1066-64-4Relevant articles and documents
Electrosynthese en chimie organosilicique: silylation selective de polychloromethanes
Pons, P.,Biran, C.,Bordeau, M.,Dunogues, J.
, p. 31 - 38 (1988)
Silylation by electroreduction of carbon tetrachloride, chloroform or methylene chloride is more selective than the common organometallic route.Me3SiCCl3 (94percent) and (Me3Si)2Cl2 (68percent) were thus obtained from CCl4, Me3SiCHCl2, (94percent) and (Me3Si)2CHCl (56percent) from CHCl3 and Me3SiCH2Cl (90percent) from CH2Cl2.Complete silylation of polychloromethanes was also successful by electrosynthesis and gave satisfactory yields.
Polychlorinated materials as a source of polyanionic synthons
Guijarro, Albert,Yus, Miguel
, p. 1797 - 1810 (1996)
The reaction of dichloromethane (1a) or dichlorodideuteriomethane (1b) with an excess of lithium powder (1:7 molar ratio) and a catalytic amount of DTBB (5 mol%) in the presence of a carbonyl compound 2 (1:2 molar ratio) in THF at -40°C yields, after hydrolysis, the corresponding 1,3-diols 3 in moderate yields. The process is applied to other gem-dichlorinated materials such as 7,7-dichloro [4.1.0]heptane (4), 1,1-dichlorotetramethylcyclopropane (7) and dichloromethyl methyl ether (10), using pivalaldehyde as electrophile. Starting from 1,1,1-trichlorinated compounds or tetrachloromethane (14) and using chlorotrimethylsilane as electrophile at temperatures ranging between -80 and -90°C, the corresponding polysilylated compounds 15-17 are prepared applying the mentioned methodology.
Crystal structures of organometallic compounds of lithium and magnesium containing the bulky ligands C(SiMe3)2(SiMe2X) X=Me, Ph, NMe2, or C5H4N-2
Al-Juaid, Salih S.,Avent, Anthony G.,Eaborn, Colin,El-Hamruni, Salima M.,Hawkes, Simon A.,Hill, Michael S.,Hopman, Martijn,Hitchcock, Peter B.,Smith, J. David
, p. 76 - 86 (2001)
The complex [Li(TMEDA){C(SiMe3)2SiMe2NMe2}] (1) (TMEDA=N,N,N′,N′-tetramethylethane-1,2,-diamine) was found to crystallise with an internally coordinated structure like that of [Li(THF)2{C(SiMe3)2SiMe2NMe 2}] (THF=tetrahydrfuran). In contrast, the compound with Ph in place of NMe2 crystallised as a dialkyllithate [Li(TMEDA)2][Li{C(SiMe3)2(SiMe 2Ph)}2] (4). The reaction of 4 with MgBr2 gave the doubly bromide-bridged lithium-magnesium complex [Li(TMEDA)(μ-Br)2Mg{C(SiMe3)2(SiMe 2Ph)}(THF)] (6), and that of [Li(THF){C(SiMe3)2(SiMe2C5H 4N-2)}] gave the singly bridged compound [Li(THF)3(μ-Br)MgBr{C(SiMe3)2(SiMe 2C5H4N-2)] (8). The Grignard reagents [Mg{C(SiMe3)3}I(OEt2)]2 (10) and [Mg{C(SiMe3)2 (SiMe2Ph)}I(OEt2)]2 (11) were obtained from the reactions between (Me3Si)3CI and (Me2Ph)(Me3Si)CI, respectively, with magnesium metal and shown to have halide-bridged structures. The unsymmetrical dialkylmagnesium [MgBu{C(SiMe3)2(SiMe2NMe2)}(THF)] (13), was prepared from a mixture of LiBu, 1 and [MgBr2 (OEt2)2].
Reaction of the (dichloromethyl)oligosilanes R(Me3Si)2Si - CHCl2 (R = Me, Ph, Me3Si) with organolithium reagents and the synthesis of novel kinetically stabilized silenes
Schmohl, Kathleen,Reinke, Helmut,Oehme, Hartmut
, p. 481 - 489 (2007/10/03)
The dichloromethyloligosilanes R1(Me3Si)2Si - CHCl2 (1a,b) (1a: R1 = Me; 1b: R1 = Ph), prepared by treatment of methylbis(trimethylsilyl)silane or phenylbis(trimethylsilyl)silane respective
ZUR HERSTELLUNG UND REAKTIVITAET VON BIS(TRIMETHYLSILYL)DILITHIOMETHAN
Eikema Hommes, N. J. R. van,Bickelhaupt, F.,Klumpp, G. W.
, p. 5237 - 5240 (2007/10/02)
At -90 deg C in THF or similar media bis(trimethylsilyl)dichloromethane 2 reacts with lithium-4,4'-di-tert-butylbiphenyl (LiDBB) or suspensions of freshly sublimed lithium to give the title compound 1 that can bind two equivalents of various electrophiles. 1 has a great propensity for proton abstraction and it is markedly less reactive towards ethyl iodide than (Me3Si)2EtCLi 6.
Preparation of Silan- and Germanimines Me2E=NR (E = Si, Ge) from Sila- and Germadihydrotriazoles
Wiberg, Nils,Karampatses, Petros,Kim, Chung-Kyun
, p. 1203 - 1212 (2007/10/02)
Sila- or germaethene Me2E=C(SiMe3)2 quantitatively react with azidoalkanes or -silanes RN3 nMe3-nSi, Ph3Si, (Me3Si)2NMe2E, Me2SiN3> at -78 deg C by cycloaddition to form sila- or germadihydrotriazoles 3 and 4, respectively.The latter decompose partly below (E = Si, R = silyl), partly at or above room temperature (E = Si, R = alkyl; E = Ge) in a first-order reaction by isomerization into diazomethane derivatives as well as by cycloreversion into (Me3Si)2C=N=N and silan- or germanimines Me2E=NR (rate constants: Table 1).The saturated compounds Me2E= NR are formed as short-lived intermediates.Their stabilization, as a rule, takes place by dimerization and, in exceptional cases, by reaction with the silan- or germanimine sources (R = SiMe3) or by intramolecular migration processes .
