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Synthesis 2011(20): 3225-3234  
DOI: 10.1055/s-0030-1260211
PAPER
© Georg Thieme Verlag Stuttgart ˙ New York

A Novel Method for Preparing Isocyanides from N-Substituted Formamides with Chlorophosphate Compounds

Genki Kobayashi, Tateo Saito, Yoshikazu Kitano*
Laboratory of Bio-organic Chemistry, Tokyo University of Agriculture and Technology, 3-5-8 Saiwai-cho, Fuchu-shi, Tokyo 183-8509, Japan
Fax: +81(42)3675700; e-Mail: kitayo@cc.tuat.ac.jp;
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Publikationsverlauf

Received 17 June 2011
Publikationsdatum:
07. September 2011 (online)

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Abstract

Treatment of N-substituted formamides with chlorophosphate compounds such as PhOPOCl2, EtOPOCl2, Me2NPOCl2, and (PhO)2POCl and tertiary amines such as triethylamine, pyridine, and N,N-diisopropylethylamine produced the corresponding isocyanides in high yields. This method can be used to prepare various alkyl and aryl isocyanides.

Key words

isocyanide - isonitrile - formamide - dehydration - dichlorophosphate - monochlorophosphate

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7

Chemicals whose acute toxicity by the oral absorption is 50 mg/kg or less are defined as specific controlled poisonous substances under the Poisonous and Deleterious Substances Control Law by National Institute of Health Sciences in Japan. Acute toxicities of POCl3, EtOPOCl2, and PhOPOCl2 are the following according to MSDS of Tokyo Chemical Industry Co., Ltd. and Wako Pure Chemical Industries, Ltd.; POCl3 36 mg/kg (orl-rat), EtOPOCl2 220 mg/kg (orl-rat), PhOPOCl2 850 mg/kg (orl-mam).