V. A. Naumov

Isomerism in metal complexes of 1,3,5-diazaphosphorinanes. Synthesis, crystal and molecular structure of conformers ofcis-bis(1,3,5-triphenyl-1,3,5-triazaphosphorinane)dichloroplatinum(II)

The crystal and molecular structures were determined for two individual conformers ofcis-bis(1,3,5-triphenyl-1,3,5-diazaphosphorinane)dichloroplatinum(II) differing in the rotation of the heterocyclic ligand planes around the P-Pt bond and in the orientation of the substituents at the phosphorus atoms in the ligands.

Reaction of 2-diethylamino-3-diethylaminomethyl-1,3,2-benzoxazaphospholine with hydroxyl-containing compounds

The reaction of 2-diethylamino-3-diethylaminomethyl-1,3,2-benzoxazaphospholine with functionally substituted alcohols and phenols occurs with the cleavage of exocyclic P-N bond followed by N→P migration of the diethylaminomethyl group and formation of imidophosphonate dimers. A similar reaction with polyhydroxy compounds (diethylene glycol, glycerol) results in symmetrical and asymmetrical spirophosphoranes.

MOLECULAR AND CRYSTAL STRUCTURE OF 2-PHENYL-2-OXO-5,6-BENZO-1,3,2-DIOXAPHOSPHEPINE

The seven-membered heterocycle in the crystal structure of 2-phenyl-2-oxo-5,6-benzo-1,3,2-dioxaphosphepine has distorted (asymmetric) twist conformation and the plane of the phenyl substituent at the phosphorus atom does not coincide with the bisector of the plane of the OPO fragment of the heterocycle and is not perpendicular to it.

Anomeric effect in eight-membered cyclic sulfites with two 1,4-planar fragments

Conclusions1.An x-ray diffraction structural analysis showed that a boat-chair conformation with axial orientation of the S=O bonds is realized in the crystal for 4,5;7,8-(4′,4″-dichloro)-dibenzo-6H-2-oxo-1,3,2-dioxathiocine and 4,5;7,8-(4′,4″-dichloro)dibenzo-6-thia-2-oxo-1,3,2-dioxathiocine.2.The expansion of the O=S-0 bond angles and extension of the S=O bonds in these compounds are attributed to an anomeric effect.

Molecular structure of the reaction product of trimethyl phosphite with 3,4,5-trichloro-2(5H)-furanone

ConclusionsThe chlorine atom in the 4 positionis replaced by a phosphono group in the reaction of 3,4,5-trichloro-2(5H)-furanone with trimethyl phosphite. The structure of dimethyl 3,5-dichloro-2(5H)-furanon-4-ylphosphonate was determined by x-ray diffraction analysis.

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.

STRUCTURE OF AMIDOTHIOPHOSPHORYLATION PRODUCTS DERIVED FROM 2,5-O-METHYLENE-D-MANNITOL

The reaction of 2,5-O-methylene-D-mannitol with tris(N-diethylamino)phosphine and powdered sulfur affords diastereomeric l,3∶4,6-bis-O-(N-diethylaminothiophosphoryl)-2,5-O-methylene-D-mannitols. The absoluteR,R-configuration of one of them was determined by X-ray analysis. In this product one of the two 1,3,2-dioxaphosphorinane rings is in the boat conformation, whereas the other is in the chair conformation. The central 1,3-dioxepane ring adopts an asymmetric chair conformation. All of the three condensed heterocycles aretrans-fused. The manifestations of the anomeric effect in amidothiophosphates of monosaccharides are discussed.

ELECTROPHILIC ADDITION OF LEAD TETRAACETATE TO 2-CARENE IN AN ACIDIC MEDIUM

Oxidation of 2-carene by lead tetraacetate in acetic acid afforded p-menth-1(10),2-dien-7-ol, 2-acetyl-6,6-dimethylbicyclo[3.1.0]hexane, p-menth-2-ene-1α,7-diol, p-menth-1-ene-3β,7-diol, and 2-(m-tolyl)propanol-2.

Molecular structure of 6,6-dimethyl-2-dimethylamino-2-oxo-4,5; 7,8-dibenzo-1,3,6,2-dioxasilaphosphocin and 2-methyl-2,6-dioxo-4,5; 7,8-dibenzo-1,3,2-dioxaphosphocin

An x-ray structural investigation of the synthesized title compounds (1) and (2) has been performed. The heterocycle of 1 has a boat-chair conformation with the P2=O2 bond in the axial position. The heterocycle of 2 has a distorted-boat conformation with the C6=O carbonyl in the plane of one of the fused benzene rings. The P2=O2 bond is in a pseudoequatorial position.

Synthesis of some substituted 1,3-thiazolines and 1,3-thiazolidines

Sodium salts of 2, 2-dimethyl-4-mercapto-5-oxo-1,3-thiazoline and 2-oxo-3-mercapto-1-thia-4-azaspiro[4.5]dec-3-ene, obtained from a solvate of sodium cyanodithioformate with three molecules of dimethylformamide, acetone, or cyclohexanone in the presence of morpholine, react with chlorothioformic dimethylamide with the formation of 2,2-dimethyl-5-oxo-4-(dimethylaminothiocarbonylthio)-1,3-thiazoline and 2-oxo-3-(dimethylaminothiocarbonylthio)-1-thia-4-azaspiro[4.5]dec-3-ene, respectively, and during acidolysis by hydrochloric acid they are converted to 2,2-dimethyl-5-oxo-4-thiono-1,3-thiazolidine and 2-oxo-3-thiono-1-thia-4-azaspiro[4.5]decane. The latter compounds are facilely phosphorylated by dialkyl chlorophosphonates at the nitrogen atom. The reaction of the solvate of sodium cyanodithioformate with three molecules of dimethylformamide with chloroacetone in the presence of morpho-line occurs anomalously with the formation of cyanothioformic morpholide.