N. F. Chernov

Reaction of phenyltrifluorosilane and phenyl(hydrocarbyl)difluorosilanes with bis(2-hydroxyethyl)-and tris(2-hydroxyethyl)amine and their N-methyl and O-trimethylsilyl derivatives. A novel route to quasisilatranes

Reaction of phenyltrifluorosilane, diphenyldifluorosilane, and methylphenyldifluorosilane with bis(2-hydroxyethyl)amine, methyl-bis(2-hydroxyethyl)amine, methyl-bis(2-trimethylsiloxyethyl)amine, leads to 1,3-dioxa-6-aza-2-silacyclooctane derivatives, (N → Si) quasisilatranes: 1,1-difluoroquasisilatrane, 1-phenyl-1-fluoro-5-methylquasisilatrane, or 1-methyl-1-fluoroquasisilatrane, containing the donor-acceptor bond N → Si and pentacoordinate silicon atom. 1-Phenylsilatrane was found to be the product of the reaction of phenyltrifluorosilane with tris(2-trimethylsiloxyethyl)amine, whereas with tris(2-hydroxyethyl)amine 1-phenylsilatrane and 1-fluorosilatrane were formed in the molar ratio of 3:1. The structure of the synthesized compounds was proved by 1H, 13C, 15N, 19F, 29Si NMR and IR spectroscopy.

The unusual reaction of phenyltrifluorosilane with 2-aminoethanol and its N-methyl derivatives

139 In the course of study of the C–Si bond cleavage in phenyltrifluorosilane (PTS) with the aim of using PTS in the synthesis of organoelement compounds [1–6], we studied the reaction of PTS with 2-aminoethanol and its Nmethyland N , N -dimethyl derivatives. Previously, we found that the reaction of protodesilylation of PTS with 8-hydroxyquinoline or 8-mercaptoquinoline leads to new intracomplex heterocyclic compounds, (N Si) 8-(trifluorosiloxy)quinoline or (N Si) 8-(trifluorosilylthio)quinoline, containing a pentacoordinated silicon atom [3] (reaction 1): (1)

Reaction of tetrafluorosilane with tris(2-hydroxyethyl)amine, tris(2-trimethylsiloxyethyl)amine and bis(2-trimethylsiloxyethyl)amine and its N-methyl derivative. 1,1-difluoroquasisilatranes

Reaction of tetrafluorosilane with tris(2-hydroxyethyl)-and tris(2-trimethylsiloxyethyl)amine results in formation of 1-fluorosilatrane and fluorosilatrane in 75 and 53% yield, respectively. Reaction of tetrafluorosilane with bis(2-trimethylsiloxyethyl)amine and its N-methyl derivative leads to the hitherto unknown 1,1-difluoroquasisilatranes (N → Si) F2Si(OCH2CH2)2NR (R = H, Me) containing donor-acceptor bond N → Si and pentacoordinate silicon atom. The structure of the synthesized compounds was proved by 1H, 13C, 15N, 19F, 29Si NMR and IR spectroscopy.

Synthesis and UV spectra of 8-mercaptoquinoline organosilicon derivatives and their metal halides complexes

Abstract IR and UV spectra of (8-quinolylthiomethyl)trimethylsilane ( 1 ), -trimethoxysilane ( 2 ), -silatrane ( 3 ) and their complexes with CuCl 2 , ZnCl 2 , PtCl 2 and SnCl 4 in MeCN have been studied. The UV spectra of 8-methylthioquinoline, its HN + cation and HN + , HS + dication were calculated at the AM1 (CI) level. It was shown that 1 ·PtCl 2 , 2 ·ZnCl 2 and 3 ·ZnCl 2 are chelates. The 2 ·SnCl 4 and 3 ·SnCl 4 compounds have a strong N→Sn bond. The 2 ·CuCl 2 and 3 ·CuCl 2 complexes are a mixture of coordination compounds having N→Cu or N→Cu←S bonds.

Intramolecular O → Si donor-acceptor interaction in R2P(=O)CH2CH2SiF3 molecules: Synthesis of dialkyl [2-(trifluorosilyl)ethyl]phosphonate and bis[(chloromethyl)dimethylsilyl] styrylphosphonate

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 σ0m constants of these substituents, relating to their interaction with π-electron systems.

Organosilicon derivatives of 2-mercapto-substituted benzoxazoles, benzothiazoles and benzimidazoles

The interactions of sodium salts of 2-mercaptobenzoxazole, 2-mercaptobenzothiazole and 2-mercaptobenzimidazole with (chloromethyl)trimethyl-, chloromethyl(dimethoxy)methylor (chloromethyl)trimethoxysilanes have been shown to result in the corresponding previously unknown (2-heterylthiomethyl)triorganylsilanes. Transetherification of (2-heteryl-thiomethyl)trimethoxysilanes with triethanolamine gives 1-(2-benzoxazolylthiomethyl)-, 1-(2-benzothiazolylthiomethyl)- and 1-(2-benzimidazolylthiomethyl)silatranes. The reaction of the corresponding alkoxysilanes with boron trifluoride etherate leads to (2-benzoxazolylthiomethyl)- and (2-benzothiazolylthiomethyl)-substituted trifluorosilanes and methyldifluorosilanes having a dragonoid chelate structure. By the hydrolysis of (2-heterylthiomethyl)trimethoxysilanes, new organosilicon sorbents, poly(2-heteryl-thiomethyl)silsesquioxanes have been synthesized.

Phenyltrifluorosilane in organoelemental and organic synthesis

Ways of phenyltrifluorosilane application in organoelementalal and organic synthesis are summarized and systematized for the first time. The methods of its synthesis, physicochemical properties, and reactivity are considered. Special attention is paid to the original experimental results obtained by the authors.

SI-SUBSTITUTED 8-QUINOLYLTHIOMETHYLSILANES

Abstract(8-Quinolylthiomethyl)trimethoxy- and methyl(8-quinolylthiomethyl)dimethoxysilanes were synthesized and transformed into the corresponding organyltrifluoro- and methyldifluorosilanes. IR spectroscopy revealed the absence of N→Si donor-acceptor interaction in (8-quinolylthiomethyl)trifluorosilane and methyl(8-quinolylthiomethyl)difluorosilane. Transesterification of (8-quinolylthiomethyl)trimethoxysilane with triethanolamine yielded 1-(8-quinolylthiomethyl)silatrane; the crystal and molecular structures of the latter were determined by X-ray study.

New route to 1,1-difluoro-5-methylquasisilatrane

A new route to 1,1-difluoro-5-methylquasisilatrane (N→Si) F2Si(OCH2CH2)2NMe is elaborated: the reaction of chlorinated methyltrifluorosilanes F3SiCH3−nCln (n = 1–3) as well as trifluoro(3-chloropropyl) silane and trifluoro(propenyl)silane with N-methyl-bis(2-hydroxyethyl)amine. The reactivity of the silanes F3SiCH3−nCln increases with the number of chlorine atoms, that is, with the electronegativity of the CH3−nCln group.

Synthesis of N-(trifluorosilylmethyl)glutarimide. Alternate intramolecular coordination of the silicon atom to two oxygen atoms

A new representative of draconoids, N-(trifluorosilylmethyl)glutarimide, was synthesized by reaction of N-(trimethyoxysilylmethyl)glutarimide with boron trifluoride-ether complex. According to the IR and 1H, 13C, 15N, 19F, and 29Si NMR data, this compound molecule is characterized by intramolecular coordination between the silicon and carbonyl oxygen atoms (alternate coordination of the silicon atom to each oxygen atom).