Acetylenedicarboxylic acid anilines

The potassium acid salt of acetylenedicarboxylic acid is commercially obtainable from the National Aniline Division, Allied Chemical and Dye Corporation, New York, New York. Directions for the preparation of the free acid are given in earlier volumes.2-3... 

Formation of the dianilide of acetylenedicarboxylic acid from still another reaction of 16d, photolysis in ether containing aniline, may involve prior reaction 49) of aniline with 16 d. The bis-anhydride (16f) of squaric acid also afforded an acetylene dicarb-... 

Malonic acid ) Citric acid Maleic acid Malic acid Bromomalic acid f Dibromomalic acid Acetylenedicarboxylic acid Acyclic and cyclic ketones Phenol, aniline and derivatives Tartaric acid/Acetone Oxalic acid or Glyoxalic acid Ce(III, IV) Zhabotinskii (Original) [Kasperek Bruice (1971)] [Beck Varady Mag Chem Foly 81 (1975) 519] [Stroot Janjic Helv Chim Acta 58 (1976) 116] [Orban Koros J. Phys. Chem. 82 (1978) 1672] [Rastogi et al. Aachen Meeting (1979) 98-107] [Nosticzius Bodiss J. Am. Chem. Soc. 101 (1979) 3177]... 

Acetylenedicarboxylic add, HOjCC CCOzH, m.p, 175°. Suppliers Farchan, A, B, F. Preparation by reaction of a, 8-dibromosuccinic acid with methanolic potassium hydroxide, isolation of the potassium acid salt, acidification, and extraction with ether. The potassium acid salt is available from National Aniline and from Eastman. 

An ab initio smdy suggests that the formation of a Diels-Alder adduct [i.e. (23)] from reaction between 1-methylpyrrole and dimethyl acetylenedicarboxylate is favoured over the formation of a possible Michael-type addition product (24). Both pathways involve an initial electrophilic substitution at the 2-position of the pyrrole to form a zwitterionic intermediate. A review, in Chinese, concerns a number of electrophilic substitutions of pyridine. A kinetic study has been made of the reaction between 4,6-dinitrobenzofuroxan (25) and various anilines in acidic H2O-DMSO... 

---