Dimethylaminomethylphenyl phenylsilane

InChI= lS/C15H19NSi/cl-16(2)12-13-8-6-7-l 1-15(13)17-14-9-4-3-5-10- 14/h3-1IH, 12,17H2,1-2H3 InChIKey = MZFJXCUWXJGJTB-UHFFFAOYSA-N 

Solubility sol ether, THF, alkanes, aromatics, chlorinated solvents. 

Preparative Methods to 67 g (0.5 mol) of WA-dimethylbenzyl-amine in 300 mL of anhydrous ether are added dropwise under nitrogen 200 mL (0.5 mol) of w-butyllithium (2.5 M in hexane). After being stirred for 48 h at 25 °C, the yellow suspension is transferred into a dropping funnel and added at 0 °C to 54 g (0.5 mol) of phenylsilane in 200 mL of ether. The mixture is stirred for 16 h, then filtered over celite. Solvents are removed under vacuum, and the residue is diluted in pentane, filtered again and fractionally distilled to give 82 g (68%) of 2-(dimethylaminomethylphenyl)phenylsilane (1).  

Related aminoarylsilanes are similarly prepared from 1-(dimethylaminomethyl)naphthalene and l-(dimethylamino)-naphthalene, giving [8-(dimethylaminomethyl)-l-naphthyl]-phenylsilane (2) and [8-(dimethylamino-l-naphthyl]phenyl-silane (3), respectively. 

Pentacoordinated hydrosilanes react with excess aryl isocyanates to give isocyanurates. Carboxylic acids are directly reduced to aldehydes in a one-pot process through the thermal decomposition of pentacoordinated silyl carboxylates (eq 4). The aldehydes are extracted from the crude product mixture by distillation, or separated from the trisiloxane by column chromatography over FlorisU. The reaction is selective, since fluoro, nitro, cyano, methoxy and heteroaryl substituents do not react with the silane. The present method also permits the reduction of Q , -unsaturated acids. The efficiency follows the order (2) (1) (3). 

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A mixture of startg. acid chloride and (o-dimethylaminomethylphenyl)phenylsilane allowed to react until reaction complete (method cf. Synth. Meth. 43, 76) - product. Y 80%. Wet silica gel retains the chlorosilane by-product before distillation of the aldehyde. The method is quick, selective and high-yielding, and work-up is simple esters, halides, ethers, olefins and nitro groups remained unaffected. F.e., work-up procedure, and reagents s. R.J.P. Corriu et al.. Tetrahedron Letters 29,1271-4 (1988). 

Related Reagents. (2-Dimethylaminomethylphenyl)phenyl-silane diphenylsilane-cesium fluoride phenylsilane-cesium fluoride triethylsilane triphenylsilane. 

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