Synthesis of analogs of pyridoxal 5′-phosphate and pyridoxamine 5′-phosphate

The following analogs of pyridoxamine 5′-phosphate (PAMP) have been synthesized by the direct phosphorylation of the corresponding amines: 2-nor-PAMP, 6-methyl-2-nor-PAMP, and 6-methyl-PAMP. A method for the synthesis of analogs of pyridoxal 5′-phosphate (PLP) by the phosphorylation of the Schiff's bases of the corresponding aldehydes with p-phenetidine and subsequent hydrolysis on a sulfonated resin has been worked out. 2-Nor-PLP, 6-methyl-2-nor-PLP, and 6-methyl-PLP have been obtained with yields of 53–73%. The spectral properties of the compounds obtained have been investigated.     

Nonglycoside analogs of nucleotides

N¹-(2′,3′-Dihydroxypropyl)uracil, -thymine, -cytosine, and N⁹-(2′,3′-dihydroxypropyl)adenine were synthesized by alkylation of nucleic bases with 2,3-O-isopropylideneglycerol chlorohydrin, subsequent separation of the resulting mixtures, and removal of the protective groupings. Phosphorylation of these compounds or of their selectively substituted derivatives gave 2′(3′)-monophosphates, which were converted to 2′,3′-cyclophosphates by reaction with N,N′-dicyclohexylcarbodiimide. Thionation of the corresponding cytosine derivatives gave N¹-(2′,3′-dihydroxypropyl)-4-thiouracil and its 2′(3′) phosphate.     

Nonglycoside analogs of nucleotides

Conclusions We synthesized nine analogs of dinucleoside monophosphates that contain 9-(2-hydroxyethyl)adenine, 9-(3-hydroxypropyl)adenine, and 9-(4-hydroxybutyl)adenine as the 3 residue, and the natural nucleosides: uridine, cytidine, adenosine, guanosine, and inosine as the 5 residue.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 4, pp. 915–916, April, 1975.     

Synthesis and properties of analogs of pyridoxal

A method for the synthesis of analogs of pyridoxal-2-norpyridoxal, 6-methyl-2, 4-pyridoxal, and 6-methylpyridoxal—has been worked out. The reaction of 5-ethoxyoxazoles with maleic diesters gave diesters of substituted 3-hydroxycinchomeric acids, which were converted by reduction with lithium aluminum hydride into analogs of pyridoxine. The latter were oxidized with magnesium dioxide to the corresponding analogs of pyridoxal. The oximes of the aldehydes and their Schiff's bases with p-phenetidine have been obtained. Analogs of pyridoxamine have been obtained by the hydrogenation of the oximes. The UV absorption spectra of the compounds and the ratios of the ionic forms in aqueous solutions have been studied.     

Synthesis of 4-thiouridine derivatives

The thionation of a protected uridine with the aid of P₂S₅ has given the corresponding 4-thiouridine derivatives, which have been phosphorylated at the 5 or the 2(3)hydroxyl. On being heated in aqueous pyridine solution with liquid hydrogen sulfide, cytidine phosphates also form 4-thiouridine phosphates. 4-Thiouridine 2,3-cyclophosphate has been obtained.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 7, pp. 996–1000, July, 1973.The authors thank M. Ya. Karpeiskii for his constant interest in the work and for valuable critical observations.     

Vitamin B6 analogs

3-O-Methylpyridoxal phosphate and 3-O-methylpyridoxamine phosphate were synthesized and their UV spectra were studied.See [7] for communication IX.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 3, pp. 368–372, March, 1971.