R. M. Kamalov

Reaction of 1,2-borylphosphinoethene with thiocyanates. Molecular and crystal structure of 2,2,3-tributyl-4,5,5-triphenyl-6-methylthio-1,5,2-azaphosphoniaboratacyclohexa-3,6-diene

The reaction of 1,2-borylphosphinoethenes with alkylthiocyanates leads to formation of substances having the structure of 6-alkylthio-1,5,2-azaphosphoniaboratacyclohexa-3,6-dienes in the crystal state. The structure of the compounds has been proven by x-ray diffraction analysis of 2,2,3-tributyl-4,4,5-triphenyl-5-methylthio-1,5,2-azaphosphoniaboratacyclohexa-3,6-diene. The heterocyclic moiety of the molecule is planar within 0.010(2) Å. The methylthio group lies practically in the plane of the heterocycle.

Reaction of 1,2-borylphosphinoethene with phenyl isothiocyanate and carbodiimides

The reaction of 1-butyl-1-dibutylboryl-2-phenyl-2-diphenylphosphinoethene with phenyl isothiocyanate is a [4 + 2]-cycloadditon that involves the C=N segment of the heterocumulene; it gives 2,2,3-tributyl-6-thioxo-1,4,5,5-tetraphenyl-1-aza-5-phosphine-2-boratacyclohex-3-ene. Similarly products of the reaction of 1,2-borylphosphinoethene with diphenyl- and dicyclohexylcarbodiimides rearrange via the 1,2-B → anionotropic C shift of the butyl fragment; the products are the respective 1,6,6-tributyl-3-imino-4,4,5-triphenyl-2-aza-4-phosphine-1-bora-tabicyclo[3.1.0]hexanes.

Experimental and theoretical investigation of intramolecular transformations of silicon-containing (haloalkyl)phosphorylated ureas and acylamides

Silicon-containing chloromethylphosphorylated ureas undergo transformation involving evolution of chlorotrimethylsilane and formation of 1,3,4-oxazaphospholes. Their analogs, silicon-containing phosphorylated acylamides, transform in another way, viz. by β-cleavage to form the corresponding siloxyphosphonates. Quantum-chemical investigation of thermodynamic characteristics of these processes was carried out.

Isothiocyanatochloromethylphosphonates and Phosphinates – Versatile Synthones for Obtaining of S (Se), N, P–Containing Heterocycles

Abstract Isothiocyanatochloromethyl(thio)phosphonates and (thio)-phosphinates 1 (X=O, S; R1 = OPh, CH2Cl, NCS; R2 = H, Cl have been found to be convenient starting material for synthesis of a variety of S (Se), N, P-containing cyclic compounds. They react with different proton containing nucleophiles in the presence of a base with formation of saturated 2 and unsaturated 3 five membered phosphacyclanes. Diisothiocyanatodichloromethylphosphonates 1 (R1 = NCS, R2 =Cl) produce with amines and thiols appropriate bicyclic compounds 4.

REACTIONS OF AMINOPHOSPHINES WITH ALKYL THIOCYANATES. 1,2-BIS[(PHOSPHORANYLIDENE)-AMINO]TETRACYANOETHANES AND N2-ALKYLDICYANOMETHYL-N1-(HEXAETHYLTRIAMINOPHOSPHORANYLIDENE)-CYANOFORMAMIDINES

Abstract Reactions of hexaethyltriaminophosphine and tetraethyldiaminophenylphosphine with alkyl thiocyanates have been found to proceed in an unusual way and to give rise to the appropriate aminophosphine sulfides, alkyl cyanides, dialkyl sulfides and disulfides along with the formation of 1,2-bis[(phosphoranylidene)amino]tetracyanoethanes and N2-alkyldicyanomethyl-N1-(hexaethyltriamino-phosphoranylidene)cyanoformamidines. These reactions were assumed to take both a heterolytic and a homolytic course. X-Ray and mass spectral studies of the polycyanides obtained have been carried out.

Synthesis of cyanamides containing the phenothiazine fragment and their reactions with dialkyldithiophosphoric acids

Reaction of phenothiazine with dialkoxyphosphoryl or chlorosulfenyl isocyanide dichlorides has given 10-cyanophenothiazine, which adds dialkyldithiophosphoric acids at the C≡N bond. The addition products rearrange to 10-[N′-(dialkoxythiophosphoryl) thiocarbamoyl]phenothiazines, which are prone to decompose to dialkoxythiophosphoryl isothiocyanates and phenothiazine, or on treatment with alkyl halides in the presence of base afford stable S-alkyl-N- dialkoxythiophosphoryl (l0-phenothiazinyl)isothioformamides. The reaction between 10-cyanophenothiazine and an excess of dithiophosphoric acids also affords 10-thiocarbamoylphenothiazine and tetraalkyl trithiopyrophosphates. An x-ray diffraction examination of the molecular structure of S-methyl-N-diisopropoxythiophosphoryl-(10-phenothiazinyl)isothioformamide has shown it to possess the Z-configuration. The dihedral angle formed by the benzene rings of the phenothiazine fragment is 125.7°. The products of the addition of dithiophosphoric acids to the C≡N bond of N,N-bis[2′-(10-phenothiazinyl)-2′-oxoethyl]cyanamide, obtained from 10-(chloroacety) phenothiazine and NaNHCN, also isomerize by 1,3S → N migration of the thiophosphoryl group. Subsequent heterocyclization, with elimination of phenothiazine, affords 2-(dialkoxythiophosphorylimino)-3-[2′-(10-phenothiazinyl)-2′-oxoethyl]thiazolidin-5-ones.

Synthesis of 1,3,4-thiaza- and 1,3,4-oxazaphosphol-2-lines based onN-phosphorylated (thio)ureas

The reactions ofO-phenyl chloromethylisothiocyanatothioxophosphonate andO-phenyl chloromethylisocyanatophosphonate with trimethylsilyldiethylamine lead to the formation of 1,3,4-thiazaphosphol-2-ine and 1,3,4-oxazaphosphol-2-ine, respectively. Phosphorylation ofN-methyl-N′-phenyl-N,N′-bis(trimethylsilyl)urea withO-phenyl chloromethylchlorophos phonate gives 1,3,4-diazaphospholidin-2-one.

Reaction of Halidemethyldithio- and Selenothiophosphonic Acids with Alkylthiocyanates – A Novel Method of Synthesizing P, N, S (Se) – Containing Heterocycles

Abstract Novel heterocyclic derivatives - 1,3,4-thiazaphospholines and 1,3,4-selenoazaphospolines 7, were obtained passing hydrogen sulfide or hydrogen selenide 2 through the solution of 0-phenylchloromethyl (chloro)thiophosphonate 1 and alkylthiocyanate followed by addition of triethylamine. It is assumed that 0-phenylchloromethylthiophosphonic and -selenophosphonic acids 3 are formed at the first stage, which further add to CN triple bond of alkylthiocyanates 4 to produce S- or Se-thiophosphonyldithio- or selenothioiminocarbonates 5. The latter undergo phosphorotropic rearrangement into appropriate S-thiophosphonyl dithio- or selenothiocarbamates 6.

Thiocyanic Acid Derivatives in Organophosphorus Syntheses

Abstract The application of thiocyanates and isothiocyanates as convenient and available synthones in the the syntheses of a wide variety of nitrogen- and sulfur-containing organophosphorus compounds with linear, cyclic, bipolar structures has been investigated. Thiocyanates react with organophosphorus reagents depending on the reactivity of the latter via cyano- or thiocyanate-groups substitutions, or addition to C≡N bond. The examples of reactions, including hemolytic routes, have been found and studied. Isothiocyanates can add organophosphorus reagents both to C=N and C=S bonds.