Ilnar D. Nizamov

Optically active dithiophosphoric acid, its ammonium salt, and S-esters on the basis of (1R)-endo-(+)-fenchyl alcohol

GRAPHICAL ABSTRACT Abstract Optically active dithiophosphoric acid was prepared by the reaction of tetraphosphorus decasulfide with (1R)-endo-(+)-fenchyl alcohol. The ammonium salt of dithiophosphoric acid prepared reacts with methyl chloroacetate and benzoyl chloride to give dithiophosphate S-esters.

O,O-Dialkyldithiophosphoric Acids in the Reactions with Nonactivated α-Olefins

Abstract Reactions of O,O-dialkyl dithiophosphoric acids with hexadec-1-ene, octadec-1-ene, and also 2-methylpentadec-1-ene and 2-methylheptadec-1-ene as impurities in commercial samples of hexadec-1-ene and octadec-1-ene, and pure 2-methylpent-1-ene were studied in the presence of zinc chloride and ultrasound irradiation. GRAPHICAL ABSTRACT

Glutathione salts of O,O-diorganyl dithiophosphoric acids: Synthesis and study as redox modulating and antiproliferative compounds

Graphical abstract Figure. No caption available. HighlightsNew bioactive glutathione O,O‐diorganyl dithiophosphates were synthesized.Improved Fenton reaction based assay was proposed to evaluate antioxidant peptides.The dithiophosphates have enhanced redox modulating and antiproliferative activity.The chemical approach can be used to develop bioactive derivatives of peptides. ABSTRACT Reactions of glutathione (GSH) with O,O‐diorganyl dithiophosphoric acids (DTPA) were studied to develop bioactive derivatives of GSH. Effective coupling reaction of GSH with DTPA was proposed to produce the ammonium dithiophosphates (GSH–DTPA) between the NH2 group in &ggr;‐glutamyl residue of GSH and the SH group in DTPA. A series of the GSH–DTPA salts based on O‐alkyl or O‐monoterpenyl substituted DTPA were synthesized. Enhanced radical scavenging activity of the GSH–DTPA over GSH was established with the use of DPPH assay and improved fluorescent assay which utilizes Co/H2O2 Fenton‐like reaction. Similarly to GSH, the dithiophosphates induced both pro‐ and antioxidant effects in vitro attributed to different cellular availability of the compounds. Whereas extracellularly applied GSH greatly stimulated proliferation of cancer cells (PC‐3, vinblastine‐resistant MCF‐7 cells), the GSH–DTPA exhibited antiproliferative activity, which was pronounced for the O‐menthyl and O‐isopinocampheolyl substituted compounds 3d and 3e (IC50 ≥ 1 &mgr;M). Our results show that the GSH–DTPA are promising redox modulating and antiproliferative compounds. The approach proposed can be extended to modification and improvement of bioactivity of various natural and synthetic peptides.

Reactions of 2,4-diaryl 1,3,2,4-dithiadiphosphetane-2,4- disulfides with disilylated resorcinols

Bis(trimethylsilyl) esters of bisaryldithiophosphonic acids were obtained in 70–81% yields by the reactions of 2,4-diaryl 1,3,2,4-dithiadiphospheta ne-2,4-disulfides with 1,3-bis(trimethylsilyloxy)benzene and 2-methyl 1,3-bis(trimethylsilyloxy)benzene. GRAPHICAL ABSTRACT

Dithiophosphorylation of paracetamol

Paracetamol smoothly reacted with 2,4-diaryl-1,3,2λ5,4λ5-dithiadiphosphetane 2,4-disulfides to give O-[4-(acetylamino)phenyl] hydrogen arylphosphonodithioates.

Dithiophosphorylation of nerol and geraniol trimethylsilyl derivatives

Reaction of tetraphosphorus decasulfide with О-(cis- and trans-3,7-dimethylocta-2,6-dien-1-yl)-trimethylsilanes affords О,О-bis(cis- and trans-3,7-dimethylocta-2,6-dien-1-yl) S-(trimethylsilyl)dithiophosphates.

Dithiophosphorylation of trimethylsilyl ethers of carvacrol and thymol

Carvacrol trimethylsilyl ether when reacting with P4S10 forms S-trimethylsilyl ester of O,O-bis(5-isopropyl-2-methylphenyl)dithiophosphoric acid. The reactions of 2,4-diorganyl-1,3,2,4-dithiadiphosphetane-2,4-disulfides with carvacrol (thymol) trimethylsilyl ether yield the S-trimethylsilyl esters of the corresponding dithiophosphoric acids.

2,4-Diorganyl 1,3,2,4-dithiadiphosphetane-2,4-disulfides, their structure and S-silyl dithiophosphonic derivatives

GRAPHICAL ABSTRACT ABSTRACT Novel 2,4-diorganyl 1,3,2,4-dithiadiphosphetane-2,4-disulfides were prepared by the reactions of tetraphosphorus decasulfide with butylphenyl ether or 3-brominephenyl-1-isoamyl ether in 1,2-dichlorobenzene. Their structures were established by X-ray single crystal diffraction. Chiral S-trimethylsilyl dithiophosphonates were prepared by the reactions of 2,4-diorganyl 1,3,2,4-dithiadiphosphetane-2,4-disulfides with trimethyl silyl ethers of monoterpenols. Unsaturated S-trimethylsilyl dithiophosphonates were synthesized by the reactions of 2,4-diorganyl 1,3,2,4-dithiadiphosphetane-2,4-disulfides with O-trimethylsilyl ethers of geraniol, nerol, and (R,S)-linalool. S-Esters of dithiophosphonic acids, which possessed antimicrobial activity, were prepared by the reactions of chiral S-trimethylsilyl dithiophosphonates with orthoformiates, acetals and thioacetals.

New phosphorus dithioacids and their derivatives containing chiral centers and pharmacophoric groups

GRAPHICAL ABSTRACT ABSTRACT New phosphorus dithioacids, their ammonium salts and S-silyl and plumbyl derivatives containing asymmetric carbon atoms and pharmacophoric groups were obtained by the reactions of tetraphosphorus decasulfide and 1,3,2,4-dithiadiphosphetane-2,4-disulfides with chiral natural terpenyl alcohols, diols, carboxylic acid esters, amino acids and monosaccharides as well as synthetic chiral amines and 1-phenylethanol. The biological activity of the ammonium salts and S-esters of phosphorus dithioacids were studied.

Dithiophosphonation of 4-(1H-pyrrol-1-yl)phenol and 4-(1H-imidazol-1-yl)phenol

Reactions of 4-(1H-pyrrol-1-yl)phenol and 4-(1H-imidazol-1-yl)phenol with 2,4-diaryl-1,3,2λ5,4λ5- dithiadiphosphetane 2,4-disulfides gave the corresponding O-4-hetarylphenyl hydrogen arylphosphonodithioates which were converted into ammonium salts. The latter showed antimicrobial activity against Grampositive bacteria and antifungal activity against fungi of the genus Candida.