- Preparation method 1,4-cyano -2-butene
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The invention discloses a preparation method of 1,4-dicyano-2-butene, and belongs to the field of organic chemistry. Acetylene is used as a raw material; after twice addition with bromine, eliminationis performed to obtain trans 1,2-acetylene dibromide; then, under the catalysis of cuprous salt, the trans 1,2-acetylene dibromide and trimethylsilylacetonitrile take a coupling reaction to obtain 1,4-dicyano-2-butene. During the synthesis, the use of a highly toxic product of hydrogen cyanide is avoided; a novel method is provided for the compound synthesis.
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Paragraph 0017; 0021
(2020/04/17)
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- N-Methyl-N,N-bis(Silatranylmethyl)amine: Structure and reactivity
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Trimethylsilylacetonitrile Me3SiCH2CN and N-methyl-N,N-bis(silatranylmethyl)amine hygrohalogenide were obtained by the interaction of N-methyl-N,N-bis(silatranylmethyl)amine MeN[CH2Si(OCH2CH2)3N]2 1 with MeCN/Me3SiX (X = Cl, I). The key stage of this reaction is the formation of the intermolecular complexes between amine 1 and Me3SiX. The alkylation of amine 1 by ICH2SiX3 (SiX3 = SiMe3, Si(OMe)3 and Si(OCH2CH2)3N) give rise to the generation of the corresponding ammonium salts {(X3SiCH2)MeN[CH2Si(OCH2CH2)3N]2}+I-. The molecular structures of N-methyl-N,N-bis(silatranylmethyl)amine (1), N-methyl-N-[(trimethylsilyl)methyl]-N,N-bis(silatranylmethyl)ammonium iodide (4) and N-methyl-N-N,N-tris(silatranylmethyl)ammonium iodide (6) were determined by single-crystal X-ray diffraction. Compound 1 exists as mix of the conformers 1A (values lN→Si are equal 2.212 ? and 2.274 ?), 1B (values of lN→Si are equal 2.252 ? and 2.272 ?) and 1C (values lN→Si are equal 2.273 ? and 2.291 ?). The length of dative bond N→Si of molecules 1A-1C is longer than in molecules 4 and 6 (Δl lie between 0.105 ? and 0.199 ?), but length of Si–CH2 bond is shorter on 0.001–0.034 ?.
- Albanov, Alexander,Gostevskii, Boris,Lazareva, Nataliya,Shagun, Vladimir,Vashchenko, Alexander
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- Metal-free deprotonative functionalization of heteroaromatics using organic superbase catalyst
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Metal-free deprotonative functionalization of heteroaromatic compounds was achieved using an organic superbase catalyst; an organosilicon additive such as trimethylsilylpropyne was employed for activating the catalytic cycle of 1,2-addition to carbonyl compounds.
- Hirono, Yutaro,Kobayashi, Koji,Yonemoto, Misato,Kondo, Yoshinori
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supporting information; experimental part
p. 7623 - 7624
(2010/12/19)
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- Cyanide initiated perfluoroorganylations with perfluoroorgano silicon compounds
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Cyanophenylphosphanes, Ph2PCN or PhP(CN)2, do not react with Me3SiCF3 or Me3SiC6F5 in the absence of cyanide ions. Catalytic amounts of ionic cyanides such as [NEt4]CN
- Panne, Patricia,Naumann, Dieter,Hoge, Berthold
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p. 283 - 286
(2007/10/03)
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- Electrosynthesis of α-(silyl)alkylnitriles
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Sacrificial anode technique has been used to synthetize title compounds in two different ways. First, use was made of α-chloronitriles as the starting materials, zinc as the anode and a THF-HMPA mixture as the solvent. Second, use of an aluminium-made anode, the nitrile being at the same time the substrate and the solvent was shown to be also efficient.
- Constantieux,Picard
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p. 3895 - 3907
(2007/10/03)
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- Ion Pair Carbon Acidities of Some Silanes in Tetrahydrofuran
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The relative solvent-separated ion pair (SSIP) lithium acidity (pKLi/THF) and contact ion pair (CIP) cesium acidity (pKCs/THF) were obtained for 9-fluorenyltrimethylsilane (1) (21.3, 21.6, respectively) and 9-fluorenyl-tert-butyldimethylsilane (2) (20.3, 20.6, respectively) in THF.Values for pKCs/THF were determined at 25 deg C for (p-biphenylylmethyl)-tert-butyldimethylsilane (3), 35.4, benzyltrimethylsilane (4), 37.5, α,α-bis(trimethylsilyl)toluene (5), 34.1, 2-(trimethylsilyl)-1,3-dithiane (6), 33.5, (trimethylsilyl)acetonitrile (7), 28.8, and tris(trimethylsilyl)methane (8), 36.8.Some thermodynamic parameters were determined by measurements at other temperatures, and some ionic acidities (pK(FI)) were determined by conductivity studies.Carbanion stabilization by these silyl substituents varies from about 1 to over 3 pK units in different systems. 9,9-Bis(trimethylsilyl)fluorene (9) was found to undergo silyl transfer on treatment with various carbanions, but this reaction is slower than proton transfer.
- Streitwieser, Andrew,Xie, Linfeng,Wang, Peng,Bachrach, Steven M.
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p. 1778 - 1784
(2007/10/02)
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- A Convenient Synthesis of 3-Chloro-1-cyanoprop-1-enes
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The one-pot synthesis of 3-chloro-1-cyanoprop-1-enes (mainly Z) from lithium trimethylsilylacetonitrile and α-chlorocarbonyl compounds is described.
- Mauze, Bernard,Miginiac, Leone
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p. 2251 - 2258
(2007/10/02)
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- 12(Et2O)6(C6H14)>, Crystal Structure with the Trimethylsilylacetonitrile Dianion
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Deprotonation of trimethylsilylacetonitrile (1) with either two molar equivalents of n-butyllithium or two molar equivalents of lithium diisopropylamide in ether/hexane leads to the "dianion" Li2(Me3SiCCN) (2) which crystallizes from this solution to give .Twelve "dianions" form an aggregate with a crytallographic inversion center.Six ether molecules (three per asymmetric unit) are coordinating to Li atoms.One molecule of hexane cocrystallizes outside this aggregate.There are three groups of "dianions" differing in the number of their N-Li and C-Li contacts.The solid-state structures of the dilithionitrile differs significantly from the solid-state structure of monolithionitriles. - Key Words: Dilithium trimethylsilylcyanomethanediide
- Zarges, Wolfgang,Marsch, Michael,Harms, Klaus,Boche, Gernot
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p. 1307 - 1312
(2007/10/02)
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- Palladium Catalyzed Coupling Reaction of α-Bromo Ketones with Hexabutylditin
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Palladium-catalyzed reaction of α-bromo ketones with hexabutylditin in the presence of trimethylsilyl chloride gave enol trimethylsilyl ether in moderate to good yields.
- Kosugi, Masanori,Koshiba, Mamoru,Sano, Hiroshi,Migita, Toshihiko
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p. 1075 - 1076
(2007/10/02)
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- Regio- and Stereocontrolled Synthesis of Allenic and Acetylenic Derivatives. Organotitanium and Boron Reagents
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The propargyltitanium reagents derived from 1-alkylpropyne condensed with aldehydes to give α-allenyl alcohol regioselectively, while the allenyltitanium reagents generated from 1-alkyl-1-butyne derivatives gave threo-β-acetylenic alcohols with high regio- and stereoselectivities.The course of the reaction was determined by the substitution pattern of starting alkynes.The similar reactions of metallated 1,3-bis(trialkylsilyl)propyne or (trialkylsilyl)acetonitrile with aldehydes were also investigated.
- Furuta, Kyoji,Ishiguro, Masaharu,Haruta, Ryuichi,Ikeda, Nobuo,Yamamoto, Hisashi
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p. 2768 - 2776
(2007/10/02)
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