Biochemically important labelled compounds. III. Reaction of orotic acid with bromine water

Morávek, J.; Lešetický, L.

doi:10.1135/cccc19681352

Cited by 3 publications

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“…The mechanism of the oxidation of ester 1 in the system gaseous chlorine -aqueous methanol (methods A-B) is apparently similar to the mechanism established in the studies [12,13] which cover the reaction of uracil and orotic acid with bromine water.…”

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confidence: 80%

Transformations of methyl 6-methyl-2-methylsulfanyl-4-oxo-3,4-dihydro-3-pyrimidinylacetate under oxidative conditions

Jakubkienė

Vainilavicius

2006

Chem Heterocycl Compd

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Keywords: methyl 6-methyl-2-methylsulfanyl-4-oxo-3,4-dihydro-3-pyrimidinylacetate, methyl 5,5-dichloro-6-methoxy-6-methyl-2,4-dioxohexahydro-3-pyrimidinylacetate, methyl 6-methyl-2,4-dioxo-1,2,3,4-tetrahydro-3-pyrimidinylacetate.The alkylsulfonyl group which readily undergoes exchange with nucleophiles is widely used for functionalization of pyrimidines [1][2][3][4][5]. We have previously synthesized the corresponding 2-amino substituted products by treating methyl 6-methyl-2-methylsulfonyl-4-pyrimidinyloxyacetate with amines to give substances having anti-inflammatory activity [6]. The starting ester indicated was readily prepared by oxidation of the corresponding 2-methylsulfanyl-substituted ester using gaseous chlorine in 70% MeOH at -5°C. In this work we have studied the oxidation of methyl 6-methyl-2-methylsulfanyl-4-oxo-3,4-dihydro-3-pyrimidinylacetate (1) by oxidants widely used for conversion of an SMe to SO 2 Me group, i.e. gaseous chlorine in aqueous methanol and water [2], hydrogen peroxide [2, 7], sodium hypochlorite [2,8], and m-chloroperoxybenzoic acid [3,5]. The results obtained are given in Table 1.The oxidation of compound 1 with gaseous chlorine in 70 or 50% methanol at -7 to -5°C (methods A and B) gave, in place of the expected methylsulfonyl-substituted ester 2, only the corresponding hexahydropyrimidinedione methyl 5,5-dichloro-6-methoxy-6-methyl-2,4-dioxohexahydro-3-pyrimidinylacetate (3) in 58 and 57% yield respectively (Scheme 1). The structure was confirmed by the results of elemental analytical and spectroscopic data.The IR spectrum shows three C=O absorption bands at 1712, 1737, and 1756 cm -1 and NH group stretching vibrations at 3357 cm -1 and the absorption characteristic of an SO 2 Me group at 1300-1330 cm -1 [4,7] is absent. The UV spectrum shows only one absorption maximum at 217 nm. It should be noted that the UV spectra of the N (3) -alkyl-substituted 4-pyrimidinones and 2,4-pyrimidinediones (including compounds 1, 4) [9,

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confidence: 80%