Yu. S. Shvetsov

SYNTHESIS OF SOME POLYCYCLIC NONCONDENSED PYRIMIDINE STRUCTURES

Methods for the synthesis of compounds containing two or more pyrimidine rings linked through aliphatic chains with different numbers of carbon atoms are described.

Interamination of some aminooxypyrimidines

Bis(pyrimidinyl)amines have been prepared by reaction of aminooxypyrimidines with aminooxypyrimidine hydrochlorides.

Reaction of the sodium salts of some hydroxypyrimidines with. cap alpha. ,omega-dihaloalkanes. Communication 4. Synthesis of N-(omega-Haloalkyl)uracils

ConclusionsA method has been developed for the preparation of 1,3-bis(ω-haloalkyl)uracils with methylene chains of different lengths in the ω-haloalkyl radicals in the N1 and N3 positions of the pyrimidine ring.

Synthesis and properties of pyrimidinylalkylsulfonamides 4. Reaction of the Na salt of p-toluenesulfonamide with mono-N-(ω-haloalkyl)uracils

The direction of reaction and the composition and yields of products obtained by reaction of the Na salt of p-toluenesulfonamide with N-(ω-bromoalkyl)uracils depend primarily on the length of the alkyl chain in the latter: When the Na salt of p-toluenesulfonamide reacts with N-(ω-bromopropyl)-6-methyluracil, the latter undergoes intramolecular cyclization, whereas the Na salt of p-toluenesulfonamide undergoes intermolecular alkylation at the sulfonamide group on reaction with N-(e-bromopentyl)-6-methyluracil. In analogous reactions, N-(ω-bromobutyl)uracils undergo both intramolecular cyclization, followed by opening of the oxazepine ring by nucleophilic reagents, and intermolecular alkylation.

Synthesis and some properties of pyrimidinylalkylphosphonic acids

A study was made of the reaction of 6-methyluracil, uracil, and 2-amino-4-hydroxy-6-methylpyrimidine with chloromethylphosphonic acid. The structures of some of the products that were formed here were established.

Reaction of the Na salts of 2-amino-6-methyl-4-hydroxypyrimidine with bis(bromomethyl)phosphinic acid

The reaction of the Na salts of 2-amino-6-methyl-4-hydroxypyrimidine and bis(bromomethyl)phosphinic acid gave 3,5-dioxo-1,2,3,4,5,8-hexahydro-7-methyl-1,8-diaza-4a-azonia-3-phosphanaphthalene-3-olate, whose structure was determined by X-ray diffraction study. The molecule has a bipolar structure, in which a positive charge is delocalized on the guanidine fragment and a negative charge is on the phosphinic acid fragment.

Transamination of aminohydroxypyrimidines

The results of the transamination depend on the structure of the aminohydroxypyrimidines, primarily on the position of the amino group in the pyrimidine ring. 5-Aminouracil undergoes this reaction most readily (up to 90% yield at 160~ 2-Amino-6-methyl-4-hydroxypyrimidine reacts with its hydrochloride only at 190-195~ (the yield of the corresponding bis(6-methyl4-hydroxy-2-pyrimidinyl)amine is only 10-15%), and its reaction with 5-aminouracil leads to the formation of only bis(2,4-dihydroxy-4-pyrimidinyl)amine.

Synthesis and properties of N-[ω-(p-toluenesulfonoxyl)alkyl]uracils

ConclusionsThe possibility of N-(ω-hydroxyalkyl)uracil tosylates undergoing intramolecular cyclization to give bicyclic pyrimidinium salts was studied.

Reaction of Na salts of some hydroxypyrimidines with α, ω-dibromoalkanes

Conclusions1.The reaction of the Na salts of hydroxypyrimidines withα,ω-dibromoalkanes gives, besides N-(ω-bromoalkyl)dihydrooxopyrimidines, also the intermolecular transalkylation products.2.The structures of the products obtained by reacting equimolar amounts of the Na salt of 6-methyluracil andα,ω-dibromoalkanes, with a variable number of methylene groups between the bromine atoms, were established and the reasons for the predominant formation of oligomeric products in the given reactions were discussed.

Synthesis and properties of pyrimidinylalkylsulfonamides: 5. Reaction of Na salt of p-toluenesulfonamide with some N-(?-bromoalkyl)uracils, devoid of groupings capable of tautomerism in the pyrimidine ring

Conclusions1.The reaction of N-(γ-bromopropyl)uracils, devoid of groupings capable of tautomerism in the pyrimidine ring, with the Na salt of p-tolue.nesulfonamide proceeds in a number of cases via the step of intramolecular cyclization to give derivatives of pyrimidooxazinium bromides, whose, oxazinium ring is opened by the p-toluenesulfonamide anion to give sulfonimidopyrimidines.2.The crystal structure of 2-oxo-3-(γ-hydroxypropyl)-4-(p-toluenesulfon)imido-1,6-dimethyl-1, 2, 3, 4-tetrahydropyrimidine was determined.