Non-phosgene synthesis of benzyl chloroformate (CbzCl)

Tetrahedron Letters

Volumn 43, Issue 43, 2002, Pages 7765-7767

  Mizuno, Takumi ^a   Takahashi, Junko ^b   Ogawa, Akiya ^b  

^a OSAKA MUNICIPAL TECHNICAL RESEARCH INSTITUTE   (Japan)

^b NARA WOMEN'S UNIVERSITY   (Japan)

Author keywords

Benzyl chloroformate; Carbobenzoxy chloride; Carbon monoxide; Carbonyl sulfide; Carbonylation; Sulfur

Indexed keywords

1,8 DIAZABICYCLO[5.4.0]UNDEC 7 ENE; BENZYL ALCOHOL; BENZYL CHLOROFORMATE; BENZYL DERIVATIVE; BICYCLO COMPOUND; CARBON MONOXIDE; CARBON SULFIDE; CARBONYL DERIVATIVE; CHLORIDE; METHYL GROUP; METHYL IODIDE; PHOSGENE; S METHYL O BENZYL CARBONOTHIOATE; SULFUR; SULFURYL CHLORIDE; UNCLASSIFIED DRUG;

ANALYTIC METHOD; ARTICLE; CHEMICAL PROCEDURES; CHLORINATION; SYNTHESIS;

EID: 0037152274     PISSN: 00404039     EISSN: None     Source Type: Journal    
DOI: 10.1016/S0040-4039(02)01834-8     Document Type: Article

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17. Typical procedure for the synthesis of S-methyl O-benzyl carbonothioate (3a) by the carbonylation with carbonyl sulfide is as follows. A THF solution (50 mL) containing benzyl alcohol (2a) (10.3 mL, 100 mmol) and DBU (22.4 mL, 150 mmol) was vigorously stirred under carbonyl sulfide (0.1 MPa) at 20°C for 1 h. Into the THF solution of carbonothioate salt, methyl iodide (7.5 mL, 120 mmol) was added slowly at 0°C under an argon atmosphere. The reaction mixture was stirred for an additional 2 h at 20°C. The resulting mixture was then poured into 1N HCl (100 mL) and extracted with t-butyl methyl ether (3×100 mL). After evaporation of solvents and purification by vaccum distillation, S-methyl O-benzyl carbonothioate (3a) was obtained in an 87% yield (15.76 g).
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