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1.
《高分子科学杂志,A辑:纯化学与应用化学》2013,50(1-2):133-143
New silicon-containing disubstituted polyacetylene was prepared by the polymerization of BTMSA having two bulky substituents (n-butyl and trimethylsilyl) using transition metal catalysts. The polymerization proceeded in a mild manner and the final polymer yield was generally lower than those of silicon-containing monosubstituted acetylenes by the similar catalyst system. The characterization on the polymer structure revealed that the resulting poly(BTMSA) have a conjugated backbone system, but the polymers have peculiar copolymer composition of poly-(BTMSA) and poly(1-hexyne) due to the spontaneous desilylation during the polymerization. The fluoride-ion induced desilylation of poly(BTMSA) using n-Bu4N+F? in THF yielded a completely desilylated product, pure poly(1-hexyne). 相似文献
2.
A general and controlled bidirectional growth strategy enable a very rapid and efficient construction of oligo(phenyleneethynylene)s possessing functional groups such as methylthio and thioacetate groups at both ends. The strategy employs only one reaction type with good to moderate yields to grow the conjugated chains. The synthesis is efficient and can give 23 benzene rings and 22 carbon-carbon triple bonds in the conjugated chains. The compounds are fully characterized by 1H and 13C NMR and UV/vis and fluorescence spectroscopy. 相似文献
3.
Arvind H. JadhavHern Kim 《Tetrahedron letters》2012,53(39):5338-5342
Selective deprotection of alkyl TBDMS ether in the presence of phenolic TBDMS ether using dicationic ionic liquid [tetraEG(mim)2][OMs]2 as a homogeneous catalyst showed significant catalytic activity in methanol at ambient temperature to produce respective alcohol in excellent yield. The present environmentally benign catalytic system is found to be very convenient, fast, high yielding, and clean method for selective desilylation of alkyl silyl ethers even in the existence of other sensitive organic functional groups such as aldehyde, methoxy, and acetate were also achieved. 相似文献
4.
Kenji Uneyama 《Journal of fluorine chemistry》2008,129(7):550-576
Preparations, reactions, and synthetic applications of functionalized fluoroalkyl and alkenyl silanes have been summarized. This review focuses mainly on the chemistries of (1) 1-substituted difluoromethylsilanes (XCF2SiR3), (2) 1-substituted 2,2-difluorovinylsilanes (CF2CXSiR3), (3) trifluoroisopropenyl, trifluoroacetimidoyl, and trifluoroacetyl silanes [CF3C(SiR3)X, XCH2, NAr, O] and (4) other fluorinated alicyclic silanes. 相似文献
5.
Chang-Eun Yeom Young Jong Kim So Young Lee Yong Je Shin B. Moon Kim 《Tetrahedron》2005,61(52):12227-12237
Fast and chemoselective desilylation of silyl-protected alcohols was achieved using a catalytic amount of 1-chloroethyl chloroformate in methanol. With a minimal amount of 1-chloroethyl chloroformate as the source for anhydrous HCl, extremely efficient cleavage of silyl ethers of primary and secondary alcohols was accomplished, and chemoselective deprotection of one silyl ether in the presence of another silyl or other acid-labile group was possible through controlling the amount of the chloroformate and reaction time. 相似文献
6.
Synthesis of Sila-bridged Titanocenes and Desilytion Reaction 总被引:2,自引:0,他引:2
《高等学校化学学报》1999,20(1):1
硅桥连双(三甲硅基环戊二烯基)双锂盐与TiCl 相似文献
7.
1,2-双(四甲基环戊二烯基)四甲基二硅烷与正丁基锂作用生成(四甲基二硅撑)双(四甲基环戊二烯基负离子盐),后者随即与六碳基钼反应形成1,1'-(四甲基二硅撑)双(四甲基环戊二烯基铝负离子盐)-(Me2SiSiMe2)[Me4CpMo(CO)3-Li+]2(I),I与冰醋酸作用,随即分别与CCl4,NBS及I2反应,生成相应的铝卤化合物(Me2SiSiMe2)[Me4CpMo(CO)3X]2[X=Cl(1),Br(2),I(3)].I与CH3I反应,在钼原子上发生烃基化,得到产物(Me2SiSiMe2)[Me4CpMo(CO)3Me]2(4);I与单质I2直接反应,生成脱硅桥产物Me4Cp(CO)>3I(5).经元素分析、IR及1HNMR表征了化合物1-5的结构。 相似文献
8.
Matthew OBrien Lisette Konings Matthew Martin Jordan Heap 《Tetrahedron letters》2017,58(25):2409-2413
An inexpensive homemade 3-axis autosampler was used to facilitate the automation of an acid catalysed flow chemical desilylation reaction. Harnessing open-source software technologies (Python, OpenCV), an automated computer-vision controlled liquid-liquid extraction step was used to provide effective inline purification. A Raspberry Pi single-board computer was employed to interface with the motors used in the autosampler and actuated fluidic valves. 相似文献
9.
Hydrolysis and desilylation reaction of 2‐[(trimethylsilyl)methyl]acrylate (=2‐[(trimethylsilyl)methyl]prop‐2‐enoate) derivatives were studied to evaluate the effect of the presence/absence of a further conjugating substituent (Schemes 3 and 4 and Tables 1 and 2). The substrates having a nonconjugating substituent at the acrylate moiety were stable to dilute alkali conditions, and afforded simple hydrolysis products under concentrated alkali conditions. In contrast, both hydrolysis and desilylation occurred from the substrates bearing conjugated substituents at the acrylate skeleton. The difference in reactivity can be explained in terms of the stabilization of the intermediate anion. 相似文献
10.
Cherif Behloul 《Tetrahedron》2005,61(28):6908-6915
The reaction of silyl protected alcohols, amines and thiols with lithium powder and a catalytic amount of naphthalene, in THF, at 0 °C led, after hydrolysis, to the recovery of the free alcohols, amines and thiols in very good yields. At least a phenyl group was required in the silyl protecting group for the success of the reaction. Some polyfunctionalised starting materials have successfully been deprotected. The stereochemical outcome of the deprotection of a silylated chiral secondary alcohol has also been studied and no racemization was observed. The process has shown to be a good alternative to the acid-catalysed desilylation procedures, the latter being not useful for the deprotection of some silylated tertiary alcohols. 相似文献