THE REACTIONS OF PRIMARY NITROPARAFFINS WITH ISOCYANATES
THE REACTIONS OF PRIMARY NITROPARAFFINS WITH ISOCYANATES
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DOI：
10.1021/ja01505a017
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发表时间：
1960-01-01
影响因子：
15
通讯作者：
HOSHINO, T
中科院分区：
文献类型：
--
作者：
MUKAIYAMA, T;HOSHINO, T
异氰酸酯与伯硝基烷烃如硝乙烷、1-硝基丙烷和苯基硝基甲烷在一定量的叔烷基胺催化下反应，以较高的产率得到缩二取代脲、呋喃和二氧化碳，而不是预期的N-取代-硝基-脂肪酸酰胺加成化合物。该反应被认为是通过中间体胺和丁腈氧化物进行的，这些中间体是由异氰酸酯和ACI-硝基石蜡的加成化合物分解而成的，并自发放出二氧化碳。二取代尿素由胺与异氰酸酯反应生成；呋喃由氧化腈二聚生成。当异氰酸酯、硝化蜡和叔胺在不饱和化合物存在下反应时，可以通过生成异恶唑啉或恶二唑啉来证明中间体氧化腈的存在。在叔烷基胺存在下或叔丁基烷与异氰酸酯发生反应时，未观察到该反应。
The reactions of isocyanates with primary nitroparaffins, such as nitroethane, 1-nitropropane and phenylnitromethane, in the presence of a catalytic amount of tertiary alkyl amine have been found to give sym-disubstituted ureas, furoxane and carbon dioxide in excellent yields, instead of the expected addition compounds of N-substituted-nitro-fatty acid amides. The reaction is thought to proceed through the intermediates amine and nitrile oxide, formed by the decomposition of the addition compound of isocyanate and aci-nitroparaffin with spontaneous evolution of carbon dioxide. The disubstituted urea is formed by the reaction of amine with isocyanate; the furoxane is formed by the dimerization of nitrile oxide. The intermediate nitrile oxide can be demonstrated by the formation of isoxazoline or oxadiazoline when isocyanate, nitroparaffin and tertiary amine are allowed to react in the presence of unsaturated compounds. The reaction is not observed in the ab-sence of teritarv alkyl amine or when tertiary nitroparaffins such as-nitrobutane are allowed to react with isocyanate.