These common heterocyclic compound, 1005-56-7, name is O-Phenyl carbonochloridothioate, its traditional synthetic route has been very mature, but the traditional synthetic route has various shortcomings, such as complicated route, low yield, poor purity, etc, below Introduce a new synthetic route. Formula: C7H5ClOS
A suspension of activated zinc dust (98.5 mg, 1.51 mmol) and ethyl bromodifluoroacetate (0.19 mL, 1.51 mmol) in THF (5 mL) was refluxed for 20 min and then cooled to 00C. To this, the solution of the aldehyde (+)- 39 (100 mg, 0.30 mmol) in THF (5 mL) was added. The reaction mixture was warmed to15 room temperature, followed by refluxing for 20 min, and then cooled to room temperature. The reaction mixture was poured into 1 M KHSO4 and extracted with EtOAc (3x 20 mL), washed with brine, dried over MgSO4, concentrated in vacuo, and then purified by column chromatography (10% EtOAc/hexanes) to give 84.5 mg (62%) of a 1:1 mixture of diastereomers of the desired alcohol as a colorless oil. To a solution of ethyl ester (84 mg,20 0.18 mmol) and pyridine (0.066 mL, 0.82 mmol) in CH2Cl2 (5 mL), phenyl chlorothionoformate (0.053 mL, 0.38 mmol) was added. After being stirred at room temperature for 20 hours, the reaction mixture was diluted with water, extracted with ether (3x 20 mL), washed with satd NaHCO3 solution and brine, dried over MgSO4, concentrated in vacuo, and then purified by column chromatography (5% EtOAc/hexanes) to give 97.825 mg (90%) of the desired carbonate as diastereomeric mixtures. To the solution of the resulting phenylthianocarbonate (97.5 mg, 0.16 mmol) in anhydrous benzene (10 mL), 2,2′- azobisisobutyronitrile (AlBN, 5 mg) and tributyltin hydride (0.066 mL, 0.24 mmol) were added at room temperature. After being refluxed for 3 hours, the mixture was cooled to 0 0C, diluted with water, extracted with EtOAc (3x 20 mL), washed with brine, dried over30 MgSO4, concentrated in vacuo, and then purified by column chromatography (3%EtOAc/hexanes) to give 58.2 mg (80%) of the desired difluoro ester 42 as a colorless oil: 1H NMR (400 MHz, CDCl3) delta 4.32 (q, J= 7.2 Hz, 2H), 4.03 (s, IH), 2.14-2.06 (m, IH), 1.98- 1.89 (m, 2H), 1.85-1.75 (m, 2H), 1.69-1.64 (m, IH), 1.61-1.53 (m, 2H), 1.49-1.43 (m, EPO
The synthetic route of O-Phenyl carbonochloridothioate has been constantly updated, and we look forward to future research findings.
Reference:
Patent; JOHNS HOPKINS UNIVERSITY; WO2006/74227; (2006); A2;,
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