carbonate (3.65 g, 26.45 mmol, 2.5 eq). The mixture was refluxed for 90 minutes and then 0,5 eq of 2-bromo-1,1-diethoxyethane was added. The mixture was refluxed for another 2 hours, cooled to room temperature and concentrated. The resulting residue was purified by flash column chromatography on silica gel using hexane/ diethyl ether (2%) as eluent to afford (2-chlorophenyl)(2,2-diethoxyethyl)sulfane as a light yellow oil (2.71 g, 97%). (0142) To a solution of polyphosphoric acid (6.0 g, 51.97 mmol, 9 eq.) in toluene (15 ml) was added under vigorous stirring a solution of (2-chlorophenyl)(2,2-diethoxyethyl)sulfane (1.5 g, 5.77 mmol, 1 eq) in toluene (5 mL). The mixture was stirred at reflux temperature for 5 hours and was then poured into ice cold water (30 mL) and stirred for 10 minutes. The mixture was washed with toluene, sat. aq. bicarbonate solution and brine, dried (Na2SO4) and concentrated. The resulting residue was purified by flash column chromatography on silica gel using hexane as eluent (as described in WO 2009/008992 A2) to afford 7-chlorobenzo[b]thiophene as a light-yellow oil (0.68 g, 70%). 1H-NMR (300 MHz, CDCl3-d) δ (ppm): 7.77 - 7.71 (m, 1H), 7.50 (d, J = 5.4 Hz, 1H), 7.41 - 7.30 (m, 3H).
	With potassium carbonate at 40℃; for 2h; Sonication;

Reference： [1]Current Patent Assignee: ELI LILLY & CO - US2008/306082, 2008, A1 Location in patent: Page/Page column 26
[2]Current Patent Assignee: ONCOSTELLAE - EP3480201, 2019, A1 Location in patent: Paragraph 0140; 0141
[3]Cardoso, Marcos Veríssimo de Oliveira; de Oliveira Filho, Gevanio Bezerra; de Siqueira, Lucianna Rabelo Pessoa; Espíndola, José Wanderlan Pontes; Silva, Elany Barbosa da; Mendes, Andresa Pereira de Oliveira; Pereira, Valéria Rêgo Alves; de Castro, Maria Carolina Accioly Brelaz; Ferreira, Rafaela Salgado; Villela, Filipe Silva; Costa, Francielly Morais Rodrigues da; Meira, Cássio Santana; Moreira, Diogo Rodrigo Magalhães; Soares, Milena Botelho Pereira; Leite, Ana Cristina Lima [European Journal of Medicinal Chemistry, 2019, vol. 180, p. 191 - 203]

24
[ 6320-03-2 ]
[ 13265-84-4 ]
[ 1073131-63-1 ]

Yield	Reaction Conditions	Operation in experiment
80%	With indium triflate In acetonitrile for 0.2h; regioselective reaction;
80%	With indium(III) triflate In acetonitrile

Reference： [1]Mukherjee, Debaraj; Yousuf, Syed Khalid; Taneja, Subhash Chandra [Organic Letters, 2008, vol. 10, # 21, p. 4831 - 4834]
[2]Mukherjee, Debaraj; Yousuf, Syed Khalid; Taneja, Subhash Chandra [Organic Letters, 2013, vol. 15, # 12, p. 3180 - 3180]

25
[ 6320-03-2 ]
[ 36367-85-8 ]
[ 1258451-51-2 ]

Yield	Reaction Conditions	Operation in experiment
79%	Stage #1: 2-chlorothiphenol With sodium hydride In N,N-dimethyl-formamide; mineral oil at 0℃; for 0.75h; Stage #2: toluene-4-sulfonic acid cyclopent-3-enyl ester In N,N-dimethyl-formamide; mineral oil at 0 - 20℃; for 48h;	48.2 Step 2: 1-Chloro-2-(cyclopent-3-enylsulfanyl)-benzene NaH (316 mg, 55% in mineral oil, 7.24 mmol) was suspended in DMF (6 ml) and the suspension was cooled to 0° C. A solution of 2-chloro-thiophenol (880 ml, 97% purity, 7.55 mmol) in DMF (2 ml) was added dropwise. After stirring for 45 min at 0° C. a solution of toluene-4-sulfonic acid cyclopent-3-enyl ester (1500 mg, 6.29 mmol) in DMF (3 ml) was added dropwise and the reaction mixture was stirred at room temperature for 2 days. Water was added and the mixture was extracted 3 times with EtOAc. The combined organic layers were washed with water, saturated NaHCO3 solution and brine, dried over Na2OS4 and evaporated. The remaining brown oil was purified by silica gel chromatography (heptane/EtOAc 100:0-99:1) to obtain the title compound (1.047 g, 79%) as colorless liquid.

Reference： [1]Current Patent Assignee: ROCHE HOLDING AG - US2010/317647, 2010, A1 Location in patent: Page/Page column 42-43

26
[ 6320-03-2 ]
[ 73568-25-9 ]
[ 1309388-90-6 ]

Yield	Reaction Conditions	Operation in experiment
89%	With sodium hydride In dimethyl sulfoxide at 90℃; for 3h;	4.2. General procedure for the preparation of 2-arylthioquinoline-3-carbaldehyde 2 General procedure: To a mixture of thiophenol (11 mmol), NaH (20 mmol), and DMSO (20 mL) was added 2-chloro-3-formylquinolines 1 (10 mmol) and the mixture was heated at 90 °C for the given time. Then the reaction was quenched with water (60 mL) and extracted with CH2Cl2 (3×50 mL). The combined organic layer was washed with brine solution, dried over anhydrous Na2SO4, and concentrated in vacuo. The desired products 2 were obtained by flash column chromatography on silica (n-hexane/EtOAc, 10:1→6:1, v/v).

Reference： [1]Location in patent: experimental part Zhong, Weihui; Ma, Wang; Liu, Yanbin [Tetrahedron, 2011, vol. 67, # 19, p. 3509 - 3518]

27
[ 6320-03-2 ]
[ 3137-63-1 ]
[ 1336933-33-5 ]

Yield	Reaction Conditions	Operation in experiment
75%	Stage #1: 2-chlorothiphenol With sodium hydride In dimethyl sulfoxide; mineral oil at 20℃; for 0.333333h; Inert atmosphere; Stage #2: 4-chloro-2-(trichloromethyl)quinazoline In dimethyl sulfoxide; mineral oil at 20℃; for 1h; Inert atmosphere;	General procedure for the preparation of compounds 2-18: 1 equiv ofthe appropriate thiophenol was dissolved in DMSO, then added onto 2 equiv ofNaH 95%, and stirred under N2 for 20 min. 1 equiv of 4-chloro-2-trichloromethylquinazoline was dissolved in DMSO, then added to themixture, and stirred at room temperature for 1 h. The reaction medium wasthen extracted three times by dichloromethane. The organic layer was washedwith water five times, dried over anhydrous Na2SO4 and concentrated in vacuo.The crude product was purified by column chromatography on silica gel withappropriate solvent to afford the corresponding nucleophilic aromaticsubstitution product.

Reference： [1]Location in patent: experimental part Verhaeghe, Pierre; Dumtre, Aurélien; Castera-Ducros, Caroline; Hutter, Sébastien; Laget, Michle; Fersing, Cyril; Prieri, Marion; Yzombard, Julien; Sifredi, France; Rault, Sylvain; Rathelot, Pascal; Vanelle, Patrice; Azas, Nadine [Bioorganic and Medicinal Chemistry Letters, 2011, vol. 21, # 19, p. 6003 - 6006]

28
[ 6320-03-2 ]
[ 762-42-5 ]
[ 1429655-23-1 ]

Yield	Reaction Conditions	Operation in experiment
82%	With benzoic acid; 9-(2-mesityl)-10-methylacridinium perchlorate In chloroform at 20℃; for 10h; Inert atmosphere; Irradiation;	The procedure for the synthesis of product 3 General procedure: An oven-dried Schlenk tube (10 mL) was equipped with a magnetic stir bar, 4-methylbenzenethiol (1a, 0.3 mmol), dimethyl but-2-ynedioate (2, 0.9 mmol), 5% Mes-Acr-Me+ (0.015 mmol), PhCOOH (2 equiv., 0.6 mmol). The flask was evacuated and backfilled with Ar for 3 times. Then CHCl3 (3.0 mL) was added with syringe. The reaction mixture was then stirred for 10 h at room temperature. After the reaction, 6 mL water was added to quench the reaction, and the resulting mixture was extracted twice with EtOAc. The combined organic extracts were washed with brine, dried over Na2SO4 and concentrated. Purification of the crude product by flash column chromatography afforded the product (petroleum ether/ethyl acetate as eluent (8:1)).
77%	With oxygen; manganese(II) acetate; benzoic acid In 1,2-dichloro-ethane at 50℃; for 2h; Schlenk technique;
66%	With air In 1,4-dioxane at 80℃;

Reference： [1]Xia, Xiao-Feng; Zhang, Guo-Wei; Zhu, Su-Li [Tetrahedron, 2017, vol. 73, # 19, p. 2727 - 2730]
[2]Liu, Kaisheng; Jia, Fan; Xi, Hui; Li, Yuanming; Zheng, Xiaojian; Guo, Qiaoxia; Shen, Baojian; Li, Zhiping [Organic Letters, 2013, vol. 15, # 8, p. 2026 - 2029]
[3]Wang, Yajun; Wu, Rui; Zhao, Shijun; Quan, Zhengjun; Su, Yingpeng; Huo, Congde [Organic and Biomolecular Chemistry, 2018, vol. 16, # 10, p. 1667 - 1671]

29
[ 6320-03-2 ]
[ 1252633-25-2 ]
[ 1252632-04-4 ]

Yield	Reaction Conditions	Operation in experiment
86%	With triethylamine at 20℃; for 48h; Inert atmosphere;	B.3A B. Synthesis of the Intermediate Thioethers 3 or 11 General Procedure B. Synthesis of the Intermediate Thioethers 3 or 11 General Procedure [0153] To a solution of the nosyl esters 2 or 10 (20.6 mmol) in propionitrile (82 mL) was added under nitrogen at room temperature the thiol (30.9 mmol) and triethylamine (5.75 mL, 41.2 mmol). The reaction was heated for 2 days. The reaction was concentrated under vacuo and the residue was diluted with ethyl acetate, washed twice with 10% aqueous sodium carbonate solution (100 mL), once with 0.1M aqueous HCl solution (100 mL) and once with saturated aqueous sodium chloride solution (100 mL). The organic layer was dried over Na2SO4, filtered and concentrated under reduced pressure. The residue was chromatographed on silica using a gradient of heptane to a mixtures of heptane and ethyl acetate (v:v 4:1) to yield the thioethers 3 or 11. 3A. The reaction of the nosylate 2 with 2-chlorobenzenethiol yielded (2S,4R)-1-tert-butyl 2-methyl 4-(2-chlorophenylthio)pyrrolidine-1,2-dicarboxylate as a light brown oil (86%). MS ISP (m/e): 272.1 (100) [(M-BOC+H)]+, 316.0 (33) [(M-Isobutylene+H)]+, 372.1 (24) [(M+H)]+.
86%	With triethylamine for 48h; Inert atmosphere; Heating;	B.3A B. Synthesis of the intermediate thioethers 3 or 11 General procedure To a solution of the nosyl esters 2 or 10 (20.6 mmol) in propionitrile (82 mL) was added under nitrogen at room temperature the thiol (30.9 mmol) and triethylamine (5.75 mL, 41.2 mmol). The reaction was heated for 2 days. The reaction was concentrated under vacuo and the residue was diluted with ethyl acetate, washed twice with 10% aqueous sodium carbonate solution (100 mL), once with 0.1M aqueous HCl solution (100 mL) and once with saturated aqueous sodium chloride solution (100 mL). The organic layer was dried over Na2S04, filtered and concentrated under reduced pressure. The residue was chromatographed on silica using a gradient of heptane to a mixtures of heptane and ethyl acetate (v:v 4: 1) to yield the thioethers 3 or 11. 3A. The reaction of the nosylate 2 with 2-chlorobenzenethiol yielded (2S,4R)-l-iert-butyl 2-methyl 4-(2-chlorophenylthio)pyrrolidine-l,2-dicarboxylate as a light brown oil (86 %). MS ISP (m/e): 272.1 (100) [(M-BOC+H)]+, 316.0 (33) [(M-Isobutylene+H)]+, 372.1 (24) [(M+H)]+.
77.6%	With triethylamine; propiononitrile In n-heptane at 100℃; Inert atmosphere;	Step C2: Step C2: (2S,4R)-1-tert-butyl 2-methyl 4-(2-chlorophenylthio)pyrrolidine-1,2-dicarboxylate Under an atmosphere of argon, (2S,4S)-1-tert-butyl 2-methyl 4-(3-nitrophenylsulfonyloxy)pyrrolidine-1,2-dicarboxylate (8.5 g, 19.7 mmol, Eq: 1.00) was combined with propionitrile (82.0 ml) to give a light brown solution. Then 2-chlorobenzenethiol (4.28 g, 3.38 ml, 29.6 mmol, Eq: 1.50) and triethylamine (4.00 g, 5.5 ml, 39.5 mmol, Eq: 2.00) were added dropwise. The reaction was stirred overnight at reflux (100° C.). The reaction was cooled to room temperature, and poured in 50 ml Na2CO3 solution (10%), and extracted with 2*100 ml ethyl acetate. The organic layers were washed with 50 ml HCl 0.1M and 50 ml satd. NaCl solution. The organic layer was stirred over Na2SO4, filtered and concentrated in vacuo. The crude material was purified by flash chromatography (70 g column, from 100% to 80% heptane in ethyl acetate). The title compound was obtained as a yellow oil (5.7 g, 77.6%, MS (m/e)=372.1 [M+H+]).

5.7 g

With triethylamine at 100℃; Inert atmosphere;

C2 Step C2: (2S,4R)-l-tert-butyl 2-methyl 4-(2-chlorophenylthio)pyrrolidine-l,2- dicarboxylate Under an atmosphere of argon, (2S,4S)-l-tert-butyl 2-methyl 4-(3- nitrophenylsulfonyloxy)pyrrolidine-l,2-dicarboxylate (8.5 g, 19.7 mmol, Eq: 1.00) was combined with propionitrile (82.0 ml) to give a light brown solution. Then 2- chlorobenzenethiol (4.28 g, 3.38 ml, 29.6 mmol, Eq: 1.50) and triethylamine (4.00 g, 5.5 ml, 39.5 mmol, Eq: 2.00) were added dropwise. The reaction was stirred overnight at reflux (100°C). The reaction was cooled to room temperature, and poured in 50 ml Na2C03 solution (10%), and extracted with 2x100 ml ethyl acetate. The organic layers were washed with 50 ml HC1 0.1M and 50 ml satd. NaCl solution. The organic layer was stirred over Na2S04, filtered and concentrated in vacuo. The crude material was purified by flash chromatography (70g column, from 100% to 80% heptane in ethyl acetate). The title compound was obtained as a yellow oil (5.7 g, 77.6 %, MS (m/e) = 372.1 [M+H+]).

Reference： [1]Current Patent Assignee: ROCHE HOLDING AG - US2013/217665, 2013, A1 Location in patent: Paragraph 0153
[2]Current Patent Assignee: ROCHE HOLDING AG - WO2013/120921, 2013, A1 Location in patent: Page/Page column 20; 21
[3]Current Patent Assignee: ROCHE HOLDING AG - US2013/137687, 2013, A1 Location in patent: Paragraph 0219
[4]Current Patent Assignee: ROCHE HOLDING AG - WO2013/76063, 2013, A1 Location in patent: Page/Page column 32; 33

30
[ 6320-03-2 ]
[ 106-93-4 ]
[ 3983-75-3 ]

Yield	Reaction Conditions	Operation in experiment
54%	With potassium carbonate; potassium iodide In acetone at 20℃; for 4h;	9 General procedure for the preparation of 1a-n General procedure: To a stirred suspension of thiophenol or its analogues (10 mmol) and K2CO3 (15 mmol) in acetone (50 mL), dibromoalkane (20 mmol) and KI (0.1 mmol) were added. After stirring at room temperature for 4 h, the mixture was filtered, and the filtrate was concentrated under vacuum to give the crude product, which was chromatographed on silica gel, with EtOAc/petroleum ether as the eluent to afford the compounds.
50.1%	With potassium carbonate; potassium iodide In acetone at 20℃;	General Synthesis of compounds 1a-29a General procedure: A stirred suspension of thiophenol or aromatic thiol (10 mmol) and K2CO3 (15 mmol) in acetone (50 mL) was added dibromoalkane (20 mmol) and KI (0.1 mmol). After stirring at room temperature for 4 h, the mixture was filtered, and the filtrate was concentrated under vacuum to give the crude product, which was chromatographed on silica gel, with EtOAc/petroleum ether as the eluent to afford the compounds 1a-29a.
	With caesium carbonate In acetonitrile at 20℃;

Reference： [1]Su, Tao; Xie, Shishun; Wei, Hui; Yan, Jun; Huang, Ling; Li, Xingshu [Bioorganic and Medicinal Chemistry, 2013, vol. 21, # 18, p. 5830 - 5840]
[2]Fei, Chengcheng; Chen, Yanfei; Jiang, Zhiyan; Jiang, Dingxin [Bioorganic and Medicinal Chemistry Letters, 2018, vol. 28, # 10, p. 1792 - 1796]
[3]Blackburn, Bryan G.; Cooke, Maria Victoria; Laulhé, Sébastien; Niu, Ben; Sachidanandan, Krishnakumar [Green Chemistry, 2021, vol. 23, # 23, p. 9454 - 9459]

31
[ 6320-03-2 ]
2,3-epoxy-2-methyl-2,3-dihydro-1,4-naphthoquinone [ No CAS ]
2-methyl-3-(2-chlorophenylthio)-1,4-naphthalenedione [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
87%	With potassium hydroxide In isopropyl alcohol at 20℃; for 3h;	3 Synthesis of 2-methyl-3-(2-chlorophenylthio)-1,4-naphthalenedione (3) General procedure: Compound 2 was synthesized following the literature method for 1 [7]. 2-Methyl-1,4-naphthoquinone oxide (103 mg,0.55 mmol) and 3-chlorobenzenethiol (80 mg, 0.55 mmol) were dissolved in isopropanol (40 mL). After that, 15% potassium hydroxide (0.025 mL) solution was added to the isopropanol solution,and the reaction mixture was stirred at room temperature for 3 h. The solvent in the reaction mixture was evaporated under vacuum,and the residue was dissolved in diethyl ether (100 mL). The combined organic layers were washed with brine, dried over MgSO4, and evaporated under vacuum to give the crude sulfide compound.

Reference： [1]Yotsumoto, Eiki; Inoue, Takafumi; Wakabayashi, Takashi; Amako, Tomoyuki; Tajima, Nobuo; Kuroda, Reiko; Imai, Yoshitane [Journal of Molecular Structure, 2014, vol. 1056-1057, # 1, p. 189 - 193]

32
[ 590-92-1 ]
[ 6320-03-2 ]
[ 99585-16-7 ]

Yield	Reaction Conditions	Operation in experiment
54.6%	With sodium carbonate; sodium hydroxide; In water;Reflux;	Weigh 2-chlorothiophenol (0.7765g, 5.37mmol) and sodium hydroxide (0.3515g, 8.79mmol) in 15ml ice water in beaker one;Another 3-<strong>[590-92-1]bromopropionic acid</strong> (0.8097 g, 5.29 mmol) and anhydrous sodium carbonate (0.5571 g, 5.26 mmol) were dissolved in 15 ml of ice water in a beaker 2;The solution in the beaker 2 was added to the beaker and stirred well, poured into a round bottom flask and heated to reflux for 2 h.After the reaction was completed, it was cooled to room temperature, washed with 20 ml of ethyl acetate, and the aqueous layer was taken;The aqueous layer was adjusted to pH 3-4 with 10% HCl, and extracted with three times of 60 ml of ethyl acetate to remove the aqueous layer;The organic layer was dried over anhydrous magnesium sulfate and solvent was evaporated on a rotary evaporator, and weighed to give a product of 0.6357 g, yield 54.6%.

Reference： [1]Patent: CN108640901,2018,A .Location in patent: Paragraph 0061; 0063; 0064; 0065
[2]Angewandte Chemie - International Edition,2013,vol. 52,p. 13642 - 13646
Angew. Chem.,2013,vol. 125,p. 13887 - 13891,5
[3]Medicinal Chemistry Research,2020

33
[ 6320-03-2 ]
[ 27317-69-7 ]
[ 1620161-72-9 ]

Reference： [1]Organic Letters,2014,vol. 16,p. 3922 - 3925

34
[ 6320-03-2 ]
acryloylferrocene [ No CAS ]
[ 1621686-68-7 ]

Yield	Reaction Conditions	Operation in experiment
76%	With lithium perchlorate In acetonitrile at 20℃; for 0.533333h; Electrolysis; Sonication;	2.2. Synthetic procedure General procedure: The electrolytic cell was filled with 10 mL of an acetonitrile solution of LiClO4 (0.1 M), 1 mmol of enone 4-6 and 2 mmol of the corresponding nuclephile 7a-h. The cell was placed in the ultrasound bath (at a frequency of 37 kHz, with an effective ultrasonic power of 30W and a peak of 240 W) and the constant current electrolysis (20 mA) was run 32 min (0.4 F mol1) at room temperature. After the electrolysis was finished, the reaction mixture was left 30 min in the same bath and the solvent evaporated. The residue was diluted with 20 mL of water, the obtained mixture extracted with three 20 mL portions of ethyl acetate and collected organic layers dried overnight (anhydrous sodium sulfate). After evaporation of the solvent the crude reaction product was purified by column chromatography to give the products of the reaction.The spectral data of known compounds were in complete agreement with those published elsewhere (1a [28], 1c [29], 1d [29],1g [29], 1h [29], 2a [30], 2h [30], and 3a [30]), whereas the data confirming structures of newly synthesized ones follow.

Reference： [1]Stevanović, Dragana; Bogdanović, Goran A.; Vukićević, Rastko D. [Polyhedron, 2014, vol. 80, p. 10 - 19]

35
[ 6320-03-2 ]
1-ferrocenyl-3-phenylprop-2-en-1-one [ No CAS ]
[ 1621686-74-5 ]

Yield	Reaction Conditions	Operation in experiment
93%	With lithium perchlorate In acetonitrile at 20℃; for 0.533333h; Electrolysis; Sonication;	2.2. Synthetic procedure General procedure: The electrolytic cell was filled with 10 mL of an acetonitrile solution of LiClO4 (0.1 M), 1 mmol of enone 4-6 and 2 mmol of the corresponding nuclephile 7a-h. The cell was placed in the ultrasound bath (at a frequency of 37 kHz, with an effective ultrasonic power of 30W and a peak of 240 W) and the constant current electrolysis (20 mA) was run 32 min (0.4 F mol1) at room temperature. After the electrolysis was finished, the reaction mixture was left 30 min in the same bath and the solvent evaporated. The residue was diluted with 20 mL of water, the obtained mixture extracted with three 20 mL portions of ethyl acetate and collected organic layers dried overnight (anhydrous sodium sulfate). After evaporation of the solvent the crude reaction product was purified by column chromatography to give the products of the reaction.The spectral data of known compounds were in complete agreement with those published elsewhere (1a [28], 1c [29], 1d [29],1g [29], 1h [29], 2a [30], 2h [30], and 3a [30]), whereas the data confirming structures of newly synthesized ones follow.

Reference： [1]Stevanović, Dragana; Bogdanović, Goran A.; Vukićević, Rastko D. [Polyhedron, 2014, vol. 80, p. 10 - 19]

36
[ 6320-03-2 ]
[ 6318-84-9 ]
3-[(2-chlorophenyl)thio]-3-ferrocenyl-1-phenylpropan-1-one [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
79%	With lithium perchlorate In acetonitrile at 20℃; for 0.533333h; Electrolysis; Sonication;	2.2. Synthetic procedure General procedure: The electrolytic cell was filled with 10 mL of an acetonitrile solution of LiClO4 (0.1 M), 1 mmol of enone 4-6 and 2 mmol of the corresponding nuclephile 7a-h. The cell was placed in the ultrasound bath (at a frequency of 37 kHz, with an effective ultrasonic power of 30W and a peak of 240 W) and the constant current electrolysis (20 mA) was run 32 min (0.4 F mol1) at room temperature. After the electrolysis was finished, the reaction mixture was left 30 min in the same bath and the solvent evaporated. The residue was diluted with 20 mL of water, the obtained mixture extracted with three 20 mL portions of ethyl acetate and collected organic layers dried overnight (anhydrous sodium sulfate). After evaporation of the solvent the crude reaction product was purified by column chromatography to give the products of the reaction.The spectral data of known compounds were in complete agreement with those published elsewhere (1a [28], 1c [29], 1d [29],1g [29], 1h [29], 2a [30], 2h [30], and 3a [30]), whereas the data confirming structures of newly synthesized ones follow.

Reference： [1]Stevanović, Dragana; Bogdanović, Goran A.; Vukićević, Rastko D. [Polyhedron, 2014, vol. 80, p. 10 - 19]

37
[ 120-72-9 ]
[ 6320-03-2 ]
3-((2-chlorophenyl)thio)-1H-indole [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
96%	With iodine; dimethyl sulfoxide In 1,2-dichloro-ethane at 60℃; for 6h; regioselective reaction;
90%	With sodium hydroxide In dimethyl sulfoxide at 70℃; for 6h;
77%	With iodine In acetonitrile at 80℃; for 16h; regioselective reaction;	2.2 General Procedure for Regioselective Synthesisof 3-Thioindoles Under Air General procedure: Acetonitrile (2 mL) was added into a mixture of indoles 1 (0.25 mmol), thiols 2 (0.375 mmol) and I2 (5 mol %) in a 25 mL round-bottomed flask at room temperature under air. The reaction vessel was allowed to stir at 80 °C for 16 h. After the reaction, the solvent was then removed under vacuum. The residue was purified by flash column chromatography using a mixture of petroleum ether and ethyl acetate as eluent to give the desired 3-thioindoles 3. The characterization of the corresponding products wasshown in Supporting Materials.

55%

With caesium carbonate In dimethyl sulfoxide at 100℃; for 3h; Schlenk technique;

Reference： [1]Yi, Shanli; Li, Meichao; Mo, Weimin; Hu, Xinquan; Hu, Baoxiang; Sun, Nan; Jin, Liqun; Shen, Zhenlu [Tetrahedron Letters, 2016, vol. 57, # 17, p. 1912 - 1916]
[2]Liu, Yunyun; Zhang, Yi; Hu, Changfeng; Wan, Jie-Ping; Wen, Chengping [RSC Advances, 2014, vol. 4, # 67, p. 35528 - 35530]
[3]Liu, Xiaoxia; Cui, Huanhuan; Yang, Daoshan; Dai, Shicui; Zhang, Guoqin; Wei, Wei; Wang, Hua [Catalysis Letters, 2016, vol. 146, # 9, p. 1743 - 1748]
[4]Song, Song; Zhang, Yiqun; Yeerlan, Adeli; Zhu, Bencong; Liu, Jianzhong; Jiao, Ning [Angewandte Chemie - International Edition, 2017, vol. 56, # 9, p. 2487 - 2491][Angew. Chem., 2017, vol. 129, p. 2527 - 2531]

38
[ 6320-03-2 ]
[ 100-52-7 ]
[ 98-86-2 ]
[ 109-77-3 ]
2-((2-chlorophenyl)thio)-4,6-diphenylnicotinonitrile [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
90%	With Triton X-100 In water at 20℃; for 0.75h;	2. Experimental General procedure: A mixture of benzaldehyde (1 mmol), acetophenone (1 mmol), malononitrile (1 mmol), with thiolphenol (1 mmol) were taken in a mixture of Triton X-100 (5 mol%) and water (2 mL) in a round bottomed flask. The resulting mixture was vigorously stirred at room temperature until completion of the reaction as monitored by thin-layer chromatography (TLC). After completion, the reaction mixture was poured onto crushed ice (70 g) with vigorous stirring. The precipitate obtained was filtered, washed with water, dried, and purified by column chromatography on silica gel (60-120 mesh, ethyl acetate/hexane, 1:3) to afford pure products. Structures of the all the products were confirmed by analytical and spectral data. Some selected data are listed below, and others please see the Supporting information.

Reference： [1]Poor Heravi, Mohammad Reza; Soufi, Amir [Chinese Chemical Letters, 2015, vol. 26, # 2, p. 263 - 266]

39
[ 87-41-2 ]
[ 6320-03-2 ]
C₁₄H₁₁ClO₂S [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
76.8%	With potassium carbonate In N,N-dimethyl-formamide at 150℃; for 4h;	1 Compound 1a (1.34 g, 10 mmol)Dissolved in DMF (20 mL),2-Chlorothiophenol (1.44 g, 10 mmol) and potassium carbonate (2.76 g, 20 mmol) were added,The mixture was heated and stirred in an oil bath at 150°C for 4 hours.Cool to room temperature, add 200 mL of ice water,Wash with ethyl acetate (100 mL×2).The aqueous phase was adjusted to pH 7 with 2N HCl solution,Then adjust the pH to 3~4 with 2N HCl solution.Extracted with ethyl acetate (70 mL×3),The organic phases were combined, washed with saturated brine (100 mL×2), dried over anhydrous sodium sulfate,After filtration, the filtrate was concentrated under reduced pressure to obtain a yellow solid. Recrystallization from ethyl acetate-petroleum ether,After drying, 2.14 g of white solid compound 1b was obtained, yield: 76.8%.
76.8%	With potassium carbonate In N,N-dimethyl-formamide at 150℃; for 4h;	1 1. 4-Chloro-6,11-dihydrodibenzo[b,e]thiazepin-11-one (Compound 1) Compound 1a (1.34 g, 10 mmol) was dissolved in DMF (20 mL), 2-chlorothiophenol (1.44 g, 10 mmol) and potassium carbonate (2.76 g, 20 mmol) were added, and the mixture was heated in an oil bath at 150 °C Stir for 4 hours. Cool to room temperature, add 200 mL of ice water, and wash with ethyl acetate (100 mL×2). The aqueous phase was adjusted to pH 7 with 2N HCl solution, and then adjusted to pH 3~4 with 2N HCl solution. Extract with ethyl acetate (70 mL×3), combine the organic phases, wash with saturated brine (100 mL×2), dry over anhydrous sodium sulfate, filter, and concentrate the filtrate under reduced pressure to obtain a yellow solid. Recrystallized from ethyl acetate-petroleum ether, and dried to obtain 2.14 g of white solid compound 1b, yield: 76.8%.
45 g	With potassium carbonate In N,N-dimethyl-formamide at 150℃; for 2h;	4 10175] To a solution of B-2 (25 g, 0.17 mol) and K2C03 (97.3 g, 0.7 mmol) in DMF (500 mE) was added B-i (19 g, 0.14 mol). The mixture was stirred for 2 h at 150° C. The solution was poured into ice-water (2 E). The suspension was extracted with EtOAc (3x500 mE). The organic layers were washed with brine (2x300 mE), dried with Na2504 and concentrated to give B-3 (45 g), which was used directly in the next step. ‘H NMR (400 MHz, d-DMSO): ö 13.08 (s, 1H), 7.83 (d, J=8.0 Hz, 1H), 7.45-7.39 (m, SH), 7.27 (m, 1H), 7.14 (m, 1H), 4.61 (s, 2H).

Reference： [1]Current Patent Assignee: GUANGZHOU NANXIN PHARMACEUTICAL CO., LTD - CN113880832, 2022, A Location in patent: Paragraph 0107
[2]Current Patent Assignee: GUANGZHOU NANXIN PHARMACEUTICAL CO., LTD - CN114057730, 2022, A Location in patent: Paragraph 0106
[3]Current Patent Assignee: JOHNSON & JOHNSON INC - US2015/72982, 2015, A1 Location in patent: Paragraph 0174; 0175

40
[ 6320-03-2 ]
[ 10432-44-7 ]
7-(2-chlorophenylthio)-5-amino-1,2-dihydro-2-methyl-2,4-di(thiophen-2-yl)-1,6-naphthyridine-8-carbonitrile [ No CAS ]

Reference： [1]ChemPlusChem,2015,vol. 80,p. 731 - 739

41
[ 6320-03-2 ]
4-bromo-8-nitroquinolin-2(1H)-one [ No CAS ]
4-(2-chlorophenylthio)-8-nitroquinolin-2(1H)-one [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
90%	Stage #1: 2-chlorothiphenol With sodium hydride In N,N-dimethyl-formamide at 20℃; for 0.5h; Inert atmosphere; Stage #2: 4-bromo-8-nitroquinolin-2(1H)-one In N,N-dimethyl-formamide at 20℃; for 2h; Inert atmosphere;	Preparation of 4-phenylthio-8-nitroquinolin-2(1H)-one derivatives (11) and (13 to 29) General procedure: To a sealed flask containing NaH (1.11 mmol, 27 mg), dry DMF (2 mL) and appropriate thiophenol (0.56 mmol) were added under N2 atmosphere. The reaction mixturewas stirred at RT for 30 min. Then a solution of 4-bromo-8-nitroquinolin-2(1H)-one 3 (0.56 mmol, 150 mg) in dry DMF (3 mL) was injected. The reaction mixture was stirred at RT for 2 h. The reaction mixture was then poured into a water-ice-mixture. The yellow precipitate was collected by filtration, washed three times with water, dried under reduced pressure and purified by column chromatography or recrystallization, affording compounds 11, 13-29.

Reference： [1]Kieffer, Charline; Cohen, Anita; Verhaeghe, Pierre; Hutter, Sébastien; Castera-Ducros, Caroline; Laget, Michèle; Remusat, Vincent; M'Rabet, Manel Kraiem; Rault, Sylvain; Rathelot, Pascal; Azas, Nadine; Vanelle, Patrice [European Journal of Medicinal Chemistry, 2015, vol. 92, p. 282 - 294]

42
[ 6320-03-2 ]
C₂₁H₁₈N₂O₂S [ No CAS ]
3-[(2-chlorophenyl)sulfanyl](phenyl)methyl}-1H-pyrrolo[2,3-b]pyridine [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
90%	With potassium carbonate In chloroform at 65℃; for 36h;	24 General procedure for Michael addition of nitrogen or sulfur nucleophiles to vinylogous imine intermediates generated in situ from 3-(1-arylsulfonylalkyl)-7-azaindoles 1 General procedure: To a solution of 3-(1-arylsulfonylalkyl)-7-azaindoles 1 (0.1mmol) and amines 2 or thiophenols or thiol 4 (0.12mmol) in CHCl3 (1.2mL) was added K2CO3 (0.12mmol). After being stirred at 65°C for 36h, the reaction mixture was purified by flash chromatography on silica gel (ethyl acetate/petroleum ether 1:5-1:3) to afford the corresponding products 3 or 5. All the products were confirmed by 1H NMR, 13C NMR and HRMS spectra.

Reference： [1]Jin, Lunqiang; Jing, Linhai; Luo, Gan; Wang, Rongming; Yin, Mingxing; Wu, Chaoling; Qin, Dabin [Tetrahedron, 2015, vol. 71, # 23, p. 4039 - 4046]

43
[ 6320-03-2 ]
[ 66726-11-2 ]
3-((2-chlorophenylthio)methyl)-3a,4,5,5a-tetrahydro-5a,9-dimethylnaphtho[1,2-b]furan-2,8(3H,9bH)-dione [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
90%	With triethylamine In methanol at 0 - 20℃; for 3.25h; stereospecific reaction;	4.4 Synthesis of Michael addition derivatives of a-santonin General procedure: In a typical procedure, to a solution of compound 8 (0.177 g,1.2 mmol) in MeOH (10 mL) stirred over a period of 10 min,maintaining the temperature between 0 and 5 C, was addedtriethylamine, followed by the methanolic solution of respectivethiols (1.1 mmol). The reaction mixture was stirred at the sametemperature for 15 min followed by stirring at ambient temperaturefor 3 h. The solvent was evaporated in vacuo and the cruderesidue was subjected to flash chromatography to afford the pureproduct, Characterization was performed using 1H NMR, 13C NMRand mass spectrometry.

Reference： [1]Khazir, Jabeena; Riley, Darren L.; Chashoo, Gousia; Mir, Bilal Ahmad; Liles, David; Islam, Md. Ataul; Singh, Shashank K.; Vishwakarma, Ram A.; Pilcher, Lynne A. [European Journal of Medicinal Chemistry, 2015, vol. 101, p. 769 - 779]

44
[ 6320-03-2 ]
[ 16932-44-8 ]
2-chlorophenyl-2,6-dimethoxyphenylsulfide [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
88%	With copper(l) iodide; bis(2-pyridylseleno)butane; potassium hydroxide; In glycerol; at 100℃; for 24h;Inert atmosphere; Green chemistry;	General procedure: An argon-filled flask wasadd the respective aryl halide (1.0 mmol), CuI (20 mg, 0.1 mmol, 10 mol%), L3(37 mg, 0.1 mmol, 10 mol%), KOH (168 mg, 3 mmol), thiol (1.5 mmol) and glycerol(10 mL). The contents were then stirred at 100 C for 24 h. After that, themixture was cool to room temperature, diluted with ethyl acetate (20 mL) and washedwith saturated NaCl solution (3 x 20 mL). The organic layer was separated,dried over MgSO4 and concentrated under vacuum. The crude productwas purified by flash chromatography on silica gel using hexane /ethyl acetateas eluent

Reference： [1]Tetrahedron Letters,2015,vol. 56,p. 5218 - 5222

45
[ 6320-03-2 ]
[ 762-04-9 ]
[ 15224-41-6 ]

Yield	Reaction Conditions	Operation in experiment
86%	With oxygen; nickel diacetate; yttrium(III) trifluoromethanesulfonate In N,N-dimethyl-formamide at 70℃; for 16h;
81%	With di-tert-butyl peroxide In dimethyl sulfoxide at 80℃; for 20h; Inert atmosphere;	1 General procedure of the coupling between thiophenol/substituted thiophenols and dialkyl phosphites (3a-3t, 5a-5j) General procedure: A Schlenk tube was charged with thiophenol 1 (1.0mmol), dialkyl phosphites 2 (2.0mmol), and DTBP (2.0mmol), then 1.5mL DMSO was added as solvent. This reaction was performed under N2 atmosphere at 80°C for 20h. After completion of the reaction, the mixture was quenched with 20mL Na2S2O4 solution (5%) then extracted with ethyl acetate (15mL×3). The organic layer was combined and dried with anhydrous Na2SO4. After the evaporation in a vacuum, the crude product was purified by a gel column chromatography using petroleum ether/ethyl acetate as eluent to afford the desired products 3 and 5.
77%	With oxygen; caesium carbonate In acetonitrile at 30℃; for 12h; Schlenk technique;

77%

With oxygen; caesium carbonate In acetonitrile at 30℃; for 12h;

20 Example 20 Synthesis of S- (2-chlorophenyl) O, O-diethyl phosphorothioate Take a 25mL reaction tube, add the catalyst cesium carbonate 8.2mg, diethyl phosphite 34.5mg, 2-chlorothiophenol43.4 mg, acetonitrile 1 mL, stirred at 30 ° C for 12 hours, and the gas atmosphere was a standard atmospheric pressure of oxygen. After the completion of the reaction, column chromatography was carried out to obtain S- (2-chlorophenyl) O, O-diethyl phosphorothioate 53.8 mg in 77% yield.

Reference： [1]Xue, Jing-Wen; Zeng, Miao; Zhang, Sicheng; Chen, Zhuqi; Yin, Guochuan [Journal of Organic Chemistry, 2019, vol. 84, # 7, p. 4179 - 4190]
[2]Wang, Jichao; Huang, Xin; Ni, Zhangqin; Wang, Sichang; Pan, Yuanjiang; Wu, Jun [Tetrahedron, 2015, vol. 71, # 41, p. 7853 - 7859]
[3]Song, Song; Zhang, Yiqun; Yeerlan, Adeli; Zhu, Bencong; Liu, Jianzhong; Jiao, Ning [Angewandte Chemie - International Edition, 2017, vol. 56, # 9, p. 2487 - 2491][Angew. Chem., 2017, vol. 129, p. 2527 - 2531]
[4]Current Patent Assignee: PEKING UNIVERSITY - CN106905361, 2017, A Location in patent: Paragraph 0175; 0176; 0177; 0178

46
[ 6320-03-2 ]
[ 562080-91-5 ]
[ 3939-23-9 ]

Reference： [1]RSC Advances,2016,vol. 6,p. 24257 - 24260

47
[ 100-42-5 ]
[ 6320-03-2 ]
[ 75-05-8 ]
N-(2-((2-chlorophenyl)sulfanyl)-1-phenylethyl)acetamide [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
89%	With iodine; dimethyl sulfoxide at 80℃; for 24h; regioselective reaction;
84%	With ammonium peroxydisulfate; sodium iodide In water at 100℃; for 12h;	10 Example 10: In a test tube, styrene (0.6 mmol), o-chlorothiophenol (0.30 mmol)Sodium iodide (0.06 mmol), ammonium persulfate (0.6 mmol), water (0.6 mmol), and acetonitrile (2 mL)The system was then sealed and heated in an oil bath at 100 ° C for 12 hours. After completion of the reaction, the solvent was distilled off,After concentration, product 10 was obtained by simple column chromatography (eluant using ethyl acetate: petroleum ether = 1: 6) for elution in 84% yield.

Reference： [1]Cui, Huanhuan; Liu, Xiaoxia; Wei, Wei; Yang, Daoshan; He, Chenglong; Zhang, Tiantian; Wang, Hua [Journal of Organic Chemistry, 2016, vol. 81, # 6, p. 2252 - 2260]
[2]Current Patent Assignee: SOUTHWEST PETROLEUM UNIVERSITY - CN105085341, 2017, B Location in patent: Paragraph 0144; 0145

48
[ 6320-03-2 ]
[ 75-36-5 ]
[ 1099-45-2 ]
ethyl (E)-3-[(2-chlorophenyl)thio]but-2-enoate [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
84%	With caesium carbonate; triethylamine In dichloromethane; N,N-dimethyl-formamide at 100℃; for 10h;	General procedure for the synthesis of β-sulfenylatedacrylates General procedure: A 25-mL round-bottom flask was charged with thiophenol 1(0.5 mmol), acetyl chloride 2a (0.5 mmol), Wittig reagent 3(0.5 mmol), Cs2CO3 (1.0 mmol), Et3N (0.5 mmol), CH2Cl2(2 mL), andDMF (2 mL).The vessel was stirred at 100°C(reflux) in air atmosphere (1 at air balloon) for 10 h. Upon completion(TLC), the reaction mixture was allowed to cool down to roomtemperature and H2O (5 mL) was added. The resulting suspensionwas extracted with ethyl acetate (3 × 8 mL). The organicphases were combined and dried over Na2SO4. After filtrationand removing the solvent at reduced pressure, the residue wassubjected to silica gel column chromatography by using 100:1(v/v) petroleum ether/ethyl acetate as an eluant to give pureproduct

Reference： [1]Liu, Yunyun; Huang, Bin [Phosphorus, Sulfur and Silicon and the Related Elements, 2016, vol. 191, # 6, p. 926 - 929]

49
[ 6320-03-2 ]
[ 75-36-5 ]
[ 21204-67-1 ]
methyl (E)-3-[(2-chlorophenyl)thio]but-2-enoate [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
78%	With caesium carbonate; triethylamine In dichloromethane; N,N-dimethyl-formamide at 100℃; for 10h;	General procedure for the synthesis of β-sulfenylatedacrylates General procedure: A 25-mL round-bottom flask was charged with thiophenol 1(0.5 mmol), acetyl chloride 2a (0.5 mmol), Wittig reagent 3(0.5 mmol), Cs2CO3 (1.0 mmol), Et3N (0.5 mmol), CH2Cl2(2 mL), andDMF (2 mL).The vessel was stirred at 100°C(reflux) in air atmosphere (1 at air balloon) for 10 h. Upon completion(TLC), the reaction mixture was allowed to cool down to roomtemperature and H2O (5 mL) was added. The resulting suspensionwas extracted with ethyl acetate (3 × 8 mL). The organicphases were combined and dried over Na2SO4. After filtrationand removing the solvent at reduced pressure, the residue wassubjected to silica gel column chromatography by using 100:1(v/v) petroleum ether/ethyl acetate as an eluant to give pureproduct

Reference： [1]Liu, Yunyun; Huang, Bin [Phosphorus, Sulfur and Silicon and the Related Elements, 2016, vol. 191, # 6, p. 926 - 929]

50
[ 7342-82-7 ]
[ 6320-03-2 ]
C₁₄H₉ClS₂ [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
95.6%	With palladium diacetate; 4,5-bis(diphenylphosphino)-9,9-dimethylxanthene; sodium t-butanolate In o-xylene at 130℃; for 1h; Inert atmosphere;	4 Synthesis Example 4 reaction substrate in the thermometer and 50ml flask equipped with a condenser, o- xylene 4.40g (41.5mmol, 0.54mol / L) , 3-bromo-benzothiophene 0 0.77 g (2.77 mmol, 1.02 mol) of orthochlorobenzenethiol, 0.39 g (4.08 mmol, 1.50 mol) of sodium tert-butoxide, palladium acetate 1. 2 mg (0.005 mmol, 0.002 mol) was charged.After replacing the air in the flask with nitrogen, 6.3 mg (0.010 mmol, 0.004 mol) of 9,9-dimethyl-4,5-bis (diphenylphosphino) xanthene [XANTphos] was added, It was heated to 130 ° C.After aging at the same temperature for 1 hour, the reaction solution was analyzed by GC to find that the reaction conversion rate was 92.0% and the selectivity was 95.7%.Thereafter, water was added to the reaction solution and the reaction mixture was separated to obtain an organic phase.Subsequently, the obtained organic phase was filtered through celite and concentrated to obtain the objective compound (1-26) in an isolated yield of 95.6% (0.72 g).The purity was analyzed by GC and it was 96.0%.

Reference： [1]Current Patent Assignee: TOSOH CORPORATION - JP2016/193868, 2016, A Location in patent: Paragraph 0067

51
[ 872-31-1 ]
[ 6320-03-2 ]
C₁₀H₇ClS₂ [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
96.1%	With palladium diacetate; 4,5-bis(diphenylphosphino)-9,9-dimethylxanthene; sodium t-butanolate In o-xylene at 130℃; for 2h; Inert atmosphere;	2 synthesis of Example 2 reaction substrate to the thermometer and 50ml flask equipped with a condenser, o- xylene 8.10g (76.3mmol, 0.54mol / L) , 3-bromothiophene 0. (5.10 mmol, 1.02 mol) of orthochlorobenzenethiol, 0.72 g (7.50 mmol, 1.50 mol) of sodium tert-butoxide, 2.2 mg of palladium acetate (0.010 mmol, 0.002 mol) was charged.11.6 mg (0.020 mmol, 0.004 mol) of 9,9-dimethyl-4,5-bis (diphenylphosphino) xanthene [XANTphos] was added to the inside of the flask, It was heated to 130 ° C.After aging at the same temperature for 2 hours, the reaction solution was analyzed by GC, and the reaction conversion was 99.9%, and the selectivity was 98.9%.Thereafter, water was added to the reaction solution and the reaction mixture was separated to obtain an organic phase.Subsequently, the obtained organic phase was filtered through Celite and then concentrated to obtain the objective compound (1-6) in an isolated yield of 96.1% (1.09 g).The purity was analyzed by GC and it was 98.6%.

Reference： [1]Current Patent Assignee: TOSOH CORPORATION - JP2016/193868, 2016, A Location in patent: Paragraph 0065

52
[ 6320-03-2 ]
4-methyl-N'-(thieno[2,3-b]pyridin-2-ylmethylene)benzenesulfonohydrazide [ No CAS ]
2-(((2-chlorophenyl)thio)methyl)thieno[2,3-b]pyridine [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
91%	With potassium carbonate In toluene at 100℃; for 24h; Inert atmosphere;	4. General procedure for metal-free reductive coupling reaction of tosylhydrazone with thiol. General procedure: A mixture of tosylhydrazone 1 (1 mmol), thiol 2 (1.5 mmol, 1.5 equiv), K2CO3 (2.5 mmol, 2.5 equiv) in toluene (4.0 mL) was stirred at 100 °C for 24h under Argon. After completion of the reaction as indicated by TLC, the mixture was cooled to room temperature. After adding CH2Cl2 (10 mL), the organic phase was washed with saturated NaHCO3, brine and dried with Na2SO4, and concentrated under reduced vacuum. The residue was then purified by flash chromatography on silica gel to afford product 3.

Reference： [1]García-Carrillo, Mario Alfredo; Guzmán, Ángel; Díaz, Eduardo [Tetrahedron Letters, 2017, vol. 58, # 20, p. 1952 - 1956]

53
[ 6320-03-2 ]
[ 108-86-1 ]
[ 33667-82-2 ]

Yield	Reaction Conditions	Operation in experiment
84%	With potassium carbonate In water; N,N-dimethyl-formamide at 90℃; for 14h;	1.3.General procedure for the S-arylation coupling reaction General procedure: Aryl halide (1.0 mmol), thiol (1.2 mmol), K2CO3 (2.0 mmol) and catalyst (0.4 mol% Cu) in DMF/H2O (v/v = 2:1, 1.5 mL) were stirred at 90 C for the appropriate time. The progress of the reaction was monitored by TLC using n-hexane-EtOAc (30:1) as eluent. After completion of the reaction, EtOAc (5 mL) was added to the mixture and filtered. The organic phase was separated and the aqueous layer was extracted with ethyl acetate (3 × 5 mL). The organic layer drying (MgSO4) and evaporation of the solvent provided a residue which was purified on preparative TLC (silica gel). All the products have been previously reported, and their identities were confirmed by comparison of their 1H and 13C NMR spectral data with the values of authentic samples.
82%	With copper(l) iodide; N,N'-dihexyloxalamide; potassium <i>tert</i>-butylate In 1,4-dioxane at 110℃; for 24h; Sealed tube; Inert atmosphere;
74%	With barium molybdate; potassium hydroxide In acetonitrile at 80℃; for 16h; Inert atmosphere;

73%

With CuMoO₄; caesium carbonate In dimethyl sulfoxide at 30℃; for 11h; Inert atmosphere;

Reference： [1]Rezaei, Nasrin; Movassagh, Barahman [Tetrahedron Letters, 2016, vol. 57, # 14, p. 1625 - 1628]
[2]Chen, Chia-Wei; Chen, Yi-Ling; Reddy, Daggula Mallikarjuna; Du, Kai; Li, Chao-En; Shih, Bo-Hao; Xue, Yung-Jing; Lee, Chin-Fa [Chemistry - A European Journal, 2017, vol. 23, # 42, p. 10087 - 10091]
[3]Panda, Subhalaxmi; Sahu, Santosh Kumar; Behera, Pradyota Kumar; Panigrahi, Reba; Garnaik, Bamakanta; Rout, Laxmidhar [New Journal of Chemistry, 2020, vol. 44, # 6, p. 2500 - 2504]
[4]Panigrahi, Reba; Sahu, Santosh Kumar; Behera, Pradyota Kumar; Panda, Subhalaxmi; Rout, Laxmidhar [Chemistry - A European Journal, 2020, vol. 26, # 3, p. 620 - 624]

54
[ 6320-03-2 ]
[ 16588-02-6 ]
2-((2-chlorophenyl)thio)-5-nitrobenzonitrile [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
89%		General procedure: To solution of 1.97 mmol (1.2 eq.) of phenol 2-8, 12-13 in 3 ml dry DMSO was added 79 mg(1.2 eq.) powdered NaOH. The mixture was heated at 50C for 20 min and to the formed clearsolution 0.300 g (1.64 mmol, 1.0 eq.) of 1 was added. The reaction mixture was heated at 80C for 8h. After cooling 40 ml water was added and extracted with DCM. The organic phase was washedwith aq. NaHCO3 and water, dried over Na2SO4, filtered and evaporated in vacuo. The crudeproducts 14-20, 24-25 were purified by column chromatography (50 g silica-gel). After column theformed solid products were powdered, washed with 3 ml hot hexane and dried in vacuo.

Reference： [1]Bioorganic and Medicinal Chemistry Letters,2017,vol. 27,p. 4540 - 4543

55
[ 6320-03-2 ]
[ 13035-61-5 ]
2-chlorophenyl 2,3,5-tetra-O-acetyl-1-thio-β-D-ribofuranoside [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
98%	With indium(III) bromide; In dichloromethane; at 20℃; for 2h;	General procedure: To a solution of peracetylated aldose (0.1mmol) in CH2Cl2 (2 mL) were added thiophenolor selenophenol (0.12mmol) and InBr3 (3mg, 0.01mol). The reaction mixture was allowedto stir for 2 h at room temperature. After completion as monitored by TLC, the reactionmixture was concentrated. The resultant residue was subjected to flash chromatograph togive the goal products.

Reference： [1]Synlett,2017,vol. 28,p. 2311 - 2314

56
[ 6320-03-2 ]
[ 99-90-1 ]
[ 869854-44-4 ]

Yield	Reaction Conditions	Operation in experiment
93%	With caesium carbonate In dimethyl sulfoxide at 25℃; for 1.5h; Irradiation; Inert atmosphere;
93%	With caesium carbonate In dimethyl sulfoxide at 25℃; for 1h; Inert atmosphere; UV-irradiation;	5; 9 1-(4-((2-Chlorophenyl)thio)phenyl)ethan-1-one (7) A 25 mL storage flask was charged with a stir bar, flame dried under vacuum and back filled with nitrogen three times. The flask was then charged with Cs2CO3 (97.7 mg, 0.3 mmol, 1.5 eq.), 4'-Bromoacetophenone (39.8 mg, 0.2 mmol, 1.00 eq.), 2-bromobenzenethiol (37.8 mg, 0.3 mmol, 1.5 eq.) and 1.5 mL DMSO. The reaction mixture was evacuated and purged with inert gas (N2) three times. The reaction mixture was then placed into an LED-lined beaker and stirred with an air gas tube for cooling. After stirred for 1.5 hours, the reaction mixture was washed with water, extracted with EtOA and concentrated in vacuum. The product was isolated by flash chromatography (1:5 EtOAc:hexanes) as white solid (X=Br, 49 mg, 93%). Physical State: white solid; Rf=0.5 (silica gel, 1:4 EtOAc:hexanes); 1H NMR (300 MHz, CDCl3) δ 7.89-7.84 (m, 2H), 7.51-7.48 (m, 1H), 7.42-7.39 (m, 1H), 7.34-7.29(m, 1H), 7.29-7.22 (m, 3H), 2.57 (s, 3H); 13C NMR (75 MHz, CDCl3) δ 197.1, 142.0, 137.0, 135.2, 134.6, 132.2, 130.4, 129.7, 129.1, 128.8, 127.6, 26.5; HRMS (ESI-TOF): m/z calcd. for C14H11ClOS ([M+H]+) 263.0297, found 263.0299.
50%	With C₂₄H₂₂N₆Ni; sodium t-butanolate In N,N-dimethyl-formamide; acetonitrile at 20℃; for 24h; Inert atmosphere; Schlenk technique;

Reference： [1]Liu, Bin; Lim, Chern-Hooi; Miyake, Garret M. [Journal of the American Chemical Society, 2017, vol. 139, # 39, p. 13616 - 13619]
[2]Current Patent Assignee: UNIVERSITY OF COLORADO (SYSTEM) - US2018/370911, 2018, A1 Location in patent: Paragraph 0101; 0204; 0205
[3]Sikari, Rina; Sinha, Suman; Das, Siuli; Saha, Anannya; Chakraborty, Gargi; Mondal, Rakesh; Paul, Nanda D. [Journal of Organic Chemistry, 2019, vol. 84, # 7, p. 4072 - 4085]

57
[ 67-56-1 ]
[ 6320-03-2 ]
2-chlorobenzenesulfinic acid methyl ester [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
80%	With eosin at 20℃; for 1.5h; Irradiation;	General Procedure for thePhotocatalysed Synthesis of SulfinicEster (3a-r) General procedure: A round bottom flask was charged with thiol RSH 1(a-r)(1.0 mmol), eosin Y (2 mol %), alcohol (ROH) 2a-f (3 mL) and the contents were stirred in open air under irradiationwith Luxeon Rebel high power green LEDs [2.50 W, λ =535 nm] at room temperature for the time specified in (Table 1). After the completion of reaction as monitored byTLC (preparative TLC), the resulting mixture was filtered and washed with ethyl acetate, and then concentrated to remove the excess of solvent under vacuum. The organic phase was dried over anhydrous magnesium sulfate and purified with TLC (preparative TLC silica gel). The eluentused was petroleum ether: ethyl acetate (20 : 1; v / v) to gavethe desire product 3a-r. with excillent yields (75-95 %).
67%	With oxygen; potassium carbonate at 60℃; for 24h; Schlenk technique; chemoselective reaction;
58%	With tetrabutylammonium tetrafluoroborate In dichloromethane at 20℃; for 20h; Electrochemical reaction; Inert atmosphere; Green chemistry;

46%	With tetrabutylammonium tetrafluoroborate In acetonitrile at 20℃; for 4h; Electrochemical reaction;
46%	With lithium perchlorate at 20℃; for 9h; Electrochemical reaction;	Electrochemical Synthesis of Sulfinic Esters 3 (Standard Conditions,Reaction Conditions A); General Procedure General procedure: Thiophenol 1 (0.5 mmol), LiClO4 (53.2 mg, 0.5 mmol) and alcohol 2 (8mL) were sequentially added into a 25-mL three-necked flaskequipped with a platinum anode and cathode (plate, 1.0 cm × 1.0 cm).The reaction mixture was stirred at a constant current of 10 mA under air at ambient temperature. After completion of the reaction(monitored by TLC), the reaction mixture was purified by columnchromatography on silica gel (PE/EtOAc) to afford pure product 3.

Reference： [1]Singh, Pravin K.; Singh, Praveen P.; Srivastava, Vishal [Croatica Chemica Acta, 2018, vol. 91, # 3, p. 383 - 387]
[2]Zhou, Changjian; Tan, Zhenda; Jiang, Huanfeng; Zhang, Min [Green Chemistry, 2018, vol. 20, # 9, p. 1992 - 1997]
[3]Ai, Chongren; Shen, Haiwei; Song, Dingguo; Li, Yujin; Yi, Xiao; Wang, Ze; Ling, Fei; Zhong, Weihui [Green Chemistry, 2019, vol. 21, # 20, p. 5528 - 5531]
[4]Gong, Fengping; Lu, Fangling; Zuo, Lin; Wang, Qi; Li, Ru; Hu, Jiaxin; Li, Zhen; Takfaoui, Abdelilah; Lei, Aiwen [Journal of the Chinese Chemical Society, 2020, vol. 67, # 2, p. 192 - 196]
[5]Zhou, Hongyan; Duan, Jiaokui; Xie, Dongtai; Yang, Jingya; Ma, Ben; Wang, Ganggang; Wu, Chengqi; Wang, Xi-Cun [Synthesis, 2020, vol. 52, # 18, p. 2705 - 2712]

58
[ 6320-03-2 ]
1-(3-bromo-1-(4-methoxybenzyl)-1H-pyrazolo[3,4-b]pyrazin-6-yl)-4-methylpiperidin-4-amine [ No CAS ]
1-(3-((2-chlorophenyl)thio)-1-(4-methoxybenzyl)-1H-pyrazolo[3,4-b]pyrazin-6-yl)-4-methylpiperidin-4-amine [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
96%	With tris-(dibenzylideneacetone)dipalladium⁽⁰⁾; N-ethyl-N,N-diisopropylamine; 4,5-bis(diphenylphosphino)-9,9-dimethylxanthene In 1,4-dioxane at 130℃; for 1.5h; Sealed tube; Inert atmosphere; Microwave irradiation;	5.a Step a To a 5 mL vial were added 1-(3-bromo-1-(4-methoxybenzyl)-1H-pyrazolo[3,4-bjpyrazin-6-yl)-4-methylpiperidin-4-amine (50 mg, 0.12 mmol), Pd2dba3 (5 mg, 5 mol %), XantPhos (7 mg, 10 mol %), 2-chloro-thiophenol (16 tL, 0.14 mmol), and N,Ndiisopropylethylamine (41 tL, 0.23 mmol), followed by dioxane (0.2 mL). The resulting mixture was sealed, degassed with nitrogen, and heated under microwave irradiation at 130 °C for 1.5 h. After full conversion, the volatiles were evaporated under reduced pressure. Theresulting residue was purified by reverse phase chromatography (eluting with acetonitrile and water with 0.1% ammonium formate) to give 1-(3-((2-chlorophenyl)thio)-1-(4-methoxybenzyl)- 1 H-pyrazolo [3 ,4-bj pyrazin-6-yl)-4-methylpiperidin-4-amine (55 mg, 96%) as+an off-white solid after lyophilization. MS m/z 496.2[M+Hj

Reference： [1]Current Patent Assignee: RELAY THERAPEUTICS INC - WO2018/81091, 2018, A1 Location in patent: Paragraph 0149; 0150; 0151

59
[ 6320-03-2 ]
6-ethyl-2,4-dimethylpyrimido[4,5-c]isoquinoline-1,3,7,10(2H,4H)-tetraone [ No CAS ]
6-ethyl-8-((2'-chlorophenyl)thio)-2,4-dimethylpyrimido[4,5-c]isoquinoline-1,3,7,10(2H,4H)-tetraone [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
82%	With cerium(III) chloride heptahydrate In ethanol; dichloromethane at 20℃; for 16h;	3.2.2. General Procedure for the Synthesis of Compounds 2-17 General procedure: A solution of 1 (150 mg, 0.4909 mmol) and CeCl3.7H2O (5% mmol respect to 1) in a mix ofethanol: dichloromethane = 1:1 (10 mL), was added dropwise slowly a solution of benzenethiol derivate (0.5 equiv.) in ethanol: dichloromethane = 1:1 (30 mL). The reaction mixture was stirred at room temperature for 16 h. The progress of the reaction was followed by thin-layer chromatography (TLC). The mixture was concentrated and the crude of reaction was purified using 65 g of silicagel (70±230 mesh) and a mix of dichloromethane, light petroleum and ethyl acetate than eluent indeterminate proportions. The resulting solution was concentrated to dryness under reduced pressure.
82%	With cerium(III) chloride heptahydrate In methanol; dichloromethane for 16h;	6 Example 6 Obtaining 8-((2-chlorophenyl)thio)-6-ethyl-2,4-dimethyl pyrimido[4,5-c]isoquinoline-1,3,7,10(2H,4H)-tetraone (6) A solution of 6-ethyl-2,4-dimethylpyrimido[4,5-c]isoquinoline-1,3,7,10 (2H,4H)-tetraone (7 1) (416,78 mg, 2,0 mmol), 10 heptahydrated cerium(III) trichloride (0,5% mole of 1) in a mixture of 6 CH2Cl2:13 MetOH=1:1 (10 ml), is added a solution of 30 2-chlorothiophenol (100.70 mg, 1.0 mmol) dissolved in CH2Cl2:23 MetOH= 1:1 (30 ml) by dripping from a side key burette at a rate of approximately 1ml/30min for 16 hours. The reaction crude is purified with 60 g of Silica gel (0,040-0,063 mm) using 14 dichloromethane: 15 petroleum ether: 16 ethyl acetate =9:14:2 as the mobile phase. An orange-colored solid of 240 mg, 0.54 mmol is obtained, with an 82% yield. (0096) Melting point 220.8(d)°C. HRMS (M+): m/z calculated C21H16ClN3O4S [M+] = 441.05500; found = 441.05521. IR (KBr) : 1660.18, 1677.88 cm-1 C=O (quinone); 1720.35 cm-1 C=O (uracil). 1H RMN (CDCl3, 400 MHz): δ 1.38 (t, 3J=7.3 Hz, 3H, 6-CH2CH3), 3.43 (c, 3J=7.2 Hz, 2H, 6-CH2CH3), 3.44 (s, 3H, 4-NCH3), 3.76 (s, 3H, 2-NCH3), 6.07 (s, 1H, 9-H), 7.41 (t, 3J=7.5 Hz, 1H, 5'), 7.50 (t, 3J=7.7 Hz, 1H, 4'), 7.64 (m, 2H, 3' and 6'). 13C RMN (CDCl3, 100 MHz): δ 12.1 (6-CH2CH3), 29.1 (4-NCH3), 30.2 (2-NCH3), 32.7 (6-CH2CH3), 105.9 (10a), 120.9 (6a), 126.9 (1'), 128.3 (9), 128.9(5'),131.6 (3'), 132.9 (4'), 138.4 (6'), 140.3 (2'), 147.6 (10b), 151.5 (3), 153.2 (1), 154.2 (8), 158.8 (4a), 171.2 (6), 181.1 (10), 181.6 (7).

Reference： [1]Campanini-Salinas, Javier; Andrades-Lagos, Juan; Rocha, Gerardo Gonzalez; Choquesillo-Lazarte, Duane; Dragnic, Soledad Bollo; Faúndez, Mario; Alarcón, Pedro; Silva, Francisco; Vidal, Roberto; Salas-Huenuleo, Edison; Kogan, Marcelo; Mella, Jaime; Gajardo, Gonzalo Recabarren; Vásquez-Velásquez, David [Molecules, 2018, vol. 23, # 7]
[2]Current Patent Assignee: UNIVERSITY OF CHILE - EP3404026, 2018, A1 Location in patent: Paragraph 0094-0096

60
[ 6320-03-2 ]
[ 2999-46-4 ]
C₁₁H₁₂ClNO₃S [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
76%	With water; rose bengal In ethyl acetate at 20℃; for 3h; Irradiation;
76%	With water; rose bengal In ethyl acetate at 20℃; for 3h; Irradiation; Green chemistry;	9 Example 9 O-chlorothiophenol (0.2 mmol) was sequentially added to a 15 mL reaction tube at room temperature.Ethyl nitrile ethyl acetate (0.5 mmol), photocatalyst bengal rose red (0.004 mmol), ethyl acetate 0.5 mL and water 0.5 mL, mixed evenly,Then under the illumination of a 3w blue LED light,The reaction was stirred in air for 3 h. After detecting by TLC until the reaction is completed,Extracted with ethyl acetate 3 times,The extract was concentrated under reduced pressure in vacuo (0.08 Mpa) to give solvent.Then rinse with a mixed eluent of 5:1 by volume of petroleum ether and ethyl acetate.Flash column chromatography on silica gel to obtain the thiocarbamate product of this example.It was 41.5 mg of a yellow solid, yield 76%.

Reference： [1]Wei, Wei; Bao, Pengli; Yue, Huilan; Liu, Sitong; Wang, Leilei; Li, Yudong; Yang, Daoshan [Organic Letters, 2018, vol. 20, # 17, p. 5291 - 5295]
[2]Current Patent Assignee: QINGDAO UNIVERSITY OF SCIENCE AND TECHNOLOGY - CN108947880, 2018, A Location in patent: Paragraph 0039

61
[ 3099-28-3 ]
[ 6320-03-2 ]
2,6-bis[[(2'-chlorophenyl)thio]methyl]pyridine [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
71%	With potassium carbonate; potassium iodide; In N,N-dimethyl-formamide; at 80℃; for 48h;Inert atmosphere;	In the presence of potassium iodide (0.166 g, 1 mmol) and potassium carbonate (0.542 g, 4 mmol), 2-methoxybenzenethiol (0.280 g, 2 mmol) was added to solutionof <strong>[3099-28-3]2,6-bis(chloromethyl)pyridine</strong> (0.176 g, 1 mmol) in30 mL DMF. The reaction mixture was stirred at 80 C over 48 h. Then, the reaction mixture was poured into icedwater and extracted three times with chloroform. The organicphase was completely evaporated to dryness. The compoundwas purified by crystallization using slow vapor diffusionof Et2O into a THF solution of compound L1. This ligandwas obtained as a yellow crystalline solid compound (90%).M.p. 73-74 C. IR, (ATR) cm-1: 3062 (C-H)aromatic, 2988,2955, 2938 (C-H)aliphatic, 1571 (C=N)pyridine, 748 (C-S-C);1H-NMR DMSO-d6,400 MHz): δ 7.63 (t, 1H, J = 8 Hz, H-4),7.31 (d, 2H, J = 8Hz, H-11), 7.27 (d, 2H, J = 8Hz, H-3),7.15 (t, 2H, J = 8Hz, H-9), 6.96 (d, 2H, J = 8Hz, H-8), 6.86(t, 2H, J = 8 Hz, H-10), 4.23 (s, 4H, H-5), 3.80 (s, 6H, H-12). 13C-NMR (DMSO-d6,400 MHz): δ 157.70 (C-2), 156.54(C-7), 137.79 (C-4), 128.26 (C-6), 127.02 (C-8), 124.85 (C-11), 122.75 (C-10), 121.50 (C-9), 111.05 (C-3), 37.35 (C-5),56.11 (C-12); UV-Vis (DMF) λmax (Abs): 285 (1.039), 275(0.929), 269 (0.898) nm. ESIMS, m/z: 384.7 [(L1) + H]+.Anal. Calc. For C21H21NO2S2 (383.53): C, 65.76: H, 5.52:

Reference： [1]Journal of Chemical Sciences,2019,vol. 131

62
[ 6320-03-2 ]
[ 100-44-7 ]
[ 106988-20-9 ]

Yield	Reaction Conditions	Operation in experiment
81%	With N,N,N-tributylbutan-1-aminium fluoride; Cs₂CO₃ In acetonitrile at 20℃; for 3h; Electrochemical reaction; Inert atmosphere;
80%	With diiodine pentaoxide; 1,8-diazabicyclo[5.4.0]undec-7-ene In toluene at 100℃; for 8h;	13 Example 13Prepare the structural formula as follows2-chlorophenylbenzyl sulfoxide In this embodiment,The 4-methylthiophenol in Example 1 was replaced with an equimolar amount of 2-chlorothiophenol, and the reaction time was shortened to 8 hours.The other steps are the same as in Embodiment 1,2-Chlorophenylbenzyl sulfoxide was obtained in a yield of 80%.
80%	With diiodine pentaoxide; 1,8-diazabicyclo[5.4.0]undec-7-ene In toluene at 90℃; for 8h;	2.Typical procedure for the synthesis of functionalized sulfoxides General procedure: Thiols (0.5 mmol) was added to a 25 mL round flask and dissolved in toluene (2mL). I2O5 (0.2g, 1.2 equiv) was added slowly into the reaction flask, followed by the addition of alkyl chlorides (0.5 mmol). 1,8-Diazabicyclo[5.4.0]undec-7-ene (0.15 g, 2 equiv) was added in portions to the reaction flask. The mixture was stirred at 90 °C until the reaction was complete (TLC analysis). The flask was allowed to cool to room temperature. Saturated sodium thiosulfate solution (10 mL) was added and the mixture was then extracted with ethyl acetate (3×10 mL). The combined extracts were washed with brine and dried over anhydrous Na2SO4. After filtration, the solvents were evaporated. The crude product was subjected to column chromatography (SiO2, eluent: petroleum ether/ethyl acetate = 1/10) to give the corresponding sulfoxides.

Reference： [1]Li, Zhen; Wu, Shao-Fen; Ye, Ke-Yin; Yu, Yi; Yuan, Yaofeng; Zhu, Xiao-Bin [Journal of Organic Chemistry, 2022]
[2]Current Patent Assignee: SHAANXI NORMAL UNIVERSITY - CN109485587, 2019, A Location in patent: Paragraph 0062; 0063; 0064; 0065
[3]Liu, Qian; Zhao, Xiaoqian; Xu, Feng; Li, Gaoqiang [Tetrahedron Letters, 2020, vol. 61, # 7]

63
[ 6320-03-2 ]
[ 90407-14-0 ]

Reference： [1]Patent: EP3480201,2019,A1

64
[ 6320-03-2 ]
[ 75-29-6 ]
[ 70398-95-7 ]

Yield	Reaction Conditions	Operation in experiment
93.6%	Stage #1: 2-chlorothiphenol; isopropyl chloride With sodium carbonate In 1,2-dichloro-ethane at 35 - 40℃; for 6h; Stage #2: With tert.-butylhydroperoxide In 1,2-dichloro-ethane at 35 - 40℃; for 4h;	14 Example 14: Preparation of 2-isopropylsulfonylchlorobenzene (IX2) To a 500 ml four-necked flask equipped with a stirring and thermometer, 300 g of 1,2-dichloroethane, 30.0 g of sodium carbonate, 29.0 g (0.2 mol) of 2-chlorothiophenol, 31.5 g (0.4 mol) were added. 2-chloropropane, stirring at 35-40 ° C for 6 hours, cooling to 20 ~ 25 ° C, filtration, filter cake washed twice with 1,2-dichloroethane 40 grams each time, the filtrate was combined, the filtrate was transferred to In another 1000 ml four-necked flask, 64.5 g (0.5 mol) of 70% t-butoxyethanol peroxide was added, and the reaction was stirred at 35 to 40 ° C for 4 hours.Add 100 g of water, layer, and extract the aqueous layer twice with 1,2-dichloroethane, 20 g each time, combine the organic phase, wash once with 50 g of 5% aqueous sodium sulfite solution, and wash with 50 g of saturated sodium chloride solution Once, 1,2-dichloroethane was recovered by distillation, 80 g of methyl tert-butyl ether, 0.5 g of activated carbon was added to the residue, decolorized, filtered, and recrystallized to obtain 40.9 g of 2-isopropylsulfonate.The acid chloride was obtained in a yield of 93.6% and the liquid phase purity was 99.4%.

Reference： [1]Current Patent Assignee: XINFA PHARMACEUTICAL CO LTD - CN109748885, 2019, A Location in patent: Paragraph 0112; 0113

65
[ 6320-03-2 ]
[ 42182-27-4 ]
[ 536-74-3 ]
2-((1-((2-chlorophenyl)thio)-2-oxo-2-phenylethyl)amino)isonicotinonitrile [ No CAS ]

Reference： [1]Organic Letters,2019,vol. 21,p. 4793 - 4797

66
[ 636-98-6 ]
[ 6320-03-2 ]
[ 33667-99-1 ]

Yield	Reaction Conditions	Operation in experiment
81%	With manganese(II) sulfate; copper(II) nitrate trihydrate; caesium carbonate In dimethyl sulfoxide at 95℃; for 6h; Molecular sieve;	4 At room temperature,The compound 2-chlorothiophenol 1 (0.15g, 1.0mmol, 1.0eqv.) was sequentially added to the reactor,DMSO (2.5 ml),Cs2CO3(0.65g, 2.0mmol, 2.0eqv.),Cu-OMS-2(10mg),4-nitroiodobenzene 2 (0.25g, 1.0mmol, 1.0eqv.),Stir at room temperature to dissolve.After dissolving, place in 95 oil bath, condense and reflux for 6h,After TLC detects the completion of the reaction, after the reaction solution is cooled to room temperature,The reaction solution was extracted with dichloromethane to obtain a crude product,Then the crude product was purified by column chromatography,The target product was obtained with a yield of 81%.
81%	With oxygen; caesium carbonate In dimethyl sulfoxide at 95℃; for 6h; Schlenk technique; Green chemistry;	Typical procedure for the synthesis of 3 General procedure: Benzenethiol 1 (1 mmol) was added to Schlenk tube with DMSO (2.5 mL) under oxygen at room temperature. Subsequently, Cs2CO3 (2.0 mmol), Cu-OMS-2 (10 mg),and substituted iodobenzene 2 (1 mmol) were added to the Schlenk tube quickly. The mixture was heated at 95 °C for 6 h. After the reaction was completed, the mixture was cooled to room temperature. Water (10 mL) was added to the mixture, and the crude was extracted with CH2Cl2. After removing the solvent, the resulting crude residue was purified by column chromatography with pure petroleum as the eluent to give compound 3.
75%	With [Ce((L)-proline)₂]₂(oxalate); potassium carbonate In ethanol at 80℃; for 6h;

Reference： [1]Current Patent Assignee: CHINA THREE GORGES UNIVERSITY - CN111978219, 2020, A Location in patent: Paragraph 0022
[2]Yu, Shao-Qiang; Liu, Na; Liu, Ming-Guo; Wang, Long [Journal of Chemical Research, 2021, vol. 45, # 3-4, p. 237 - 241]
[3]Tavares Junior, José M. Da C.; Da Silva, Caren D. G.; Dos Santos, Beatriz F.; Souza, Nicole S.; De Oliveira, Aline R.; Kupfer, Vicente L.; Rinaldi, Andrelson W.; Domingues, Nelson L. C. [Organic and Biomolecular Chemistry, 2019, vol. 17, # 47, p. 10103 - 10108]

67
[ 6320-03-2 ]
[ 591-50-4 ]
[ 33667-82-2 ]

Yield	Reaction Conditions	Operation in experiment
89%	With copper dichloride; N,N`-dimethylethylenediamine at 110℃; for 24h; Inert atmosphere; Green chemistry;	General procedure for the synthesis of diphenylsulfanes by iodobenzenes and benzenethiols (2c-29c). General procedure: An oven-dried Schlenk tube equipped with a Teflon valve was charged with a magnetic stir bar, CuCl2 (15 mol%), iodobenzenes a (0.3 mmol) and benzenethiols d (0.3 mmol). The tube was placed under vacuum for 20 min and backfilled with N2. Then DMEDA (0.35 mL) was added through a syringe. The reaction mixture was stirred at 110 °C for 24 h. The reaction was monitored by TLC. When iodobenzenes a was consumed completely, the reaction was stopped and cooled to room temperature, the crude reaction mixture was filtered through the filter paper with EtOAc (20 mL) for 3 times. The combined organic phase was washed with water (30mL × 3), then concentrated and the residue was purified directly by column chromatography on silica gel using petrol/EtOAc as eluent to give the pure products c.
81%	With barium molybdate; potassium hydroxide In acetonitrile at 80℃; for 16h; Inert atmosphere;
80%	With CuMoO₄; caesium carbonate In dimethyl sulfoxide at 30℃; for 6h; Inert atmosphere;

Reference： [1]Shen, Guodong; Lu, Qichao; Wang, Zeyou; Sun, Weiwei; Zhang, Yalin; Huang, Xianqiang; Sun, Manman; Wang, Zhiming [Synthesis, 2022, vol. 54, # 1, p. 184 - 198]
[2]Panda, Subhalaxmi; Sahu, Santosh Kumar; Behera, Pradyota Kumar; Panigrahi, Reba; Garnaik, Bamakanta; Rout, Laxmidhar [New Journal of Chemistry, 2020, vol. 44, # 6, p. 2500 - 2504]
[3]Panigrahi, Reba; Sahu, Santosh Kumar; Behera, Pradyota Kumar; Panda, Subhalaxmi; Rout, Laxmidhar [Chemistry - A European Journal, 2020, vol. 26, # 3, p. 620 - 624]

68
[ 6320-03-2 ]
[ 621-23-8 ]
(2-chlorophenyl) (2,4,6-trimethoxyphenyl)sulfane [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
73%	With sodium tetrafluoroborate; potassium iodide In acetonitrile at 60℃; for 6h; Electrochemical reaction;	2.3 Electrolysis experiments Electrolysis experiments were performed on Vertex Potentiostat/Galvanostat. Both the working electrode and the counter electrode were made of platinum (1.5cm×1.5cm). Ag/Ag+ electrode (0.1mol/L AgNO3 in CH3CN) was employed as the reference electrode. The 0.1mol/L of NaBF4/CH3CN solution (15mL) with 1,3,5-trimethoxybenzene (1a, 0.5mmol, 84mg), 4-chlorothiophenol (2a, 0.6mmol, 86mg) and KI (0.05mmol, 8.3mg) was added into a 25mL undivided beaker and the resulting mixture was stirred at 60°C. After completion of the reaction (analysed by GC or TLC), the resulting mixture was concentrated under reduced pressure and purified by column chromatography on 200-300 mesh silica gel using petroleum ether: ethyl acetate (50:1) as eluent to afford (4-chlorophenyl) (2,4,6-trimethoxyphenyl)sulfane (3aa) as a white solid in 90% yield.

Reference： [1]Liu, Xin; Niu, Pengfei; Jin, Jiali; Shen, Zhenlu; Li, Meichao [Electrochimica Acta, 2020, vol. 331]

69
[ 6320-03-2 ]
[ 1753-75-9 ]
C₁₂H₇ClN₂S₂ [ No CAS ]

Reference： [1]Applied Organometallic Chemistry,2020

70
[ 6320-03-2 ]
[ 122-52-1 ]
[ 15224-41-6 ]

Yield	Reaction Conditions	Operation in experiment
90%	Stage #1: 2-chlorothiphenol With trichloroisocyanuric acid In acetonitrile at 20℃; for 0.166667h; Stage #2: triethyl phosphite In acetonitrile at 20℃; for 0.166667h;	16 Example 16: Preparation of O,O-diethyl-S-o-chlorophenyl phosphorothioate (formula (11)) In a 15mL reaction tube equipped with a magnetic stir bar, add o-chlorothiophenol (1mmol), trichloroisocyanuric acid (0.35mmol) and 2mL of acetonitrile,Stir the reaction at room temperature for 10 min, then add triethyl phosphite (1.2 mmol),Continue stirring at room temperature for 10 min. Filtration, the filtrate was evaporated under reduced pressure,Separate with column chromatography, and use the mixture of petroleum ether/ethyl acetate volume ratio of 20:1 as the eluent to collect the eluent containing the target compound.Distilling off the solvent yields the product O,O-diethyl-S-o-chlorophenyl phosphorothioate,The separation yield was 90%.

Reference： [1]Current Patent Assignee: ZHEJIANG UNIVERSITY OF TECHNOLOGY - CN111116645, 2020, A Location in patent: Paragraph 0051-0052

71
[ 6320-03-2 ]
[ 62-53-3 ]
[ 4726-27-6 ]

Yield	Reaction Conditions	Operation in experiment
93%	With 5-ethyl-1,3,7,8-tetramethylalloxazinium triflate; iodine; oxygen In acetonitrile at 60℃; for 30h; Schlenk technique; Green chemistry;	2. General procedures General procedure: A 25 mL Schlenk tube equipped with a magnetic stirring bar was charged with aniline 1a (93mg, 1.0 mmol), 4-methylbenzenethiol 2a (62 mg, 0.5 mmol), flavin II (11 mg, 0.025 mmol), I2(6 mg, 0.025 mmol) and MeCN (0.5 mL). The reaction mixture was heated at 60 oC for 24 hunder O2 atmosphere. After the reaction was complete as determined by TLC, it was quenched with saturated Na2S2O3 solution (5 mL) at room temperature, and then extracted with ethyl acetate (15 mL x 3). The organic layers were combined, washed with water andbrine, dried over Na2SO4, filtered, and then concentrated in vacuum. The residue was purified by flash column chromatography (hexane:EtOAc = 60:1) to give product 3a (92 mg,85%).
60%	With iodine; dimethyl sulfoxide In N,N-dimethyl-formamide at 120℃; for 12h; Molecular sieve; Sealed tube;

Reference： [1]Jiang, Xinpeng; Shen, Zhifeng; Zheng, Cong; Fang, Liyun; Chen, Keda; Yu, Chuanming [Tetrahedron Letters, 2020, vol. 61, # 33]
[2]Zhao, Wenqi; Zhang, Feng; Deng, Guo-Jun [Journal of Organic Chemistry, 2021, vol. 86, # 1, p. 291 - 301]

72
[ 6320-03-2 ]
[ 100-61-8 ]
4-((2-chlorophenyl)thio)-N-methylaniline [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
88%	With 5-ethyl-1,3,7,8-tetramethylalloxazinium triflate; iodine; oxygen In acetonitrile at 60℃; for 24h; Schlenk technique; Green chemistry;	2. General procedures General procedure: A 25 mL Schlenk tube equipped with a magnetic stirring bar was charged with aniline 1a (93mg, 1.0 mmol), 4-methylbenzenethiol 2a (62 mg, 0.5 mmol), flavin II (11 mg, 0.025 mmol), I2(6 mg, 0.025 mmol) and MeCN (0.5 mL). The reaction mixture was heated at 60 oC for 24 hunder O2 atmosphere. After the reaction was complete as determined by TLC, it was quenched with saturated Na2S2O3 solution (5 mL) at room temperature, and then extracted with ethyl acetate (15 mL x 3). The organic layers were combined, washed with water andbrine, dried over Na2SO4, filtered, and then concentrated in vacuum. The residue was purified by flash column chromatography (hexane:EtOAc = 60:1) to give product 3a (92 mg,85%).

Reference： [1]Jiang, Xinpeng; Shen, Zhifeng; Zheng, Cong; Fang, Liyun; Chen, Keda; Yu, Chuanming [Tetrahedron Letters, 2020, vol. 61, # 33]

73
[ 6320-03-2 ]
[ 2905-16-0 ]

Yield	Reaction Conditions	Operation in experiment
99%	With water monomer; 1-(chloromethyl)-4-fluoro-1,4-diazoniabicyclo-[2.2.2]octane bis(tetrafluoroborate) In acetonitrile at 20℃; for 0.0833333h;	Thiosulfonates 5; General Procedure General procedure: In air, to a vial containing a magnetic stirring bar were added 4 (0.8 mmol), MeCN (2 mL), H2O (29 L, 1.6 mmol), and Selectfluor (425 mg, 1.2 mmol). Then the contents of the vial were stirred in air at rt for the indicated time (Table 3). The reaction could be monitored by TLC analysis. The reaction mixture was concentrated under reduced pressure and subjected to column chromatography using PE/EtOAc (from 20:1 to 4:1) as eluent to afford the desired products 5.
83.8%	With aluminum tris(dihydrogenphosphate); nitric acid In acetonitrile at 85℃; for 24h;	4.3. General procedure using Al(H2PO4)3 / HNO3 /ACN (dry) (System B) General procedure: 32 mmol of halogenated thiol was dissolved in anhydrous ACN.0.16 mmol of aluminium dihydrogen phosphate (freshly prepared) andconcentrated HNO3 (3 mL) were added to this solution, which wasstirred at room temperature (r.t.) and monitored by TLC for 24 h, whenit was observed that the consumption of the starting material wascomplete. The method was optimized by increasing the temperature to85 °C, leading to faster formation of the thiosulfonate products withhigh yields. The workup was performed by neutralizing the mixture bycareful addition of a sodium bicarbonate solution. The mixture wasextracted using ethyl acetate. The organic layer was washed with distilledwater and brine and dried over MgSO4, followed by filtrationunder reduced pressure. The products were purified by silica gel (GF DE500 μm, UNIPLAT) chromatography using hexane/EtOAc (9:1) as theeluent.

Reference： [1]Guo, Xuqiang; Jiang, Mengmeng; Sun, Xuejun; Zhao, Yulei [Synthesis, 2022, vol. 54, # 8, p. 1996 - 2004]
[2]Bai, Ruoli; Barbosa, Euzébio Guimarães; Beatriz, Adilson; Hamel, Ernest; Khodyuk, Rejane Gonçalves Diniz; Lourenço, Estela Mariana Guimarães; de Lima, Dênis Pires; dos Santos, Edson dos Anjos [Bioorganic Chemistry, 2020, vol. 101]

74
[ 6320-03-2 ]
[ 31121-19-4 ]
[ 2905-16-0 ]

Yield	Reaction Conditions	Operation in experiment
1: 69.9% 2: 11.5%	With aluminum dihydrogen phosphate; nitric acid In acetonitrile at 20℃; for 24h;	4.3. General procedure using Al(H2PO4)3 / HNO3 /ACN (dry) (System B) General procedure: 32 mmol of halogenated thiol was dissolved in anhydrous ACN.0.16 mmol of aluminium dihydrogen phosphate (freshly prepared) andconcentrated HNO3 (3 mL) were added to this solution, which wasstirred at room temperature (r.t.) and monitored by TLC for 24 h, whenit was observed that the consumption of the starting material wascomplete. The method was optimized by increasing the temperature to85 °C, leading to faster formation of the thiosulfonate products withhigh yields. The workup was performed by neutralizing the mixture bycareful addition of a sodium bicarbonate solution. The mixture wasextracted using ethyl acetate. The organic layer was washed with distilledwater and brine and dried over MgSO4, followed by filtrationunder reduced pressure. The products were purified by silica gel (GF DE500 μm, UNIPLAT) chromatography using hexane/EtOAc (9:1) as theeluent.

Reference： [1]Bai, Ruoli; Barbosa, Euzébio Guimarães; Beatriz, Adilson; Hamel, Ernest; Khodyuk, Rejane Gonçalves Diniz; Lourenço, Estela Mariana Guimarães; de Lima, Dênis Pires; dos Santos, Edson dos Anjos [Bioorganic Chemistry, 2020, vol. 101]

75
[ 6320-03-2 ]
[ 60480-83-3 ]
(2-chlorophenyl)(2,4-dimethylphenyl)sulfane [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
65%	With tert.-butylhydroperoxide; caesium carbonate; potassium iodide In water at 20℃; for 20h;	(3-Methoxyphenyl)(phenyl)sulfane (3a); Typical Procedure General procedure: A vial equipped with a stir bar was charged with thiol 2 (0.2 mmol, 2equiv), arylhydrazine hydrochloride 1 (0.1 mmol, 1 equiv), Cs2CO3(0.1 mmol, 1 equiv), KI (50 mol%), and TBHP (0.4 mmol, 4 equiv). H2O (0.3 mL) was added and the vial was capped. The resulting mixture was stirred at rt for 20 h. Upon completion of the reaction, the resulting mixture was extracted with EtOAc. The combined organic layer was dried (anhyd Na2SO4). After the removal of the solvent under reduced pressure, the crude product was purified by column chromatography(silica gel, EtOAc/hexane gradient) to provide the desired product 3a as a pale yellow oil; yield: 19 mg (87%).

Reference： [1]Asadpour, Mohammad; Azizzade, Meysam; Ghasemi, Mehran; Jafarpour, Farnaz; Rajai-Daryasarei, Saideh [Synthesis, 2020, vol. 52, # 5, p. 727 - 734]

76
[ 127427-45-6 ]
[ 6320-03-2 ]
2-((2-chlorophenyl)thio)-2,2-difluoro-N-phenylacetamide [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
85%	With sodium hydride In N,N-dimethyl-formamide at 80℃; for 12h;	Typical procedures for the synthesis of compounds 3 General procedure: A 10 mL round-bottom flask was charged with compound 1 (0.20 mmol, 1.0 equiv.), 2 (0.3 mmol), NaH (0.6 mmol) and DMF (2.0 mL) under Air atmosphere. The reaction mixture was stirred at 80 °C for 12 h. After the reaction was completed, the crude product was directly purified by silica gel chromatography, to give the desired product 3.

Reference： [1]Deng, Hongmei; Du, Pengcheng; Jiang, Haizhen; Wang, Pingyang; Wang, Wei; Zhang, Jianhua; Zhang, Qian [Tetrahedron, 2020]

77
[ 6320-03-2 ]
tert-butyl (2-oxo-1-propylindolin-3-ylidene)carbamate [ No CAS ]
tert-butyl (3-((2-chlorophenyl)thio)-2-oxo-1-propylindolin-3-yl)carbamate [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
75%	With C₁₂H₁₅CoN₂O₆^(1-)*K⁽¹⁺⁾ In dichloromethane at 20℃; for 0.0833333h; Schlenk technique; Green chemistry;	Thiol Addition to Ketimines; General Procedure General procedure: In a Schlenk tube was added ketimine 1 (0.3 mmol), thiol 2 (0.33mmol) in DCM (0.3 M), and the cobalt catalyst Co(II)-L (1.5 mol%). Thereaction mixture was stirred at r.t. for 5 min. After completion of thereaction, the solvent was evaporated under vacuum. The residue waspurified by silica gel column chromatography (EtOAc/hexane 5:95) toafford the desired isatin-derived N,S-acetal derivative 3.

Reference： [1]Albuquerque, Tábata B.; Da Silva, Caren D. G.; Domingues, Nelson L. C.; Dos Santos, Beatriz F.; Katla, Ramesh; Kupfer, Vicente L.; Rinaldi, Andrelson W.; Tavares Junior, José M. C. [Synthesis, 2019, vol. 51, # 21, p. 4014 - 4022]

78
[ 6320-03-2 ]
[ 539-74-2 ]
ethyl 3-(2-chlorophenylthio)propionate [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
97%	With potassium carbonate In ethanol at 80℃; for 1h;	1-8 S1 thiolation alkylation: Weigh 50g o-chlorothiophenol, transfer it into a 2000mL three-necked flask, add 1000mL ethanol, stir at 300 rpm, add 143.8 potassium carbonate and 94.2g ethyl 3-bromopropionate, heat up to 80 for reaction , TLC dot plate (developing solvent is petroleum ether/ethyl acetate solvent with a volume ratio of 20:1) to monitor the progress of the reaction. After 60 minutes of reaction, TLC shows that the reaction is complete; cool to room temperature, filter, and concentrate the filtrate under reduced pressure to remove Solvent; the crude product is purified by chromatography on a silica gel column (the eluent is a petroleum ether/ethyl acetate solvent with a volume ratio of 20:1),It was concentrated under reduced pressure to remove the solvent to obtain 82.4 g of ethyl 3-(2-chlorophenylthio)propionate in the form of a colorless oil with a yield of 97%.

Reference： [1]Current Patent Assignee: XIAN BIRDO TECH - CN111574475, 2020, A Location in patent: Paragraph 0054-0058; 0080-0091

79
[ 6320-03-2 ]
2-[(3-pentadecylphenoxy)methyl]oxirane [ No CAS ]
1-((2-chlorophenyl)thio)-3-(3-pentadecylphenoxy)propan-2-ol [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
90%	With sodium hydroxide In ethanol at 30℃; for 2h;	Synthesis of -hydroxy sulfides 5a-5j General procedure: A 2 mL volume of 0.03 M sodium hydroxide in ethanolwas added to an ethanol solution (2 mL) of 1 mmol cardanolepoxide 311 and 1.0 mmol thiol at ambient temperatureand the mixture stirred at 30 °C for 2 h. The reaction wasmonitored by TLC, the resulting mixture allowed to coolto room temperature, and ethanol finally removed undervacuum. The remaining mixture was partitioned betweenwater (20 mL) and ethyl acetate (25 mL), the organiclayer separated, and the aqueous layer extracted with ethylacetate (2 × 20 mL) and dried over MgSO4. The solventwas removed under vacuum and the crude compound waspurified by column chromatography using 20-50% EtOAcin hexane as the eluent to yield the desired -hydroxysulfides (5a-5j).

Reference： [1]Beatriz, Adilson; Copini, Suély; De Lima, Dênis P.; Gomes, Roberto S.; Meza, Alisson; Micheletti, Ana C. [Journal of the Brazilian Chemical Society, 2020, vol. 31, # 12, p. 2569 - 2582]

80
[ 63224-42-0 ]
[ 6320-03-2 ]
4,7-bis((2-chlorophenyl)thio)-2,1,3-benzoselenadiazole [ No CAS ]

Reference： [1]Journal of Organic Chemistry,2020,vol. 85,p. 10561 - 10573

81
[ 6320-03-2 ]
[ 31618-90-3 ]
diethyl (((2-chlorophenyl)thio)methyl)phosphonate [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
85%	With caesium carbonate In N,N-dimethyl-formamide at 20℃; for 12h;	General procedure for diethyl ((phenylthio)methyl)phosphonate derivatives (4a-4f) (Method A) General procedure: To a dimethylformamide (DMF) solution of 3 ([C]~0.4-0.6M) was added the desired benzenethiol (1.2 equiv), cesium carbonate (Cs2CO3) (1.2 equiv). The reaction mixture was stirred at room temperature (12 h). The reaction mixture was diluted with EtOAc and washed with H2O. The organic layer was dried with anhydrous Na2SO4 and concentrated in vacuo. The residue was purified by column chromatography on SiO2.
	With caesium carbonate In N,N-dimethyl-formamide at 70℃;	4.1.3. General synthesis of intermediates 3 (3a ~ e) and 4 (4a ~ e) General procedure: Intermediates 3 (3a ~ e) and 4 (4a ~ e) were synthesized according to the methods described by Park et al. [54]. In brief, corresponding thiophenol (1a 4.4 g, 1b 4.97 g, 1c 5.13 g, 1d 5.78 g, 1e 5.61 g, 40mmol, 1 eq), commercially available intermediate 2 (15.47 g, 48 mmol,1.2 eq), and Cs2CO3 (26.07 g, 80 mmol, 2 eq) were mixed in an appropriate volume (~200 mL) of N, N-Dimethylformamide (DMF), the mixture of which was stirred at 70°C overnight. After concentration of the reaction, the residue was washed with a large amount (~450 mL) of H2O and extracted with ethyl acetate. The combined organic layer was dried with MgSO4 and evaporated to afford oil materials as corresponding intermediates 3 (3a ~ e), which were used for next without further purification, and the yields ranged from 85.2% ~ 94.8%. The corresponding oily 3 (3a 7.809 g, 3b 8.229 g, 3c 8.348 g, 3d 8.842 g, 3e8.709 g, 30 mmol, 1 eq) was dissolved in an appropriate volume (~200mL) of dichloromethane, and then the reaction was placed in ice. After it was thoroughly cooled, 3-chloroperoxybenzoic acid (m-CPBA) (20.708g, 120 mmol, 4 eq) was added portion-wise. After the addition was completed, it was stirred at room temperature for ~ 5 h and quenched with aqueous Na2S2O3 until 3 (3a ~ e) disappeared. Then it was washed well with aqueous Na2S2O3 and water, and extracted with dichloromethane.The combined organic layer was concentrated to give a residue,which was purified on column chromatography to afford pure intermediates 4 (4a ~ e).

Reference： [1]Choi, Ji Won; Kim, Siwon; Yoo, Jong Seok; Kim, Hyeon Jeong; Kim, Hyeon Ji; Kim, Byung Eun; Lee, Elijah Hwejin; Lee, Yong Sup; Park, Jong-Hyun; Park, Ki Duk [European Journal of Medicinal Chemistry, 2021, vol. 212]
[2]Song, Zi-Long; Hou, Yanan; Bai, Feifei; Fang, Jianguo [Bioorganic Chemistry, 2021, vol. 107]

82
[ 6320-03-2 ]
[ 1076-38-6 ]
3-((2-chlorophenyl)thio)-4-hydroxy-2H-chromen-2-one [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
75%	With sodium tetrafluoroborate; potassium iodide In acetonitrile at 60℃; for 6h; Electrolysis;	Electrolysis experiments.- General procedure: Electrolysis experiments were performedon Vertex Potentiostat/Galvanostat. Both the working electrodeand the counter electrode were platinum electrodes (1.5 cm ×1.5 cm). The reference electrode was Ag/Ag+ electrode (0.1 mol l-1AgNO3 in CH3CN). 4-Hydroxycoumarin (1a, 0.5 mmol, 81.1 mg),4-chlorothiophenol (2a, 0.75 mmol, 108.5 mg), KI (0.05 mmol,8.3 mg) and 0.1 mol l-1 NaBF4/CH3CN solution (15 ml) were addedinto 25 ml undivided cell. The electrolysis reactions were operated at0.4 V under 60 °C for 6 h. The resulting mixture was concentratedunder reduced pressure and purified by column chromatography onsilica gel using petroleum ether/ethyl acetate (5:1) as eluent to afford3-((4-chlorophenyl)thio)-4-hydroxy-2H-chromen-2-one (3aa) as a white solid in 94% yield.

Reference： [1]Jin, Jiali; Zhao, Lingmin; Zhang, Chao; Liu, Xin; Yin, Wenxu; Shen, Zhenlu; Li, Meichao [Journal of the Electrochemical Society, 2021, vol. 168, # 2]

83
[ 32601-86-8 ]
[ 6320-03-2 ]
2-(2-chlorophenylthio)-3-methylquinoxaline [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
100%	With caesium carbonate In N,N-dimethyl-formamide at 70℃; for 12h; Inert atmosphere; Sealed tube;	4.1.3. General procedure for 3-methyl-2-substituted-quinoxaline(2a-2p) General procedure: To a solution of 2-chloro-3-methylquinoxaline (1) (500 mg,2.8 mmol) and the appropriate thiophenol (2.8 mmol, 1.0 equiv) inanhydrous DMF (10 mL), Cs2CO3 (912 mg, 2.8 mmol, 1.0 equiv) wasadded under inert atmosphere. The mixture was stirred at 70 Covernight. After completion of the reaction, water was added,leading to a precipitate which was separated by filtration. Theresulting precipitate was then thoroughly washed with water. Theprecipitate was dissolved in CH2Cl2 and dried with Na2SO4. Afterfiltration and evaporation, the resulting solid was purified by silicagel column chromatography (using the appropriate eluant) toafford the desired compound.4.1.3.1. 2-(2-Chlorophenylthio)-3-methylquinoxaline (2a). Yield100% (803 mg). White solid. Mp 155 C. 1H NMR (250 MHz, CDCl3)d 7.97e7.93 (m, 1H), 7.70e7.51 (m, 5H), 7.46e7.31 (m, 2H), 2.82 (s,3H) . 13C NMR (63 MHz, CDCl3) d 154.6, 151.5, 141.6, 139.6, 139.6,137.6,131.0,130.4,129.2,128.7,128.3,128.2,128.1,127.5, 22.4. LC-MS(ESI) tR 6.54 min; m/z [MH] 286.36/289.00. MW:286.78 g mol1. HRMS (ESI): m/z calcd. for C15H11ClN2S [MH]287.0404. Found: 287.0402.

Reference： [1]Amanzougaghene, Nadia; Amrane, Dyhia; Azas, Nadine; Azqueta, Amaya; Mazier, Dominique; Primas, Nicolas; Sanz-Serrano, Julen; Tajeri, Shahin; Vanelle, Patrice; Verhaeghe, Pierre; Arnold, Christophe-Sébastien; Botté, Cyrille; Hutter, Sébastien; Louis, Béatrice [European Journal of Medicinal Chemistry, 2021, vol. 224]

84
[ 6320-03-2 ]
[ 2039-88-5 ]
(2-(2-bromophenyl)-2-fluoroethyl)(2-chlorophenyl)sulfane [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
87%	With triethylamine tris(hydrogen fluoride) In acetonitrile at 40℃; for 6h; Inert atmosphere; Electrochemical reaction;	Method A: General procedure for the electrochemical vicinal fluorosulfenylation of alkenes(constant cell-potential electrolysis) General procedure: In an oven-dried undivided three-necked glassware (25 mL) equipped with a stirring bar, thiophenolsubstrate (0.3 mmol) were added. The glassware was equipped with carbon cloth (15 mm × 15 mm ×0.1 mm) as the anode and platinum plate (15 mm × 15 mm × 0.3 mm) as the cathode. Under theprotection of N2, olefin substrate (1.5 equiv.), Et3N3HF (0.5 mL), and CH3CN (10 mL) were injectedrespectively into the glassware via syringes. The reaction mixture was stirred and electrolyzed at aconstant cell potential of 1.8 V at 40 oC for 6 h. The reaction mixture was subsequently poured into asaturated sodium bicarbonate solution (ca. 15 mL). The aqueous layer was separated and extracted withdichloromethane (3×5 mL), and the combined organic layers were washed with brine and dried oversodium sulfate. Following concentration in vacuo, the crude residue was subjected to flash columnchromatography on silica gel to yield the desired product.

Reference： [1]Yu, Yi; Jiang, Yimin; Wu, Shaofen; Shi, Zhaojiang; Wu, Jinnan; Yuan, Yaofeng; Ye, Keyin [Chinese Chemical Letters, 2022, vol. 33, # 4, p. 2009 - 2014]

85
[ 530-48-3 ]
[ 6320-03-2 ]
(2-((2-chlorophenyl)sulfinyl)-1-fluoroethane-1,1-diyl)dibenzene [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
70%	With tetrachloromethane; acetic acid; triethylamine tris(hydrogen fluoride) In acetonitrile at 40℃; for 4h; Inert atmosphere; Electrochemical reaction;	Method E: General procedure for the electrochemical vicinal fluorosulfoxidation of alkenes(constant cell-potential electrolysis) General procedure: In an oven-dried undivided three-necked glassware (25 mL) equipped with a stir bar, 4-chlorobenzenethiol (0.3 mmol) were added. The glassware was equipped with carbon cloth (15 mm ×15 mm × 0.1 mm) as the anode and platinum plate (15 mm × 15 mm × 0.3 mm) as the cathode. Underthe protection of N2, olefin substrate (1.7 equiv.), Et3N3HF (1 mL), CH3COOH (3 equiv.), CCl4 (1.0equiv.) and CH3CN (10 mL) were injected respectively into the glassware via syringes. The reactionmixture was stirred and the electrolysis was initiated at a constant cell potential of 2.8 V at 40 oC. Theelectrical input was removed after 4 h. The reaction mixture was subsequently poured into a saturatedsodium bicarbonate solution (ca. 15 mL). The aqueous layer was separated and extracted withdichloromethane (3×5 mL), and the combined organic layers were washed with brine and dried oversodium sulfate. Following concentration in vacuo, the crude residue was subjected to flash columnchromatography on silica gel to yield the desired product.

Reference： [1]Yu, Yi; Jiang, Yimin; Wu, Shaofen; Shi, Zhaojiang; Wu, Jinnan; Yuan, Yaofeng; Ye, Keyin [Chinese Chemical Letters, 2022, vol. 33, # 4, p. 2009 - 2014]

86
[ 6320-03-2 ]
[ 103-05-9 ]
(2-chlorophenyl)(2-methyl-4-phenylbutan-2-yl)sulfane [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
86%	With copper(II) bis(trifluoromethanesulfonate) In 1,2-dichloro-ethane at 70℃; for 12h; Schlenk technique;	General procedure for the reaction of tertiary alkyl alcohols with thiols General procedure: To a flame-dried Schlenk tube was charged with a tertiary alcohol (0.30 mmol, 100 mol %), Cu(OTf)2 (1.1 mg, 0.003 mmol, 1 mol %). The tube was capped with a rubber septum. Mercaptan (0.30 mmol, 100 mol %) was added followed by addition of DCE (1 mL) via syringes. The reaction mixture was allowed to stir in an oil bath for 12 h under an air atmosphere at 70oC. Then, the reaction mixture was directly loaded onto a silica column without work-up. The residue was rinsed with PE or the eluent for column chromatography, with which the product was isolated.

Reference： [1]Xu, Bing; Ye, Yang; Lin, Ying; Bai, Renren; Ye, Xiang-Yang; Xie, Tian [Tetrahedron Letters, 2022, vol. 89]

87
[ 6320-03-2 ]
ethyl 2-(bromomethyl)-3-fluorobenzoate [ No CAS ]
C₁₆H₁₄ClFO₂S [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
67.2%	With potassium carbonate In N,N-dimethyl-formamide at 20 - 60℃;	3 Compound 3c (2.32 g, 8.89 mmol) was dissolved in DMF (20 mL),Potassium carbonate (2.46 g, 17.77 mmol) was added, 2-chlorothiophenol (1.01 mL, 8.89 mmol) was added dropwise, and the mixture was stirred at room temperature for 45 min. Then, it was heated and stirred in an oil bath at 60°C, and the reaction was carried out overnight. cooled to room temperature,120 mL of ethyl acetate and 120 mL of water were added, shaken uniformly, and the organic layer was separated; the aqueous layer was extracted with ethyl acetate (60 mL×2). Combine organic phases, saturated brine (120 mL×2)Washed, dried over anhydrous sodium sulfate, filtered,The filtrate was concentrated under reduced pressure to obtain a yellow liquid. Purified by silica gel column chromatography (petroleum ether/ethyl acetate (V/V)=40/1) to obtain 1.94 g of colorless liquid compound 3d, yield: 67.2%.
67.2%	With potassium carbonate In N,N-dimethyl-formamide at 20 - 60℃;	3 Compound 3c (2.32 g, 8.89 mmol) was dissolved in DMF (20 mL), potassium carbonate (2.46 g, 17.77 mmol) was added, 2-chlorothiophenol (1.01 mL, 8.89 mmol) was added dropwise, and the mixture was stirred at room temperature 45min. Then, it was heated and stirred in an oil bath at 60°C, and the reaction was carried out overnight. Cool to room temperature, add 120 mL of ethyl acetate and 120 mL of water, shake evenly, and separate the organic layer; the aqueous layer is extracted with ethyl acetate (60 mL×2). The organic phases were combined, washed with saturated brine (120 mL×2), dried over anhydrous sodium sulfate, filtered, and the filtrate was concentrated under reduced pressure to obtain a yellow liquid. Purified by silica gel column chromatography (petroleum ether/ethyl acetate (V/V)=40/1) to obtain 1.94 g of colorless liquid compound 3d, yield: 67.2%.

Reference： [1]Current Patent Assignee: GUANGZHOU NANXIN PHARMACEUTICAL CO., LTD - CN113880832, 2022, A Location in patent: Paragraph 0114; 0116
[2]Current Patent Assignee: GUANGZHOU NANXIN PHARMACEUTICAL CO., LTD - CN114057730, 2022, A Location in patent: Paragraph 0110; 0112

88
[ 6320-03-2 ]
[ 343942-94-9 ]
C₁₆H₁₄ClFO₂S [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
67.2%	With potassium carbonate In N,N-dimethyl-formamide at 20 - 60℃;	2 Compound 2c (2.32 g, 8.89 mmol) was dissolved in DMF (20 mL),Potassium carbonate (2.46 g, 17.77 mmol) was added, 2-chlorothiophenol (1.01 mL, 8.89 mmol) was added dropwise, and the mixture was stirred at room temperature for 45 min. Then, it was heated and stirred in an oil bath at 60°C, and the reaction was carried out overnight. Cool to room temperature, add 120 mL of ethyl acetate and 120 mL of water, shake evenly, and separate the organic layer; the aqueous layer is extracted with ethyl acetate (60 mL×2). The organic phases were combined, washed with saturated brine (120 mL×2), dried over anhydrous sodium sulfate, filtered, and the filtrate was concentrated under reduced pressure to obtain a yellow liquid. Purified by silica gel column chromatography (petroleum ether/ethyl acetate (V/V)=40/1) to obtain 1.94 g of colorless liquid compound 2d (structure confirmed by NMR), yield: 67.2%.
67.2%	With potassium carbonate In N,N-dimethyl-formamide at 20 - 60℃;	2 Compound 2c (2.32 g, 8.89 mmol) was dissolved in DMF (20 mL), potassium carbonate (2.46 g, 17.77 mmol) was added, 2-chlorothiophenol (1.01 mL, 8.89 mmol) was added dropwise, and the mixture was stirred at room temperature 45min. Then, it was heated and stirred in an oil bath at 60°C, and the reaction was carried out overnight. Cool to room temperature, add 120 mL of ethyl acetate and 120 mL of water, shake evenly, and separate the organic layer; the aqueous layer is extracted with ethyl acetate (60 mL×2). The organic phases were combined, washed with saturated brine (120 mL×2), dried over anhydrous sodium sulfate, filtered, and the filtrate was concentrated under reduced pressure to obtain a yellow liquid. Purified by silica gel column chromatography (petroleum ether/ethyl acetate (V/V)=40/1) to obtain 1.94 g of colorless liquid compound 2d (structure confirmed by NMR), yield: 67.2%.

Reference： [1]Current Patent Assignee: GUANGZHOU NANXIN PHARMACEUTICAL CO., LTD - CN113880832, 2022, A Location in patent: Paragraph 0109; 0111
[2]Current Patent Assignee: GUANGZHOU NANXIN PHARMACEUTICAL CO., LTD - CN114057730, 2022, A Location in patent: Paragraph 0107; 0109

Type	HazMat fee for 500 gram (Estimated)
Excepted Quantity	USD 0.00
Limited Quantity	USD 15-60
Inaccessible (Haz class 6.1), Domestic	USD 80+
Inaccessible (Haz class 6.1), International	USD 150+
Accessible (Haz class 3, 4, 5 or 8), Domestic	USD 100+
Accessible (Haz class 3, 4, 5 or 8), International	USD 200+

Purity	Size	Price	VIP Price	USA Stock *0-1 Day	Global Stock *5-7 Days	Quantity
{[ item.p_purity ]}	{[ item.pr_size ]}	{[ getRatePrice(item.pr_usd, 1,1) ]} {[ getRatePrice(item.pr_usd,item.pr_rate,item.mem_rate) ]}	{[ getRatePrice(item.pr_usd, 1,1) ]}	Inquiry {[ getRatePrice(item.pr_usd,item.pr_rate,item.mem_rate) ]} {[ getRatePrice(item.pr_usd,1,item.mem_rate) ]}	{[ item.pr_usastock ]}	Inquiry -	{[ item.pr_chinastock ]}	Inquiry -

CAS No. :	6320-03-2	MDL No. :	MFCD00004830
Formula :	C₆H₅ClS	Boiling Point :	-
Linear Structure Formula :	-	InChI Key :	PWOBDMNCYMQTCE-UHFFFAOYSA-N
M.W :	144.62	Pubchem ID :	80599
Synonyms :

Signal Word:	Danger	Class:	8
Precautionary Statements:	P210-P264-P270-P271-P280-P303+P361+P353-P304+P340-P305+P351+P338-P310-P330-P331-P363-P370+P378-P403+P233-P501	UN#:	3265
Hazard Statements:	H227-H302-H314	Packing Group:	Ⅲ
GHS Pictogram:

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P337 + P313	IF eye irritation persists: Get medical advice/attention.
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P401
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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

[ CAS No. 6320-03-2 ] {[proInfo.proName]}

Quality Control of [ 6320-03-2 ]

Related Doc. of [ 6320-03-2 ]

Product Details of [ 6320-03-2 ]

Safety of [ 6320-03-2 ]

Application In Synthesis of [ 6320-03-2 ]

[ 6320-03-2 ] Synthesis Path-Upstream 1~2

[ 6320-03-2 ] Synthesis Path-Downstream 1~88

Related Functional Groups of
[ 6320-03-2 ]

Aryls

Chlorides

Precautionary Statements-General

Prevention

Response

Storage

Disposal

Physical hazards

Health hazards

Environmental hazards

Inquiry

[ CAS No. 6320-03-2 ] {[proInfo.proName]}

Quality Control of [ 6320-03-2 ]

Related Doc. of [ 6320-03-2 ]

Product Details of [ 6320-03-2 ]

Safety of [ 6320-03-2 ]

Application In Synthesis of [ 6320-03-2 ]

[ 6320-03-2 ] Synthesis Path-Upstream 1~2

[ 6320-03-2 ] Synthesis Path-Downstream 1~88

Related Functional Groups of [ 6320-03-2 ]

Aryls

Chlorides

Precautionary Statements-General

Prevention

Response

Storage

Disposal

Physical hazards

Health hazards

Environmental hazards

Inquiry

Related Functional Groups of
[ 6320-03-2 ]