F. J. Aparicio, F. Herrera, M. V. Fernandez
Mar 1, 1979
Citations
0
Influential Citations
9
Citations
Journal
Carbohydrate Research
Abstract
Abstract The reaction of derivatives of polyhydroxyalkyl-β-ketoesters with urea derivatives allowed the synthesis of pyrimidines having a C -polyhydroxyalkyl substituent. Thiourea, S -methylthiourea, and guanidine react with methyl (4 R )-4,5-isopropylidene-dioxy-3-oxopentanoate to give 4-1(4 S )-2,2-dimethyl-1,3-dioxolan-4-yl]-2-methylthio-1,6-dihydropyrimidin-6-one ( 3a ), 4-[(4 S )-2,2-dimethyl-1,3-dioxolan-4-yl]-2-mercap-to-1,6-dihydropyrimidin-6-one ( 3b ), and 2-amino-4-[(4 S )-2,2-dimethyl-1,3-dioxolan-4-yl]-1,6-dihydropyrimidin-6-one ( 3c ), respectively. These structures were proved by physical methods, correlation with well-known reactions, and degradation to orotic acid. Hydrolysis of 3a-c gave 4-[( S )-1,2-dihydroxyethyl]-2-methylthio-1,6-dihydropyrimidin-6-one ( 5a ), 4-[( S )-1,2-dihydroxyethyl]-2-mereapto-1,6-dihydro-pyrimidin-6-one ( 5b ), and 2-amino-4- [( S )- 1,2-dihydroxyethyl]- 1,6-dihydropyrimidin-6-one ( 5c ), respectively. Vigorous hydrolysis of 3a or 3b gave 4-[( S )- 1,2-dihydroxyethyl]- 1,2,3,6-tetrahydropyrimidine-2,6-dione ( 6 ). Desulphuration of 3a or 3b gave 4-[(4 S )-2,2-dimethyl-1,3-dioxolan-4-yl]-1,6-dihydropyrimidin-6-one. Periodate oxidation of 5a and 6 gave 4-formyl-2-methylthio-1,6-dihydropyrimidin-6-one and 4-formyl-1,2,3,6-tetrahydropyrimidine-2,6-dione, respectively.