Carbylamine reaction: Difference between revisions
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The '''carbylamine reaction''' (also known as the |
The '''carbylamine reaction''' (also known as the Saytzeff isocyanide synthesis) is the synthesis of an isocyanide by the reaction of a [[primary amine]], [[chloroform]], and base. The conversion involves the intermediacy of [[dichlorocarbene]]. |
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Illustrative is the synthesis of [[tert-Butyl isocyanide|''tert''-butyl isocyanide]] from [[Tert-Butylamine|''tert''-butylamine]] in the presence of [[catalytic]] amount of the [[phase transfer catalyst]] benzyltriethylammonium [[chloride]].<ref>{{cite journal|author1= Gokel, G.W. |author2=Widera, R.P. |author3=Weber, W.P. | title = Phase-transfer Hofmann Carbylamine Reaction: tert-Butyl Isocyanide| volume=55|doi=10.15227/orgsyn.055.0096| pages = 232| year = 1988 }}</ref> |
Illustrative is the synthesis of [[tert-Butyl isocyanide|''tert''-butyl isocyanide]] from [[Tert-Butylamine|''tert''-butylamine]] in the presence of [[catalytic]] amount of the [[phase transfer catalyst]] benzyltriethylammonium [[chloride]].<ref>{{cite journal|author1= Gokel, G.W. |author2=Widera, R.P. |author3=Weber, W.P. | title = Phase-transfer Hofmann Carbylamine Reaction: tert-Butyl Isocyanide| volume=55|doi=10.15227/orgsyn.055.0096| pages = 232| year = 1988 }}</ref> |
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Revision as of 14:57, 24 July 2019
The carbylamine reaction (also known as the Saytzeff isocyanide synthesis) is the synthesis of an isocyanide by the reaction of a primary amine, chloroform, and base. The conversion involves the intermediacy of dichlorocarbene.
Illustrative is the synthesis of tert-butyl isocyanide from tert-butylamine in the presence of catalytic amount of the phase transfer catalyst benzyltriethylammonium chloride.[1]
- Me3CNH2 + CHCl3 + 3 NaOH → Me3CNC + 3 NaCl + 3 H2O
Similar reactions have been reported for aniline.
Test for primary amines
As it is only effective for primary amines, the carbylamine reaction can be used as a chemical test for their presence. In this context, the reaction is also known as Saytzeff's isocyanide test.[2] In this reaction, the analyte is heated with alcoholic potassium hydroxide and chloroform. If a primary amine is present, the isocyanide (carbylamine) is formed, as indicated by a foul odour. The carbylamine test does not give a positive reaction with secondary and tertiary amines.
Mechanism
The mechanism involves the addition of amine to dichlorocarbene, a reactive intermediate generated by the dehydrohalogenation of chloroform. Two successive base-mediated dehydrochlorination steps result in formation of the isocyanide.
See also
References
- ^ Gokel, G.W.; Widera, R.P.; Weber, W.P. (1988). "Phase-transfer Hofmann Carbylamine Reaction: tert-Butyl Isocyanide". 55: 232. doi:10.15227/orgsyn.055.0096.
{{cite journal}}: Cite journal requires|journal=(help) - ^ Carbylamine reaction