2,3-dichlorobenzenethiol

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: To a 500 ml flask equipped with a thermometer, a condenser and a stirrer were added 45.2 g (0.2 mol) of 1-bromo-2,5-dichlorobenzene, 23.7 g (0.4 mol) of 95% potassium hydroxide, 18.4 g (0.2 mol) of thioglycolic acid and 320 g of N-methyl-2-pyrrolidone, followed by stirring at 140° to 150° C. for 2 hours. Assay of the reaction solution by high performance liquid chromatography identified the solution as a mixture of dichlorophenylthioglycolate and dichlorothiophenol salt. Then, after distilling off the solvent, 300 g of water and 50 g of toluene were added for layer separation. To the water layer was added 45 g of concentrated hydrochloric acid, and the mixture was cooled to room temperature. The resulting crystal was filtered and dried to yield 28.7 g of 2,5-dichlorophenylthioglycolic acid. Its melting point was 129° to 131° C., and the yield was 60.5%. The results are given in Table 2. To a 500 ml flask equipped with a thermometer, a condenser and a stirrer Then, after distilling off the solvent, 300 g of water and 50 g of toluene were added for layer separation To the water layer was added 45 g of concentrated hydrochloric acid The resulting crystal was filtered dried

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: To a 500 ml flask equipped with a thermometer, a condenser and a stirrer were added 45.2 g (0.2 mol) of 1-bromo-2,5-dichlorobenzene, 23.7 g (0.4 mol) of 95% potassium hydroxide, 18.4 g (0.2 mol) of thioglycolic acid and 320 g of N-methyl-2-pyrrolidone, followed by stirring at 140° to 150° C. for 2 hours. Assay of the reaction solution by high performance liquid chromatography identified the solution as a mixture of dichlorophenylthioglycolate and dichlorothiophenol salt. Then, after distilling off the solvent, 300 g of water and 50 g of toluene were added for layer separation. To the water layer was added 45 g of concentrated hydrochloric acid, and the mixture was cooled to room temperature. The resulting crystal was filtered and dried to yield 28.7 g of 2,5-dichlorophenylthioglycolic acid. Its melting point was 129° to 131° C., and the yield was 60.5%. The results are given in Table 2. To a 500 ml flask equipped with a thermometer, a condenser and a stirrer Then, after distilling off the solvent, 300 g of water and 50 g of toluene were added for layer separation To the water layer was added 45 g of concentrated hydrochloric acid The resulting crystal was filtered dried

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: The method in which trichlorobenzene and sodium hydrosulfide are reacted at 125° C. under increased pressure in liquid ammonia solvent in the presence of copper acetate catalyst for 10 hours to yield dichlorothiophenol, which is then reacted with sodium monochloroacetate to yield dichlorophenylthioglycolic acid with a yield of 14 to 29% [Kogyo Kagaku Zasshi, 70, 1384 (1967)].

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: The method in which trichlorobenzene and sodium hydrosulfide are reacted at 125° C. under increased pressure in liquid ammonia solvent in the presence of copper acetate catalyst for 10 hours to yield dichlorothiophenol, which is then reacted with sodium monochloroacetate to yield dichlorophenylthioglycolic acid with a yield of 14 to 29% [Kogyo Kagaku Zasshi, 70, 1384 (1967)].

Conditions: temp:50.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: 2,3-Dichlorothiophenol (4.94 g, 28 mmol) was placed in a flask with acrylic acid (2.11 g, 29 mmol) and stirred at 50° C. for 3 hours. The reaction mixture was poured into 10% Na2CO3 and extracted with ether. The aqueous layer was acidified with concentrated hydrochloric acid, extracted with ether, washed with brine, dried over MgSO4, and concentrated in vacuo to give the 3-(2,3-dichlorophenylthio)propanoic acid (3.88 g), contaminated with some acrylic acid, as a clear oil which was used without further purification in the next step. extracted with ether extracted with ether washed with brine dried over MgSO4 concentrated in vacuo

Conditions: temp:50.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: 2,3-Dichlorothiophenol (4.94 g, 28 mmol) was placed in a flask with acrylic acid (2.11 g, 29 mmol) and stirred at 50° C. for 3 hours. The reaction mixture was poured into 10% Na2CO3 and extracted with ether. The aqueous layer was acidified with concentrated hydrochloric acid, extracted with ether, washed with brine, dried over MgSO4, and concentrated in vacuo to give the 3-(2,3-dichlorophenylthio)propanoic acid (3.88 g), contaminated with some acrylic acid, as a clear oil which was used without further purification in the next step. extracted with ether extracted with ether washed with brine dried over MgSO4 concentrated in vacuo

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: Using the method of Example 3, Step A, 2,3-dichlorobenzenethiol (1.69 g, 9.46 mmol), 60% sodium hydride in mineral oil (378 mg, 9.46 mmol), and 2-chloro-4-nitropyridine (1.50 g, 9.46 mmol) were reacted to provide 2-chloro-4-(2,3-dichlorophenylthio)pyridine (1.55 g, 56% yield) as a white powder. 1H NMR (CDCl3) δ 8.19 (d, 1H), 7.61 (d, 1H), 7.54 (d, 1H), 7.29 (t, 1H), 6.95 (s, 1H), 6.87 (d, 1H). were reacted

Conditions: temp:50.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: 2,3-Dichlorothiophenol (4.94 g, 28 mmol) was placed in a flask with acrylic acid (2.11 g, 29 mmol) and stirred at 50° C. for 3 hours. The reaction mixture was poured into 10% Na2CO3 and extracted with ether. The aqueous layer was acidified with concentrated hydrochloric acid, extracted with ether, washed with brine, dried over MgSO4, and concentrated in vacuo to give the 3-(2,3-dichlorophenylthio)propanoic acid (3.88 g), contaminated with some acrylic acid, as a clear oil which was used without further purification in the next step. extracted with ether extracted with ether washed with brine dried over MgSO4 concentrated in vacuo

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: The title compound was prepared as described in Example C(70), where 3-chloro-6-[2-(3-chloro-4-methoxyphenyl)ethyl]-6-cyclopentyldihydro-2H-pyran-2,4(3H)-dione was used in place of 3-chloro-6-[2-(5-chloro-2,4-dimethoxyphenyl)ethyl]6-cyclopentyldihydro-2H-pyran-2,4(3H)-dione and 2,3-dichlorothiophenol was used in place of 6-hydroxy-8-mercaptopurine monohydrate.

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: To a 500 ml flask equipped with a thermometer, a condenser and a stirrer were added 45.2 g (0.2 mol) of 1-bromo-2,5-dichlorobenzene, 23.7 g (0.4 mol) of 95% potassium hydroxide, 18.4 g (0.2 mol) of thioglycolic acid and 320 g of N-methyl-2-pyrrolidone, followed by stirring at 140° to 150° C. for 2 hours. Assay of the reaction solution by high performance liquid chromatography identified the solution as a mixture of dichlorophenylthioglycolate and dichlorothiophenol salt. Then, after distilling off the solvent, 300 g of water and 50 g of toluene were added for layer separation. To the water layer was added 45 g of concentrated hydrochloric acid, and the mixture was cooled to room temperature. The resulting crystal was filtered and dried to yield 28.7 g of 2,5-dichlorophenylthioglycolic acid. Its melting point was 129° to 131° C., and the yield was 60.5%. The results are given in Table 2. To a 500 ml flask equipped with a thermometer, a condenser and a stirrer Then, after distilling off the solvent, 300 g of water and 50 g of toluene were added for layer separation To the water layer was added 45 g of concentrated hydrochloric acid The resulting crystal was filtered dried

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: The method in which trichlorobenzene and sodium hydrosulfide are reacted at 125° C. under increased pressure in liquid ammonia solvent in the presence of copper acetate catalyst for 10 hours to yield dichlorothiophenol, which is then reacted with sodium monochloroacetate to yield dichlorophenylthioglycolic acid with a yield of 14 to 29% [Kogyo Kagaku Zasshi, 70, 1384 (1967)].

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: 15.0 g (83.8 mmol) of 2,3-dichloro-thiophenol are introduced into 50 ml of absolute methanol, 4.5 g (83.8 mmol) of sodium methanolate are added in portions, with cooling, and the mixture is stirred for 15 minutes at room temperature. 6.3 g (83.8 mmol) of chloroacetonitrile are subsequently added dropwise, and the mixture is stirred for 2 hours at room temperature and for a further 5 hours at reflux temperature. The entire batch is then filtered while hot and concentrated in vacuo. 10.8 g (59.1% of theory) of 2,3-dichloro-phenylthioacetonitrile are obtained. are added in portions with cooling the mixture is stirred for 2 hours at room temperature and for a further 5 hours at reflux temperature The entire batch is then filtered while hot and concentrated in vacuo