Cyanoethylation and (Methoxycarbonyl)ethylation of Icosahedral ortho-Carborane Derivatives at Carbon Vertices via Michael Additions

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Title:Cyanoethylation and (Methoxycarbonyl)ethylation of Icosahedral ortho-Carborane Derivatives at Carbon Vertices via Michael Additions
Creators:
Plešek, Jaromír
Bačkovský, Jaroslav
Fusek, Jiří
Plzák, Zbyněk
Journal or Publication Title:
Collection of Czechoslovak Chemical Communications, 66, 10, pp. 1499-1507
Uncontrolled Keywords:Michael additions, (Methoxycarbonyl)ethylation, Boranes, Heated-inlet mass spectrometry, Cyanoethylation, Carboranes, <sup>1</sup>H and <sup>11</sup>B NMR spectroscopy, Phase-transfer catalysis

Abstract

The C-H vertices of <i>ortho</i>-carborane and its derivatives can be smoothly cyanoethylated with acrylonitrile in the presence of benzyl(triethyl)ammonium hydroxide in a two-phase system: dichloromethane/water or 1,2-dimethoxyethane/water. The reaction is highly specific and not transferable to its <i>meta</i> and <i>para</i> isomers. No Michael addition with methyl acrylate takes place under these conditions. However, with NaH as catalyst (methoxycarbonyl)ethylation can be accomplished with <i>ortho</i>-carborane; <i>meta</i> and <i>para</i> isomers react neither with acrylonitrile, nor with methyl acrylate even under such forcing conditions. The syntheses, properties and constitutions of 1-(2-cyanoethyl)-<i>ortho</i>-carborane, 1-(2-cyanoethyl)-2-phenyl-<i>ortho</i>-carborane, 1,2-bis(2-cyanoethyl)-<i>ortho</i>-carborane, 1-[2-(methoxycarbonyl)ethyl]-<i>ortho</i>-carborane and 1,2-bis[2-(methoxycarbonyl)ethyl]-<i>ortho</i>-carborane, along with their respective acids, are described. Melting points, TLC, "heated-inlet" mass spectrometry, and the <sup>1</sup>H and <sup>11</sup>B NMR spectra of all compounds, are presented. The scope of cyanoethylations and (methoxycarbonyl)ethylations of other deltahedral carbaboranes and heteroboranes is considered. <p>

Title:Cyanoethylation and (Methoxycarbonyl)ethylation of Icosahedral ortho-Carborane Derivatives at Carbon Vertices via Michael Additions
Creators:
Plešek, Jaromír
Bačkovský, Jaroslav
Fusek, Jiří
Plzák, Zbyněk
Uncontrolled Keywords:Michael additions, (Methoxycarbonyl)ethylation, Boranes, Heated-inlet mass spectrometry, Cyanoethylation, Carboranes, <sup>1</sup>H and <sup>11</sup>B NMR spectroscopy, Phase-transfer catalysis
Divisions:Life and Chemical Sciences > Institute of Organic Chemistry and Biochemistry > Collection of Czechoslovak Chemical Communications
Journal or Publication Title:Collection of Czechoslovak Chemical Communications
Volume:66
Number:10
Page Range:pp. 1499-1507
ISSN:0010-0765
E-ISSN:1212-6950
Publisher:Institute of Organic Chemistry and Biochemistry
Related URLs:
URLURL Type
http://dx.doi.org/10.1135/cccc20011499UNSPECIFIED
ID Code:1873
Item Type:Article
Deposited On:06 Feb 2009 17:13
Last Modified:06 Feb 2009 16:13

Citation

Plešek, Jaromír; Bačkovský, Jaroslav; Fusek, Jiří; Plzák, Zbyněk (2001) Cyanoethylation and (Methoxycarbonyl)ethylation of Icosahedral ortho-Carborane Derivatives at Carbon Vertices via Michael Additions. Collection of Czechoslovak Chemical Communications, 66 (10). pp. 1499-1507. ISSN 0010-0765

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