Malondiamide Synthesis in Liquid Ammonia

概要

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The Malondiamide Synthesis has been studied by conducting metalation and alkylation all in liquid ammonia instead of the malonic Ester Synthesis, obtaining the following results : 1. By conducting benzylation of malondiamide and malondiethyl in liquid ammonia, C-benzyl malondiamide was synthesized. Metallic sodium, sodium amide and alcoholate and potassium amide were used as metalation reagents, obtaining benzyl derivatives in high yield in each case. 2. Alkylation of malondiamide has been conducted using methyl, ethyl, propyl and butyl halides as alkylating reagents, obtaining corresponding C-alkyl malondiamide in each case. The relation between the kind of halogens and alkyl radicals used and the incerasing yields of alkyl compounds produced are as follows : I>Br>Cl ; C_3H_7>C_2H_5≫CH_3, n-C_3H_7>iso-C_3H_7, and n-C_4H_9>iso-C_4H_9≫tert-C_4H_9. 3. Alkylation with alkyl chloride took longer time than that with other halides. It gave, however, the corresponding alkyl derivatives in the yield of 45〜70 per cent. It should be noticed that alkyl chlorides have not been used in the alkylation of active methylene group in the forgoing Malonic Ester Synthesis. The reactions, in the persent experiment, went on very quickly, although the reaction temperature was low. It has been shown that liquid ammonia was a very beneficial solvent for ionic reaction, because these reactions was ionic.
東北大学の論文