Name: 29490-19-5|5-Methyl-1,3,4-thiadiazole-2-thiol|97%
Brand: Ambeed
SKU: A153687
Price: 5.0 USD
Availability: InStock
Rating: 99 (25 reviews)

1
[ 3034-48-8 ]
[ 29490-19-5 ]
[ 40045-40-7 ]

Reference： [1]European Journal of Medicinal Chemistry,1981,vol. 16,p. 233 - 239

2
[ 112-16-3 ]
[ 29490-19-5 ]
[ 134403-81-9 ]

Yield	Reaction Conditions	Operation in experiment
68%	With triethylamine; In dichloromethane; at 0 - 20℃;	3-Dodecanoyl-5-methyl-1,3,4-thiadiazole-(3H)-2-thione was prepared using the method described by Baczko and Plusquellec (1991). Thus, to a stirred solution of <strong>[29490-19-5]2-mercapto-5-methyl-1,3,4-thiadiazole</strong> (4.74 g, 36 mmol) and triethylamine (5.6 ml) in CH2Cl2 (80 ml) at 0-5 C was added a solution of freshly prepared dodecanoyl chloride (8.75 g, 40 mmol) in CH2Cl2 (40 ml). Stirring was continued overnight, and the reaction mixture subsequently washed successively with 0.5 M HCl (2 × 20 ml), 5% NaHCO3 (3 × 40 ml) and water (2 × 20 ml). The organic phase was dried and the solvent removed under vacuum. The residue was purified by recrystallisation from n-hexane. The crystal structures of two homologues of this series have been published (Low et al., 1999).Yield 68%; mp 50 C; elemental analysis: Anal. % Calcd. for C15H26N2S2O: C 57.26, H 8.34, N 8.91, S 20.40. Found: C 57.62, H 8.10, N 8.98, S 20.44; 1H NMR (CDCl3) delta (ppm): 0.86 (t, 3H, CH3-CH2-R-CO, J = 6.8 Hz), 1.24 (m, 16H alkyl chain), 1.7 (qn, 2H, R-CH2CH2CO, J = 7.5 Hz), 2.42 (s, 3H CH3-C), 2.95 (t, 2H, R-CH2-CH2-CO, J = 7.5 Hz); 13C NMR (CDCl3) delta (ppm): 15.15 (CH3-CH2 alkyl chain), 17.35 (CH3-C thione ring), 23.72-32.94 (alkyl chain), 25.16 (CH2-CH2-CO), 38.87 (CH2-CO), 156.02 (CN), 172.63 (CO), 189.51 (CS); IR upsilon (cm-1) 1753 (CO), 2850-2900 (C-H).

Reference： [1]Tetrahedron Letters,1991,vol. 32,p. 1557 - 1560
[2]Chemistry and Physics of Lipids,2011,vol. 164,p. 118 - 124

3
[ 29490-19-5 ]
[ 957-68-6 ]
[ 30246-33-4 ]

Yield	Reaction Conditions	Operation in experiment
95%	With boron trifluoride dimethyl carbonate complex; acetic acid; at 5 - 10℃;	The boron trifluoride-dimethyl carbonate complex (2.5 mol) was dissolved in 150 ml of dimethyl carbonate, and then 132.26 g (1 mol) of compound II was added. The solution was stirred and dissolved at room temperature, and the temperature was controlled at 5-10 C Add glacial acetic acid (1mol), and then slowly add 7-ACA 299.51g (1.1mol), control at 5-10 for 1-1.5h, transfer to water, adjust the pH to 3.8 with ammonia water, precipitate crystals, and grow. The crystal was crystallized for 1 h, filtered, washed with purified water, and dried under vacuum to obtain compound III327.21g, with a molar yield of 95%, a purity of 99.4%, and a maximum single impurity of 0.08%.
92.1%	With boron trifluoride dimethyl carbonate complex; carbonic acid dimethyl ester; at 20 - 30℃; for 1h;	(1) Add 500 mL of dimethyl carbonate and 9.86 g of 2-hydroxysuccinic acid to a 500 mL three-necked flask, add 4.85 g of MMTD with stirring, and add 10.00 g of 7-ACA.Slowly adding 40.62g of boron trifluoride-dimethyl carbonate complex,The temperature was controlled at 20 to 30 C, and after 1 h, the HPLC monitoring reaction was completed.Add 1.28 g of sodium dithionite, stir for 10 min, transfer to water and add 80 mL of n-butanol, slowly add triethylamine to adjust the pH to 4.5, control the dropping time for 30-60 min, and cool down to 0-10 C for 1 h. The mixture was suction filtered and dried under vacuum to give a crystals of 7-tDA, 11.65 g, yield 92.1%, purity by HPLC, 99.2%, and the maximum amount of 0.10%.

Reference： [1]Patent: CN110563750,2019,A .Location in patent: Paragraph 0024-0032
[2]Patent: CN109651402,2019,A .Location in patent: Page/Page column 6-9
[3]Chemical and Pharmaceutical Bulletin,1985,vol. 33,p. 5534 - 5538
[4]Chemistry Letters,1999,p. 487 - 488
[5]Tetrahedron,1985,vol. 41,p. 5133 - 5139
[6]Pharmazie,1987,vol. 42,p. 160 - 161
[7]Patent: CN105541870,2016,A .Location in patent: Paragraph 0022-0024
[8]Patent: CN108084213,2018,A .Location in patent: Paragraph 0017; 0030-0038
[9]Patent: CN109553630,2019,A .Location in patent: Paragraph 0034; 0035; 0038; 0039; 0042; 0043; 0046; 0047

4
[ 79239-19-3 ]
[ 25953-19-9 ]
[ 29490-19-5 ]
(6R,7R)-3-(5-Methyl-[1,3,4]thiadiazol-2-ylsulfanylmethyl)-8-oxo-7-(2-tetrazol-1-yl-acetylamino)-5-thia-1-aza-bicyclo[4.2.0]oct-3-ene-2-carboxylic acid [ No CAS ]
[ 117929-10-9 ]

Reference： [1]Chemical and Pharmaceutical Bulletin,1996,vol. 44,p. 599 - 601

5
[ 32510-61-5 ]
[ 29490-19-5 ]
[ 25953-19-9 ]

Reference： [1]Tetrahedron Letters,1997,vol. 38,p. 4693 - 4696
[2]Journal of Organic Chemistry,1997,vol. 62,p. 9099 - 9106

6
[ 7496-46-0 ]
[ 29490-19-5 ]
[ 658072-07-2 ]

Reference： [1]Dalton Transactions,2003,p. 4742 - 4748

7
[ 29490-19-5 ]
[ 74-88-4 ]
[ 1925-78-6 ]

Yield	Reaction Conditions	Operation in experiment
60.3%	With potassium hydroxide; In ethanol; at 10 - 20℃;	General procedure: The title compounds were prepared by following the Scheme 1. To a cold solution (10 C) of potassium hydroxide (10 mmol) in absolute ethyl alcohol (50 mL), 5-methyl/amino-1,3,4-thidiazole-2-thiol (5 mmol) was added in small lots. The reaction mixture was stirred and cooled to 10 C followed by the addition of a solution of alkyl iodide/bromide or allyl bromide/benzyl chloride (5.5 mmol) or dibromopropane (2.5 mmol) in ethyl alcohol (20 mL). The reaction mixture was stirred at ambient temperature for 7-8 h and thin layer chromatography was used to monitor the progress of reaction by using the solvent system of 1:1 mixture of hexane and ethyl acetate. The solid product was obtained which was filtered followed bywashing with water and recrystallization from ethanol/water.

Reference： [1]Journal of Medicinal Chemistry,2004,vol. 47,p. 5567 - 5578
[2]Journal of Molecular Structure,2020,vol. 1219

8
[ 638-07-3 ]
[ 29490-19-5 ]
[ 877052-29-4 ]

Yield	Reaction Conditions	Operation in experiment
81%	With potassium carbonate; In N,N-dimethyl-formamide; at 60℃; for 2h;Inert atmosphere;	To a solution of 5-methyl-l,3,4-thiadiazole-2-thiol (10.0 g, 75.6 mmol) and ethyl 4-chloro-3-oxobutanoate (14.9 g, 90.5 mmol) in DMF (100 mL) was added K2CO3 (15.7 g, 113.6 mmol) at room temperature. The reaction mixture was heated at 60 C under nitrogen atmosphere for 2 h at which time it was cooled and diluted with CH2CI2 (500 mL) and washed with brine (250 mL x 3). The separated organic phase was dried over anhydrous Na2S04, filtered and concentrated under vacuum. The residue was purified by silica gel column chromatography, eluting with p-ether and ethyl acetate (10 : 1 to 1 : 1) to afford ethyl 4- [(5 -methyl- 1,3,4- thiadiazol-2-yl)sulfanyl]-3-oxobutanoate (16 g, 61 mmol, yield 81%) as an off-white solid: LCMS (ESI) calc'd C9H12N2O3S2 for [M+H]+: 261, found 261; NMR (300 MHz, DMSO-^e) delta ppm 4.47 (s, 2H), 4.10 (q, J= 7.1 Hz, 2H), 3.79 (s, 2H), 2.67 (s, 3H), 1.19 (t, J= 7.1 Hz, 3H).

Reference： [1]Patent: WO2019/55540,2019,A1 .Location in patent: Paragraph 0203
[2]Russian Journal of General Chemistry,2005,vol. 75,p. 303 - 310

9
[ 49619-82-1 ]
[ 29490-19-5 ]
3-[(5-methyl-1,3,4-thiadiazol-2-yl)sulfanyl]-4H-1-benzopyran-4-one [ No CAS ]

Reference： [1]Bioorganic and Medicinal Chemistry,2007,vol. 15,p. 5191 - 5197

10
2,6-Dichloro-7-methylsulfanyl-3-trifluoromethylquinoxaline [ No CAS ]
[ 29490-19-5 ]
[ 281210-17-1 ]

Yield	Reaction Conditions	Operation in experiment
50%	With potassium carbonate; In DMF (N,N-dimethyl-formamide); at 50℃; for 2h;	2,6-Dichloro-7-methylsulfanyl-3-trifluoromethylquinoxaline (116 mg, 0.37 mmol, prepared similarly as described above from 6-chloro-7-methylsulfanyl-3-trifluoromethyl-1H-quinoxaline-2-one, dimethylaminopyridine and POCl3) and <strong>[29490-19-5]2-mercapto-5-methyl-1,3,4-thiadiazole</strong> (146 mg, 1.1 mmol) was dissolved in DMF (3.3 ml). Potassium carbonate (20 mg) was added and the reaction mixture was stirred at 50 C. for 2 hours. The cooled mixture was partitioned between diethyl ether and water. The organic layer separated, evaporated and the residue recrystallised from ethanol to afford 80 mg (50%) of the title compound as a yellow solid.1H NMR (CDCl3): delta 2.64 (s, 3H), 2.92 (s, 3H), 7.50 (s, 1H), 8.15 (s, 1H).MS (APCI (M+H)+) m/z 409.

Reference： [1]Patent: US6927214,2005,B1 .Location in patent: Page/Page column 99

11
[ 281210-25-1 ]
[ 29490-19-5 ]
[ 281210-26-2 ]

Yield	Reaction Conditions	Operation in experiment
27%	With cesium fluoride; In DMF (N,N-dimethyl-formamide); at 20℃; for 16h;	A mixture of (3-bromo-2-trifluoromethylquinoxalin-6-yl)phenyl methanone (144 mg, 0.299 mmol), 2-mercapto-5 methylthiadiazole (38 mg, 0.28 mmol) and caesium fluoride (55 mg, 0.36 mmol) in DMF (1.5 ml) was stirred for 16 hours at room temperature. The reaction mixture was purified by preparative HPLC (Gilson) to yield 35 mg (27%) of the title compound as a pale yellow solid.M.p. 176-9 C. 1H NMR (DMSO-d6): delta 2.82(s, 3H) 7.57-7.88 (m, 1H), 8.19 (dd, 5H), 8.30 (d, 1H), 8.43 (d, 1H).

Reference： [1]Patent: US6927214,2005,B1 .Location in patent: Page/Page column 103

12
[ 281210-31-9 ]
[ 29490-19-5 ]
[ 281210-32-0 ]

Yield	Reaction Conditions	Operation in experiment
38%	With cesium fluoride; In DMF (N,N-dimethyl-formamide); at 20℃; for 16h;	A mixture of (2-bromo-3-trifluoromethylquinoxalin-6-yl)phenyl methanone (100 mg, 0.263 mmol), 2-mercapto-5-methylthiadiazole (40 mg, 0.30 mmol) and caesium fluoride (54 mg, 0.36 mmol) in 1.0 ml of DMF was stirred for 16 hours at room temperature. The reaction mixture was purified by preparative HPLC (Gilson) to yield 44 mg (38%) of the title compound as a pale yellow solid.M.p. 160-2 C. 1H NMR (DMSO-d6): delta 2.78(s, 3H) 7.60-7.90 (m, 5H), 8.25 (d, 1H), 8.38 (dd, 1H), 8.44 (d, 1H).Analysis: Calculated for C19H11F3N4O1S2: C, 52.77; H, 2.56; N, 12.96%. Found: C, 52.56; H, 2.51; N, 12.89%.

Reference： [1]Patent: US6927214,2005,B1 .Location in patent: Page/Page column 105-106

13
[ 694-05-3 ]
[ 91-21-4 ]
[ 38521-46-9 ]
[ 61607-68-9 ]
[ 34803-66-2 ]
C₂₃H₁₉BrNO₂Pol [ No CAS ]
[ 20980-22-7 ]
[ 40481-13-8 ]
[ 6325-91-3 ]
[ 38026-46-9 ]
[ 37052-78-1 ]
[ 2637-37-8 ]
[ 64415-07-2 ]
[ 57658-36-3 ]
[ 34272-64-5 ]
[ 29490-19-5 ]
[ 24854-43-1 ]
[ 2252-63-3 ]
[ 6670-13-9 ]
[ 131242-36-9 ]
[ 35071-17-1 ]
[ 13906-09-7 ]
[ 2349-58-8 ]
[ 6640-24-0 ]
[ 51639-48-6 ]
C₂₈H₂₇N₂O₂Pol [ No CAS ]
C₂₇H₂₂N₃O₂PolS [ No CAS ]
C₂₆H₂₃N₄O₂PolS [ No CAS ]
C₂₆H₂₂N₃O₂PolS₂ [ No CAS ]
C₂₈H₂₄N₃O₂PolS [ No CAS ]
C₃₂H₂₅N₂O₂PolS [ No CAS ]
C₂₉H₂₃N₂O₄PolS [ No CAS ]
C₂₈H₂₉N₆O₂PolS [ No CAS ]
C₃₂H₂₉N₂O₂Pol [ No CAS ]
C₂₆H₂₂N₅O₄PolS [ No CAS ]
C₃₂H₃₁N₄O₂Pol [ No CAS ]
C₃₁H₃₀N₅O₂Pol [ No CAS ]
C₃₁H₂₆N₃O₃PolS [ No CAS ]
C₃₁H₂₄N₃O₃PolS [ No CAS ]
C₂₉H₂₅N₂O₄PolS₂ [ No CAS ]
C₃₃H₃₁FN₃O₂Pol [ No CAS ]
C₃₀H₂₆N₃O₅PolS [ No CAS ]
C₃₀H₂₃N₄O₄PolS [ No CAS ]
C₃₅H₃₂N₃O₂Pol [ No CAS ]
C₃₃H₃₁ClN₃O₂Pol [ No CAS ]
C₃₈H₂₉N₂O₃PolS [ No CAS ]
C₃₃H₂₄F₃N₂O₂PolS [ No CAS ]
C₃₅H₃₄N₃O₃Pol [ No CAS ]
C₃₈H₃₀N₃O₂PolS [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	With N-ethyl-N,N-diisopropylamine; In 1-methyl-pyrrolidin-2-one; for 20h;Combinatorial reaction / High throughput screening (HTS);	Each resin from Step 3 was distributed into 24 fritted syringes (Torvig, 50 mg each, 50 mumol), for a total of 96 syringes, and was swelled in NMP (1 mL) for 30 min. The solvent was removed by filtration. Twenty-four solutions of the building blocks listed below (10 mmol each) and DIBA (3.5 mL, 20 mmol) in NMP (10 mL) were prepared. 3 mL of the 24 solutions was added to the 24 syringes for each resin from Step 3, accordingly. The suspensions were then shaken for 20 h on a Titer Plate Shaker. The reaction mixture was filtered and washed 5 times with methylene chloride (5 mL), 3 times with THF (5 mL), 3 times THF/H2O (3/1 v/v, 5 mL), and 3 times with THF (5 mL). The resins were then dried overnight under vacuum.

Reference： [1]Patent: US2006/167057,2006,A1 .Location in patent: Page/Page column 80-82

14
[ 694-05-3 ]
[ 91-21-4 ]
[ 38521-46-9 ]
[ 61607-68-9 ]
[ 34803-66-2 ]
C₂₂H₁₈BrN₂O₂Pol [ No CAS ]
[ 20980-22-7 ]
[ 40481-13-8 ]
[ 6325-91-3 ]
[ 38026-46-9 ]
[ 37052-78-1 ]
[ 2637-37-8 ]
[ 64415-07-2 ]
[ 57658-36-3 ]
[ 34272-64-5 ]
[ 29490-19-5 ]
[ 24854-43-1 ]
[ 2252-63-3 ]
[ 6670-13-9 ]
[ 131242-36-9 ]
[ 35071-17-1 ]
[ 13906-09-7 ]
[ 2349-58-8 ]
[ 6640-24-0 ]
[ 51639-48-6 ]
C₂₇H₂₆N₃O₂Pol [ No CAS ]
C₂₆H₂₁N₄O₂PolS [ No CAS ]
C₂₅H₂₂N₅O₂PolS [ No CAS ]
C₂₅H₂₁N₄O₂PolS₂ [ No CAS ]
C₂₇H₂₃N₄O₂PolS [ No CAS ]
C₃₁H₂₄N₃O₂PolS [ No CAS ]
C₂₈H₂₂N₃O₄PolS [ No CAS ]
C₂₇H₂₈N₇O₂PolS [ No CAS ]
C₃₁H₂₈N₃O₂Pol [ No CAS ]
C₂₅H₂₁N₆O₄PolS [ No CAS ]
C₃₁H₃₀N₅O₂Pol [ No CAS ]
C₃₀H₂₅N₄O₃PolS [ No CAS ]
C₃₀H₂₉N₆O₂Pol [ No CAS ]
C₃₀H₂₃N₄O₃PolS [ No CAS ]
C₃₂H₃₀ClN₄O₂Pol [ No CAS ]
C₂₉H₂₂N₅O₄PolS [ No CAS ]
C₂₈H₂₄N₃O₄PolS₂ [ No CAS ]
C₂₉H₂₅N₄O₅PolS [ No CAS ]
C₃₂H₃₀FN₄O₂Pol [ No CAS ]
C₃₄H₃₁N₄O₂Pol [ No CAS ]
C₃₄H₃₃N₄O₃Pol [ No CAS ]
C₃₂H₂₃F₃N₃O₂PolS [ No CAS ]
C₃₇H₂₈N₃O₃PolS [ No CAS ]
C₃₇H₂₉N₄O₂PolS [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	With N-ethyl-N,N-diisopropylamine; In 1-methyl-pyrrolidin-2-one; for 20h;Combinatorial reaction / High throughput screening (HTS);	Each resin from Step 3 was distributed into 24 fritted syringes (Torvig, 50 mg each, 50 mumol), for a total of 96 syringes, and was swelled in NMP (1 mL) for 30 min. The solvent was removed by filtration. Twenty-four solutions of the building blocks listed below (10 mmol each) and DIBA (3.5 mL, 20 mmol) in NMP (10 mL) were prepared. 3 mL of the 24 solutions was added to the 24 syringes for each resin from Step 3, accordingly. The suspensions were then shaken for 20 h on a Titer Plate Shaker. The reaction mixture was filtered and washed 5 times with methylene chloride (5 mL), 3 times with THF (5 mL), 3 times THF/H2O (3/1 v/v, 5 mL), and 3 times with THF (5 mL). The resins were then dried overnight under vacuum.

Reference： [1]Patent: US2006/167057,2006,A1 .Location in patent: Page/Page column 80-82

15
[ 694-05-3 ]
[ 91-21-4 ]
[ 38521-46-9 ]
[ 61607-68-9 ]
[ 34803-66-2 ]
C₂₉H₂₃BrNO₂Pol [ No CAS ]
[ 20980-22-7 ]
[ 40481-13-8 ]
[ 6325-91-3 ]
[ 38026-46-9 ]
[ 37052-78-1 ]
[ 2637-37-8 ]
[ 64415-07-2 ]
[ 57658-36-3 ]
[ 34272-64-5 ]
[ 29490-19-5 ]
[ 24854-43-1 ]
[ 2252-63-3 ]
[ 6670-13-9 ]
[ 131242-36-9 ]
[ 35071-17-1 ]
[ 13906-09-7 ]
[ 2349-58-8 ]
[ 6640-24-0 ]
[ 51639-48-6 ]
C₃₃H₂₆N₃O₂PolS [ No CAS ]
C₃₄H₃₁N₂O₂Pol [ No CAS ]
C₃₂H₂₇N₄O₂PolS [ No CAS ]
C₃₄H₂₈N₃O₂PolS [ No CAS ]
C₃₂H₂₆N₃O₂PolS₂ [ No CAS ]
C₃₈H₂₉N₂O₂PolS [ No CAS ]
C₃₅H₂₇N₂O₄PolS [ No CAS ]
C₃₈H₃₃N₂O₂Pol [ No CAS ]
C₃₄H₃₃N₆O₂PolS [ No CAS ]
C₃₂H₂₆N₅O₄PolS [ No CAS ]
C₃₇H₂₈N₃O₃PolS [ No CAS ]
C₃₈H₃₅N₄O₂Pol [ No CAS ]
C₃₇H₃₄N₅O₂Pol [ No CAS ]
C₃₇H₃₀N₃O₃PolS [ No CAS ]
C₃₅H₂₉N₂O₄PolS₂ [ No CAS ]
C₃₆H₂₇N₄O₄PolS [ No CAS ]
C₃₆H₃₀N₃O₅PolS [ No CAS ]
C₄₁H₃₆N₃O₂Pol [ No CAS ]
C₃₉H₃₅FN₃O₂Pol [ No CAS ]
C₃₉H₃₅ClN₃O₂Pol [ No CAS ]
C₃₉H₂₈F₃N₂O₂PolS [ No CAS ]
C₄₄H₃₃N₂O₃PolS [ No CAS ]
C₄₁H₃₈N₃O₃Pol [ No CAS ]
C₄₄H₃₄N₃O₂PolS [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	With N-ethyl-N,N-diisopropylamine; In 1-methyl-pyrrolidin-2-one; for 20h;Combinatorial reaction / High throughput screening (HTS);	Each resin from Step 3 was distributed into 24 fritted syringes (Torvig, 50 mg each, 50 mumol), for a total of 96 syringes, and was swelled in NMP (1 mL) for 30 min. The solvent was removed by filtration. Twenty-four solutions of the building blocks listed below (10 mmol each) and DIBA (3.5 mL, 20 mmol) in NMP (10 mL) were prepared. 3 mL of the 24 solutions was added to the 24 syringes for each resin from Step 3, accordingly. The suspensions were then shaken for 20 h on a Titer Plate Shaker. The reaction mixture was filtered and washed 5 times with methylene chloride (5 mL), 3 times with THF (5 mL), 3 times THF/H2O (3/1 v/v, 5 mL), and 3 times with THF (5 mL). The resins were then dried overnight under vacuum.

Reference： [1]Patent: US2006/167057,2006,A1 .Location in patent: Page/Page column 80-82

16
[ 694-05-3 ]
[ 91-21-4 ]
[ 38521-46-9 ]
[ 61607-68-9 ]
[ 34803-66-2 ]
C₂₉H₂₃ClNO₂Pol [ No CAS ]
[ 20980-22-7 ]
[ 40481-13-8 ]
[ 6325-91-3 ]
[ 38026-46-9 ]
[ 37052-78-1 ]
[ 2637-37-8 ]
[ 64415-07-2 ]
[ 57658-36-3 ]
[ 34272-64-5 ]
[ 29490-19-5 ]
[ 24854-43-1 ]
[ 2252-63-3 ]
[ 6670-13-9 ]
[ 131242-36-9 ]
[ 35071-17-1 ]
[ 13906-09-7 ]
[ 2349-58-8 ]
[ 6640-24-0 ]
[ 51639-48-6 ]
C₃₃H₂₆N₃O₂PolS [ No CAS ]
C₃₄H₃₁N₂O₂Pol [ No CAS ]
C₃₂H₂₇N₄O₂PolS [ No CAS ]
C₃₄H₂₈N₃O₂PolS [ No CAS ]
C₃₂H₂₆N₃O₂PolS₂ [ No CAS ]
C₃₈H₂₉N₂O₂PolS [ No CAS ]
C₃₅H₂₇N₂O₄PolS [ No CAS ]
C₃₄H₃₃N₆O₂PolS [ No CAS ]
C₃₈H₃₃N₂O₂Pol [ No CAS ]
C₃₂H₂₆N₅O₄PolS [ No CAS ]
C₃₇H₃₀N₃O₃PolS [ No CAS ]
C₃₇H₃₄N₅O₂Pol [ No CAS ]
C₃₈H₃₅N₄O₂Pol [ No CAS ]
C₃₇H₂₈N₃O₃PolS [ No CAS ]
C₃₅H₂₉N₂O₄PolS₂ [ No CAS ]
C₃₆H₂₇N₄O₄PolS [ No CAS ]
C₃₉H₃₅FN₃O₂Pol [ No CAS ]
C₃₆H₃₀N₃O₅PolS [ No CAS ]
C₃₉H₃₅ClN₃O₂Pol [ No CAS ]
C₄₁H₃₆N₃O₂Pol [ No CAS ]
C₃₉H₂₈F₃N₂O₂PolS [ No CAS ]
C₄₄H₃₃N₂O₃PolS [ No CAS ]
C₄₁H₃₈N₃O₃Pol [ No CAS ]
C₄₄H₃₄N₃O₂PolS [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	With N-ethyl-N,N-diisopropylamine; In 1-methyl-pyrrolidin-2-one; for 20h;Combinatorial reaction / High throughput screening (HTS);	Each resin from Step 3 was distributed into 24 fritted syringes (Torvig, 50 mg each, 50 mumol), for a total of 96 syringes, and was swelled in NMP (1 mL) for 30 min. The solvent was removed by filtration. Twenty-four solutions of the building blocks listed below (10 mmol each) and DIBA (3.5 mL, 20 mmol) in NMP (10 mL) were prepared. 3 mL of the 24 solutions was added to the 24 syringes for each resin from Step 3, accordingly. The suspensions were then shaken for 20 h on a Titer Plate Shaker. The reaction mixture was filtered and washed 5 times with methylene chloride (5 mL), 3 times with THF (5 mL), 3 times THF/H2O (3/1 v/v, 5 mL), and 3 times with THF (5 mL). The resins were then dried overnight under vacuum.

Reference： [1]Patent: US2006/167057,2006,A1 .Location in patent: Page/Page column 80-82

17
[ 29490-19-5 ]
[ 81-07-2 ]
[ 81589-00-6 ]

Yield	Reaction Conditions	Operation in experiment
91.3%	With 1,1,1,3,3,3-hexamethyl-disilazane; In toluene;	(a) 15.6 ml (0.075 mmole) of hexamethyldisilazane were added to a refluxing solution of 13.2 g (0.1 mole) of 5-mercapto-2-methyl-1,3,4-thiadiazole and 92 mg (0.5 mole) of saccharin in 25 ml of toluene and the reaction was completed after 30 minutes. Toluene was removed by distillation at normal pressure and the residue was vacuum distilled to obtain 18.63 g (91.3% yield) of 2-methyl-5-trimethylsilylthio-1,3,4-thiadiazole with a boiling point of 150-152 C. at 15 mg Hg and the distillate solidified to a solid melting at 67-69 C.

Reference： [1]Patent: US4379923,1983,A

18
[ 29490-19-5 ]
3-acetoxymethyl-7-aminoceph-3-em-4-carboxylic acid [ No CAS ]
[ 30246-33-4 ]

Yield	Reaction Conditions	Operation in experiment
96%	With boric acid; triethylamine; In water;	EXAMPLE 2 7-amino-3[(5-methyl-1,3,4-thiadiazol-2-yl)thiomethyl]-3-cephem-4-carboxylic acid (7-ACA-TD) A suspension of 40 g (0.30 mole) of <strong>[29490-19-5]2-mercapto-5-methyl-1,3,4-thiadiazole</strong> (TD) in 3.15 liters of water, with 30 g of boric acid and 30.4 ml ( 0.217 mole) of triethylamine was heated to 70/72 C. While the mixture was being vigorously stirred, at the same temperature, one 40 g shot (0.147 mole) of 7-amino-3-acetoxymethyl-3-cephem-4-carboxylic acid (92%) was added. The resulting solution, with a reaction isoelectric pH of 4.98, dropped to 4.92 (71-72 C.) and was stirred for 60 min. The precipitation started after 6 to 8 min and the isoelectric pH evolved to a value of 5.3. Thereafter it was cooled to 50 C. and the pH was adjusted to 4.8 with 1N hydrochloric acid ( 15.2 ml in all) and was finally readjusted at 20 C. After cooling to 5-10 C. for 15 min, the solid was isolated by filtration, washed successively with water and acetone and after drying at 40 C., it gave 46.0 g of the compound of the title, with a 97% yield, 96% purity (determined by the usual methods) and a melting point of 225 C. with decomposition. IR (KBr)nu: 1802 (beta-lactam), 1618 (carboxylate), 1543 (NH3+, broad) cm-1. 1 H-NMR (F3 CCOOH)delta ppm: 2,76 (3H,s,CH3); 3,50 (2H,s,H-2); 4,37 (2H,c,CH2 S; J=15,0 Hz); 5,05 (2H,s, H-6, H-7).
	In water; acetone;	EXAMPLE 7 3-[[(5-methyl-1,3,4-thiadiazol-2-yl)thio]methyl]-7-amino-8-oxo-5-thia-1-azabicyclo[4.2.0]oct-2-ene-2-carboxylic acid A mixture of 13.6 g. (0.5 M) of 7-aminocephalosporanic acid (7-ACA) in 100 ml. of water and 50 ml. of acetone are brought to pH 8 with sodium hydroxide while stirring. 9.8 g. (0.57 M) of 2-methyl-1,3,4-thiadiazole-5-thiol are added and the mixture is heated at 80 for 4 hours. After cooling to 5, this is acidified to pH 3.5 with dilute hydrochloric acid and stirred for 15 minutes. The precipitated solid is filtered under suction and washed with acetone. This 3-[[(5-methyl-1,3,4-thiadiazol-2-yl)thio]-methyl]-7-amino-8-oxo-5-thia-1-azabicyclo[4.2.0]oct-2-ene-2-carboxylic acid is purified by dissolving in sodium bicarbonate solution and reprecipitating with 2N hydrochloric acid; yield 12.7 g., m.p. 206.
	In water; acetone;	EXAMPLE 19 3-[[(5-Methyl-1,3,4-thiadiazol-2-yl)thio]methyl]-7-amino-8-oxo-5-thia-1-azabicyclo[4.2.0]oct-2-ene-2-carboxylic acid A mixture of 13.6 g. (0.5 M) of 7-aminocephalosporanic acid (7-ACA) in 100 ml. of water and 50 ml. of acetone are brought to pH 8 with sodium hydroxide while stirring. 9.8 g. (0.57 M) of 2-methyl-1,3,4-thiadiazole-5-thiol are added and the mixture is heated at 80 for four hours. After cooling to 5, this is acidified to pH 3.5 with dilute hydrochloric acid and stirred for 15 minutes. The precipitated solid is filtered under suction and washed with acetone. This 3-[[(5-methyl-1,3,4-thiadiazol-2-yl)thio]-methyl]-7-amino-8-oxo-5-thia-1-azabicyclo[4.2.0]oct-2-ene-2-carboxylic acid is purified by dissolving in sodium bicarbonate solution and reprecipitating with 2N hydrochloric acid; yield 12.7 g., m.p. 206.

	In water; acetone;	EXAMPLE 4 3-[[(5-Methyl-1,3,4-thiadiazol-2-yl)thio]methyl]-7-amino-8-oxo-5-thia-1-azabicyclo[4.2.0]oct-2-ene-2-carboxylic acid A mixture of 13.6 g. (0.5 M) of 7-aminocephalosporanic acid (7-ACA) in 100 ml. of water and 50 ml. of acetone are brought to pH 8 with sodium hydroxide while stirring. 9.8 g. (0.57 M) of 2-methyl-1,3,4-thiadiazole-5-thiol are added and the mixture is heated at 80 for 4 hours. After cooling to 5, this is acidified to pH 3.5 with dilute hydrochloric acid and stirred for 15 minutes. The precipitated solid is filtered under suction and washed with acetone. This 3-[[(5-methyl-1,3,4-thiadiazol-2-yl)thio]methyl]-7-amino-8-oxo-5-thia-1-azabicyclo[4.2.0]oct-2-ene-2-carboxylic acid is purified by dissolving in sodium bicarbonate solution and reprecipitating with 2N hydrochloric acid; yield 12.7 g., m.p. 206.
	In water; acetone;	EXAMPLE 1 3-[[(5-methyl-1,3,4-thiadiazol-2-yl)thio]methyl]-7-amino-8-oxo-5-thia-1-azabicyclo[4.2.0]oct-2-ene-2-carboxylic acid A mixture of 13.6 g. (0.05 M) of 7-aminocephalosporanic acid (7-ACA) in 100 ml. of water and 50 ml. of acetone are brought to pH 8 with sodium hydroxide while stirring. 7.5 g. (0.057 M) of 2-methyl-1,3,4-thiadiazole-5-thiol are added and the mixture is heated at 80 for four hours. After cooling to 5, this is acidified to pH 3.5 with dilute hydrochloric acid and stirred for 15 minutes. The precipitated solid is filtered under suction and washed with acetone. This 3-[[(5-methyl-1,3,4-thiadiazol-2-yl)thio]methyl]-7-amino-8-oxo-5-thia-1-azabicyclo[4.2.0]oct-2-ene-2-carboxylic acid is purified by dissolving in sodium bicarbonate solution and reprecipitating with 2N hydrochloric acid; yield 12.7 g., m.p. 206.
	In water; acetone;	EXAMPLE 7 3-[[(5-Methyl-1,3,4-thiadiazole-2-yl)thio]methyl]-7-amino-8-oxo-5-thia-1-azabicyclo[4.2.0]oct-2-ene-2-carboxylic acid A mixture of 13.6 g. (0.05 M) of 7-aminocephalosporanic acid in 100 ml. of water and 50 ml. of acetone are brought to pH 8 with sodium hydroxide while stirring. 9.8 g. (0.57 M) of 2-methyl-1,3,4-thiadiazole-5-thiol are added and the mixture is heated at 80 for 4 hours. After cooling to 5, this is acidified to pH 3.5 with dilute hydrochloric acid and stirred for 15 minutes. The precipitated solid is filtered under suction and washed with acetone. This 3 -[[(5-methyl-1,3,4-thiadiazol-2-yl)thio]methyl]-7-amino-8-oxo-5-thia-1-azabicyclo[4.2.0]oct-2-ene-2-carboxylic acid is purified by dissolving in sodium bicarbonate solution and reprecipitating with 2N hydrochloric acid; yield 12.7 g., m.p. 206.

Reference： [1]Patent: US4481357,1984,A
[2]Patent: US3931170,1976,A
[3]Patent: US4003893,1977,A
[4]Patent: US3960850,1976,A
[5]Patent: US3996219,1976,A
[6]Patent: US3978050,1976,A

19
[ 3855-09-2 ]
[ 29490-19-5 ]
[ 30246-33-4 ]

Yield	Reaction Conditions	Operation in experiment
	With sodium hydrogencarbonate; In water;	EXAMPLE 12 3-[(2-Methyl-1,3,4-thiadiazol-5-ylthio)methyl]-7-amino-8-oxo-5-thia-1-azabicyclo[4,2,0]oct-2-ene-2-carboxylic acid In about 1 liter of water is dissolved 0.1 mole of the sodium salt of 3-[(acetyloxy)methyl]-7-amino-8-oxo-5-thia-1-azabicyclo[4.2.0]oct-2-ene-2-carboxylic acid at 70C under nitrogen atmosphere. To the solution is added 1 equivalent of sodium bicarbonate and 2 equivalents of 2-methyl-1,3,4-thiadiazol-5-ylthiol. The mixture is stirred at 70C for 3 hours after which the pH is adjusted to 3.5, and the resulting precipitate collected giving 3-[(2-methyl-1,3,4-thiadiazol-5-ylthio)methyl]-7-amino-8-oxo-5-thia-1-azabicyclo[4.2.0]oct-2-ene-2-carboxylic acid.
	With sodium hydrogencarbonate; In water;	EXAMPLE 12 3[(2-Methyl-1,3,4-thiadiazol-5-ylthio)methyl]-7-amino-8-oxo-5-thia-1-azabicyclo[4.2.0]oct-2-ene-2-carboxylic acid In about 1 liter of water is dissolved 0.1 mole of the sodium salt of 3-[(acetyloxy)methyl]-7-amino-8-oxo-5-thia-1-azabicyclo[4.2.0]oct-2-ene-2-carboxylic acid at 70 C. under nitrogen atmosphere. To the solutionis added 1 equivalent of sodium bicarbonate and 2 equivalents of 2-methyl-1,3,4-thiadiazol-5-ylthiol. The mixture is stirred at 70 C. for 3 hours after which the pH is adjusted to 3.5, and the resulting precipitate collected giving 3-[(2-methyl-1,3,4-thiadiazol-5-ylthio)methyl]-7-amino-8-oxo-5-thia-1-azabicyclo[4.2.0]oct-2-ene-2-carboxylic acid.
	With sodium hydrogencarbonate; In water;	EXAMPLE 12 3-[(2-Methyl-1,3,4-thiadiazol-5-ylthio)methyl]-7-amino-8-oxo-5-thia-1-azabicyclo[4,2,0]oct-2-ene-2-carboxylic acid In about 1 liter of water is dissolved 0.1 mole of the sodium salt of 3-[(acetyloxy)methyl]-7-amino-8-oxo-5-thia-1-azabicyclo[4.2.0]oct-2-ene-2-carboxylic acid at 70 C under nitrogen atmosphere. To the solution is added 1 equivalent of sodium bicarbonate and 2 equivalents of 2-methyl-1,3,4-thiadiazol-5-ylthiol. The mixture is stirred at 70 C for 3 hours after which the pH is adjusted to 3.5, and the resulting precipitate collected giving 3-[(2-methyl-1,3,4-thiadiazol-5-ylthio)methyl]-7-amino-8-oxo-5-thia-1-azabicyclo[4.2.0]oct-2-ene-2-carboxylic acid.

With sodium hydrogencarbonate; In water;

EXAMPLE 12 3-[(2-Methyl-1,3,4-thiadiazol-5-ylthio)methyl]-7-amino-8-oxo-5-thia-1-azabicyclo[4,2,0]oct-2-ene-2-carboxylic acid In about 1 liter of water is dissolved 0.1 mole of the sodium salt of 3-[(acetyloxy)methyl]-7-amino-8-oxo-5-thia-1-azabicyclo[4.2.0]oct-2-ene-2-carboxylic acid at 70 C. under nitrogen atmosphere. To the solution is added 1 equivalent of sodium bicarbonate and 2 equivalents of 2-methyl-1,3,4-thiadiazol-5-ylthiol. The mixture is stirred at 70 C. for 3 hours after which the pH is adjusted to 3.5, and the resulting precipitate collected giving 3-[(2-methyl-1,3,4-thiadiazol-5-ylthio)methyl]-7-amino-8-oxo-5-thia-1-azabicyclo[4.2.0]oct-2-ene-2-carboxylic acid. When in the above procedure an equivalent amount of 1,3,4-thiadiazol-5-ylthiol, 3-methyl-1,2,4-thiadiazol-5-ylthiol, tetrazol-5-ylthiol, 1-methyltetrazol-5-ylthiol or 2-methyl-1,3,4,-oxadiazol-5-ylthiol is substituted for 2-methyl-1,3,4-thiadiazol-5-ylthiol the following respective products are obtained:

Reference： [1]Patent: US3948904,1976,A
[2]Patent: US4026887,1977,A
[3]Patent: US4031083,1977,A
[4]Patent: US4045438,1977,A

20
[ 10025-83-9 ]
[ 29490-19-5 ]
Ir⁽³⁺⁾*C₂N₂S(SH)CH₃*3Cl^(1-)*H₂O=Ir(C₂N₂S(SH)CH₃)Cl₃*H₂O [ No CAS ]

Reference： [1]Polyhedron,1986,vol. 5,p. 1927 - 1930
[2]Polyhedron,1986,vol. 5,p. 1927 - 1930

21
[ 27721-02-4 ]
silver nitrate [ No CAS ]
[ 29490-19-5 ]
[silver(I)(μ-1,5-bis(diphenylphosphino)pentane)(5-methyl-1,3,4-thiadiazole-2-thione)(nitrate)]n [ No CAS ]

Reference： [1]Polyhedron,2005,vol. 24,p. 853 - 863

22
[ 5122-82-7 ]
[ 29490-19-5 ]
[ 393128-76-2 ]

Yield	Reaction Conditions	Operation in experiment
87%	With triethylamine; In acetonitrile; at 20℃;	To a solution of adamantan-1-yl bromomethyl ketone (643 mg, 2.5 mmol) in acetonitrile (20 mL) was added 5-methyl-l,3,4-thiadiazole-2-thiol (331 mg, 2.5 mmol), followed by triethylamine (1 mL). The mixture was stirred at ambient temperature overnight, partitioned between ethyl acetate and saturated sodium carbonate. The organic phase was washed with brine, dried over MgSO4 and concentrated in vacuo. Purification with flash <n="98"/>column (DCM-ethyl acetate; gradient elution) yielded the title compound as white solid (670 mg, 87 %). mp 102-105 C; TLC single spot at Rf. 0.37 (8 % EtOAc/DCM); 1H NMR (270 MHz, CDCl3) delta 1.65-1.80 (6H, m, 3 x CH2), 1.90 (6H, d, J = 2.8 Hz, 3 x CH2), 2.06 (3H, br, 3 x CH), 2.69 (3H, s, CH3) and 4.48 (2H, s, CH2); LC/MS (ESI) m/z 309 (M++H); tr = 2.58 min in 10 % water-methanol; HRMS (ESI) calcd. for C15H20N2OS2Na (MVNa) 331.0915, found 331.0873; HPLC tr = 2.67 min (>99 %) in 10% water-acetonitrile.

Reference： [1]ChemMedChem,2011,vol. 6,p. 1439 - 1451
[2]Patent: WO2009/106817,2009,A2 .Location in patent: Page/Page column 95-96

23
[ 5460-29-7 ]
[ 29490-19-5 ]
[ 511304-52-2 ]

Yield	Reaction Conditions	Operation in experiment
99%	With potassium carbonate; In N,N-dimethyl-formamide; at 90℃; for 6h;Inert atmosphere;	General procerure: To a suspension of mercaptan substituent heterocyclic in DMF, one equivalent of N-(3-bromopropyl) phthalimide and K2CO3 (1 equivalent) were added. The reaction was stirred for 6 h at 90 C before cooled to room temperature. After evaporation of the DMF under vacuum, the residue was diluted with methylene chloride, washed with water and brine, and dried over MgSO4. After evaporation of the solution, the crude products were purified by column chromatography eluting with 2.5:1 petroleum ether/acetone to afford the desired products as yellow or white solid.

Reference： [1]European Journal of Medicinal Chemistry,2011,vol. 46,p. 208 - 217

24
[ 29490-19-5 ]
[ 56899-24-2 ]
[ 1314803-53-6 ]

Yield	Reaction Conditions	Operation in experiment
70%		General procedure: NaH (2 or 4 equiv) was added to a suspension of heterocycle (2 equiv) in DMF and the mixture was stirred at room temperature for 1 h. Dibromide (1 equiv) in DMF was dropped and contents were stirred at room temperature until the consumption of the dibromide on TLC plates (6-12 h). The solvent was removed in a vacuum and the residue was treated with CHCl3, filtered, concentrated and subjected to column chromatography on SiO2.

Reference： [1]Russian Journal of Organic Chemistry,2011,vol. 47,p. 746 - 752
[2]Tetrahedron,2011,vol. 67,p. 7370 - 7378

25
[ 13745-86-3 ]
[ 29490-19-5 ]
[ 1345730-56-4 ]

Reference： [1]Indian Journal of Chemistry - Section B Organic and Medicinal Chemistry,2011,vol. 50,p. 1196 - 1201

26
[ 70-11-1 ]
[ 29490-19-5 ]
[ 245106-56-3 ]

Yield	Reaction Conditions	Operation in experiment
88%		General procedure: In a two-necked flask, 5-methyl-1,3,4-thiadiazole-2-thiol (1) (0.06 mol; 7.93 g) and KOH (0.06 mol; 0.336 g) were dissolved in absolute ethanol (100 mL) and the solution was stirred for 30min at room temperature. Phenacyl bromide derivative (2a-d) (0.06 mol) was dissolved in absolute ethanol (50 mL) and added dropwise to this solution at room temperature with the assistance of a dropping funnel. The mixture was then refluxed and stirred for 4-6 h. The progress of the reaction was monitored by TLC at appropriate time intervals. After completion of the reaction, the solution was filtered and recrystallized from the ethanol. The synthesized compounds were dried with P2O5 in a vacuum oven. 4.2.1 2-((5-Methyl-1,3,4-thiadiazol-2-yl)thio)-1-phenylethanone (3a)32 Yield: 13.21g (88%), m.p. 86-87C (from EtOH). (lit32 m.p. 83-85C).

Reference： [1]Tetrahedron,2017,vol. 73,p. 4418 - 4425
[2]Journal of Chemical Sciences,2012,vol. 124,p. 463 - 468

27
[ 29490-19-5 ]
[ 536-38-9 ]
[ 307343-39-1 ]

Yield	Reaction Conditions	Operation in experiment
87%	With potassium hydroxide; In ethanol; at 20℃; for 0.5h;	In a two-necked flask, compound 1 (0.0567 mol; 7.5 g) and KOH (0.0567 mol; 3.18 g) were dissolved in absolute ethyl alcohol (about 100 mL) and for about 30 minutes, the solution was stirred at room temperature. 2-Bromo-1-(4-chlorophenyl)ethanone (2) (0.0567 mol; 13.24 g) was added quite slowly to this solution at room temperature. The mixture was then refluxed and stirred for 6 h. Thin Layer Chromatography (TLC) was used to observe the progress of the reaction. After the reaction was ended, the solution was filtered and recrystallized from the ethanol. The pure matter was dried with phosphorus pentoxide in a vacuum oven. Yield: 14.16 g (87%), m.p. 116-118 C (from EtOH) (lit38 m.p. 112-115 C).
85%		General procedure: In a two-necked flask, 5-methyl-1,3,4-thiadiazole-2-thiol (1) (0.06 mol; 7.93 g) and KOH (0.06 mol; 0.336 g) were dissolved in absolute ethanol (100 mL) and the solution was stirred for 30min at room temperature. Phenacyl bromide derivative (2a-d) (0.06 mol) was dissolved in absolute ethanol (50 mL) and added dropwise to this solution at room temperature with the assistance of a dropping funnel. The mixture was then refluxed and stirred for 4-6 h. The progress of the reaction was monitored by TLC at appropriate time intervals. After completion of the reaction, the solution was filtered and recrystallized from the ethanol. The synthesized compounds were dried with P2O5 in a vacuum oven.

Reference： [1]Synthetic Communications,2019,vol. 49,p. 2357 - 2368
[2]Tetrahedron,2017,vol. 73,p. 4418 - 4425
[3]Journal of Chemical Sciences,2012,vol. 124,p. 463 - 468

28
[ 29490-19-5 ]
[ 2632-13-5 ]
[ 307343-41-5 ]

Yield	Reaction Conditions	Operation in experiment
81%		General procedure: In a two-necked flask, 5-methyl-1,3,4-thiadiazole-2-thiol (1) (0.06 mol; 7.93 g) and KOH (0.06 mol; 0.336 g) were dissolved in absolute ethanol (100 mL) and the solution was stirred for 30min at room temperature. Phenacyl bromide derivative (2a-d) (0.06 mol) was dissolved in absolute ethanol (50 mL) and added dropwise to this solution at room temperature with the assistance of a dropping funnel. The mixture was then refluxed and stirred for 4-6 h. The progress of the reaction was monitored by TLC at appropriate time intervals. After completion of the reaction, the solution was filtered and recrystallized from the ethanol. The synthesized compounds were dried with P2O5 in a vacuum oven.

Reference： [1]Tetrahedron,2017,vol. 73,p. 4418 - 4425
[2]Journal of Chemical Sciences,2012,vol. 124,p. 463 - 468

29
[ 13965-31-6 ]
[ 29490-19-5 ]
[ 1402610-63-2 ]

Reference： [1]Chemistry - A European Journal,2012,vol. 18,p. 11196 - 11200,5

30
[ 29490-19-5 ]
[ 179162-55-1 ]
[ 1426839-93-1 ]

Yield	Reaction Conditions	Operation in experiment
92%	With 1-ethyl-(3-(3-dimethylamino)propyl)-carbodiimide hydrochloride; In tetrahydrofuran; N,N-dimethyl-formamide; at 20℃; for 3h;	Example 2": Process for the preparation of a compound of formula (lb") (PP1B-MMTDA). To a stirred suspension of PPIB (1.00 g, 2.85 mmol) in a mixture of THF (10 mL) und DMF (8 mL) 2-Mercapto-5-methyl-1 ,3,4-thiadiazole (528 mg, 3.99 mmol) and EDCI (770 mg, 4.02 mmol) was added at room temperature. The reaction was stirred at room temperature and was monitored by HPLC (reaction time approx. 3 hours). Acetic ester (50 mL) was added over a period of 30 min. The solid was filtered off, washed with acetic ester and dried overnight under reduced pressure at room temperature. Yield: 1.22 g PPIB-MMTDA, = 92%. Melting point: 198 C - 233 C. Colourless, in common solvents insoluble powder, (no HPLC or NMR measurement possible).
92%	With 1-ethyl-(3-(3-dimethylamino)propyl)-carbodiimide hydrochloride; In tetrahydrofuran; N,N-dimethyl-formamide; at 20℃; for 3h;	To a stirred suspension of PPIB (1.00 g, 2.85 mmol) in a mixture of THF (10 mL) und DMF (8 mL) 2-Mercapto-5-methyl-1,3,4-thiadiazole (528 mg, 3.99 mmol) and EDCI (770 mg, 4.02 mmol) was added at room temperature. The reaction was stirred at room temperature and was monitored by HPLC (reaction time approx. 3 hours). Acetic ester (50 mL) was added over a period of 30 min. The solid was filtered off, washed with acetic ester and dried overnight under reduced pressure at room temperature. Yield: 1.22 g PPIB-MMTDA, =92%. Melting point: 198 C.-233 C. Colourless, in common solvents insoluble powder. (no HPLC or NMR measurement possible).

Reference： [1]Patent: WO2013/34670,2013,A1 .Location in patent: Page/Page column 43
[2]Patent: US2014/329989,2014,A1 .Location in patent: Paragraph 0068

31
[ 7669-54-7 ]
[ 29490-19-5 ]
[ 1402734-89-7 ]

Yield	Reaction Conditions	Operation in experiment
89%	In diethyl ether; at 28℃; for 12h;	General procedure: For the preparation of the asymmetric aromatic disulfides (3, 4 and 5), a solution of freshly prepared 2 (1 mmol) in 5 mL anhydrous ethyl ether was added dropwise to a solution of 1 (1 mmol) in 5 mL anhydrous ethyl ether at 28 C. The reaction mixture was stirred for 12 h at 28 C 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.

Reference： [1]Bioorganic and Medicinal Chemistry Letters,2013,vol. 23,p. 3723 - 3727

32
[ 29490-19-5 ]
[ 931-59-9 ]
[ 1402734-86-4 ]

Yield	Reaction Conditions	Operation in experiment
89%	In diethyl ether; at 28℃; for 12h;	General procedure: For the preparation of the asymmetric aromatic disulfides (3, 4 and 5), a solution of freshly prepared 2 (1 mmol) in 5 mL anhydrous ethyl ether was added dropwise to a solution of 1 (1 mmol) in 5 mL anhydrous ethyl ether at 28 C. The reaction mixture was stirred for 12 h at 28 C 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.

Reference： [1]Bioorganic and Medicinal Chemistry Letters,2013,vol. 23,p. 3723 - 3727

33
[ 29490-19-5 ]
[ 933-01-7 ]
[ 1402734-87-5 ]

Yield	Reaction Conditions	Operation in experiment
96%	In diethyl ether; at 28℃; for 12h;	General procedure: For the preparation of the asymmetric aromatic disulfides (3, 4 and 5), a solution of freshly prepared 2 (1 mmol) in 5 mL anhydrous ethyl ether was added dropwise to a solution of 1 (1 mmol) in 5 mL anhydrous ethyl ether at 28 C. The reaction mixture was stirred for 12 h at 28 C 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.

Reference： [1]Bioorganic and Medicinal Chemistry Letters,2013,vol. 23,p. 3723 - 3727

34
[ 1762-76-1 ]
[ 29490-19-5 ]
[ 1402734-91-1 ]

Yield	Reaction Conditions	Operation in experiment
90%	In diethyl ether; at 28℃; for 12h;	General procedure: For the preparation of the asymmetric aromatic disulfides (3, 4 and 5), a solution of freshly prepared 2 (1 mmol) in 5 mL anhydrous ethyl ether was added dropwise to a solution of 1 (1 mmol) in 5 mL anhydrous ethyl ether at 28 C. The reaction mixture was stirred for 12 h at 28 C 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.

Reference： [1]Bioorganic and Medicinal Chemistry Letters,2013,vol. 23,p. 3723 - 3727

35
2-fluorobenzenesulfenyl chloride [ No CAS ]
[ 29490-19-5 ]
[ 1402734-90-0 ]

Yield	Reaction Conditions	Operation in experiment
95%	In diethyl ether; at 28℃; for 12h;	General procedure: For the preparation of the asymmetric aromatic disulfides (3, 4 and 5), a solution of freshly prepared 2 (1 mmol) in 5 mL anhydrous ethyl ether was added dropwise to a solution of 1 (1 mmol) in 5 mL anhydrous ethyl ether at 28 C. The reaction mixture was stirred for 12 h at 28 C 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.

Reference： [1]Bioorganic and Medicinal Chemistry Letters,2013,vol. 23,p. 3723 - 3727

36
[ 70347-73-8 ]
[ 29490-19-5 ]
[ 1402734-92-2 ]

Yield	Reaction Conditions	Operation in experiment
84%	In diethyl ether; at 28℃; for 12h;	General procedure: For the preparation of the asymmetric aromatic disulfides (3, 4 and 5), a solution of freshly prepared 2 (1 mmol) in 5 mL anhydrous ethyl ether was added dropwise to a solution of 1 (1 mmol) in 5 mL anhydrous ethyl ether at 28 C. The reaction mixture was stirred for 12 h at 28 C 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.

Reference： [1]Bioorganic and Medicinal Chemistry Letters,2013,vol. 23,p. 3723 - 3727

37
[ 1447966-38-2 ]
[ 29490-19-5 ]
[ 1447966-40-6 ]

Yield	Reaction Conditions	Operation in experiment
80%	With sodium hydrogencarbonate; In acetone; at 20℃; for 48h;	General procedure: A mixture of alkyl 3-bromo-5-phthalimido-levulinate 7a or 7b (1.0mmol), 5-methyl-1,3,4-thiadiazole-2-thiol (0.13g, 1.0mmol), NaHCO3 (0.21g, 2.5mmol) and acetone (10mL) was stirred at rt for 48h (TLC control). The solvent was evaporated in vacuo and water (30mL) was added to the residue. The precipitate was filtered and washed successively with water (5mL) and n-hexane (5mL) to afford corresponding sulfide 8a or 8b.

Reference： [1]Tetrahedron,2013,vol. 69,p. 6975 - 6980

38
[ 1447966-39-3 ]
[ 29490-19-5 ]
[ 1447966-41-7 ]

Yield	Reaction Conditions	Operation in experiment
84%	With sodium hydrogencarbonate; In acetone; at 20℃; for 48h;	General procedure: A mixture of alkyl 3-bromo-5-phthalimido-levulinate 7a or 7b (1.0mmol), 5-methyl-1,3,4-thiadiazole-2-thiol (0.13g, 1.0mmol), NaHCO3 (0.21g, 2.5mmol) and acetone (10mL) was stirred at rt for 48h (TLC control). The solvent was evaporated in vacuo and water (30mL) was added to the residue. The precipitate was filtered and washed successively with water (5mL) and n-hexane (5mL) to afford corresponding sulfide 8a or 8b.

Reference： [1]Tetrahedron,2013,vol. 69,p. 6975 - 6980

39
[ 113591-42-7 ]
[ 29490-19-5 ]
[ 1489231-03-9 ]

Yield	Reaction Conditions	Operation in experiment
93%	In N,N-dimethyl-formamide; at 20℃; for 4h;	General procedure: To a solution of 5-methyl-1,3,4-thiadiazole-2-thiol (3.31 g, 25 mmol) in 10 mL of DMF, was added 2.92 g (10 mmol) of compound 4i, slowly [19]. After stirring at room temperature for 4 h, the solution was poured into 100 mL of distilled water with slight yellow solid precipitation. After standing for 20 min the slight yellow solid was filtered with suction, pressed to remove excess water, and allowed to dry in air. The dry residues were recrystallized with MeOH to give title compound 5i1 as yellow powder. Yield: 93%, mp: 184.6-185.9 C. 1H NMR (DMSO-d6) delta 2.61 (s, 3H, CH3), 6.91 (d, J = 8.40 Hz, 1H, aromatic H), 7.07 (d, J = 3.00 Hz, 1H, aromatic H), 7.11 (dd, J = 8.40 Hz, 3.00 Hz, 1H, aromatic H), 7.88 (d, J = 9.00 Hz, 2H, aromatic H), 8.37 (d, J = 9.00 Hz, 2H, aromatic H), 10.29 (s, 1H, phenolic OH), 10.55 (s, 1H, aromatic NH). 13C NMR (100 MHz, DMSO-d6) delta: 116.7, 117.5, 125.0, 127.6, 128.8, 129.0, 129.7, 144.8, 150.2, 156.0, 166.6, 167.0. ESI-MS m/z 425.3 [M + H]+.

Reference： [1]European Journal of Medicinal Chemistry,2013,vol. 69,p. 191 - 200

40
[ 76960-33-3 ]
[ 29490-19-5 ]
[ 1489235-57-5 ]

Yield	Reaction Conditions	Operation in experiment
90%	In N,N-dimethyl-formamide; at 20℃; for 4h;	General procedure: To a solution of 5-methyl-1,3,4-thiadiazole-2-thiol (3.31 g, 25 mmol) in 10 mL of DMF, was added 2.92 g (10 mmol) of compound 4i, slowly [19]. After stirring at room temperature for 4 h, the solution was poured into 100 mL of distilled water with slight yellow solid precipitation. After standing for 20 min the slight yellow solid was filtered with suction, pressed to remove excess water, and allowed to dry in air. The dry residues were recrystallized with MeOH to give title compound 5i1 as yellow powder.

Reference： [1]European Journal of Medicinal Chemistry,2013,vol. 69,p. 191 - 200

41
[ 29490-19-5 ]
2-(halomethyl)-4H-chromen-4-one [ No CAS ]
[ 1449385-21-0 ]

Yield	Reaction Conditions	Operation in experiment
87%	With sodium hydroxide; In d7-N,N-dimethylformamide; water; at 90℃;Microwave irradiation;	General procedure: The intermediates M1-4 were synthesized according to previously reported methods [8,9]. A solution of thiol (1 mmol) was prepared in 1% aqueous NaOH (5 mL). Then, we added, dropwise, 1 mL of halogenated-methyl flavonoids, M1-4 (1 mmol), in DMF. The mixture was heated to 90 C in an oil bath; alternatively it was sealed, and then irradiated in a Smith Creator microwave at 50-100 W to 90 C. After completion of the reaction, the mixture was diluted with water (40 mL) and the precipitate was filtered. Finally, the precipitate was recrystallized from an appropriate solvent to give the title compounds, 5-8.

Reference： [1]European Journal of Medicinal Chemistry,2013,vol. 66,p. 161 - 170

42
[ 29490-19-5 ]
2-(halomethyl)-6-methyl-4H-chromen-4-one [ No CAS ]
[ 1449385-31-2 ]

Yield	Reaction Conditions	Operation in experiment
86%	With sodium hydroxide; In d7-N,N-dimethylformamide; water; at 90℃;Microwave irradiation;	General procedure: The intermediates M1-4 were synthesized according to previously reported methods [8,9]. A solution of thiol (1 mmol) was prepared in 1% aqueous NaOH (5 mL). Then, we added, dropwise, 1 mL of halogenated-methyl flavonoids, M1-4 (1 mmol), in DMF. The mixture was heated to 90 C in an oil bath; alternatively it was sealed, and then irradiated in a Smith Creator microwave at 50-100 W to 90 C. After completion of the reaction, the mixture was diluted with water (40 mL) and the precipitate was filtered. Finally, the precipitate was recrystallized from an appropriate solvent to give the title compounds, 5-8.

Reference： [1]European Journal of Medicinal Chemistry,2013,vol. 66,p. 161 - 170

43
[ 29490-19-5 ]
3-(halomethyl)-4H-chromen-4-one [ No CAS ]
[ 1449385-43-6 ]

Yield	Reaction Conditions	Operation in experiment
85%	With sodium hydroxide; In d7-N,N-dimethylformamide; water; at 90℃;Microwave irradiation;	General procedure: The intermediates M1-4 were synthesized according to previously reported methods [8,9]. A solution of thiol (1 mmol) was prepared in 1% aqueous NaOH (5 mL). Then, we added, dropwise, 1 mL of halogenated-methyl flavonoids, M1-4 (1 mmol), in DMF. The mixture was heated to 90 C in an oil bath; alternatively it was sealed, and then irradiated in a Smith Creator microwave at 50-100 W to 90 C. After completion of the reaction, the mixture was diluted with water (40 mL) and the precipitate was filtered. Finally, the precipitate was recrystallized from an appropriate solvent to give the title compounds, 5-8.

Reference： [1]European Journal of Medicinal Chemistry,2013,vol. 66,p. 161 - 170

44
[ 29490-19-5 ]
3-halo-4H-chromen-4-one [ No CAS ]
3-[(5-methyl-1,3,4-thiadiazol-2-yl)sulfanyl]-4H-1-benzopyran-4-one [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
80%	With sodium hydroxide; In d7-N,N-dimethylformamide; water; at 90℃;Microwave irradiation;	General procedure: The intermediates M1-4 were synthesized according to previously reported methods [8,9]. A solution of thiol (1 mmol) was prepared in 1% aqueous NaOH (5 mL). Then, we added, dropwise, 1 mL of halogenated-methyl flavonoids, M1-4 (1 mmol), in DMF. The mixture was heated to 90 C in an oil bath; alternatively it was sealed, and then irradiated in a Smith Creator microwave at 50-100 W to 90 C. After completion of the reaction, the mixture was diluted with water (40 mL) and the precipitate was filtered. Finally, the precipitate was recrystallized from an appropriate solvent to give the title compounds, 5-8.

Reference： [1]European Journal of Medicinal Chemistry,2013,vol. 66,p. 161 - 170

45
[ 29490-19-5 ]
6-chloro-2-(halomethyl)-4H-chromen-4-one [ No CAS ]
[ 1449385-37-8 ]

Yield	Reaction Conditions	Operation in experiment
90%	With sodium hydroxide; In d7-N,N-dimethylformamide; water; at 90℃;Microwave irradiation;	General procedure: The intermediates M1-4 were synthesized according to previously reported methods [8,9]. A solution of thiol (1 mmol) was prepared in 1% aqueous NaOH (5 mL). Then, we added, dropwise, 1 mL of halogenated-methyl flavonoids, M1-4 (1 mmol), in DMF. The mixture was heated to 90 C in an oil bath; alternatively it was sealed, and then irradiated in a Smith Creator microwave at 50-100 W to 90 C. After completion of the reaction, the mixture was diluted with water (40 mL) and the precipitate was filtered. Finally, the precipitate was recrystallized from an appropriate solvent to give the title compounds, 5-8.

Reference： [1]European Journal of Medicinal Chemistry,2013,vol. 66,p. 161 - 170

46
[ 29490-19-5 ]
6-chloro-3-(halomethyl)-4H-chromen-4-one [ No CAS ]
[ 1449385-55-0 ]

Yield	Reaction Conditions	Operation in experiment
81%	With sodium hydroxide; In d7-N,N-dimethylformamide; water; at 90℃;Microwave irradiation;	General procedure: The intermediates M1-4 were synthesized according to previously reported methods [8,9]. A solution of thiol (1 mmol) was prepared in 1% aqueous NaOH (5 mL). Then, we added, dropwise, 1 mL of halogenated-methyl flavonoids, M1-4 (1 mmol), in DMF. The mixture was heated to 90 C in an oil bath; alternatively it was sealed, and then irradiated in a Smith Creator microwave at 50-100 W to 90 C. After completion of the reaction, the mixture was diluted with water (40 mL) and the precipitate was filtered. Finally, the precipitate was recrystallized from an appropriate solvent to give the title compounds, 5-8.

Reference： [1]European Journal of Medicinal Chemistry,2013,vol. 66,p. 161 - 170

47
[ 29490-19-5 ]
2-(5-methyl-1,3,4-thiadiazole-2-ylthio)-5-methyl-1,3,4-thiadiazole [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
70%	With manganese (II) acetate tetrahydrate; In methanol; acetonitrile; for 2h;Reflux;	Mn(OAc)24H2O (0.125 g, 0.5 mmol) was added to a methanol-acetonitrile suspension of 5-methyl-1,3,4-thiadiazole-2-thiol(0.101 g, 1 mmol) and the reaction mixture refluxed for 2 h. Theclear solution obtained upon cooling was filtered off and kept forcrystallization. Colorless crystals of 3 suitable for X-ray analyseswere obtained by slow evaporation of the above solution over aperiod of 10 days. Yield: 70%. m.p. 192 C. Anal. Found: C,31.24%; H, 2.60%; N, 24.33%; S, 41.66%. Calc. for C6H6N4S3 (230.36): C, 31.25%; H, 2.61%; N, 24.31%; S, 41.68%. Found: IR(KBr, cm1): m(CN) 1602; m(NAN) 1065; m(CAS) 727. 1H NMR(DMSO-d6; d ppm): 2.50 (3H, ACH3. 13C NMR (DMSO-d6; d ppm):190.31 (CAS), 168.80 (CN), 38.66 (CH3).

Reference： [1]Journal of Molecular Structure,2013,vol. 1054-1055,p. 251 - 261
[2]RSC Advances,2016,vol. 6,p. 9132 - 9138

48
[ 1581683-53-5 ]
[ 29490-19-5 ]
[ 1581682-43-0 ]

Yield	Reaction Conditions	Operation in experiment
58%	With potassium tert-butylate; In N,N-dimethyl-formamide; at 150℃; for 2h;	Example lr - Preparation of Compound of Formula I [0281] The methyl sulfone starting material (40 mgs, 0.06 mmol) in DMF (0.3 mL) was added 5-methyl-l,3,4-thiadiazole-2-thiol (20 mgs, 0.152 mmol) and potassium tertbutoxide (17 mgs, 0.152 mmol). The soution was heated to 150 C in an oil bath. After two hours, LC/MS showed formation of desired peak and consumption of starting material. Reaction was purified without aq work up. Purification was done via RP ISCO to get 25 mgs of tan solids (58%). LC/MS 657 (M++l).

Reference： [1]Patent: WO2014/43272,2014,A1 .Location in patent: Paragraph 0280; 0281

49
[ 1446203-33-3 ]
[ 29490-19-5 ]
4-chloro-N-(4-hydroxy-3-((5-methyl-1,3,4-thiadiazol-2-yl)thio)naphthalen-1-yl)benzamide [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
86%	In N,N-dimethyl-formamide; at 20℃; for 4h;	General procedure: To a solution of 1H-1,2,4-triazole-5-thiol (2.53 g, 25 mmol) in 10 mL of DMF, was added 3.11 g (10 mmol) of compound 5a, slowly. After stirring at room temperature for 4 h, the solution was poured into 100 mL of distilled water with slight yellow solid precipitation. After standing for 20 min the slight yellow solid was filtered with suction, pressed to remove excess water, and allowed to dry in air. The dry residues were recrystallized with MeOH to give 2.84 g of title compound 6a as white powder.

Reference： [1]European Journal of Medicinal Chemistry,2013,vol. 64,p. 377 - 388

50
[ 98760-08-8 ]
[ 29490-19-5 ]
[ 1346158-03-9 ]

Yield	Reaction Conditions	Operation in experiment
80%	With triethylamine; In methanol; at 20℃; for 2h;	<strong>[29490-19-5]2-mercapto-5-methyl-1,3,4-thiadiazole</strong> 4 (1.5 mmol),triethylamine (TEA) (1.6 mmol) and epoxide 1 (1.6 mmol)were dissolved in methanol (10 mL) and stirred at roomtemperature for 2 hours. After this period, the solvent wasremoved by evaporation and the crude product was purifiedby crystallization in methanol/water (7:3). Yield 80%, mp114-116C, 1H-NMR (DMSO-d6) : 7.26 (t, 2H, J = 7.3;Ph); 7.19-7.13 (m, 3H; Ph); 6.76 (d, 1H, J = 8.7; NH); 5.54(d, 1H, J = 6.2; OH); 3.66-3.54 (m, 3H; H3, H2 and H4b);3.21 (dd, 1H, 1J = 13.0; 2J = 8.2; H4a); 3.05 (dd, 1H, 1J =14.1; 2J = 2.8; H1b); 2.66 (s, 3H; CH3); 2.56 (dd, 1H, 1J =13.8; 2J = 10.1; H1a); 1.26 (s, 9H; Boc), 13C-NMR (DMSOd6): 165.9 (C17); 165.0 (C18); 155.3 (C=O); 139.3 (C11);129.3 (C13 and C15); 127.9 (C12 and C16); 125.7 (C14);77.6 (C(Boc)); 71.7 (C3); 56.2 (C2); 39.2 (C4); 35.9 (C1);28.2 (CH3(Boc)); 15.2 (CH3(Het)), MS (ESI+) m/z (relintensity): 418.1 (M+ + Na, 100%), C18H25N3O3S2.

Reference： [1]Medicinal Chemistry,2014,vol. 10,p. 271 - 276

51
[ 74367-78-5 ]
[ 29490-19-5 ]
2-((3,5-dinitrobenzyl)sulfanyl)-5-methyl-1,3,4-thiadiazole [ No CAS ]

Reference： [1]Journal of Medicinal Chemistry,2016,vol. 59,p. 2362 - 2380
[2]Patent: WO2014/161516,2014,A1 .Location in patent: Page/Page column 10

52
[ 33263-43-3 ]
[ 29490-19-5 ]
4-[(5-methyl-1,3,4-thiadiazol-2-yl)thio]-3-pyridinesulfonamide [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
86%	In acetonitrile; at 20 - 100℃; for 26h;	In a closed glass pressure tube, a mixture of 4-chloro-3- pyridinesulfonamide (1.92 g, 10 mmol) and 5-methyl-1,3,4-thiadiazole-2-thiol (1.57 g, 12 mmol) in dry acetonitrile (16.5 mL) was stirred at room temperature for 2 h and then at 100 °C for 24 h. The precipitate of the hydrochloride was collected by filtration, washed with acetonitrile (3 × 2 mL) and dried, then suspended in water (8 mL) and slowly djusted to pH 8 with 1percent solution of NaOH. After stirring at room temperature for 3 h, the precipitate was filtered off, washed with water (2 × 1 mL), and dried. Yield 2.49 g (86percent); mp 132?135 °C; IR (KBr) numax 3546, 3344 (NH), 1572 (C=C), 1330, 1163 (SO2) cm?1; 1H-NMR (DMSO-d6, 200 MHz) delta: 2.83 (s, 3H, CH3); 7.09 (d, 1H, H-5 pyrid.); 8.00 (s, 2H, NH2); 8.56 (d, 1H, H-6 pyrid.); 8.95 (s, 1H, H-2 pyrid.) ppm; anal. C 33.32, H 2.80, N 19.43percent calcd. for C8H8N4O2S3 C 33.02, H 2.84, N 19.33percent.

Reference： [1]Molecules,2015,vol. 20,p. 12029 - 12044

53
[ 29490-19-5 ]
[ 768-60-5 ]
2-((1-(4-methoxyphenyl)vinyl)thio)-5-methyl-1,3,4-thiadiazole [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
76%	With palladium diacetate; copper(II) bis(trifluoromethanesulfonate); In 5,5-dimethyl-1,3-cyclohexadiene; at 120℃; for 4h;Inert atmosphere;	General procedure: A test tube was charged with pyridine-2-thiol (0.2 mmol), Pd(OAc)2 (0.004 mmol), Cu(OTf)2 (0.01 mmol), phenylacetylene (0.24 mmol), in xylene (1 mL). The reaction tube was evacuated and back-filled with N2 (3 times, balloon). Then the reaction mixture was stirred at 120C (oil bath temperature) under N2 balloon for 4 h. After cooling to room temperature, the solvent was extracted with ethyl acetate and washed with brine. After the solvent was evaporated in vacuo, the residues were purified by column chromatography, eluting with petroleum ether/EtOAc to afford pure 2-((1-phenylvinyl)thio)pyridine.

Reference： [1]Tetrahedron Letters,2015,vol. 56,p. 6022 - 6029

54
[ 29490-19-5 ]
[ 154419-91-7 ]
1-[(5-methyl-1,3,4-thiadiazol-2-yl)thioacetyl]-3-(2-thienyl)-5-(4-chlorophenyl)-2-pyrazoline [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
82%	In acetone; at 20℃; for 8h;	General procedure: A mixture of 1-(chloroacetyl)-3-(2-thienyl)-5-(4-chlorophenyl)-2-pyrazoline (0.005 mol) and aryl thiol (0.005 mol) was treated in acetone (30 mL) at room temperature for 8 h. The solvent was evaporated, the residue was washed with water and recrystallized from ethanol [37].

Reference： [1]Molecules,2015,vol. 20,p. 19066 - 19084

55
[ 656825-78-4 ]
[ 29490-19-5 ]
2-[5-difluoromethoxy-1-methyl-3-trifluoromethyl-1H-pyrazol-4-yl]methylthio-5-methyl-1,3,4-thiadiazole [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
83.5%	With triethylamine; In chloroform; at 20℃;Inert atmosphere;	2.10 ml (15.2 mmoles) of triethylamine were added dropwise at room temperature to a suspension under nitrogen of 2 g (15.2 mmoles) of 5-methyl-1,3,4-thiadiazole-2-thiol in 10 ml of chloroform; 4.70 g(15.2 mmoles) of (4-(bromomethyl)-5-(difluoromethoxy)-1-methyl-3-(trifluoromethyl)-1H-pyrazole, dissolved in4 ml of chloroform were then added. Finally 3.15 ml(22.8 mmoles) of triethylamine were added dropwise.The mixture was left under magnetic stirring atroom temperature for a night.After control in GC-MS and LC-MS, the mixture was diluted with water and the phases were then separated; the aqueous phase was re-extracted twice withdichloromethane. The organic phases joined together, were washed with water and a saturated solution of sodium chloride.After anhydrification on sodium sulfate, filtration and evaporation of the solvent at reduced pressure,4.57 g (68.0 mmoles) of the desired product were obtained, as a brown oil. Yield 83.5% LC-MS [M+H] =361.

Reference： [1]Patent: WO2016/42435,2016,A1 .Location in patent: Page/Page column 23

56
[ 2014-83-7 ]
[ 29490-19-5 ]
2-[(2,6-dichlorobenzyl)thio]-5-methyl-1,3,4-thiadiazole [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
90%	With triethylamine; In chloroform; at 20℃;Inert atmosphere;	10.5 ml (75.6 mmoles) of triethylamine were added dropwise at room temperature to a suspension under nitrogen atmosphere of lOg (75.6 mmoles) of 5-methyl-1,3,4-thiadiazole-2-thiol in 40 ml of chloroform; 14.8g (75.6 mmoles) of 1,3-dichloro-2-(chloromethyl)benzene, dissolved in 10 ml of chloroform were then added.Finally, additional 15.7 ml (0.11 moles) oftriethylamine were added dropwise.The mixture was left under stirring at room temperature for a night. After control in GC-MS and LCMS, the mixture was diluted with water and the phases were then separated; the aqueous phase was re-extracted twice with dichloromethane. The organic phases joinedtogether, were washed with water and a saturated solution of sodium chloride.After anhydrification on sodium sulfate, filtration and evaporation of the solvent at reduced pressure,19.8 g (68.0 mmoles) of the desired product wereobtained, as a yellow oil. Yield 90.0% LC-MS [M+H] =292.

Reference： [1]Patent: WO2016/42435,2016,A1 .Location in patent: Page/Page column 20

57
[ 60699-01-6 ]
[ 29490-19-5 ]
1,3,8-trimethoxy-6-(((5-methyl-1,3,4-thiadiazol-2-yl)thio)methyl)anthracene-9,10-dione [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
82.3%	With potassium carbonate; potassium iodide; In acetone; at 25℃; for 2h;	General procedure: To an oven-dried three-neck 50-mL round-bottom flask fitted with a magnetic stirring bar, emodin (1.0 equiv.), (CH3)2SO4 (9.0 equiv.), K2CO3 (9.0 equiv.), and acetone (25 mL) were added. The reaction mixture was refluxed for 8 h and cooled down to room temperature; then the mixture was poured into water and the precipitate was separated to obtain intermediate 1.The intermediate 1 (1.0 equiv.), NBS (1.16 equiv.), and acetone(25 mL) were slowly added into a 50-mL three-necked round bottom flask. The reaction mixture was refluxed with AIBN asa catalyst for 24 h and then cooled down to room temperature.Then the solvent was poured into water and separated to obtainintermediate 2. Finally, the target compounds Y1-Y14 were synthesized via condensation of intermediates 2 (1.0 equiv.) and 3(1.0 equiv.) and K2CO3 (3.0 equiv.) with KI in acetone (25 mL)at room temperature for 2 h. The purified compounds were obtained from column chromatography on silica gel

Reference： [1]Phosphorus, Sulfur and Silicon and the Related Elements,2016,vol. 191,p. 904 - 907

58
[ 128564-57-8 ]
[ 29490-19-5 ]
C₉H₆ClF₃N₄OS₂ [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
78%	With potassium carbonate; In acetonitrile; at 20 - 50℃; for 12h;	Equipped with a magnetic stirrer, a thermometer, a condenser and a 100 ml three-necked flask was added 4 mmol of anhydrous K2CO3 was slowly added dropwise 4 mmol of aniline, 30 ml of chloroform, at room temperature (20 ~ 30 ) at 1-methyl-3-trifluoromethyl-5-chloro-4-pyrazolecarboxylic acid chloride 20 the dubbed ml of chloroform was added dropwise complete, warm slowly to 50 ± 5 , heat the reaction was stirred for 3 hours, cooled to room temperature.The reaction mixture was filtered under reduced pressure, and the resulting filtrate was off the solvent to obtain crude compound T111025, T111025 with ethanol crude compound was recrystallized to obtain white flaky crystal compound T111025, yield 89%.

Reference： [1]Patent: CN103524419,2016,B .Location in patent: Paragraph 0029; 0034

59
[ 146374-27-8 ]
[ 29490-19-5 ]
2-(tert-butyldisulfanyl)-5-methyl-1,3,4-thiadiazole [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
91%	With copper(l) iodide; magnesium sulfate; In N,N-dimethyl-formamide; at 100℃; for 24h;Sealed tube;	General procedure: 2-Mercaptobenzothiazole (167 mg, 1.0 mmol, 1.0 equiv.)and 121 mg tert-butanesulfinamide (1.0 mmol, 1.0 equiv.)were added into a clean oven-dried test tube equipped witha stirring bar, then 10 mg CuI (0.05 mmol, 5 mol %) and2.0 equiv. of anhydrous MgSO4 were added to the mixture,seal the tube, and then 4 cm3 of DMF was injected in thetube by syringe. The mixture stirred in an oil bath heated at100 C for 24 h. After cooled to room temperature, 4 cm3water was injected into the mixture and extracted themixture with ethyl acetate (15 cm3 9 3); the organic layerwas washed with brine, and then dried over anhydrousNa2SO4. After the solution was filtered and the solvent wasevaporated under vacuum, the residue was subjected tosilica gel column chromatography to give product 3a.

Reference： [1]Monatshefte fur Chemie,2016,vol. 147,p. 1101 - 1105

60
5-fluoro-4-(chloromethyl)-1-methyl-3-(trifluoromethyl)-1H-pyrazole [ No CAS ]
[ 29490-19-5 ]
2-([5-fluoro-1-methyl-3-(trifluoromethyl)-1H-pyrazol-4-yl]methyl}thio)-5-methyl-1,3,4-thiadiazole [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
90%	With triethylamine; In chloroform;Inert atmosphere;	3.20 ml (23.09 mmoles) of triethylamine were added dropwise at room temperature to a suspension under nitrogen of 3.05 g (23.09 mmoles) of 5-methyl-l, 3, 4- thiadiazole-2-thiol (IX) in 30 ml of chloroform; 5.0 g (23.09 mmoles) of 5-fluoro-4- (chloromethyl) -l-methyl-3- (trifluoromethyl) -lH-pyrazole (VIII) dissolved in 10 ml of chloroform were then added. 4.8 ml (34.64 mmoles) of triethylamine were finally added dropwise. The mixture was left under magnetic stirring at room temperature for a night. After control in GC-MS and LC-MS, the mixture was diluted with water and the phases were then separated; the aqueous phase was re-extracted twice with dichloromethane. The organic phases were combined and washed with water and with a saturated solution of sodium chloride. After anhydrification on sodium sulfate, filtration and evaporation of the solvent at reduced pressure, 6.48 g of the desired product were obtained (20.78 mmoles) as a brown oil. Yield 90%. LC-MS [M+H] = 313.

Reference： [1]Patent: WO2016/142918,2016,A1 .Location in patent: Page/Page column 32-33

61
[ 141-32-2 ]
[ 29490-19-5 ]
3-[(5-methyl-1,3,4-thiadiazol-2-yl)thio]butyl propanoate [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
93%	With triethylamine; In methanol; for 8h;Inert atmosphere; Reflux;	10.6 g (83.2 mmoles) of butyl acrylate (XIII) and 11.0 ml (79.4 mmoles) of triethylamine were added, at room temperature, to a solution under nitrogen of 10. Og (75.6 mmoles) of 5-methyl-l , 3, 4-thiadiazole-2-thiol (IX) in 300 ml of MeOH. The mixture was heated to reflux temperature for 8 hours . After control in GC-MS, the solvent was removed at reduced pressure, obtaining 18.3 g of the desired product (70.4 mmoles), as a yellow oil. Yield 93%. GC-MS [m/z] = 260.

Reference： [1]Patent: WO2016/142918,2016,A1 .Location in patent: Page/Page column 38

62
[ 29490-19-5 ]
[ 113100-61-1 ]
C₉H₁₀N₄OS₂ [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
48.3%	With potassium carbonate; In chloroform; at 0 - 20℃; for 12h;Green chemistry;	General procedure: In a 100 ml three-necked flask equipped with a thermometer and an electromagnetic stir bar were added 0.01 mol of anhydrous K2CO3 powder, 0.01 mol of 2-nitroaniline,30 ml of acetone,A solution prepared by dissolving 0.01 mol of 1,3-dimethyl-4-pyrazolecarboxylic acid chloride in 20 ml of acetone was gradually added dropwise at low temperature (0 to 5 C), and the reaction was continued at room temperature for 10 hours. The reaction mixture was filtered under reduced pressure, and the resulting filtrate was decompressed to yield a crude product of compound Q110907. The crude product of compound Q110907 was recrystallized from acetonitrile to give the compound (Q110907) in a yield of 42.9%. Using2 -mercapto-5-methyl-3,4-thiadiazole instead of 2-nitroaniline; chloroform asreaction solvent; reaction time 12 hours; ethanol recrystallization

Reference： [1]Patent: CN103524417,2016,B .Location in patent: Paragraph 0026; 0030

63
[ 98-86-2 ]
[ 29490-19-5 ]
[ 245106-56-3 ]

Yield	Reaction Conditions	Operation in experiment
77%	With dipotassium peroxodisulfate; potassium iodide; In dimethyl sulfoxide; at 20℃; for 24h;Schlenk technique;	1.0 mmol of acetophenone,0.5 mmol of <strong>[29490-19-5]2-mercapto-5-methyl-1,3,4-thiadiazole</strong>,20 mol% of potassium iodide,0.3 mmol of potassium persulfate,1 ml of DMSO was added to the Schlenk tube under an air atmosphere and stirred at room temperature for 24 hours. After completion of the reaction, 2 - ((5-methyl-1,3,4-thiadiazol-2-yl) thio) -1-phenylethanone in 77% isolated yield was obtained by isolation and purification. The product was identified by 1H, 13C NMR.

Reference： [1]Organic Letters,2016,vol. 18,p. 6090 - 6093
[2]Patent: CN106986843,2017,A .Location in patent: Paragraph 0037; 0038
[3]Synlett,2017,vol. 28,p. 2325 - 2329

64
[ 29490-19-5 ]
[ 14867-28-8 ]
5-methyl-2-[3-(trimethoxysilyl)propylthio]-1,3,4-thiadiazole [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
99.9%		A suspension composed of 7.9 g (60 mmol) of 5-methyl-1,3,4-thiadiazole-2-thiol and 100 ml of dehydrated methanol was cooled to 10C, thereto was added 11.6 g (60 mmol) of a 28% sodium methoxide methanol solution to form an uniform solution, followed by returning to room temperature and stirring for 30 minutes, and thereto was added dropwise a solution composed of 17.4 g (60 mmol) of 3-iodopropyltrimethoxysilane and 20 ml of dehydrated methanol at room temperature over a period of 30 minutes, followed by further stirring at from 34 to 40C for 4 hours.The reaction solution was concentrated under a reduced pressure, and 26.5 g of the resulting white viscous substance was extracted three times with 80 ml of diethyl ether, and the extract was filtered and concentrated under a reduced pressure to obtain 16.9 g (60 mmol, yield of 99.9%) of a slightly yellow-brown colored oily substance.

Reference： [1]Patent: KR2016/29029,2016,A .Location in patent: Paragraph 0417-0420; 0425

65
[ 29490-19-5 ]
[ 773893-02-0 ]
5-methyl-2-[5-(trimethoxysilyl)pentylthio]-1,3,4-thiadiazole [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
75.7%		A suspension composed of 3.3 g (25 mmol) of <strong>[29490-19-5]2-mercapto-5-methyl-1,3,4-thiadiazole</strong> and 40 ml of dehydrated methanol was cooled to 10C, thereto was added 4.8 g (25 mmol) of a 28% sodium methoxide methanol solution to form an uniform solution, followed by returning to room temperature and stirring for 30 minutes, and thereto was added dropwise a solution composed of 6.8 g (25 mmol) of 5-bromopentyltrimethoxysilane and 10 ml of dehydrated methanol at room temperature over a period of 10 minutes, followed by further stirring at 60C for 6 hours.The reaction solution was concentrated under a reduced pressure, and 10.4 g of the resulting white viscous substance was extracted three times with 40 ml of diethyl ether, and the extract was filtered and concentrated under a reduced pressure to obtain 6.1 g (19 mmol, yield of 75.7%) of a slightly yellow-brown colored oily substance.

Reference： [1]Patent: KR2016/29029,2016,A .Location in patent: Paragraph 0426-0429; 0434

66
[ 10493-44-4 ]
[ 29490-19-5 ]
2-(3,4,4-trifluoro-3-butenylthio)-5-methyl-1,3,4-thiadiazole [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
82%	With triethylamine; In chloroform; at 20 - 50℃; for 2.5h;Inert atmosphere;	Preparation of 2-(3,4,4-trifluoro-3-butenylthio)-5-methyl-l,3,4-thiadiazole Tthioether having general formula (11)1 1.1 ml (7.9 mmoles) of triethylamine were added at room temperature to a suspension under ni- trogen of 0.7 g (5.3 mmoles) of 5-methyl-l,3,4-thiadiazole-2-thiol in 15 ml of chloroform. After 30 minutes, 1 g (5.3 mmoles) of 4-bromo- 1 , 1 ,2-trifluorobutene were then added and the reaction mixture was heated to 50C for 2 hours. After control in GC-MS and LC-MS, the mixture was diluted with water and dichloromethane, and the phases were then separated; the aqueous phase was re-extracted twice with dichloro- ethane. The organic phases were joined and washed with water and a saturated solution of sodium chloride. After anhydrification on sodium sulfate, filtration and evaporation of the solvent at reduced pressure, 1.03 g of the desired product were obtained (4.3 mmoles), as a white solid. Yield 82% LC- MS [M+H] = 239.

Reference： [1]Patent: WO2017/2100,2017,A1 .Location in patent: Page/Page column 20-21

67
[ 104146-10-3 ]
[ 29490-19-5 ]
7-phenylacetylamino-3-[[2-(5-methyl-1,3,4-thiadiazolyl)thio]methyl]cephalosporanic acid p-methoxybenzyl ester [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
94%	With triethylamine; In dichloromethane; at 0℃; for 10h;	16.5 g of 2-mercapto-5-methyl-1,3,4 thiadiazole, 750 mL of dichloromethane was added to the reaction flask,0 C under the conditions of triethylamine 15mL, adding GCLE50g, reaction 10h,Washed with saturated sodium carbonate solution to neutral, dried and concentrated to 56.5 g of a white solid in 94% yield.

Reference： [1]Patent: CN102731530,2016,B .Location in patent: Paragraph 0098-0100

68
C₃H₄N₂S₂*H₃N [ No CAS ]
[ 29490-19-5 ]

Yield	Reaction Conditions	Operation in experiment
99.9%	With hydrogenchloride; In water; at 30 - 35℃; for 0.5h;pH 4 - 4.5;	In a 500 ml synthetic reaction flask, 50 g of 100% hydrazine hydrate and 120 g of 20% aqueous ammonia were added, stirred below 5C under ice-water cooling. 80 grams of carbon disulfide was added, and maintained below 5C for 1 hour to obtain an aqueous solution of ammonium dithiocarbamate. The above solution was transferred to a 1000 ml reaction flask, 100 g of acetonitrile was added, the mixture was stirred for half an hour, and then heated to 85 ~ 90 C for 1 hour. The solution is then cooled below 40C, 35% hydrochloric acid is added dropwise at 30C to 35C, the pH is adjusted to 4 to 4. 5, stirred for half an hour, filtered, and washed 3 times to get thiadiazole wet product 142g. The resulting wet product was dissolved in aqueous ammonia ,decolorized, insulated, filtered, acidified, filtered and dried to obtain thiadiazole product quality 85 g. After HPLC liquid phase analysis, the product content is 99.9%.

Reference： [1]Patent: CN103360337,2016,B .Location in patent: Paragraph 0023-0026

69
[ 51762-67-5 ]
[ 29490-19-5 ]
3-((5-methyl-1,3,4-thiadiazol-2-yl)thio)phthalonitrile [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
55%	With potassium carbonate; In N,N-dimethyl-formamide; at 50℃; for 72h;Inert atmosphere;	Under inert N2 atmosphere, 5-Methyl-1,3,4-thiadiazole-2-thiol(1) (2.00 g, 15.13 mmol) and 3-nitrophthalonitrile (2) (2.62 g.15.13 mmol) were dissolved in dry DMF (15 mL). Finely powderedanhydrous K2CO3 (6.26 g 45.39 mmol) was added portion wisewithin 2 h to reaction mixture at 50 C. The mixture was stirred for3 days at this temperature. Then it was poured into 250 mL icewater,stirred for 1 h at room temperature and filtered off. Thesolid product was crystallized from ethanol. Yield 2.15 g (55%), mp137e139 C, C11H6N4S2. IR (KBr tablet) ymax/cm1: 3076, 3055,2924, 2231 (C^N), 1614, 1574, 1446, 1379, 1331, 1186, 1041, 1027,818, 732.1H NMR (DMSO-d6), (d: ppm): 8.25e8.23 (d, 1H, ArH),8.14e8.12 (d, 1H, Ar-H), 7.99e7.95 (t, 1H, Ar-H), 2.72 (s, 3H, CH3). 13CNMR (DMSO-d6), (d: ppm): 169.21 (C]N), 161.52 (C]N), 139.22,137.07, 135.14, 130.99, 119.29, 117.25, 115.69 (C^N), 114.62 (C^N),16.93 (CH3).MS (ESI), (m/z): Calculated: 258.00; Found: 259.11[MH].
	With potassium carbonate; In N,N-dimethyl-formamide;	The phthalonitrile compund ( 5) was synthesized by the reaction between 5-Methyl-1,3,4-thiadiazole-2-thiol (1) and 3-nitrophthalonitrile (3) in dry DMF in the presence of K2CO3 according to literature [25].

Reference： [1]Journal of Molecular Structure,2017,vol. 1144,p. 112 - 119
[2]Journal of Molecular Structure,2019,vol. 1197,p. 594 - 602

70
[ 29490-19-5 ]
[ 99-73-0 ]
[ 307343-40-4 ]

Yield	Reaction Conditions	Operation in experiment
85%		General procedure: In a two-necked flask, 5-methyl-1,3,4-thiadiazole-2-thiol (1) (0.06 mol; 7.93 g) and KOH (0.06 mol; 0.336 g) were dissolved in absolute ethanol (100 mL) and the solution was stirred for 30min at room temperature. Phenacyl bromide derivative (2a-d) (0.06 mol) was dissolved in absolute ethanol (50 mL) and added dropwise to this solution at room temperature with the assistance of a dropping funnel. The mixture was then refluxed and stirred for 4-6 h. The progress of the reaction was monitored by TLC at appropriate time intervals. After completion of the reaction, the solution was filtered and recrystallized from the ethanol. The synthesized compounds were dried with P2O5 in a vacuum oven.

Reference： [1]Tetrahedron,2017,vol. 73,p. 4418 - 4425

71
[ 628-89-7 ]
[ 29490-19-5 ]
2-(2-((5-methyl-1,3,4-thiadiazol-2-yl)thio)ethoxy)ethan-1-ol [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
55%		2.3.1 2-(2-((5-Methyl-1,3,4-thiadiazol-2-yl)thio)ethoxy)ethan-1-ol (2) After dissolving 5-methyl-1,3,4-thiadiazole-2-thiol (4 g, 0.030 mol) in ethanol (35 mL), KOH (2.15 g, 0.038 mol) was added in it by stirring at 50 C for 1.5 h and then, 2-(2-chloroethoxy)-ethanol (4.88 g, 0.05 mol) in ethanol (10 mL) was put by dropwise to the first solution while stirring vigorously for 45 min. Then, this crude product was refluxed for 36 h under nitrogen and cooled down. After cooling, the solution was removed under vacuum and the obtained residue was dissolved in CH2CI2 (100 mL) and cleaned two times with 15% NaOH (2.2 mL) and two times with water (150 mL). The organic phase was dried over NaSO4, filtered and evaporated. The crude product was purified with an aluminum oxide column using CH2Cl2 as a solvent. White waxy product was soluble in THF, CHCl3, CH2Cl2, DMF and DMSO. Yield: 3.63 g (55%). Anal. calcd. for (%) C7H12N2O2S2 (220.31 g/mol): C, 38.16; H, 5.49; N, 12.72; O, 14.52; S, 29.11. Found C, 38.31; H, 5.46; N, 12.62. FT-IR (upsilonmax/cm-1): 3390 (O-H), 3089 (Ar-H), 2911-2855 (Aliph. C-H), 1456, 1573, 1382, 1288, 1189, 1118, 1068, 1038, 947, 888, 760, 731, 760 (S-N), 653, 617. 1H NMR (300 MHz, CDCl3): delta, ppm; 3.61 (t, J = 5.9 Hz, 2H, -CH2-OH) 3.51 (t, J = 3.5 Hz, 2H, -CH2-O) 3.38 (t, J = 3.4 Hz, 2H, -CH2-O) 3.28 (t, J = 5.9 Hz, 2H, -CH2-S) 2.50 (s, 3H, -CH3) 4.25 (bs, 1H, -OH). MS (MALDI-MS, 2,5-dihydroxybenzoic acid as matrix): [M+H]+: 221.32.

Reference： [1]Inorganica Chimica Acta,2017,vol. 467,p. 169 - 176

72
C₁₅H₁₂BrCl₂N₃O₅S [ No CAS ]
[ 29490-19-5 ]
[ 56187-47-4 ]

Yield	Reaction Conditions	Operation in experiment
93.86%	With triethylamine; In ethanol; for 10h;Reflux;	In a 1 L round bottom flask,Add 800ml absolute ethanol,Triethylamine 1.012g, heated to reflux.Compound V46.39g was dissolved,<strong>[29490-19-5]2-mercapto-5-methyl-1,3,4-thiadiazole</strong> 12.30g,Stirring reaction 10h,After the reaction,Remove the solvent,Extraction with chloroform (3 x 250 ml)Then washed with a small amount of water extraction twice,Then dried over anhydrous magnesium sulphate overnight.After removing the solvent,The crude product is recrystallized from petroleum ether,48.08 g of a solid was obtained,Yield 93.86%HPLC purity 99.58%.

Reference： [1]Patent: CN106967092,2017,A .Location in patent: Paragraph 0013; 0014; 0046; 0047; 0048; 0049; 0050-0054

73
[ 56187-37-2 ]
[ 29490-19-5 ]
C₁₀H₉Cl₂N₃O₂S₂ [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
97%		In a dry reaction flask, 200 ml of acetone,3,5-Dichloro-4-pyridone-1-acetic acid 22.2 g (Formula I,0.1 mol) and 14.3 g of 2-mercapto-5-methyl-1,3,4-thiadiazole (Formula II, 0.108 mol) were added, followed by stirring,(0.05 mol), 0.8 g (0.01 mol) of pyridine,The reaction was stirred at room temperature for 1 hour, and then slowly added dropwise with an acetone solution of triethyl phosphite catalyst (triethyl phosphite 18.3g dissolved in 60ml of acetone, 0.11mol) dropwise within 1 hour,Temperature 20-25 C 1 hour stirring reaction, filtered,The filtrate cooling down below 10 C , crystallization, filtration, vacuum drying below 40 C ,That is, 33.0 g of the thioester compound (formula III, 0.0936 mol)The yield was 97.0% and the HPLC purity was 98.9%

Reference： [1]Patent: CN105017285,2017,B .Location in patent: Paragraph 0023; 0035-0037; 0040-0042; 0045-0047; 0050-0052

74
C₂₅H₂₆N₂O₅S [ No CAS ]
[ 29490-19-5 ]
[ 107447-96-1 ]

Yield	Reaction Conditions	Operation in experiment
97%	In acetone; at 50 - 55℃; for 3h;	In a dry reaction vessel, add 1000 mL of acetone and heat to 50 C. Add 263 g of GCLE (92.5%, technical grade, 0.5 mol) to acetone, stir and dissolve.76.02 g of <strong>[29490-19-5]2-mercapto-5-methyl-1,3,4-thiadiazole</strong> (MMTD, 0.575 mol) was added, the reaction temperature was controlled at 50-55C, and the reaction time was 3 hours.After the reaction was completed, water was added for crystallization, suction filtration, washing with a small amount of water, and vacuum drying below 40 C. to obtain 284.6 g of GTDE (0.485 mol) in a yield of 97%. The HPLC purity was 99.3%.

Reference： [1]Patent: CN105017286,2017,B .Location in patent: Paragraph 0018; 0029; 0030; 0038; 0039; 0047; 0048

75
[ 5394-18-3 ]
[ 29490-19-5 ]
2-(4-((5-methyl-1, 3, 4-thiadiazol-2-yl)thio) butyl) isoindoline-1, 3-dione [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
95%	With tetrabutylammomium bromide; potassium carbonate; In N,N-dimethyl-formamide; at 20℃; for 6h;Inert atmosphere;	General procedure: 2-(4-((1-methyl-1H-tetrazol-5-yl)thio)butyl)isoindoline-1, 3-dione (3a?): N-(4-bromobutyl) phthalimide (2.81 g, 10mmol), 5-mercapto-1-methyltetrazole (1.16 g, 10 mmol),TBAB (1.00 g) and potassium carbonate (1.66 g, 12 mmol)were dissolved in DMF (30 mL) and stirred at room temperatureunder N2 atmosphere for 6 h. The resulting solutionwas slowly poured into a stirring, ice-chilled bath of water(80 mL). The precipitate was collected by filtration, washedwith cold water, and recrystallized with methanol to yieldproduct 3a

Reference： [1]Letters in Organic Chemistry,2018,vol. 15,p. 206 - 213

76
[ 57753-80-7 ]
[ 29490-19-5 ]
C₁₄H₉ClN₂O₂S₂ [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
73%	With sodium hydroxide; In dichloromethane; at 50℃;	Add 15 mmol to a 50 mL three-necked flask equipped with a thermometer1,3,4-thiadiazole-2-thiol(or 5-methyl-1,3,4-thiadiazole-2-thiol)With 10mL dichloromethane,A 10% (wt.) solution containing 15 mmol sodium hydroxide was added at room temperature to control the acceleration.Keep the temperature at room temperature.After completion, a dichloromethane solution containing 7.5 mmol of 5-(4-chlorophenyl)-2-furoyl chloride was added dropwise.Control the acceleration so that both are added at the same time.After the addition was completed, the temperature was gradually raised to 50C, and the reaction was conducted at 50C for 3 to 10 hours.After the reaction was completed, the precipitate was filtered off, the precipitate was removed, and the filtrate was evaporated to remove the solvent to give a pale yellow solid.The silica gel column (eluent V petroleum ether / V ethyl acetate = 3/1) was isolated to give the H-4 compound, yield: 68%, Alternatively, the H-23 compound was isolated in a yield of 73%.

Reference： [1]Patent: CN107535504,2018,A .Location in patent: Paragraph 0038-0040

77
2,2,2-trichloroethyl ((2S,3S)-1-hydroxy-2-(iodomethyl)-4-oxoazetidin-3-yl)carbamate [ No CAS ]
[ 29490-19-5 ]
2,2,2-trichloroethyl ((2S,3S)-1-hydroxy-2-(((5-methyl-1,3,4-thiadiazol-2-yl)thio)methyl)-4-oxoazetidin-3-yl)carbamate [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
65.1%		General procedure: 5-Mercapto-1-methyltetrazole (615 mg, 1.47 mmol) was dissolved in 15 mL dry DMF and NaH 60% dispersion in mineral oil (82 mg, 2.06 mmol) was added at 0C. After the resulting mixture was stirred at 0C for 10 min, 65 was added and stirred at room temperature for 30 h. The resulting solution was extracted with ethyl acetate and the organic phase was washed with water and brine, dried over anhydrous Na2SO4, filtered and then the filtrate was concentrated in vacuo. The residue was purified by chromatography on silica gel with PE/EA (1:1) to give 66a (464 mg, 77.6%) as a colorless oil.

Reference： [1]European Journal of Medicinal Chemistry,2018,vol. 151,p. 98 - 109

78
[ 106-93-4 ]
[ 29490-19-5 ]
2-((2-bromoethyl)thio)-5-methyl-1,3,4-thiadiazole [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
44.5%	With potassium carbonate; potassium iodide; In acetone; at 20℃;	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.

Reference： [1]Bioorganic and Medicinal Chemistry Letters,2018,vol. 28,p. 1792 - 1796

79
[ 29490-19-5 ]
[ 109-64-8 ]
2-((3-bromopropyl)thio)-5-methyl-1,3,4-thiadiazole [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
45.5%	With potassium carbonate; potassium iodide; In acetone; at 20℃;	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.

Reference： [1]Bioorganic and Medicinal Chemistry Letters,2018,vol. 28,p. 1792 - 1796

80
[ 14104-20-2 ]
[ 29490-19-5 ]
[ 603-35-0 ]
C₅₇H₄₈AgN₂P₃S₂ [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
57%		A portion of AgBF4 (0.097 g, 0.5 mmol) was dissolved in a 10-mLmixture of CH3CN:CH3OH (1:1 v/v) and then PPh3 (0.262 g, 1.0mmol) was added in small portions. The resulting mixture wasstirred at 50 C for 20 min in dark and then a 20-mL methanolicsolution of mtdzt in the same solvent mixture, obtained from thedeprotonation of the corresponding amount of mtdztH (0.066 g,0.5 mmol) with 1.0 mL of 0.5 M solution of KOH in CH3OH, wasadded dropwise. After stirring at 65 C for 1 h, the resulting suspensionwas filtered in order to remove a small amount of anoff-white solid. The filtrate was set aside in dark to evaporateslowly at room temperature and, after 5 days, crystals of 3 startedgrowing, which were collected. Yield: 0.300 g (57%). Anal. Calc. forC58H52AgN2OP3S2: C, 65.85; H, 4.95; N, 2.65. Found: C, 66.01; H,4.70; N, 2.83%. FTIR (KBr, cm-1): 3448br, 3052w, 1579m, 1481s,1437vs, 1368m, 1307m, 1281w, 1179s, 1087s, 996s, 743vs,698vs, 516vs, 500vs. UV-Vis (CH3CN), k/nm (log epsilon): 257 (4.34).

Reference： [1]Polyhedron,2018,vol. 151,p. 131 - 140

81
[ 27164-46-1 ]
C₁₁H₁₁N₆O₅S^(1-)*Na⁽¹⁺⁾ [ No CAS ]
[ 29490-19-5 ]

Reference： [1]Journal of Materials Chemistry B,2018,vol. 6,p. 3922 - 3926

82
[ 2449-49-2 ]
[ 29490-19-5 ]
2-methyl-5-((1-phenylethyl)mercapto)-1,3,4-thiadiazole [ No CAS ]

Reference： [1]ACS Catalysis,2018,vol. 8,p. 9899 - 9906

83
[ 2449-49-2 ]
[ 29490-19-5 ]
C₁₁H₁₂N₂S₂ [ No CAS ]

Reference： [1]ACS Catalysis,2018,vol. 8,p. 9899 - 9906

84
[ 623-15-4 ]
[ 29490-19-5 ]
(E)-4-(furan-2-yl)-1-((5-methyl-1,3,4-thiadiazol-2-yl)thio)but-3-en-2-one [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
65%	With deuterium iodide; dimethyl sulfoxide In water at 80℃; for 2.5h; regioselective reaction;

Reference： [1]Siddaraju, Yogesh; Prabhu, Kandikere Ramaiah [Journal of Organic Chemistry, 2018, vol. 83, # 5, p. 2986 - 2992]

85
[ 1401307-67-2 ]
[ 29490-19-5 ]
2-(((4,5-bis(methylthio)-1,3-dithiol-2-ylidene)(naphthalen-1-yl)methyl)thio)-5-methyl-1,3,4-thiadiazole [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
71%	With iodine; In dimethyl sulfoxide; at 25℃; for 12h;Inert atmosphere;	Dithiafulvalenyl compound 1 (0.2 mmol), mercapto-thiazole 2 (2 mmol, 10 equiv.), and I2 (0.6 mmol, 3 equiv., 152.4 mg) were dissolved in DMSO (3 mL). The reaction mixture was stirred at 25 C for 12 h under N2 atomsphere. Then quenched with a saturated solution of Na2S2O3 and stirred for half an hour, the solution was extracted with dichloromethane (CH2Cl2). The organic layer was separated, and dried over Na2SO4. Then the organic solvent was removed in vacuo to afford the respective thiadiazole-based dithiafulvalene (DTF) derivatives (3), which were purified by column chromatography (silica gel, PE / CH2Cl2) to afford pure substances.

Reference： [1]Tetrahedron Letters,2019,vol. 60,p. 124 - 128

86
C₂₀H₁₆S₄ [ No CAS ]
[ 29490-19-5 ]
2-((anthracen-9-yl(4,5-bis(methylthio)-1,3-dithiol-2-ylidene)methyl)thio)-5-methyl-1,3,4-thiadiazole [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
68%	With iodine; In dimethyl sulfoxide; at 25℃; for 12h;Inert atmosphere;	Dithiafulvalenyl compound 1 (0.2 mmol), mercapto-thiazole 2 (2 mmol, 10 equiv.), and I2 (0.6 mmol, 3 equiv., 152.4 mg) were dissolved in DMSO (3 mL). The reaction mixture was stirred at 25 C for 12 h under N2 atomsphere. Then quenched with a saturated solution of Na2S2O3 and stirred for half an hour, the solution was extracted with dichloromethane (CH2Cl2). The organic layer was separated, and dried over Na2SO4. Then the organic solvent was removed in vacuo to afford the respective thiadiazole-based dithiafulvalene (DTF) derivatives (3), which were purified by column chromatography (silica gel, PE / CH2Cl2) to afford pure substances.

Reference： [1]Tetrahedron Letters,2019,vol. 60,p. 124 - 128

87
[ 29490-19-5 ]
2-Naphthalen-1-ylmethylene-5,6-dihydro-[1,3]dithiolo[4,5-b][1,4]dithiine [ No CAS ]
C₁₉H₁₄N₂S₆ [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
59%	With iodine; In dimethyl sulfoxide; at 25℃; for 12h;Inert atmosphere;	Dithiafulvalenyl compound 1 (0.2 mmol), mercapto-thiazole 2 (2 mmol, 10 equiv.), and I2 (0.6 mmol, 3 equiv., 152.4 mg) were dissolved in DMSO (3 mL). The reaction mixture was stirred at 25 C for 12 h under N2 atomsphere. Then quenched with a saturated solution of Na2S2O3 and stirred for half an hour, the solution was extracted with dichloromethane (CH2Cl2). The organic layer was separated, and dried over Na2SO4. Then the organic solvent was removed in vacuo to afford the respective thiadiazole-based dithiafulvalene (DTF) derivatives (3), which were purified by column chromatography (silica gel, PE / CH2Cl2) to afford pure substances.

Reference： [1]Tetrahedron Letters,2019,vol. 60,p. 124 - 128

88
C₂₀H₁₄S₄ [ No CAS ]
[ 29490-19-5 ]
C₂₃H₁₆N₂S₆ [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
57%	With iodine; In dimethyl sulfoxide; at 25℃; for 12h;Inert atmosphere;	Dithiafulvalenyl compound 1 (0.2 mmol), mercapto-thiazole 2 (2 mmol, 10 equiv.), and I2 (0.6 mmol, 3 equiv., 152.4 mg) were dissolved in DMSO (3 mL). The reaction mixture was stirred at 25 C for 12 h under N2 atomsphere. Then quenched with a saturated solution of Na2S2O3 and stirred for half an hour, the solution was extracted with dichloromethane (CH2Cl2). The organic layer was separated, and dried over Na2SO4. Then the organic solvent was removed in vacuo to afford the respective thiadiazole-based dithiafulvalene (DTF) derivatives (3), which were purified by column chromatography (silica gel, PE / CH2Cl2) to afford pure substances.

Reference： [1]Tetrahedron Letters,2019,vol. 60,p. 124 - 128

89
C₂₀H₁₆N₂S₄ [ No CAS ]
[ 29490-19-5 ]
3,3'-((2-(((5-methyl-1,3,4-thiadiazol-2-yl)thio)(naphthalen-1-yl)methylene)-1,3-dithiole-4,5-diyl)bis(thio))dipropanonitrile [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
67%	With iodine; In dimethyl sulfoxide; at 25℃; for 12h;Inert atmosphere;	Dithiafulvalenyl compound 1 (0.2 mmol), mercapto-thiazole 2 (2 mmol, 10 equiv.), and I2 (0.6 mmol, 3 equiv., 152.4 mg) were dissolved in DMSO (3 mL). The reaction mixture was stirred at 25 C for 12 h under N2 atomsphere. Then quenched with a saturated solution of Na2S2O3 and stirred for half an hour, the solution was extracted with dichloromethane (CH2Cl2). The organic layer was separated, and dried over Na2SO4. Then the organic solvent was removed in vacuo to afford the respective thiadiazole-based dithiafulvalene (DTF) derivatives (3), which were purified by column chromatography (silica gel, PE / CH2Cl2) to afford pure substances.

Reference： [1]Tetrahedron Letters,2019,vol. 60,p. 124 - 128

90
C₂₄H₁₈N₂S₄ [ No CAS ]
[ 29490-19-5 ]
3,3'-((2-(anthracen-9-yl((5-methyl-1,3,4-thiadiazol-2-yl)thio)methylene)-1,3-dithiole-4,5-diyl)bis(thio))dipropanonitrile [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
62%	With iodine; In dimethyl sulfoxide; at 25℃; for 12h;Inert atmosphere;	Dithiafulvalenyl compound 1 (0.2 mmol), mercapto-thiazole 2 (2 mmol, 10 equiv.), and I2 (0.6 mmol, 3 equiv., 152.4 mg) were dissolved in DMSO (3 mL). The reaction mixture was stirred at 25 C for 12 h under N2 atomsphere. Then quenched with a saturated solution of Na2S2O3 and stirred for half an hour, the solution was extracted with dichloromethane (CH2Cl2). The organic layer was separated, and dried over Na2SO4. Then the organic solvent was removed in vacuo to afford the respective thiadiazole-based dithiafulvalene (DTF) derivatives (3), which were purified by column chromatography (silica gel, PE / CH2Cl2) to afford pure substances.

Reference： [1]Tetrahedron Letters,2019,vol. 60,p. 124 - 128

91
[ 957759-13-6 ]
[ 29490-19-5 ]
C₁₉H₁₆N₄O₃S₃ [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
61%	With potassium carbonate; In acetone; at 20℃; for 8h;	General procedure: A mixture of 1-(chloroacetyl)-3-(2-thienyl)-5-(1,3-benzodioxol-5-yl)-2-pyrazoline (0.005 mol) and aryl thiol (0.005 mol) in acetone (30 mL) was stirred at room temperature for 8 h in the presence of potassium carbonate (0.005 mol). The solvent was evaporated. The residue was washed with water and dried. The product was recrystallized from ethanol [18, 25].

Reference： [1]Letters in drug design and discovery,2018,vol. 16,p. 82 - 92

92
[ 5535-49-9 ]
[ 29490-19-5 ]
2-methyl-5-((2-(phenylthio) ethyl) thio)-1,3,4-thiadiazole [ No CAS ]

Reference： [1]European Journal of Organic Chemistry,2019,vol. 2019,p. 2635 - 2638
[2]Synlett,2019,vol. 30,p. 1479 - 1483

93
[ 106-94-5 ]
[ 29490-19-5 ]
2-methyl-5-(propylthio)-1,3,4-thiadiazole [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
47.1%	With potassium hydroxide; In ethanol; at 10 - 20℃;	General procedure: The title compounds were prepared by following the Scheme 1. To a cold solution (10 C) of potassium hydroxide (10 mmol) in absolute ethyl alcohol (50 mL), 5-methyl/amino-1,3,4-thidiazole-2-thiol (5 mmol) was added in small lots. The reaction mixture was stirred and cooled to 10 C followed by the addition of a solution of alkyl iodide/bromide or allyl bromide/benzyl chloride (5.5 mmol) or dibromopropane (2.5 mmol) in ethyl alcohol (20 mL). The reaction mixture was stirred at ambient temperature for 7-8 h and thin layer chromatography was used to monitor the progress of reaction by using the solvent system of 1:1 mixture of hexane and ethyl acetate. The solid product was obtained which was filtered followed bywashing with water and recrystallization from ethanol/water.

Reference： [1]European Journal of Organic Chemistry,2019,vol. 2019,p. 2635 - 2638
[2]Synlett,2019,vol. 30,p. 1479 - 1483
[3]Journal of Molecular Structure,2020,vol. 1219

94
[ 29490-19-5 ]
[ 957-68-6 ]
C₁₁H₁₂N₄O₃S₃*ClH [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
95%	With boron trifluoride diethyl etherate; acetic acid; at 5 - 10℃;	Boron trifluoride-dimethyl carbonate complex (2.5mol)Dissolved in 150ml of dimethyl carbonate,Add 132.26 g (1 mol) of compound II,Dissolve with stirring at room temperature,Control the temperature at 5-10 ,Add acetic acid (1mol),Then slowly add 7-ACA 299.49g (1.1mol),Controlled at 5-10 for 1-1.5h,Add hydrochloric acid solution (mass fraction 18%) to pH to 2.5 for crystallization,Filtered, washed with purified water,Vacuum drying to obtain compound III361.85g,Molar yield of 95%,The purity is 99.93%, and the maximum single impurity is 0.03%.

Reference： [1]Patent: CN110437256,2019,A .Location in patent: Paragraph 0025-0033

95
[ 72235-90-6 ]
[ 29490-19-5 ]
1-(5-isopropyl-4-methoxy-2-methylphenyl)-2-((5-methyl-1,3,4-thiadiazol-2-yl)thio)ethan-1-one [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
87%	With potassium carbonate; potassium iodide; In acetonitrile; at 20℃;	General procedure: KI (1.2 equiv) was added to a stirred solution of compound 3(150 mg, 0.62 mmol) in dry acetonitrile (20 mL) at room temperature.After 5 min, the aromatic thiol (1.05 equiv) was added to the resultingcloudy mixture, followed by K2CO3 (1.5 equiv). The mixture was stirredat room temperature for 4 to 24 h, followed by removal of the acetonitrilein vacuo. Column chromatography of the residue using ethylacetate mixtures (100% hexanes to 60% ethyl acetate-hexanes; 12 gcolumn; flow rate 4 mL/min) gave the target compounds in 45-96%yields, based on compound 3. For benzimidazole, amino thiadiazole,and amino triazole, only one equivalent of K2CO3 was used and thesolvent included 20% of water. The mercapto-oxadiazole nucleophilesused in the synthesis of compounds 10-12 were obtained by treatmentof the corresponding pyridine hydrazides with carbon disulfide underbasic conditions, as previously reported [24].

Reference： [1]Inorganica Chimica Acta,2020,vol. 505

96
[ 88284-48-4 ]
[ 29490-19-5 ]
[ 1298111-54-2 ]

Yield	Reaction Conditions	Operation in experiment
100%	With cesium fluoride; In acetonitrile; for 6h;Sealed tube; Inert atmosphere; Reflux;	Add to a three-necked bottle connected to the thermometer, rubber stopper and condenser, and N2 balloon0.037g (0.28mmol) of 5-methyl-2-mercapto-1,3,4-thiadiazole, 0.1g (2.4eq) of cesium fluoride and 3ml of acetonitrile. The device was sealed and replaced with N2 three times. The stirring was started and the temperature was raised to Reflux.Inject the phenylyne precursor through a rubber stopper with a syringe0.1 g (1.2 eq) of 2-trimethylsilyl phenyl trifluoromethanesulfonate, kept at reflux for 6 h, stopped heating and stirring, and cooled to room temperature. 20 ml of water was added, and extracted three times with 10 ml of ethyl acetate. The organic layers were combined, washed twice with 10 ml of saturated NaCl solution, dried with 1 g of anhydrous MgSO 4, filtered, and concentrated to remove the solvent. EA: PE = 1: 5 column chromatography There was obtained 0.058 g of 5-methyl-2-benzenethiol-1,3,4-thiadiazole as a pure product,The reaction near quantitative yield, as a white solid.

Reference： [1]Patent: CN110698422,2020,A .Location in patent: Paragraph 0035; 0036; 0053; 0054

97
[ 1112152-67-6 ]
[ 29490-19-5 ]
2-[(2,3-dihydro-1,4-thiaselenin-2-yl)sulfanyl]-5-methyl-1,3,4-thiadiazole [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
84%	With potassium carbonate; In acetonitrile; at 20℃; for 24h;Inert atmosphere;	General procedure: Method I. Powdered K2CO3 (1 equiv, 0.96-1.36 mmol) was added to a solution of 1,3-thiaselenole 1 (1 equiv, 0.96-1.36 mmol) and heterocyclic thiol 2a,c-f (1 equiv, 0.96-1.36 mmol) in MeCN (3-32 ml). The resulting mixture was stirred under argon atmosphere at room temperature for 17-28 h (Table 1). The reaction mixture was diluted with H2O (6-40 ml) and extracted with CHCl3 (3×3-5 ml). The combined organic extracts were dried over anhydrous MgSO4. For product 3c, the reaction mixture was filtered and the filtrate was concentrated under reduced pressure. The obtained residue was dissolved in Et2O (10 ml) and washed with 5% aq NaOH (5×3 ml). The organic layer was dried over anhydrous MgSO4. Products 3c-f were recrystallized from hexane-CHCl3.

Reference： [1]Chemistry of Heterocyclic Compounds,2020,vol. 56,p. 226 - 232
Khim. Geterotsikl. Soedin.,2020,vol. 56,p. 226 - 232,7

98
[ 56187-37-2 ]
[ 29490-19-5 ]
C₁₀H₇Cl₂N₃O₂S₂ [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
99.7%		In a dry reaction flask, add 200 ml of dichloromethane, add 22.2 g (0.1 mol) of 3,5-dichloro-4-pyridone-1-acetic acid and 2-mercapto-5-methyl-1,3,4 -Thiadiazole 14.55g (0.11mol), stirred, then added triethylamine 10.1g (0.1mol), DMF 1.83g (0.025mmol) stirred at room temperature for 1 hour,Then slowly add dichloromethane solution (triphenyl phosphite 31g dissolved in 50ml of dichloromethane, 0.1mol) dissolved in catalyst triphenyl phosphite, drop within 1 hour, stir at 20-25 After cooling for 1 hour, it was cooled to below 10C, filtered, and the filtrate was spin-dried, and dried under vacuum below 40C to obtain 33.5g (0.099mol) of the thioester compound, with a yield of 99.7% and a HPLC purity of 99.5%.

Reference： [1]Patent: CN111187283,2020,A .Location in patent: Paragraph 0023; 0025; 0027; 0029; 0031; 0033; 0035; 0037

99
[ 75-03-6 ]
[ 29490-19-5 ]
[ 1925-79-7 ]