ISSN:
0894-3230
Keywords:
Organic Chemistry
;
Physical Chemistry
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
,
Physics
Notes:
The stereochemistry and kinetics of the methoxide ion substitution reactions (Z)- and (E)-methylbenzohydroximoyl cyanidc [PhC(CN)=NOCH3] were investigated. The reaction of the (Z)-hydroximoyl cyanide with sodium methoxide in DMSO-methanol (9:1) solution at 44·8°C gives a mixture of methyl (Z)-O-methylbenzohydroximate [PhC(OCH3)=NOCH3] and the O-methyloxime of α-ketophenylacetamide PhC(CONH2)=NOCH3. The (E)-hydroximoyl cyanide undergoes methoxide ion-catalyzed isomerization to the E-isomer faster than it undergoes nucleophilic substitution. These observations were interpreted in terms of an addition-elimination mechanism in which the rate-limiting step is elimination of the nucleofuge (AN + DN#).
Additional Material:
2 Tab.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1002/poc.610070704
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