Electrochemical reduction of unsaturated nitriles in acetonitrile and nitromethane
The electrochemical reduction of five conjugated and non-conjugated nitriles, CH 3CHCHCN ( 1a, trans/cis = 62/38%); CH 3CH 2CHCHCN ( 1b, cis); CH 3CHCHCH 2CN ( 1c, trans), CH 3CHC(CH 3)CN ( 1d) and CH 2CHCH(CH 3)CN ( 1e) have been investigated in acetonitrile, and of two derivatives, 1a and CH...
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Published in | Electrochimica acta Vol. 39; no. 13; pp. 2067 - 2071 |
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Main Authors | , |
Format | Journal Article |
Language | English |
Published |
Oxford
Elsevier Ltd
01.09.1994
Elsevier |
Subjects | |
Online Access | Get full text |
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Summary: | The electrochemical reduction of five conjugated and non-conjugated nitriles, CH
3CHCHCN (
1a, trans/cis = 62/38%); CH
3CH
2CHCHCN (
1b, cis); CH
3CHCHCH
2CN (
1c, trans), CH
3CHC(CH
3)CN (
1d) and CH
2CHCH(CH
3)CN (
1e) have been investigated in acetonitrile, and of two derivatives,
1a and CH
2C(CH
3)CN (
1f) in nitromethane. The results show that unlike activated nitriles which undergo the known electrohydrodimerization (EHD) process in protic media, forming “tail-to-tail” dimeric products, the dimerization in acetonitrile affords mainly “head-to-tail” dimers and other products involving addition of “H” and “CH
2CN” moieties to the carbon—carbon double bond. Moreover, it is noteworthy that the electrochemical dimerization in acetonitrile affords branched dinitriles with an odd number of carbons between the two nitrile groups, rather than the common dimers with an even number of carbons. This type of dimer could serve as a precursor for branched diamines (and diacids) in the polyamide industry.
In nitromethane, no dimeric but “condensation” products were formed, involving one molecule of solvent and one or two molecules of nitrilic substrate. |
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ISSN: | 0013-4686 1873-3859 |
DOI: | 10.1016/0013-4686(94)85090-9 |