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Orthoamide, XLVI. Beiträge zur Chemie von Bis(dialkylamino)malononitrilen
Author(s) -
Kantlehner Willi,
Greiner Ulrich
Publication year - 1990
Publication title -
liebigs annalen der chemie
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.825
H-Index - 155
eISSN - 1099-0690
pISSN - 0170-2041
DOI - 10.1002/jlac.1990199001177
Subject(s) - chemistry , sodium hydride , malononitrile , sodium ethoxide , medicinal chemistry , organic chemistry , carbamic acid , ketene , morpholine , polymer chemistry , catalysis , ethanol
Ortho Amides, XLVI. — Contributions to the Chemistry of Bis(dialkylamino)malononitriles The reaction of chloroformamidinium chlorides 2 with sodium cyanide in the two‐phase system ether/water affords bis(di‐alkylamino)malononitriles 3 with good yields. From 3a and morpholine or aniline the guanidines 5 and 6 can be obtained, respectively. Alcohol‐free sodium ethoxide transforms 3a into the urea acetal 10b , whereas in the reaction of 3a with alkoxides in alcohol ortho carbamic esters 11a , b are produced. The malonic esters and acetoacetic esters 12 react with 3a in the presence of two equivalents of sodium hydride to give the ketene aminals 13 . The reactions of 3a with malononitrile furnishes the guanidinium salt 14 , which is cyclized by hydrogen chloride to the pyridinetricarbonitrile 15 . In the presence of sodium hydride, 3a and malononitrile or cyanoacetic esters 17 form the ketene aminal 16 and the 1,2,3‐tricyanopropenides 18a – c , respectively. The analogous salts 20 and 21 result from the reaction of 3a with the barbituric acid derivatives 19a , and b , respectively. Hydrogen chloride reacts in ether with 3a to afford the piperazinetetracarbonitrile 22 . Reaction of carboxylic acid chloride yields the cyanoformamidinium salt 28a ; byproducts are acyl cyanides 29 and dimeric acyl cyanides 30 . Triethyloxonium tetrafluoroborate transforms 3a into the salt 28b . Bromine and iodine react with 3a to produce the salts 28c , d and 28e , f , respectively, depending on the stoichiometric ratios of the starting materials. The thiocyanate 28g is prepared from sulfur and 3a .