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1.
The products of the reaction of Me3SiCl with PhTeMgBr in THF have been identified with the aid of high resolution 29Si and 129Te NMR spectroscopy. In addition to the expected product Me2SiTePh (40%), the symmetrical telluride (Me3Si)2Te (10%) and the ether Me3SiO(CH2)4TePh (45%) are also formed. The latter results from ring-opening of the solvent THF by Me3SiCl followed by reaction of the product with PhTeMgBr. 相似文献
2.
Alkyltrichlorosilanes react with DMSO (molar ratio 1 : 1 0 °C) to give cyclic oligoalkylchlorosiloxanes of the general formula
[R(Cl)SiO]
n
(where R=Me or Et;n=3–6). With an excess of alkyltrichlorosilane (2: 1), linear oligoalkylchlorosiloxanes Cl[R(Cl)SiO]
m
SiCl2R (where R=Me or Et;m=1–5) are also formed. In the presence of hexamethyldisiloxane (molar ratio Cl3SiR : DMSO: (Me3Si)2O=1:1:2, 20 °C), the reaction products are both cyclic and linear oligoalkyl(trimethylsilyloxy)siloxanes [R(Me3SiO)SiO]
n
(n=3–5) and Me3Si[OSi(OSiMe3)R]
m
OSiMe3 (m=1–3), respectively. The reaction of DMSO with trichloro(vinyl)silane and hexamethyldisiloxane occurs in a similar manner.
A plausible scheme of formation of the final products via intermediate alkylchlorosilanones RClSi=O and alkyl(trimethylsilyloxy)silanones
is discussed.
Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 2, pp. 361–364, February, 2000. 相似文献
3.
《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2017,129(45):14465-14469
The indium compounds In(N(SiMe3)2)2Cl⋅THF ( 2 ) and In(N(SiMe3)2)Cl2⋅(THF)n ( 3 ) were shown to react with CO2 to give [(Me3Si)2N)InX(μ‐OSiMe3)]2 (X=N(SiMe3)2 4 , Cl 5 ). 0.05–2.0 mol % of the species 3 acts as a pre‐catalyst for the conversion of aryl and alkyl silylamines under CO2 (2–3 atm) to give the corresponding ureas in 70–99 % yields. A proposed mechanism is supported by experimental and computational data. 相似文献
4.
Joerg Harloff 《Journal of organometallic chemistry》2008,693(7):1283-1291
The reaction pathway for the formation of the trimethylsiloxysilyllithium compounds (Me3SiO)RR′SiLi (2a: R = Et, 2b: R = iPr, 2c: R = 2,4,6-Me3C6H2 (Mes); 2a-c: R′ = Ph; 2d: R = R′ = Mes) starting from the conversion of the corresponding trimethylsiloxychlorosilanes (Me3SiO)RR′SiCl (1a-d) in the presence of excess lithium in a mixture of THF/diethyl ether/n-pentane at −110 °C was investigated.The trimethylsiloxychlorosilanes (Me3SiO)RPhSiCl (1a: R = Et, 1b: R = iPr, 1c: R = Mes) react with lithium to give initially the trimethylsiloxysilyllithium compounds (Me3SiO)RPhSiLi (2a-c). These siloxysilyllithiums 2 couple partially with more trimethylsiloxychlorosilanes 1 to produce the siloxydisilanes (Me3SiO)RPhSi-SiPhR(OSiMe3) (Ia-c), and they undergo bimolecular self-condensation affording the trimethylsiloxydisilanyllithium compounds (Me3SiO)RPhSi-RPhSiLi (3a-c). The siloxydisilanes I are cleaved by excess of lithium to give the trimethylsiloxysilyllithiums (Me3SiO)RPhSiLi (2). In the case of the two trimethylsiloxydisilanyllithiums (Me3SiO)RPhSi-RPhSiLi (3a: R = Et, 3b: R = iPr) a reaction with more trimethylsiloxychlorosilanes (Me3SiO)RPhSiCl (1a, 1b) takes place under formation of siloxytrisilanes (Me3SiO)RPhSi-RPhSi-SiPhR(OSiMe3) (IIa: R = Et, IIb: R = iPr) which are cleaved by lithium to yield the trimethylsiloxysilyllithiums (Me3SiO)RPhSiLi (2a, 2b) and the trimethylsiloxydisilanyllithiums (Me3SiO)RPhSi-RPhSiLi (3a, 3b). The dimesityl-trimethylsiloxy-silyllithium (Me3SiO)Mes2SiLi (2d) was obtained directly by reaction of the trimethylsiloxychlorosilane (Me3SiO)Mes2SiCl (1d) and lithium without formation of the siloxydisilane intermediate. Both silyllithium compounds 2 and 3 were trapped with HMe2SiCl giving the products (Me3SiO)RR′Si-SiMe2H and (Me3SiO)RPhSi-RPhSi-SiMe2H. 相似文献
5.
Michael Veith Prof. Dr. Dr. h.c. Andreas Rammo Oliver Schütt Volker Huch 《无机化学与普通化学杂志》2010,636(7):1212-1221
The branched tripodal chloro‐methyl‐siloxanes of the general formula tBuSi[{OSiMe2}yOSiMe3–xClx]3 [x = 0–3; y = 0–2] were synthesized, starting with tert‐Butyl‐trisilanol ( 1 ). The treatment of 1 with the chloro‐methyl‐silanes (Me3–xSiClx+1) (x = 0–3) in the presence of triethylamine leads to the compounds tBuSi(OSiMe2Cl)3 ( 2 ), tBuSi(OSiMeCl2)3 ( 3 ) and tBuSi(OSiCl3)3 ( 4 ). The siloxanes 2 – 4 are colourless oily liquids, which can be purified by distillation. Their yields decrease with the number of chloro substituents. In the reaction of compound 2 with three equivalents of water the silantriol tBuSi(OSiMe2OH)3 ( 5 ) is generated which is used to create the branched tripodal chloro‐methyl‐siloxanes tBuSi(OSiMe2OSiMe3)3 ( 6 ), tBuSi(OSiMe2OSiMe2Cl)3 ( 7 ), tBuSi(OSiMe2OSiMeCl2)3 ( 9 ) and tBuSi(OSiMe2OSiCl3)3 ( 10 ). Compound ( 7 ) is only a side product with a yield of 25 %., The cyclic tBuSi[{(OSiMe2)2Cl}(OSiMe2)3O] ( 8 ) can be isolated and characterised. The transformation of the compound tBuSi(OSiMe2OSiMe2Cl)3 ( 7 ) into the trisilanol tBuSi(OSiMe2OSiMe2OH)3 ( 11 ) allows to prepare the tripodale siloxane tBuSi(OSiMe2OSiMe2OSiMe3)3 ( 12 ) in good yields., The reaction of tBuSi(OSiMe2Cl)3 ( 2 ) with tert‐butyl trisilanol 1 leads to the formation of bicyclic tBuSi(OSiMe2O)3SitBu ( 13 ). An X‐ray structure determination on 13 reveals a [3.3.3]‐bicycle with a C3 axis, which crystallizes in the cubic crystal system in the space group Pa . The reported compounds 2 – 13 were characterised by NMR‐ and IR spectroscopy ( 5 , 11 ) and show correct elemental analyses. The 29Si‐NMR‐data of the compounds show interesting trends with respect to the Si–O chain length and the chloro substistuents. 相似文献
6.
Preparation and Spectroscopic Investigations of Highly Branched Functional Siloxanes The preparation of the siloxanes [(Me3SiO)3SiO]n(Me3SiO)3?nSiX and (Me3SiO)3Si[OSi(OSiMe3)2]2X (n = 1?3, X = H, Cl, OC2H5, OH) is described. The hydride-siloxanes and the siloxanoles have been investigated by i.r. and 29Si-n.m.r. spectroscopy. The frequencies of the Si? H stretching vibration, the 29Si? 1H coupling constants and the 29Si-chemical shifts of the Si(H) signal for the hydride-siloxanes as well as the frequencies of the (Si)O? H stretching vibration, the relative (Si)O? H acidity, and the 29Si-chemical shifts of the Si(OH) signal for the siloxanoles show a dependence on the number of the (Me3SiO)3SiO groups. The spectroscopic data are discussed with respect to the silicate environment of the Si(H) and Si(OH) atom, respectively. In the siloxanoles intramolecular hydrogen bondings were observed. 相似文献
7.
Tatyana V. Balashova Dmitry M. Kusyaev Tatyana I. Kulikova Olga N. Kuznetsova Frank T. Edelmann Prof. Dr. Stephan Gießmann Steffen Blaurock Mikhail N. Bochkarev Prof. Dr. 《无机化学与普通化学杂志》2007,633(2):256-260
The reactivity of neodymium diiodide, NdI2 ( 1 ), towards organosilicon, ‐germanium and ‐tin halides has been investigated. Compound 1 readily reacts with Me3SiCl in DME to give trimethylsilane (6 %), hexamethyldisilane (4 %) and (Me3Si)2O (19 %). The reaction with Et3SiBr in THF results in formation of Et3SiSiEt3 (17 %) and Et3SiOBun (34 %). Alkylation of Me3SiCl with PrnCl in the presence of 1 in THF affords Me3SiPrn (10 %), Me3SiOBun (52 %) and Me3SiSiMe3 (1 %). The main product identified in the reaction mixture formed upon interaction of 1 with dichlorodimethylsilane Me2SiCl2 in THF is di‐n‐butoxydimethylsilane Me2Si(OBun)2 (54 %) together with minor amounts of Me2Si(OBun)Cl. The reaction of 1 with Me3GeBr under the same conditions produces Me3GeGeMe3 (44 %), Me3GeH (3 %), and Me3GeI (7 %). An analogous set of products was obtained in the reaction with Et3GeBr. Treatment of trimethyltin chloride with 1 causes reduction of the former to tin metal (74 %). Me3SnH (7 %) and hexamethyldistannane (11 %) were identified in the volatile products. The reaction of 1 with Me3SiI provides straightforward access to hepta‐coordinated NdI3(THF)4 ( 2 ), the structure of which was determined by X‐ray diffraction. 相似文献
8.
V. N. Myakov Yu. A. Kurskii V. N. Sedel’nikova T. V. Makhrova M. A. Lopatin 《Russian Journal of Coordination Chemistry》2008,34(7):522-526
The reaction of PcSi(OSiMe3)2 with Mg in the presence of Me3SiCl at 20–100°C was shown to cause the phthalocyamine macrocycle contraction and give the silicon α,β,γ-triazatetrabenzocorrole macrocycle. The reaction proceeds in the polar donor solvents (THF, pyridine), but does not occur in aromatic hydrocarbons. The electronic and EPR spectra indicate that the silicon phthalocyanine mono- and dianions are active intermediate reaction products. 相似文献
9.
Gerd-Volker Rschenthaler Rainer Bohlen Rudolph Francke Joachim Heine Reinhard Schmutzler 《无机化学与普通化学杂志》1986,533(2):18-22
Bis(trimethylsilyl)phosphates of 1,1,1,4,4,4-Hexafluoro-2,3-bis(trifluoromethyl)-2,3-butanediol and 1,1,1,3,3-Pentafluoro-2-propenol The monocyclic phosphorane (EtO)3P[OC(CF3)2C(CF3)2O] 1 was hydrolized to give a mixture of an acyclic and a cyclic phosphate, 3 and 4 . The trihydroxyphosphorane 2 could not be obtained. Iodotrimethylsilane 6 converts 1 into the silylated derivative of 4 which was found also besides (Me3SiO)2P(O)OC(CF3)2C(CF3)2OSiMe3 8 in the reaction of 3 and 4 with Me3SiCl/(Me3Si)2NH. (Me3SiO)3P 10 and hexafluoroacetone did not yield the tris(trimethylsiloxy)phosphorane 5 , but the phosphonate 11 which gave (Me3SiO)2P(O)OC(CF3) ? CF2 12 upon heating with the loss of fluorotrimethylsilane. 相似文献
10.
Reactions of organo(trichloromcthyl)silanes RMc2SiCCl3 (R = Me, Ph, Mc3Si) with aluminum chloride have been studied. The interaction of trimetltyl(tricltlorometltyl)silane with AlCl3 carried out in cyclohexane or in benzene leads to Me3SiCHCI2 (in 75 % yield) or ClMe2SiCPh2Me (in 70 % yield), respectively; whereas no conversions are observed inn-hexane and methylene chloride. Treatment of dimetltyl(phenyl)(ricltloromethyl)silane with aluminum chloride in an-C5H12/CH2CI2 mixture gives an aromatic cross-linked insoluble polymer. The reaction of pentamethyl(trichloromcthyl)disilane (R = Mc3Si) with AICl3 in pentane affords the rearrangement product, Me3SiCCl2SiMc2Cl, in 65 % yield. In methylene chloride the further cleavage of the disilane occurs to yield Me2SiCl2 and CH2=CHMe2SiCl.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 6, pp. 1511-1515, June, 1996. 相似文献
11.
N-Silylation and Si? O Bond Splitting at the Reaction of Lithiated Siloxy-silylamino-silanes with Chlorotrimethylsilane Lithiated Siloxy-silylamino-silanes were allowed to react in tetrahydrofurane (THF) and in n-octane (favoured) and n-hexane, resp., with chlorotrimethylsilane. The monoamide (Me3SiO)Me2Si(NLiSiMe3) gives in THF and in n-octane the N-substitution product (Me3SiO)Me2Si · [N(SiMe3)2] 1 , the diamide (Me3SiO)MeSi(NLiSiMe3)2 only in THF the N-substitution products (Me3SiO)MeSi[N(SiMe3)2]2 2 (main product) and (Me3SiO)MeSi[N(SiMe3)2](NHSiMe3) 3 . In n-octane the diamide reacts mainly under Si? O bond splitting. The cyclodisilazane [(Me3SiNH)MeSi? NSiMe3]2 6 is obtained as the main product. Byproducts are 2, 3 and the tris(trimethylsilylamino) substituted disilazane (Me3SiO)(Me3SiNH)MeSi? N · (SiMe3)? SiMe(NHSiMe3)2 7 . The triamide (Me3SiO)Si · (NLiSiMe3)3 reacts under Si? O and Si? N bond splitting in n-octane as well as in THF. The cyclodisilazanes [(Me3SiNH)2 · Si? NSiMe3]2 10 and ( 11 : R = Me3SiNH, 12 : R = (Me3Si)2N) are formed. in THF furthermore the N-substitution products (Me3SiO)Si[N(SiMe3)2] · (NHSiMe3)2 4 and (Me3SiO)Si[N(SiMe3)2]2(NHSiMe3) 5 . The Si? O bond splitting occurs in boiling n-octane also in absence of the chlorotrimethylsilane. An amide solution of (Me3SiO)MeSi(NHSiMe3)2 with n-butyllithium in the molar ratio 1 : 1 leads in n-octane and n-hexane to 6 and 7 , in THF to 3 . The amide solutions of (Me3SiO)Si · (NHSiMe3)3 with n-butyllithium the molar ratio 1 : 1 and 1 : 2 give in THF 4 and 5 , respectively. 相似文献
12.
M. G. Voronkov L. V. Klyba S. V. Basenko R. G. Mirskov V. N. Bochkarev 《Russian Chemical Bulletin》1999,48(1):114-116
The mass spectra of some linear and branched methyl(vinyl)siloxanes Me3SiOSi(Me)(R)(OSiMeVin)
n
Y (R=Vin, OSiMe3; Y=OSiMe3, Cl;n=0–2) were studied. The regularities of their fragmentation and an anomalously high probability of elimination of the ethylene
molecule to form the stable 1,3-dioxa-2,4,6-trisilacyclohexane skeleton were revealed.
Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 1, pp. 113–115, January, 1999. 相似文献
13.
1-Trimethylsiloxyalkyl-bis(trimethylsilyl)silanes ( 5 ), obtained by a base induced isomerization of easily accessable 1-hydroxyalkyl-tris(trimethylsilyl)silanes ( 1 ) were hydrolized to give 1-hydroxyalkyl-bis(trimethylsilyl)silanes ( 6 ), which in presence of sodium hydride underwent a further 1,3-Si,O-trimethylsilyl migration resulting in the formation of 1-trimethylsiloxyalkyl-disilanes Me3SiSiH2–C(OSiMe3)R1R2 ( 7 ). Under acidic conditions, the alkoxysilanes 5 isomerized in a Me3Si/OSiMe3 exchange under formation of the 1-trimethylsilylalkyldisiloxanes 10 , which were hydrolyzed affording the silanols 11 . Chlorination of the H-silanes 5 with CCl4 gave the chlorosilanes 12 , which underwent rapid thermal isomerizations to give via the 1-chloroalkyldisiloxanes 13 the 1-trimethylsilylalkyl-chlorodisiloxanes 15 . Hydrolysis of 12 or 15 , resp., finally afforded the 1-trimethylsilylalkyl-silanediols 18 . Possible mechanisms of the various isomerization processes are discussed. The structures of the products described were elucidated by full spectral analyses. For 18 a the results of an X-ray structural analysis are given. 相似文献
14.
Beatrice Kern Hannes Vitze Michael Bolte Matthias Wagner Hans‐Wolfram Lerner 《无机化学与普通化学杂志》2008,634(11):1830-1832
The lithium silanolate LiOSiMe3 is accessible from the reaction of Me3SiOSiMe3 with LiMe in tetrahydrofuran. Single crystals of [Li7(OSiMe3)7(THF)] were obtained from toluene at 25 °C. The structure of [Li7(OSiMe3)7(THF)] (C2/c) features a capped trigonal antiprismatic arrangement of seven Li atoms. The Li atoms in [Li7(OSiMe3)7(THF)] are μ3‐bridged by seven O atoms of the silanolate ligand. 相似文献
15.
Reaction of the iodides TsiSiMe2I and TsiSiPh2I, (Tsi (Me3Si)3C) with AgClO4 in t-BuOH provides a route to the silanols TsiSiMe2OH and (Me3Si)2-C(SiPh2Me)(SiMe2OH), respectively. TsiSiMe2OH gives the disiloxane TsiSiMe2OSiMe3 when treated with either (a) Me3SiOClO3 (prepared in situ from AgClO4 and Me3SiCl) in benzene, (b) Me3SiI (in the presence of a little (Me3Si)2-NH), (c) O,N-bis(trimethylsilyl)acetamide, or (d) MeLi followed by Me3SiCl. It does not react with Me3SiCl, but with Me2SiCl2 gives TsiSiMe2OSiMe2Cl, and with CH3COCl gives TsiSiMe2OCOCH3. The disiloxane is stable to methanolic acid or base, but reacts with KOH in H2O/Me2SO and with CF3COOH to give TsiSiMe2OH. The disiloxane (Me3Si)2C(SiPh2Me)(SiMe2OSiMe3) is formed by treatment of (Me3Si)2C(SiPh2Me)(SiMe2OH) with Me3SiI/(Me3Si)2NH. Treatment of TsiSiPhMeI with AgClO4 in t-BuOH gives the silanols TsiSiPhMeOH and (Me3Si)2C(SiPhMe2)(SiMe2OH) (which with Me3SiI/(Me3Si)2NH give the corresponding disiloxanes) along with some of the t-butoxide (Me3Si)2C(SiPhMe2)(SiMe2OBut). 相似文献
16.
Lithiated Siloxy-silylamino-silanes — Preparation and Reactions with Chlorodimethylsilane The siloxy-silylamino-silanes (Me3SiO)Me3–nSi(NHSiMe3)n ( 1 : n = 1, 2 : n = 2, 3 : n = 3) are obtained by coammonolysis of the chlorosiloxysilanes (Me3SiO)Me3–nSiCln (n = 1–3) with chlorotrimethylsilane. The reaction of 1, 2 , and 3 with n-butyllithium in appropriate molar ratio in n-hexane gives the siloxy-silylamido-silanes (Me3SiO)Me3–nSi(NLiSiMe3)n ( 4 : n = 1, 5 : n = 2, 6 : n = 3), which were spectroscopically characterized (IR, 1H-, 7Li-, 29Si-NMR) and allowed to react in solution (n-hexane, THF) with Me2Si(H)Cl. 4 reacts to the N-substitution product (Me3SiO)Me2SiN(SiMe3)SiMe2H 7, 5 to (Me3SiO)MeSi[N(SiMe3)SiMe2H](NHSiMe3) 8 , (Me3SiO)MeSi[N(SiMe3)SiMe2H]2 9 and to the cyclodisilazane 10. 6 gives in THF the cyclodisilazanes 11 : R = H; 12 : R = HMe2Si) and ( 13 , in n-hexane only 11 in small amounts. An amide solution of 2 with n-butyllithium in the molar ratio 1:1 in n-hexane leads to 8 (main product), 2 and 10; in THF 10 and 2 are obtained nearly in same amounts and 8 and 9 as byproducts. The amide solutions of 3 with n-butyllithium in the molar ratio 1:1 and 1:2, resp., show nearly the same behaviour in n-hexane and THF. In THF 3, 11 , and 12 and in n-hexane 3, 11, 12 , and (Me3SiO)Si[N(SiMe3)SiMe2H](NHSiMe3)2 14 are formed. 相似文献
17.
Lithium Hydridosiloxysilylamides – Reactions in n-Octane and Tetrahydrofuran in Presence of Chlorotrimethylsilane The hydrido-siloxy-silylamino-silanes (Me3SiO)HSiMe(NHSiMe3) 1 , (Me3SiO)HSi(NHSiMe3)2 2 and (Me3SiO)2HSi(NHSiMe3) 3 were prepared by coammonolysis of the chlorosiloxysilanes (Me3SiO)HSiMeCl and (Me3SiO)3–nHSiCln (n = 1, 2) with chlorotrimethylsilane. The reaction behaviour of lithiated compounds 1 , 2 and 3 has been investigated in n-octane and tetrahydrofuran (THF) in presence of chlorotrimethylsilane. 相似文献
18.
Michel Laguerre Jacques Dunogues Raymond Calas 《Journal of organometallic chemistry》1978,145(3):C34-C36
The 1,3-bis(trimethylsilyl)propyne can be easily prepared by reductive silylation of HCCCH2OR (R = Me, SiMe3) by the Me3SiCl/Li/THF reagent. 相似文献
19.
M. G. Voronkov V. K. Roman E. A. Maletina I. M. Korotaeva 《Russian Chemical Bulletin》1982,31(3):621-623
Conclusions The reaction of bis(trimethylsilyl) sulfate (BTS) with HBr leads to trimethylbromosilane, hexamethyldisiloxane, and free bromine. Its reaction products with HI are hexamethyldisiloxane and free iodine. The reaction of BTS with PCl3 leads to the formation of Me3SiCl, SO2, and a polymeric product whose composition approximates [(CH3)3SiO]8Cl2O27P8S4. The reaction of SOCl2 with BTS gives in high yield Me3SiOSO2Cl, Me3SiCl, and SO2. POCl3 and SO2Cl2 do not react with BTS under analogous conditions.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 3, pp. 696–698, March, 1982. 相似文献
20.
Dietmar Brandes 《Journal of organometallic chemistry》1977,136(1):25-31
Novel organylthio(alkoxy)silanes (I, II, III and XII) and organylthio(diethylamino)silanes (IV, V) are described. They were prepared by treating lithium or lead thiolates with the corresponding chlorosilanes or by cleavage of dimethylbis(diethylamino)silane with thiols. Phenylthiosilanes (Me3SiSPh, III and XIII) furthermore can be obtained by reaction of chlorosilanes with benzenethiol in the presence of tertiary amines. The SiS bond of Me3SiSPh is cleaved by chlorosilanes like Me2Si(NEt2)Cl or Me2Si(OPr)Cl. This reaction is a convenient route to prepare compounds I and IV. The physical and chemical properties of the novel compounds were investigated. 相似文献