The chemistry of heterocyclic methine bases and of their acyl and thioacyl derivatives

Abstract

The work described in this thesis has been dtvided into six sections . The first section involves the reaction of 3,5-diphenyl-2-methyl-l,3,4-oxadiazolium perchlorate with acetic and benzoic anhydrides. The second section deals with the preparation and reactions of 1,3,4-thia diazolium salts. Some monomeric 1,3,4-thiadiazoline methine bases have also been prepared by reacting 1,3,4-thia d iaz ol ium s al t s with concen trated ammonium hydroxide solution. Variable temperature p.m.r. of 2-(3-acetylacetonylidene)-3,5-diphenyl-A4 -1,3,4-thiadiazoline has also been described. The third section deals with prepar a tion and reactions of some compounds in benzoxazole series. The fourth section deals with the prep a ration and reactions of N-alkyl-2-methylbenzothi azolium salts with base , a nd with some a cetylating and thioacetylating agents. Treatment of 2,3-dimethylbenzothiazolium iodide and of 3-ethyl-2-methylbenzothia zolium iodide with base wa s found to give the corresponding dimeric methine b a ses and evidence supporting their structure is also given. Thiol acetic acid was found to exchange 0 for S in its reactions with 2-acetonylidene-3-methylbenzothiazoline and 2-acetophenonylidene-3-methylbenzothi a zoline. (ii) In th e fifth section, the r eactions of 2,3-dimethylbenzselenazolium iodide with a variety of ac e tylating and thioacetylating agents has been described. The treatment of 2,3-dimethylbenzselenazolium iodide with base was found to give rise to a dimeric methine base and evidence supporting its structure is also given. The reactions of this dimeric methine b a se with benzoic anhydride and phenylisothiocyanate have also been described. The sixth section deals with the preparation and reactions of l-alkyl-2-methylquinolinium salts. Treatment of 1,2-dimethylquinolinium iodide and l-ethyl-2-methylquinolinium iodide was found to give the corresponding monomeric methine bases and evidence supporting their structure is also given. The E-type geometry of the olefinic bond in 2-acetonylidene-l-methylquinoline has been established on the basis of an N.O.E. experiment.