Alexander M. Pinchuk

Synthesis of 7-amino-1-nitro-2-heptanone derivatives

Abstract New N-substituted 7-amino-1-nitro-2-heptanone derivatives have been obtained starting from readily accessible 2-(nitromethylidene)hexahydro-1H-azepine. These compounds have been further used as starting materials for the synthesis of some heterocycles with 5-aminopentyl fragment.

C-Phosphorylation of Azoles in Synthesis of Novel Fused Phosphorus-Containing Heterocycles

Direct C-phosphorylation with phosphorus(III) halides in basic medium has proved to be an efficient and convenient method for the introduction of a variety of phosphorus functions in the electron-rich heteroaromatic1 compounds. When applied to functionalized pyrroles,2 this reaction has afforded a number of novel phosphorus-containing fused heterocycles. Herein, we report on our recent findings concerning the construction of phosphorus-containing fused heterocycles having azole nuclei. Readily available derivatives of 5-amino-1-aryl-3-methylpyrazoles— amides, ureas, and azomethines3—have been subjected to the phosphorylation with P(III) halides in basic medium to produce biand even tricyclic (as in the last case) heterocyclic compounds having an endocyclic phosphorus atom (Figure 1). We explored the same approach concerning 1,3-azoles, known to be phosphorylated via a different mechanism.4 We have shown that the amide 5 (X = CH) reacts with phosphorus tribromide as well as with dibromophenylphosphine in basic medium to yield the 4,5-dihydrobenzo[e]imidazo[2,1-c][1,4,2]diazaphosphinine derivatives, which could be converted into P(V) derivatives 8 and 95 (Figure 2).

C-Thiocarbamoylation of Electron-Rich Heterocycles and Enamines with Amidophosphonium Isothiocyanates

Amidophosphonium isothiocyanates thiocarbamoylate a series of electron-rich heterocycles and enamines at the nucleophilic carbon atom to form phosphazothiocarbonyl compounds. From the most active heterocycles, bis(phosphazothiocarbonyl) derivatives can be obtained.

Phosphorylation of Electron-Rich Aromatic and Heteroaromatic Carboxylic Acid Derivatives

Hitherto unknown direct phosphorylation of electron-rich aromatic and heteroaromatic acid derivatives was used for synthesis of different fused phosphorus-containing heterocycles 1–5. These systems undergo hydrolitical cleavage of a phosphorus-containing ring resulting in o-phosphorylated derivatives of aromatic acids 6,7. 2,3Dihydro-1H-3-phosphindolone 5 undergoes ring transformation into dihydrophosphindolo[3,2-c]pyrazole 8 upon treatment with hydrazine.

C-Phosphorylation of Formamidines

C-Phosphorylation of formamidines by trivalent phosphorus halides was researched. Direction of the phosphorylation depends on nature of substituents at the amidine nitrogens. C-Phosphorylated products was shown to be of valuable possibilities to construct phosphoruscontaining heterocycles

Reaction of Nucleophilic Polyhalogenalkylation in Two and Three-Component Systems

Abstract The halophilic reactions of the derivatives of PIII R3 P (R = R2N, Alk, Ar) with CCl4, having preparative signifi-cance, are studied thoroughly. As far as the compounds of R2PHlg type are concerned, at the beginning of our re-searches there was was an opinion that the interaction of R2PHlg with CC14 cannot be possible because of the low nucleophility of phosphorus. We determined for the first time that diamidochlorophosphites 1 react with CC14 at the temperature 20°C and form the compounds 2, 3.1