4424-00-4

[Figure not available: see fulltext.] Alkoxylation of N-substituted heterocyclic aminomethylsilyl moieties was studied using primary and tertiary alcohols. The reaction of 4-(silylmethyl)morpholine and 1-(silylmethyl)azepane under catalyst- and solvent-free conditions leads to the formation of dialkoxy- and trialkoxyaminomethylsilyl derivatives. The methanolysis of 4-(silylmethyl)morpholine resulted in trimethoxyaminomethylsilane formation as the main product and two byproducts, i.e., tetramethoxysilane and N-methylmorpholine.

The purpose of the present invention is to provide silanol compounds that can be used as raw materials of siloxane compounds and the like, and a composition of the silanol compounds, as well as to provide a production method that makes it possible to produce silanol compounds at excellent yield. A composition comprising 5 mass % to 100 mass % of a silanol compound represented by Formulas (A) to (C) can be prepared by devising to produce silanol compounds under water-free conditions, to produce silanol compounds in a solvent having the effect of suppressing the condensation of silanol compounds, and to perform other such processes, the composition being able to be used as a raw material or the like of siloxane compounds because the silanol compounds can be stably present in the resulting composition.

The reaction of complex (ArN=)2Mo(PMe3)3 (Ar = 2,6-diisopropylphenyl) with PhSiH3 gives the β-agostic NSi-H ...Msilyamido complex (ArNd)Mo(SiH2Ph) (PMe3)- (η3-ArN-SiHPh-H) (3) as the first product. 3 decomposes in the mother liquor to a mixture of hydride compounds, including complex {η3-SiH(Ph)-N(Ar)-SiHPh-H ... }MoH 3(PMe3)3 characterized by NMR. Compound 3 was obtained on preparative scale by reacting (ArN=)2Mo(PMe 3)3 with 2 equiv of PhSiH3 under N2 purging and characterized by multinuclear NMR, IR, and X-ray diffraction. Analogous reaction of (Ar′N=)2Mo(PMe3)3 (Ar′ = 2,6-dimethylphenyl) with PhSiH3 affords the nonagostic silylamido derivative (Ar′N=)Mo(SiH2Ph)(PMe3) 2(NAr′{SiH2Ph}) (5) as the first product. 5 decomposes in the mother liquor to a mixture of {η3-PhHSi- N(Ar′)-SiHPh-H ... }MoH3(PMe3)3, (Ar′N=)Mo(H)2(PMe3)2(η2- Ar′N=SiHPh), and other hydride species. Catalytic and stoichiometric reactivity of 3 was studied. Complex 3 undergoes exchange with its minor diastereomer 3′ by an agostic bond-opening/closing mechanism. It also exchanges the classical silyl group with free silane by an associative mechanism which most likely includes dissociation of the Si-H agostic bond followed by the rate-determining silane σ-bond metathesis. However, labeling experiments suggest the possibility of an alternative (minor) pathway in this exchange including a silanimine intermediate. 3 was found to catalyze dehydrogenative coupling of silane, hydrosilylation of carbonyls and nitriles, and dehydrogenative silylation of alcohols and amines. Stoichiometric reactions of 3 with nitriles proceed via intermediate formation of η2- adducts (ArN=)Mo(PMe3)(η2-ArN=SiHPh) (η2-NtCR), followed by an unusual Si-N coupling to give (ArN=)Mo(PMe3)(κ2-NAr-SiHPh-C(R)=N-). Reactions of 3 with carbonyls lead to η2-carbonyl adducts (ArN=) 2Mo(OdCRR0)(PMe3) which were independently prepared by reactions of (ArN=)2Mo(PMe3)3 with the corresponding carbonyl OdCRR′. In the case of reaction with benzaldehyde, the silanimine adduct (ArN=)Mo(PMe3)(η2-ArN=SiHPh)- (η2-O=CHPh) was observed by NMR. Reactions of complex 3 with olefins lead to products of Siag-C coupling, (ArN=)Mo(Et)(PMe 3)(η3-NAr-SiHPh-CH=CH2) (17) and (ArN=)Mo(H)(PMe3)(η3-NAr-SiHPh-CH=CHPh), for ethylene and styrene, respectively. The hydride complex (ArN=)Mo(H)(PMe 3)(η3-NAr-SiHPh-CH=CH2) was obtained from 17 by hydrogenation and reaction with PhSiH3. Mechanistic studies of the latter process revealed an unusual dependence of the rate constant on phosphine concentration, which was explained by competition of two reaction pathways. Reaction of 17 with PhSiH3 in the presence of BPh3 leads to agostic complex (ArN=)Mo(SiH2Ph)(η3-NAr-Si(Et)Ph-H) (η2-CH2=CH2) (24) having the Et substituent at the agostic silicon. Mechanistic studies show that the Et group stems from hydrogenation of the vinyl substituent by silane. Reaction of 24 with PMe 3 gives the agostic complex (ArN=)Mo(SiH2Ph)(PMe 3)(η3-NAr-Si(Et)Ph-H), which slowly reacts with PhSiH3 to furnish silylamide 3 and the hydrosilylation product PhEtSiH2. A mechanism involving silane attack on the imido ligand was proposed to explain this transformation.

Amyloxy and benzyloxysiloxanes were obtained by reacting n-amyl and benzyl alcohols and their water mixtures with SiCl4 in the liquid phase.Their properties, such as refractive index, surface tension, specific heat, coefficient of cubical expansion, silica content, molecular weight, flash and fire points, viscosity and its variation with temperature and pressure, viscosity-temperature coefficient were determined.Based on the experimental data, their tentative structures have been proposed.