The author of 《Pyrimidines. II. Nucleophilic substitution reactions of ethyl 4-chloro-2-methylthiopyrimidine-5-carboxylate》 were Shadbolt, Roy S.; Ulbricht, Tilo L. V.. And the article was published in Journal of the Chemical Society [Section] C: Organic in 1967. Application In Synthesis of Ethyl 2,4-diaminopyrimidine-5-carboxylate The author mentioned the following in the article:
cf. CA 56: 470b. Treatment of ethyl 4-chloro-2-(methylthio)pyrimidine-5-carboxylate (I) with dimethylamine, PhONa, PhSNa, KF, or the triethylamine salt of N-hydroxyphthalimide yielded normal substitution products. However, when the chloropyrimidine was treated with NaCN in Me2SO, or LiCN in dimethylformamide, in attempts to prepare the 4-cyano derivative, ethyl 2,4-bis(methylthio)pyridmidine-5-carboxylate was obtained. Investigation of this reaction, and of the other products, suggested that the methylthio group in ethyl-4-chloro-2-(methylthio)pyrimidine-5-carboxylate is displaced by cyanide ion. 4-Chloro-2-(methylthio)pyrimidine reacts similarly to give 2,4-bis(methylthio)pyrimidine, indicating that this reaction may be a general one. The lability of the methylthio group in ethyl 4-chloro-2-(methylthio)pyrimidine-5-carboxylate is also shown by the reaction with an excess of MeONa to give methyl 2,4-dimethoxy-pyrimidine-5-carboxylate. A number of other nucleophilic substitution products derived from ethyl 4-chloro-2-(methylthio)pyrimidine-5-carboxylate are described. 33 references. The experimental part of the paper was very detailed, including the reaction process of Ethyl 2,4-diaminopyrimidine-5-carboxylate(cas: 15400-54-1Application In Synthesis of Ethyl 2,4-diaminopyrimidine-5-carboxylate)
Ethyl 2,4-diaminopyrimidine-5-carboxylate(cas: 15400-54-1) belongs to anime. Primary amines having a tertiary alkyl group (R3CNH2) are difficult to prepare with most methods but are made industrially by the Ritter reaction. In this method a tertiary alcohol reacts with hydrogen cyanide (HCN) in the presence of a concentrated strong acid; a formamide, RNH―CHO, is formed first, which then undergoes hydrolysis.Application In Synthesis of Ethyl 2,4-diaminopyrimidine-5-carboxylate
Referemce:
Pyrimidine | C4H4N2 – PubChem,
Pyrimidine – Wikipedia