Search

Reaction of red phosphorus with acetylene in multiphase superbasic KOH-DMSO system has been studied. The phosphorylation of acetylene results in poly(divinylphosphinic acid).

Dimethyldiselenide reacts with 2,3-dichloro-1-propene at 20–25°C in the hydrazine hydrate-KOH medium to form 2-chloro-3-methylselanyl-1-propene with 90% yield. Diphenyldiselenide in the reaction with 2,3-dichloro-1-propene, depending on the conditions, can give quite selectively four products: 2-chloro-3-phenylselanyl-1-propene, phenylselanylpropadiene, 1-phenylselanyl-1-propyne, and Z-1,2-bis(phenylselanyl)-1-propene. The effect of the selenium atom on the reaction direction and the products structure is discussed.

2,3-Dichloroprop-1-ene reacted with diphenyl disulfide in the system hydrazine hydrate-potassium hydroxide at 30–35°C to give three products: 2-chloro-3-phenylsulfanylprop-1-ene, 1-phenylsulfanylpropadiene, and 1-phenylsulfanylprop-1-yne. Variation of temperature ensures selective synthesis of one of the above products, which confirms their successive formation (domino reaction). The domino reaction at 60°C goes further to afford (Z)-1,2-bis(phenylsulfanyl)prop-1-ene.

The results of the synthesis of tellurium-containing oligomers based on 1-bromo-2-methyl-3-chloropropane are presented. By the example of the reductive splitting of tellurocol the possibility is demonstrated of the synthesis of methyltellanyl derivatives, which are valuable reagents for organic synthesis and for the design of coordination compounds.

Tellurium reacts with dichloromethane in the system hydrazine hydrate-alkali substituting one chlorine atom by tellurium whereas the second chlorine atom undergoes reductive substitution by hydrogen leading to the formation of methyltellanyl derivatives. Tentative mechanism of reduction is discussed. The discovered reaction allows the preparation of organotellurium compounds containing the MeTe group, including those involving other chalcogens.

2,3-Dichloro-1-propene reacts with sulfur dissolved in the system hydrazine hydrate-KOH (with formation of K2S2 or K2S) to afford bis(2-chloro-1-propene-3-yl)sulfide as the main product in both cases. Under similar conditions tellurium induces β-elimination of both chlorine atoms resulting in the formation of allene and complete regeneration of tellurium metal.

A fundamentally new method for the synthesis of 1-halogermatranes and germatranyl esters of oxygen-containing acids has been developed. Using this method germatranes XGe(OCH2CH2)3N (X = Hal, ClO4)were synthesized, their elemental analysis was determined, and their stereoelectronic structure was studied by the methods of multinuclear NMR, mass spectrometry, and IR spectroscopy. The obtained data correlate with the results of quantum chemical calculations.

Methods of synthesis of compounds MeY(CH2Y)nMe (Y=S, Se, Te; n = 1–3) containing several identical or different chalcogen atoms are suggested. The methods are based on the reactions of dichloromethane with elemental chalcogens (Y2−) and dimethyl dichalcogenides (MeY−) activated in the system hydrazine hydrate-alkali. The effect of the chalcogen on the reactivity toward dichloromethane is qualitatively assessed. With elemental tellurium in the system hydrazine hydrate-alkali, reduction of one chlorine atom in dichloromethane and formation of methyltellanyl derivatives are observed.

Ethylene chlorohydrin when reacted with elemental chalcogens or dimethyl dichalcogenides in the hydrazine hydrate-alkali system forms chalcogen-containing analogs of ethylene glycol and its derivatives (dichalcogenated β-diglycols, chalcogenated ethanols, and chalcogenated methyl cellosolves).

The mixtures of mono-and dihalothiophenesulfonyl chlorides, formed in the sulfochlorination reaction of 2,5-dichlorothiophene and 2,5-dibromothiophene, were treated with aqueous ammonia and thus converted into mixtures of the corresponding stable thiophenesulfonamides. The structure and composition of the latter were studied by physicochemical methods: GC-MS and 1H, 13C, 1H-13C HSQC, 1H-13C HMBC, and NOESY NMR spectroscopy. As a result of the above chemical transformations, 2,5-dichlorothiophene afforded a mixture of 5-chlorothiophene-2-sulfonamide and 4,5-dichlorothiophene-3-sulfonamide in a roughly 70:30 ratio. In the case of 2,5-dibromothiophene, a mixture of 5-bromothiophene-2-sulfonamide, 4,5-dibromothiophene-3-sulfonamide, and 3,5-dibromothiophene-2-sulfonamide (3:54:43) was formed.

Oligomeric trimethylene dichalcogenides and the corresponding 1,2-dichalcogenolanes having both similar and different chalcogen atoms in the molecule were synthesized by reactions of 1-bromo-3-chloropropanes with two elemental chalcogens (S, Se; S, Te; Se, Te) activated by the system hydrazine hydrate-alkali. Reductive cleavage of the oligomeric products in the system hydrazine hydrate-alkali, followed by alkylation with methyl iodide or ethyl bromide gave 1,3-bis(alkylchalcogeno)propanes. The latter were also obtained from the corresponding dialkyl dichalcogenides and 1-bromo-3-chloropropane in the alkaline reducing system.

The reaction of diethyl [2-(triethoxysilyl)ethyl]phosphonate with boron trifluoride etherate was used to synthesize diethyl [2-(trifluorosilyl)ethyl]phosphonate. The reaction of bis(trimethylsilyl) styrylphosphonate with chloro(chloromethyl)dimethylsilane gave bis[(chloromethyl)dimethylsilyl] styrylphosphonate. Multinuclear 1H, 13C, 19F, 29Si, and 31P NMR spectroscopy established the absence of a P=O → Si coordination bond in these compounds and the four-coordinate state of the silicon atom. Evidence for this finding was obtained by B3LYP/6-31G(d) quantum-chemical calculations. However, the same calculations for R2P(=O)· CH2CH2SiF3 (R = Me, Me2N) showed the presence in such molecules of an O → Si coordination bond both in the gas phase and in CHCl3 solution. The distance between the O and Si atoms in this series molecules decreases with R in the order: MeO > Me > Me2N. The axial Si-F bond length increases in the same order and parallels the order of the Hammet σ 0 m constants of these substituents, relating to their interaction with π-electron systems.

Direct reaction of propan-1,3-diselenol with thiophene-2-carbaldehydes in trimethylchlorosilane medium is studied. Synthetic procedure for preparation of the previously unknown 1,3-diselenanes of thiophene series is developed. Structure of the newly obtained compounds is established by 1H, 13C, and 77Se NMR spectroscopy. Chromatomass spectrometric stidy of the products obtained is carried out. In some cases reaction may be directed to the synthetis of new types of polymers of original structure.

A synthesis of oligomeric substance of thiocol type, the poly(trimethyleneditelluride), from 1-bromo-3-chloropropane and elemental tellurium is performed using a hydrazine hydrate-alkali system. Reductive splitting of the tellurocol followed by alkylation with methyl iodide give rise to preparation of bis(methyltelluro)propane, which was synthesized also from dimethyltelluride and 1,3-dihalopropanes using the N2H4·H2O/KOH system. Mass spectra of the synthesized low molecular weight organotellurium compounds are considered.

1-Bromo-3-chloropropane and elemental selenium react in hydrazine hydrate-alkali and hydrazine hydrate-amine systems to form poly(trimethylene diselenides). The reductive cleavage of the resulting selenokols yielded 1,3-propanediselenol, 1,2-diselenolane, and bis(alkylseleno)propanes. These compounds are important reagents for organic synthesis and ligands for complex formation. The products obtained were studided by GC-MS.

Alkylthiochloroacetylenes dimerize at room temperature in the system sodium sulfite-polar nonhydroxyl solvent (DMSO, DMF, HMPA) to form in 40-63% yields (Z)-1,4-bis(alkylthio)-1,2-dichloro-1- buten-3-ynes which are promising polyfunctional monomers and building blocks for fine organic synthesis. The structure of the resulting dimers was established by means of IR and 1H and 13C NMR spectroscopy, X-ray fluorescent analysis, and dielcometry and confirmed by mass spectrometry and elemental analysis.

A multistep method is developed for the synthesis of polyunsaturated 15- and 18-membered macrocyclic silicohydrocarbons containing endocyclic CH = CH and C≡C groups in various structures. For the synthesis an intermolecular hydrosilylation reaction of specially synthesized polyfunctional silicohydrocarbons was applied.

Received April 3, 2008 LETTERS TO THE EDITOR ISSN 1070-3632, Russian Journal of General Chemistry, 2008, Vol. 78, No. 9, pp. 1816–1818. © Pleiades Publishing, Ltd., 2008. Original Russian Text © B.A. Trofimov, S.I. Verkhoturova, V.L. Mikhailenko, T.I. Kazantseva, S.N. Arbuzova, А.А. Tatarinova, L.V. Klyba, N.K. Gusarova, 2008, published in Zhurnal Obshchei Khimii, 2008, Vol. 78, No. 9, pp. 1578–1579.

The reaction of BrMgC≡CSiMe2C≡CSiMe2C≡CSiMe2C≡CSiMe2C≡CMgBr with chloro(cyclopentyl)(methyl)silane in a large excess of THF gave 1-cyclopentyl-1,4,4,7,7,10,10,13,13-nonamethyl-1,4,7,10, 13-pentasilacyclopentadeca-2,5,8,11,14-pentayne. Similarly, 1,10-di(cyclopentyl)- or 1,6-di(cyclopentylmethyl)-1,4,4,7,7,10,13,13,16,16-decamethyl-1,4,7,10,13,16-hexasilacyclooctadeca-2,5,8,11,14,17-hexaynes were synthesized from BrMgC≡CSiMe2C≡CSiMe2C≡CMgBr and dichloro(cyclopentyl)methylsilane or dichloro(cyclopentylmethyl)(methyl)silane. Condensation of Me2Si(C≡CMgBr)2 with dichloro(cyclohexyl)-methylsilane afforded 1,7-di(cyclohexyl)-1,4,4,7,10,10-hexamethyl-1,4,7,10-tetrasilacyclododeca-2,5,8,11-tetrayne.

Previously unknown 1,1-diethylnylsilacycloalkanes (CH2)4nSi(C& = CH)2 (n = 3, 4) were prepared by the reaction of HC& = CMgBr with 1,1-dichlorosilacycloalkanes (CH2)4nSiCl2 (n = 3, 4). The reaction of (CH2)4Si(C& = CMgBr)2 with (CH2)4SiCl2 in THF under conditions of high dilution gives cyclo(tetramethylene)- silethynes [(CH2)4SiC& = C]4 with an admixture of cyclodi(tetramethylene)silethyne [(CH2)4SiC& = C]2. The re- action of Me2Si(C& = CSiMe2C& = CMgBr)2 with (CH2)4SiCl2 was used to prepare 1,1,4,4,7,7-hexamethyl-10,10- tetramethylene-1,4,4,10-tetrasilacyclododeca-2,5,8,11-tetrayne.

Selenophosphoryl chlorides R2P(Se)Cl are highly reactive selenophosphorylating reagents widely used in the synthesis of organoelement compounds [1–5]. They readily react with alkylmagnesium halides [1], al-cohols [2], amines [3] and other compounds [4, 5] to form tertiary phosphine selenides as well as esters, amides, and salts of selenophosphinic acids: ligands for the design of single-source precursors of nanomaterials [6, 7], efficient iniferters [8], prospective extragents of the rare-earth elements [9] and coordination media for synthesis of semiconducting nanomaterials [10].