CONVERSION OF PRIMARY AMINES TO CARBAMATE ESTERS USING PALLADIUM-CHLORIDE AND DI-TERT-BUTYL PEROXIDE - DOUBLE CARBONYLATION OF SECONDARY-AMINES
CONVERSION OF PRIMARY AMINES TO CARBAMATE ESTERS USING PALLADIUM-CHLORIDE AND DI-TERT-BUTYL PEROXIDE - DOUBLE CARBONYLATION OF SECONDARY-AMINES
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DOI：
10.1021/om00154a020
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发表时间：
1987-11-01
期刊：
影响因子：
2.8
通讯作者：
MORRIS, GE
中科院分区：
文献类型：
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作者：
ALPER, H;VASAPOLLO, G;MORRIS, GE
1985年，我们报道了伯芳胺与一氧化碳、氧气、酒精、盐酸、氯化铜和氯化钯的反应，以16-99%的产率合成了氨基甲酸酯。2虽然这种反应是在室温和大气压下进行的，但由于一氧化碳和一氧化碳混合物的爆炸性，这种反应速度太慢，商业上不可行，而使用加压是不安全的。此外，与水的联合生产相关的一个不受欢迎的副反应是一氧化碳转化为二氧化碳。因此，在这一过程中，人们努力利用氧气的替代品。最近发现过氧化二铁对钯和铜催化的甲醇氧化甲酸化合成草酸二甲酯和碳酸二甲酯是有效的。3我们现在想报告：(I)这种过氧化氢作为氧的替代品，在脂肪族和芳香族伯胺转化为碳氢化合物方面是非常有用的。
In 1985, we described the reaction ofprimary aromatic amines with carbon monoxide, oxygen, alcohol, hydrochloric acid, cupric chloride, and palladium chloride as the catalyst togive the carbamate ester in 16-99% yield. 2 While this reaction occurs at room temperature and atmospheric pressure, it is too slow to be commercially viable, while the use of elevated pressures is unsafe due to the explosive nature of mixtures of carbon monoxide and ox-ygen. Also, an undesirable side reaction, associated with the coproduction of water, is the conversion of carbon monoxide to carbon dioxide. Therefore, an effort was made to utilize a substitute for oxygen in this process. Recently, di-ferf-butyl peroxide was found to be effective for the palladium-and copper-catalyzed oxidative carbo-nylation of methanol to dimethyl oxalate and dimethyl carbonate. 3 We now wish to report (i) that this peroxide is very useful, as an oxygen substitute, in the conversion of both aliphatic and aromatic primary amines to carba-