Mechanism of methyl esterification of carboxylic acids by trimethylsilyldiazomethane

被引：149

作者：

Kuehnel, Erik

Laffan, David D. P.

Lloyd-Jones, Guy C.

del Campo, Teresa Martinez

Shepperson, Ian R.

Slaughter, Jennifer L.

机构：

[1] Univ Bristol, Sch Chem, Bristol BS8 1TS, Avon, England

[2] AstraZeneca, Macclesfield Works, Macclesfield SK10 2NA, Cheshire, England

来源：

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION | 2007年 / 46卷 / 37期

关键词：

diazo compounds; diazomethane; esterification; isotopic labeling; reaction mechanisms;

D O I：

10.1002/anie.200702131

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

Minimal hazard: A deuterium-labeling study reveals that, contrary to prior assumption, the safe, reliable, and widely adopted method for methyl esterification of carboxylic acids using trimethylsilyldiazomethane (TMS-CHN2) proceeds through the concurrent acid-catalyzed methanolytic liberation of diazomethane (see scheme). © 2007 Wiley-VCH Verlag GmbH & Co. KGaA.

引用

收藏

页码：7075 / 7078

页数：4

相关论文

共 29 条

[1] SOLVOLYSIS OF 2-PYRIDYLTRIMETHYL-SILANE -GERMANE AND -STANNANE BY ALCOHOLS AND BY WATER [J].

ANDERSON, DG ;

WEBSTER, DE .

JOURNAL OF THE CHEMICAL SOCIETY B-PHYSICAL ORGANIC, 1968, (07) :765-&

[2]

AOYAMA T, 1984, CHEM PHARM BULL, V32, P3759

[3] NEW METHODS AND REAGENTS IN ORGANIC-SYNTHESIS .91. TRIMETHYLSILYLDIAZOMETHANE - A CONVENIENT REAGENT FOR THE O-METHYLATION OF ALCOHOLS [J].

AOYAMA, T ;

SHIOIRI, T .

TETRAHEDRON LETTERS, 1990, 31 (38) :5507-5508

[4] Preparation, derivatization with trimethylsilyldiazomethane, and Gc/Ms analysis of a "pool" of alkyl methylphosphonic acids for use as qualitative standards in support of counterterrorism and the chemical weapons convention [J].

Crenshaw, MD ;

Cummings, DB .

PHOSPHORUS SULFUR AND SILICON AND THE RELATED ELEMENTS, 2004, 179 (06) :1009-1018

[5]

CRENSHAW MD, 1999, CHEM BIOL DEFENSE RE, P715

[6] REMARKABLE BRONSTED TYPE CORRELATION FOR BASE CLEAVAGE OF CARBON-SILICON BONDS - KINETIC ISOTOPE-EFFECTS FOR INTERACTION OF CARBANIONS WITH METHANOL [J].

EABORN, C ;

WALTON, DRM ;

SECONI, G .

JOURNAL OF THE CHEMICAL SOCIETY-CHEMICAL COMMUNICATIONS, 1975, (23) :937-939

[7] REACTION OF AMINOMETHYLTRIMETHYLSILANE WITH NITROUS ACID [J].

FESSENDEN, R ;

FREENOR, FJ .

JOURNAL OF ORGANIC CHEMISTRY, 1961, 26 (05) :1681-&

[8] THE MECHANISM OF THE PROTODESILYLATION OF ALLYLSILANES AND VINYLSILANES [J].

FLEMING, I ;

LANGLEY, JA .

JOURNAL OF THE CHEMICAL SOCIETY-PERKIN TRANSACTIONS 1, 1981, (05) :1421-1423

[9] On the distribution of picric acid between benzene and mixtures of light and heavy water. [J].

Gross, P ;

Wischin, A .

TRANSACTIONS OF THE FARADAY SOCIETY, 1936, 32 (01) :0879-0882

[10] SOLUTION AND GAS-PHASE DEUTERIUM DERIVATIZATION REACTIONS FOR GAS-CHROMATOGRAPHY MICROWAVE EMISSION DETECTION [J].

HAGEN, DF ;

HADDAD, LC ;

MARHEVKA, JS .

SPECTROCHIMICA ACTA PART B-ATOMIC SPECTROSCOPY, 1987, 42 (1-2) :253-267