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1.
A series of (hydroxymethyl)hydroxyphenyldimethylsiloxanes of linear and branched structures were synthesized by the reaction with formaldehyde in aqueous alkaline medium of organosilicon phenols of general formula R′[Si(CH3)2O] n [Si(CH3)RO] m SiMe2R′, where R′ was 4-hydroxy-3-methoxyphenylpropyl, R was methyl or 4-hydroxy-3-methoxyphenylpropyl. The structure and composition of the siloxanes were confirmed by elemental analysis, NMR and IR spectroscopy. The homocondensation of (hydroxymethyl)hydroxyphenyldimethylsiloxanes at the hydroxymethyl groups was investigated. A possibility of reaction of (hydroxymethyl) hydroxyphenyldimethylsiloxanes with phenol-formaldehyde resin to form copolymers was demonstrated.  相似文献   

2.
Hydrosilylation of terminal acetylenes, HC≡CR (R = CMe3,n-C7H15, SiMe3, Ph, COOEt, CH2N(CH2)4, and CH2N(CH2)5) with 5-dimethylsilylfurfural diethyl acetal (1) gives a mixture of products of bothtrans-β- and α-addition. When R = CMe3 or SiMe3, the reaction proceeds regio- and stereospecifically to give only thetrans-β-derivatives. The formation of β-adducts is favored by pronounced electron-donating substituents and steric hindrance at the Cα atom. Terminal alkenes, H2C=CHR (R = CH2CN, CH2N(CH2)4, CH2N(CH2)5, SiMe3, SiMe(α-furyl)2, SiMe2(α-furyl), SiMe2(α-thienyl), and SiMe2(5-chloro-2-thienyl)), react with silane1 to give only the products of β-addition; the reaction of1 with H2C=CHCH2NHC6H13-n affords a mixture of β- and α-adducts in a ratio of 1.8∶1. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 10, pp. 1784–1788, October, 1993.  相似文献   

3.
Herein, we report the syntheses of silicon‐ and tin‐containing open‐chain and eight‐membered‐ring compounds Me2Si(CH2SnMe2X)2 ( 2 , X=Me; 3 , X=Cl; 4 , X=F), CH2(SnMe2CH2I)2 ( 7 ), CH2(SnMe2CH2Cl)2 ( 8 ), cyclo‐Me2Sn(CH2SnMe2CH2)2SiMe2 ( 6 ), cyclo‐(Me2SnCH2)4 ( 9 ), cyclo‐Me(2?n)XnSn(CH2SiMe2CH2)2SnXnMe(2?n) ( 5 , n=0; 10 , n = 1, X= Cl; 11 , n=1, X= F; 12 , n=2, X= Cl), and the chloride and fluoride complexes NEt4[cyclo‐ Me(Cl)Sn(CH2SiMe2CH2)2Sn(Cl)Me?F] ( 13 ), PPh4[cyclo‐Me(Cl)Sn(CH2SiMe2CH2)2Sn(Cl)Me?Cl] ( 14 ), NEt4[cyclo‐Me(F)Sn(CH2SiMe2CH2)2Sn(F)Me?F] ( 15 ), [NEt4]2[cyclo‐Cl2Sn(CH2SiMe2CH2)2SnCl2?2 Cl] ( 16 ), M[Me2Si(CH2Sn(Cl)Me2)2?Cl] ( 17 a , M=PPh4; 17 b , M=NEt4), NEt4[Me2Si(CH2Sn(Cl)Me2)2?F] ( 18 ), NEt4[Me2Si(CH2Sn(F)Me2)2?F] ( 19 ), and PPh4[Me2Si(CH2Sn(Cl)Me2)2?Br] ( 20 ). The compounds were characterised by electrospray mass‐spectrometric, IR and 1H, 13C, 19F, 29Si, and 119Sn NMR spectroscopic analysis, and, except for 15 and 18 , single‐crystal X‐ray diffraction studies.  相似文献   

4.
Concerning the Cleavage of Si? C Bonds in Si-methylated Carbosilanes The chances for the cleavage of Si? Me bonds (Me ? CH3) and Si? C? Si bonds in their molecular skeletons using ICl or ICl/AlBr3 are examined in 13 carbosilanes; i. e. (Me2Si? CH2)3 1 , 1,3,5,7-tetramethyl-1,3,5,7-tetrasilaadamantane 2 , (Me3Si? CH2)2SiMe2 3 , HC(SiMe3)3 4 , the 1,3,5,7-tetrasilaadamantane. carrying bhe ? CH2? SiMe, group at one Si atom 5 , the 1,3,5-trisilacyclohexane, carrying the ? CH2? SiNe3 group 6 , three derivatives of the 1,3,5-trisilacyclohexane, carrying SiMe3 groups at skeletal C atoms 7 , 8 , 9 , three derivatives of the 1,3,5-trisilacyclohexane, carrying CH3, groups at skeletal C atoms 10 10, 11 , 12 and 13 , derived from (Me2Si? CH2)3 having one ?CBr2 group. Using ICl one Me group at each Si atom in 1 can be split off successively, finally yielding (ClMeSi? CH2)3. 2 is transformed to the Si-chlorinated 1,3,5,7-tetrasilaadamantane. 3 , treated with ICl yields (ClMeSi? CH2)2SiMeCl, as 4 forms HC(SiMe2Cl)3. Higher chlorinated compounds can be obtained by using ICl and AlBr3 in catalytic amounts. Thus 1 leads to (Cl2Si? CH2)3, no ring-opening is observed. However, in the reaction of 1 with HBr/AlBr3 bromination at the Si atoms and ring-opening (ratio 1:1) proceed coincidently. The reaction of either 3 or (ClMe2Si? CH2)2SiMeCl with ICl/AlBr3 leads to (Cl2MeSi? CH2)2SiCl2, and (Me3Si)2CH3 forms (Cl2MeSi? )2CH2 similarly. The ? CH2? SiMe3 group in 5 and 6 is not cleaved off by ICl; the introduction of a Cl group at each Si atom is observed instead. Furthermore, 6 undergoes cleavage (≈8%) of the Si? C ring adjacent to the chain-substituted Si atom [formation of ClMe2Si? (CH2? SiMeCl)2CH2? SiMe2? CH2Cl]. 7 , 8 , 9 (having the ? SiMe3 group at the C atoms) react with ICl by splitting off one Si? Me group from each Si atom. In 7 we also observe the ring-opening to an amount of ≈25% [formation of (ClMe2Si)CH2? SiMeCl? CH2? SiMe2? CH2Cl]. In 8 (having two CH(SiMe3) groups the ring-opening reaction is reduced to about 5% [formation of ClMe2? CH(SiMe2Cl)? SiMeCl? CH(SiMe2Cl)? SiMe2? CH2Cl], while in 9 (having three CH(SiMe3) groups) it is not found at all. In 10 , 11 , 12 (having the CH3 group at the C atoms) ICl substitutes one Me group (formation of SiCl) at each Si atom (no ring-opening). The CBr2 group reduces the reactivity of 13 towards ICl. Only the split-off of one Me group at the Si atom in para-position to the CBr2 group is observed. Using ICl/AlBr3 higher chlorinated derivatives are obtained (no ring-opening). Most of the mentioned compounds were identified via their Si? H-containing derivatives, thus facilitating the chromatographic separation as well as the 1H-NMR-spectroscopic investigations.  相似文献   

5.
In the cross-metathesis reaction of tri(methyl, ethoxy)vinylsilanes with propene and/or 1-butene catalyzed by RuCl2(PPh3)3 activated in benzene at 115–130 °C, a series of l-alkenylsilanes of general formula CH3(CH2)mCH = CHSiMe3−n(OEt)n, where m=0, 1, and n=0–3 (1-silyl-1-alkenes), as well as of formula CH2=C(Me)SiMe3−n(OEt)n, where n=1, 2 (2-silyl-1-alkenes), were obtained. Additional products determined were allysilanes of general formula CH2=CHCH2SiMe3−n(OEt)n and CH3CH= CHCH2SiMe3−n(OEt)n, where n=1–3. © 1997 John Wiley & Sons, Ltd.  相似文献   

6.
Si-containing mono- and disubstituted polyacetylenes(? [CMe?C(SiMe3)] n? , ? [CH?H(n? C5H11)SiMe3]n? , etc.) underwent degradation in air; many of them exhibited relatively high yields of main-chain scission (Gs > 1). The Gs values for the polymers having a long n-alkyl group were usually large (ca. 2). In contrast, no polymer degradation occurred in vacuum, indicating that oxygen is necessary for the radiolysis. The polymers irradiated in air contained C?O and Si? O groups, and dissolved in polar solvents, which are nonsolvents of the starting polymers. From the radiation sensitivity and thermal degradability of these polymers, it is concluded that disubstituted polymers with high Si contents (? [CMe?C(SiMe3)]n? , ? [CMe?C(SiMe2CH2SiMe3)]n? , etc.) are not only radiation-sensitive but also thermally stable.  相似文献   

7.
The main product of the photoinduced reaction of N-bromohexamethyldisilazane with trialkyl-(benzyloxy)derivatives of silicon and tin R3MO(CH2) n Ph (R = Me, Et; M = Si, Sn; n = 1) is N,N-dibenzylidene-C-phenylmethanediamine (hydrobenzamide). For M = Si, with increase of the length of the methylene chain between the oxygen atom and the phenyl group (n = 2, 3), the similar reaction affords the product of bromination of the benzylic carbon atom R3MO(CH2) n−1CHBrPh. For M = Sn, the reaction results in the formation of 2-phenyloxacycloalkanes PhCHO(CH2) n−1.  相似文献   

8.
The strain energies and through-space distances between the two bridgehead E atoms of a selection of 1,3-dimethyl-1,3-ditetrelbicyclo[1.1.1]pentanes (tetrel E = Si, Ge or Sn) were examined by quantum chemical calculations at MP2 and B3LYP levels. The aim is to identify which bridges lead to short through-space E,E distances, and simultaneously, to as low strain as possible. A short E,E distance should improve through-space interaction, and a low strain should promote the thermal stability and possibly also facilitate their synthesis. The bridges examined included CH2, CMe2, CtBu2, C(CH2)n (n = 2–4), O, NMe, S, PMe, SiMe2, GeMe2, and SnMe2. The calculations indicate that the phospha bridge is a good compromise providing reasonably low strain as well as E,E through-space distances which are only longer than normal E–E single bonds by factors of 1.06–1.10. This paper is dedicated to Professor Mitsuo Kira in recognition of his stimulating Si chemistry and his 2005 Wacker Award.  相似文献   

9.
A new route to 1,1-difluoro-5-methylquasisilatrane (N→Si) F2Si(OCH2CH2)2NMe is elaborated: the reaction of chlorinated methyltrifluorosilanes F3SiCH3−n Cln (n = 1–3) as well as trifluoro(3-chloropropyl) silane and trifluoro(propenyl)silane with N-methyl-bis(2-hydroxyethyl)amine. The reactivity of the silanes F3SiCH3−n Cl n increases with the number of chlorine atoms, that is, with the electronegativity of the CH3−n Cl n group.  相似文献   

10.
The hydrolysis of 1,2-dichlorotetramethyldisilane was studied at different temperatures. At reduced temperatures, the hydrolysis gave permethylcyclo(oxadisilanes) [(Me2Si)2O]n (n = 2 and 3) and α,ω-dihydroxypermethyloligo(oxadisilanes) HO[(SiMe2)2O]mH (m = 1–5). The formation of the latter was proved by the GC-MS method. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 4, pp. 722–724, April, 2006.  相似文献   

11.
Treatment of dichloromethyl‐tris(trimethylsilyl)silane (Me3Si)3Si–CHCl2 ( 1 ), prepared by the reaction of tris(trimethylsilyl)silane with chloroform in presence of potassium tertbutoxide, with organolithium reagents (molar ratio 1 : 3) affords the bis(trimethylsilyl)methyl‐disilanes Me3SiSiR2–CH(SiMe3)2 ( 12 a–d ) ( a : R = Me, b : R = n‐Bu, c : R = Ph, d : R = Mes). The formation of 12 a–d is discussed as proceeding through an exceptional series of isomerization and addition reactions involving intermediate silyl substituted carbenoids and transient silenes. The carbenoid (Me3Si)2PhSi–C(SiMe3)LiCl ( 8 c ) is moderately stable at low temperature and was trapped with water to give (Me3Si)2PhSi–CH(SiMe3)Cl ( 9 c ) and with chlorotrimethylsilane affording (Me3Si)2PhSi–CCl(SiMe3)2 ( 7 c ). For 12 d an X‐ray crystal structure analysis was performed, which characterizes the compound as a highly congested silane with bond parameters significantly deviating from standard values.  相似文献   

12.
Formation of Organosilicon Compounds. 109. Reactions of Perhydrogenated Carbosilanes with Alkyl-Lithium Compounds Si-hydrogenated linear carbosilanes react with MeLi or nBuLi to give the Si-alkylated derivatives. In contrast to the Si-methylated derivatives of (H3Si? CH2)2SiH2 1 and (H3Si)2CH2 2 and to (Me2Si? CH2)3 no lithiation of CH2 groups is observed. Such, 1 with nBuLi yields nBuH2Si? CH2? SiH2? CH2? SiH3 5 and (nBuH2Si? CH2)2SiH2 6 . 2 reacts with nBuLi to give nBuH2Si? CH2SiH3 7 and (nBuH2Si)2CH2 8 besides of 1, 5 und 6 . The latter results from a cleavage of a Si? C bond in 2 Producing nBuSiH3 and LiCH2? SiH3 which combines with 2 to 1 . Subsequently 1 forms 5 and 6 . No higher alkylated derivatives of 1 or 2 could be detected.  相似文献   

13.
Perfluoroadipic bis(trialkoxysilylpropyl)amide was synthesized as a mixture of five compounds with the general formula (EtO) n (MeO)3-n Si(CH2)3NHC(O)(CF2)4C(O)NH(CH2)3-Si(OMe) n (OEt)3-n (1, n = 1, 2). Hydrolysis of this product by a specified amount of water (1: 4) gave oligomers EtO[(HO)(EtO)Si(CH2)3NH(O)C(CF2)4C(O)NH(CH2)3Si(OEt)2O]nH ( n = 7–9). From oligomer solutions, transparent glassy thermally stable films were obtained. The film material was studied by IR spectroscopy, atomic force microscopy, transmission electron microscopy, and powder X-ray diffraction. Compound 1 and oligomers can efficiently solvate lanthanide diketonate complexes. They displace water from the metal coordination sphere, and this water is then spent for hydrolysis of trialkoxysilyl groups. The luminescence intensity of matrix films based on the oligomers depends on the concentration of lanthanide complexes and is very low at 7nexc = 330 nm, whereas the luminescence intensity of the Eu3+ cation is very high.  相似文献   

14.
Synthesis, NMR Spectra and Structure of [(CH3)2Ga{μ‐P(H)Si(CH3)3}2Ga(CH3)2{μ‐P(Si(CH3)3)2}Ga(CH3)2] The title compound has been prepared in good yield by the reaction of [Me2GaOMe]3 (Me = CH3) with HP(SiMe3)2 in toluene (ratio 1 : 1,1) and purified by crystallization from pentane or toluene, respectively. This organogallium compound forms (Ga–P)3 ring skeletons with one Ga–P(SiMe3)2–Ga and two Ga–P(H)SiMe3–Ga bridges and crystallizes in the monoclinic space group C2/c. The known homologous Al‐compound is isotypic, both (MIII–P)3 heterocycles have twist‐conformations, the ligands of the monophosphane bridges have trans arrangements.  相似文献   

15.
Gas-phase dehalogenation of 1,2-bis[chloro(dimethyl)silyl]-2-trimethylsilylethane with alkali metals gave 1,1,2,2-tetramethyl-3-trimethylsilyl-1,2-disilacyclobutane (3). Its spontaneous ring-opening polymerization at room temperature afforded an amorphous linear polymer with T g = ?8.9°C, M w = 3.47·105–3.85·105, and M w /M n = 2.43—2.86. According to spectroscopic data (IR and 1H, 13C, and 29Si NMR), the backbone of the polymer consists of alternating monomer units joined in the “head-to-tail” ([Me2SiCH(SiMe3)CH2SiMe2SiMe2CH-(SiMe3)CH2SiMe2]) and “head-to-head” ways ([Me2SiCH2CH(SiMe3)SiMe2SiMe2CH-(SiMe3)CH2SiMe2]).  相似文献   

16.
Dehalogenation of 1-[(chloro)(ethyl)(methyl)silyl]-2-[chloro(climethyl)silyl]ethane with the alkali metal vapors gave l-ethyl-l,2,2-trimethyl-1,2-disilacyclobutane. Its spontaneous ring-opening polymerization at room temperature afforded an amorphous linear polymer with T g = −75 °C, M w = 454 200–512 800, and M w/Mn = 1.87–2.82. According to NMR data, the backbone of the polymer consists of alternating monomeric units linked in the “head-to-tail” (SiMe 2CH2CH2SiMeEtSiMe2CH2CH2SiMeEt) and “head-to-head” ways (SiMeEtCH2CH2SiMe2SiMe2CH2CH2SiMeEt) in a ratio of 1: 0.96. Spontaneous copolymerization of the above disilacyclobutane with 1,1,2,2-tetramethyl-l,2-disilacyclobutane gave partially crystalline copolymers with different glass transition and melting temperatures, depending on the ratio of the components in the reaction mixture. The compositions of the copolymers were examined by 1H, 13C, and 29Si NMR spectroscopy.  相似文献   

17.
Photolytic vulcanization of siloxane rubber films in the presence of trimethylsiloxy-substituted di- and trisilanes, oligodimethylsilanosiloxanes (Me2SiO) m (SiMe2) n , Me(Me2SiO) m (SiMe2) n Me, oligodimethylsilanes Me(Me2Si) n Me, and volatile pyrolysis products of polydimethylsilane was studied.  相似文献   

18.
The end-functionalization of living polymers with bases (methanol, benzylamine, diethyl sodiomalonate, and sodium methoxide) and organosilicon compounds [X ? Si(CH3)3;X ? : CH2?C(CH3)COO? , CH3COO? , CH2?CHCH2? , C6H5? ] was investigated in the living cationic polymerization of styrene initiated with the 1-phenylethyl chloride/SnCl4/nBu4NCl system in CH2Cl2 at ?15°C. The four bases and C6H5SiMe3, independent of their structures, were apparently incapable of reacting with the living end and invariably led to polystyrenes with the ω-end chlorine [~ ~ ~ CH2CH(Ph)Cl] originated from the initiating system. The number-average end-functionality (F?n) of the chloride, determined by 1H-NMR, was close to unity (F?n > 0.9). The presence of chlorine in the polymer was also confirmed by elemental analysis. In contrast, the quenching by the trimethylsilyl compounds with X = methacryloxy, acetoxy, and allyl gave ω-end-functionalized polystyrenes with the corresponding terminal groups (X) for which the F?n values were close to unity (F?n > 0.9). The effects of the structure of silyl compounds on end-capping are also discussed. © 1994 John Wiley & Sons, Inc.  相似文献   

19.
The syntheses of several dialkyl complexes based on rare‐earth metal were described. Three β‐diimine compounds with varying N‐aryl substituents (HL1=(2‐CH3O(C6H4))N?C(CH3)CH?C(CH3)NH(2‐CH3O(C6H4)), HL2 = (2,4,6‐(CH3)3 (C6H2))N?C(CH3)CH?C(CH3)NH(2,4,6‐(CH3)3(C6H2)), HL3 = PhN?C(CH3)CH(CH3) NHPh) were treated with Ln(CH2SiMe3)3(THF)2 to give dialkyl complexes L1Ln (CH2SiMe3)2 (Ln = Y ( 1a ), Lu ( 1b ), Sc ( 1c )), L2Ln(CH2SiMe3)2(THF) (Ln = Y ( 2a ), Lu ( 2b )), and L3Lu(CH2SiMe3)2(THF) (3). All these complexes were applied to the copolymerization of cyclohexene oxide (CHO) and carbon dioxide as single‐component catalysts. Systematic investigation revealed that the central metal with larger radii and less steric bulkiness were beneficial for the copolymerization of CHO and CO2. Thus, methoxy‐modified β‐diiminato yttrium bis(alkyl) complex 1a , L1Y(CH2SiMe3)2, was identified as the optimal catalyst, which converted CHO and CO2 to polycarbonate with a TOF of 47.4 h?1 in 1,4‐dioxane under a 15 bar of CO2 atmosphere (Tp=130 °C), representing the highest catalytic activity achieved by rare‐earth metal catalyst. The resultant copolymer contained high carbonate linkages (>99%) with molar mass up to 1.9 × 104 as well as narrow molar mass distribution (Mw/Mn = 1.7). © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 6810–6818, 2008  相似文献   

20.
α,ω-Dibromopermethyloligosilanes, Br(SiMe2) n Br (n=2–4, 6), were prepared by the reaction of dodecamethylcyclohexasilane with bromine. The reaction of (Me2Si)6 with MCl4 (M=Sn, Ti) proceeds with the cleavage of Si−Si- and Si−C-bonds with the formation of α,ω-dichloropermethyloligosilanes, Cl(SiMe2) n Cl (n=2–4, 6), and chloro derivatives of cyclohexasilane, Cl m Si6Me12−m (m=1, 2). Silane-siloxane copolymers of regular structure were obtained by heterofunctional copolycondensation of α,ω-dihalopermethyloligosilanes with 1,5-dihydroxyhexamethyltrisiloxane. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 8, pp. 1513–1517, August, 1997.  相似文献   

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