Studies of nitriles part 10 synthesis and reactions of 2 acylamino 3 3 bis substituted mercapto acrylonitriles and their derivatives a new synthesis of 2 substituted 5 substituted mercapto oxazole 4 carbonitriles and their derivatives
Matsumura, K.; Miyashita, O.; Shimadzu, H.; Hashimoto, N.
Chemical and Pharmaceutical Bulletin 24(5): 948-959
ISSN/ISBN: 0009-2363 Accession: 006501741
[In the course of investigating the reactivity of ADAN, 2-amino-3,3-dichloroacrylonitrile, the fact that some fluorinated amino acids act as antagonists or antimetabolites of essential amino acids prompted the investigation of the possibility of synthesizing fluorinated amino acids from ADAN.] The reaction of 2-acylamino-3,3-dichloroacrylonitriles with various mercaptans in the presence of base gives 2-acylamino-3,3-bis(substituted mercapto)acrylonitriles or 2-acylamino-3-chloro-3(substituted mercapto)acrylonitriles, each in good yield, depending upon the amount of mercaptans used. Similar nucleophilic substitutions are possible with the corresponding amides, N-acylamides, esters and acid. Treating the 3-mercapto acrylic acid derivatives thus obtained with Ag compounds, such as Ag2O, Ag2CO3 and CH3COOAg, gives an excellent new method for synthesizing 5-(substituted mercapto)oxazoles. The scope and limitations of this new cyclization are described.