New methods and reagents in organic synthesis. 17. Trimethylsilyldiazomethane(TMSCHN2) as a stable and safe substitute for hazardous diazomethane. Its application to the arndt-eistert synthesis.

• AOYAMA TOYOHIKO

• SHIOIRI TAKAYUKI

Abstract

Although diazomethane is used in the Arndt-Eistert synthesis, it is both highly toxic and also explosive, and hence should be very carefully handled. In place of this hazardous diazomethane, stable and safe trimethylsilyldiazomethane (TMSCHN₂) was found to be very useful for the Arndt-Eistert synthesis. TMSCHN₂ was easily acylated with a carboxylic acid chloride in tetrahydrofuran-acetonitrile, and thermal treatment of the acylated product in benzyl alcohol and 2, 4, 6-trimethylpyridine smoothly gave the benzyl ester of a homologated acid. Nucleophiles other than benzyl alcohol could also be used. TMSCHN₂ may also be able to replace diazomethane in other areas of chemistry.

Journal

• Chemical and Pharmaceutical Bulletin

  Chemical and Pharmaceutical Bulletin 29 (11), 3249-3255, 1981

  The Pharmaceutical Society of Japan

Keywords

• diazomethane

Details

• CRID: 1390001204167185152
• NII Article ID: 110003633566
• NII Book ID: AA00602100
• DOI: 10.1248/cpb.29.3249
• COI: 1:CAS:528:DyaL38XosVyiug%3D%3D
• ISSN: 13475223
• ISSN: 00092363
• ISSN: http://id.crossref.org/issn/00092363
• Web Site: http://www.jstage.jst.go.jp/article/cpb1958/29/11/29_11_3249/_pdf
• Web Site: https://search.jamas.or.jp/link/ui/1982209134
• Text Lang: en
• Data Source:
  • JaLC
  • Crossref
  • CiNii Articles
• Abstract License Flag: Disallowed