Cyanoacetamide Synthesis in Liquid Ammonia

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概要

• 論文の詳細を見る

• Just analogical to liquid ammonia-malondiamide synthesis, liquid ammonia-cyanoacetamide synthesis has been established, obtaining the following results : 1. Conducting the benzylation of ethyl cyanoacetate, cyanoacetamide and malononitrile in liquid ammonia, C-dibenzyl cyanoacetamide and C-dibenzyl malononitrile have been obtained in high yields. As metalation reagents, metallic sodium, sodium alcoholate, sodium amide and potassium amide were smoothly used. Alkali metals gave, however, slightly lower yields. When an excess of cyanoacetamide was used, monobenzylation predominated, producing monobenzyl cyanoacetamide alone. When benzylation was conducted in benzene solution, dibenzylcyanoacetamide was obtained in very low yield although they were heated for a long time. 2. By alkylating cyanoacetamide with ethyl, propyl and butyl halides, corresponding C-alkyl cyanoacetamides and C-dialkyl cyanoacetamides were obtained respectively. Almost same yields were obtained when alkyl bromides and iodides were used as alkylating reagents. 3. Dialkylating reactions were promoted according to the kind of active methylene group as follows : malondiamide<cyanoacetamide<malononitrile. The effect of alkyl groups on these methylene group was distinct and the alkylating result of cyanoacetamide showed that the tendency of dialkylation was increased according to the following order : C_6H_5CH_2≫n-C_4H_9>iso-C_4H_9=n-C_3H_7>C_2H_5>iso-C_3H_7≫tert-C_4H_9. The system was in coincidence with the order of the+I effect.

• 東北大学の論文

著者

• SHIMO Kotaro

  The Chemical Research Institute of Non-Aqueous Solutions

• ASAMI Ryuzo

  The Chemical Research Institute of Non-Aqueous Sotutions

• Asami Ryuzo

  The Chemical Research Institute Of Non-aqueous Solutions

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