- β-Cyanoethyl anion: Lusus naturae
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A stable El(cb) intermediate, β-cyanoethyl anion (1β), has been synthesized in the gas phase at room temperature under thermal conditions via the fluoride-induced desilylation of 3-(trimethylsilyl)propionitrile. The reactivity and thermodynamic properties of this ion are reported. The cyano group is found to lower the proton affinity of 1β by 29 ± 6 kcal/mol, which represents a particularly large substituent effect. High-level ab initio and density functional calculations have been carried out on 1β and several related species. The computational results are compared to each other, and their accuracy is evaluated.
- Merrill, Grant N.,Dahlke, Gregg D.,Kass, Steven R.
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- Synthesis method of cyano-containing organosilicon compound
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The invention relates to the technical field of synthesis of organosilicon compounds and particularly relates to a synthesis method of a cyano-containing organosilicon compound. The synthesis method is characterized by taking chlorinated nitrile and methyl-containing chlorosilane as raw materials, taking dibromoethane as an initiator and reacting through a one-step Grignard reagent method to generate the cyano-containing organosilicon compound. The structural general formula of chlorinated nitrile is ClCH2(CH2)nCN, wherein n is an integer ranging from 0 to 6; the structural general formula ofmethyl-containing chlorosilane is (CH3)mSiCl4-m, wherein m is an integer ranging from 1 to 3. The synthesis method has the advantages that simple and feasible effects are realized, the raw material reaction rate is high, the synthesis period is short, separation of product is easy and the yield and purity of a target product are high.
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Paragraph 0046-0050
(2019/07/01)
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- Cobalt Carbonyl Catalyzed Hydrosilylation of Nitriles: A New Preparation of N,N-Disilylamines
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Cobalt carbonyl catalyzed hydrosilylation of a wide variety of nitriles with HSiMe3 has been examined.The reaction generally proceeded at 60 deg C to give N,N-disilylamines in good yields.Electron-donating groups on aromatic nitriles facilitated the react
- Murai, Toshiaki,Sakane, Takehiko,Kato, Shinzi
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p. 449 - 453
(2007/10/02)
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- C-Silylated Aldehydes
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By oxidation of 2-(tripropylsilyl))ethanol (4) with N-chlorosuccinimide 2-(tripropylsilyl)acetaldehyde (8) is obtained.By heating 8 is rearranged to tripropylsilyl vinyl ether (9). - The silylating hydrogenation of the acrolein acetals 10 and 11 with trim
- Birkofer, Leonhard,Quittmann, Wilhelm
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p. 2874 - 2882
(2007/10/02)
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- β-Silylcarbonyl Compounds as Masked Enones
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β-Trimethylsilylketones and lactones can be brominated (3)->(4) and desilylbrominated (4)->(5) specifically to place a double bond between the carbonyl group and the β-carbon atom to which the silicon had originally been bound.The silyl group therefore is a base- and acid stable group masking the α,β-unsaturation of enones.Several α-methylene-ketones and -lactones have been prepared in this way.With ketones, the bromination step seems always to introduce bromine mainly or exclusively at the α-position on that side of the ketone on which the β-silyl group is placed, regardless of whether it is more or the less substituted α-position.
- Fleming, Ian,Goldhill, Jon
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p. 1493 - 1498
(2007/10/02)
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