67751-11-5Relevant academic research and scientific papers
Orthoamides. LII. Contributions to the synthesis of carboxylic ortho acid amides
Kantlehner, Willi,Stieglitz, Ruediger,Hauber, Michael,Haug, Erwin,Regele, Claudia
, p. 256 - 268 (2007/10/03)
The formamidinium salts 11a, c as well as the nitrile 12 react with sodiumhydride/dimethylamine in the presence of trimethylborate to give the ortho formic acid amide 3a. The orthoamides 6a and 16 can be prepared from the iminium salts 15 and 14, resp. by the same procedure. Treatment of the azavinylogous formamidinium salt 15 with sodiumhydride and piperidine or morpholine in the presence of trime-thylborate affords the orthoamides 6c and 6d, resp. By transamination of the azavinylogous aminalester 5a are accessible the orthoamides 6b-d. The vinylogous orthocarbonic acid derivative 17 can be obtained from the salt 14 and sodium alcoholates. The action of sodiumhydride, dimethylamine and trimethylborate on the iminium salt 18 produces a mixture of the orthocarbonic acid derivatives 7a, 8a, 9a. When the guanidinium salt 20 is treated with the same reagents the ortho-amides 3a and 10a are obtained. The reduction of the salt 20 with sodiumhydride in the presence of several activating reagents (e.g. tetrabutyl orthotitanate, aluminiumisopropylate, trimethylborate) affords the orthoamide 3a. The reduction of the iminium salts 18 and 24 does not proceed clean, giving mixtures of various orthoformic acid derivatives. The form-amidine 25 can be prepared by reduction of the salt 15 with sodiumhydride/trimethylborate with good yields. By the action of the corresponding carbanions on the guanidinium salt 20 can be obtained the carboxylic acid orthoamides 26-33. By the same procedure the orthoamides of alkyne carboxylic acids 36a-h, j-n are accessible. Wiley-VCH Verlag GmbH, 2000.
Ortho Amides, XLVI. - Contributions to the Chemistry of Bis(dialkylamino)malononitriles
Kantlehner, Willi,Greiner, Ulrich
, p. 965 - 973 (2007/10/02)
The reaction of chloroformamidinium chlorides 2 with sodium cyanide in the two-phase system ether/water affords bis(dialkylamino)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 reactionof 3a with malononitrile furnishes the guanidinium salt 14, which cyclized by hydrogen chloride to the pyridinetricarbonitrile 15.In the presence of sodium hydride, 3a and malononitrile or cyanoacetic esters 17 from 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 chlorides 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.
