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《有机化学》2017,(3)
设计合成确切结构的异官能基笼型倍半硅氧烷一直是国际性的研究热点问题.用"自下而上"的方法,以半笼型结构倍半硅氧烷为模板,成功地制备出具有Janus结构的四乙烯基四氨基苯基、四乙烯基四苯基异官能基笼型倍半硅氧烷.并且,产物在一些极性溶剂(如四氢呋喃、氯仿及二甲基亚砜)中有较好的溶解性,为其衍生化及应用提供了保证.对所制备的异官能基笼型倍半硅氧烷进行了全面的表征分析,证明其具有Janus异官结构特征及完整的笼型结构.紫外可见及荧光发射光谱证实了倍半硅氧烷笼型结构的电子携带及传输作用,反过来证明其具有完整的笼型结构,同时也为其在有机光电材料中应用提供可能.提供了一类通用合成方法,拓宽了倍半硅氧烷功能单体的种类,并拓展了其应用范围. 相似文献
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以甲醇为溶剂 ,浓盐酸为催化剂 ,γ-氯丙基三乙氧基硅烷在室温下经水解缩合高产率地制备了笼形八聚( γ-氯丙基 )倍半硅氧烷。合成的化合物分别用元素分析 ,1 H,1 3C,2 9Si NMR,FT- IR和 GPC进行了表征。 相似文献
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反应性梯形聚氢基倍半硅氧烷合成方法的改进 总被引:7,自引:0,他引:7
对反应性梯形聚氢基倍半硅氧烷 (H T)的合成方法进行了改进 .首先利用硅羟基与硅氯基之间的脱氯化氢缩聚来代替以前采用的硅羟基间脱水缩聚反应 ,进一步提高了作为梯撑的对苯二胺之间氢键在聚合反应中的模板作用 .另外利用三甲基氯硅烷与对苯二胺梯撑的聚硅氧烷中间体的末端硅羟基进行封端反应 ,从而保证在脱除对苯二胺梯撑模板分子过程中避免进一步的无规缩合导致支化或交联 ,得到的反应性梯形聚氢基倍半硅氧烷 (H T)的规整性有所改善 .热分析结果表明与单链聚二甲基硅氧烷的Tg(- 12 3℃ )相比 ,其Tg 高达 117 0℃ ,证明这种梯形高分子具有刚性链结构 .尤其是2 9Si NMR谱中代表梯形主链上硅原子 (SiO3 2 )峰的基线宽度Δ =5 ,而采用硅羟基间脱水缩合方法得到聚合物的Δ =8~ 10 .表明该反应性梯形聚氢基倍半硅氧烷H T的规整性得到了明显的提高 .而且 ,该聚合物又是第一个可溶性、反应性、纯梯形主链无机高分子 ,它可以进一步通过硅 氢侧基接枝反应制备不同类型的梯形无机主链功能高分子 . 相似文献
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以笼型低聚八苯基硅倍半氧烷(OPS)为原料,AlCl3为催化剂,苯磺酰氯为磺酰化试剂,在二氯甲烷溶液中反应72h,合成了笼型八(二苯砜基)硅倍半氧烷(ODPSS).该方法合成过程简单稳定,产率高.通过FTIR、MALDI-TOF MS、1H NMR、13C NMR、29Si NMR和元素分析对产物进行了表征,证明OPS已完全转化为ODPSS.通过改变溶剂、催化剂、反应时间和各反应物物质的量之比,优化了反应条件,分析了反应机理,建立了该体系下OPS的磺酰化反应机理模型. 相似文献
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feasible new preparation was reported for an octacarboxylphenyl functionalized spherosilicate, octakis[(pcarboxyphenyl) dimethylsilyl]silicate, which was a versatile monomer leading to other functional spherosilicate derivatives. The synthesis was started from octakis[dimethyl(p-methylphenyl)silyl]silicate. Octakis[dimethyl(pmethylphenyl) silyl]silicate was brominated by NBS to produce octakis[dimethyl(4-tribromomethylphenyl)silyl]silicate. Finally, octakis[dimethyl(4-tribromomethylphenyl)silyl]silicate was hydrolyzed in the presence of AgNO3 and formic acid to give the desired compound. Octakis[(pcarboxyphenyl) dimethylsilyl]silicate was fully characterized by FTIR, 1H NMR, 13C NMR, 29Si NMR spectra, ESI-MS, and elemental analysis. 相似文献
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Murat AltunkayaErgün Gonca 《Polyhedron》2011,30(6):1035-1039
Magnesium porphyrazinate substituted with eight 3,5-bis(trifluoromethyl)phenyl groups on the peripheral positions has been synthesized by the cyclotetramerization of 3,4-[3,5-bis(trifluoromethyl)phenyl]pyrroline-2,5-diimine in the presence of magnesium butanolate. Acid-mediated demetallation of the magnesium porphyrazine resulted in peripheral oxidation of one pyrrole ring to reveal the seco-porphyrazine, octakis[3,5-bis(trifluoromethyl)phenyl]-2-seco-porphyrazine-2,3-dione. Further reaction of this product with copper (II) acetate, zinc (II) acetate and cobalt (II) acetate has led to the metallo-derivatives, {octakis[3,5-bis(trifluoromethyl)phenyl]-2-seco-2,3-dioxoporphyrazinato} M(II) [M = Cu(II), Zn(II), Co(II)]. These new soluble complexes were characterized by elemental analysis, together with FT-IR, 1H NMR, 13C NMR, 19F NMR, UV-Vis and mass spectral data. 相似文献
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Zhou L Thompson R Reamer RA Lin Z French M Ellison D Wyvratt J 《Electrophoresis》2003,24(15):2448-2455
The possible mechanisms for the chiral recognition of 2-(R)-N-[1-(6-aminopyridin-2-ylmethyl)piperidin-4-yl]-2-[(1R)-3,3-difluorocyclopentyl]-2-hydroxy-2-phenylacetamide (RR-M3), and its enantiomer (SS-M3) with octakis(2,3-di-O-acetyl-6-sulfo)-gamma-cyclodextrin (ODAS-gamma-CD) and octakis(6-sulfo)-gamma-cyc?pdextrom enantiomer; (OS-gamma-CD), were investigated using capillary electrophoresis (CE), proton ((1)H), fluorine ((19)F) and carbon ((13)C) nuclear magnetic resonance spectroscopy (NMR), and infrared (IR) spectroscopy. Clear evidence for the formation of diastereomeric complexes between the enantiomers and the two CDs was observed. NMR spectra suggest that the phenyl and difluorocyclopentyl rings are involved in the complexation. The phenyl ring on the guest molecule is deeply penetrated into the cavity of OS-gamma-CD, but it is not included into the cavity of ODAS-gamma-CD. The continuous variation plots built based on the (1)H NMR and IR spectra indicate a 1:1 complex stoichiometric ratio of the M3 enantiomers for both CDs. The affinity of the enantiomers for the two CDs is opposite. 相似文献
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Chizhova N. V. Khelevina O. G. Berezin B. D. 《Russian Journal of General Chemistry》2003,73(10):1645-1647
Palladium(II) and nickel(II) complexes with octaphenyltetraazaporphyrin, octakis(4-bromophenyl)tetraazaporphyrin, and octakis(4-nitrophenyl)tetraazaporphyrin were obtained by reactions of octaphenyltetraazaporphyrin, Mg octaphenyltetraazaporphyrin, octakis(4-bromophenyl)tetraazaporphyrin, and octakis(4-nitrophenyl)tetraazaporphyrin with palladium(II) and nickel(II) chlorides in DMF. 相似文献
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Magnesium porphyrazinate substituted with eight 4-biphenyl groups on the periphery positions has been synthesized for the first time from cyclotetramerization of 1,2-bis(4-biphenyl)maleonitrile in the presence of magnesium butanolate. Its demetalation by treatment with trifluoroacetic acid, resulted in a partially oxidized product, namely, octakis(4-biphenyl)-2-seco-porphyrazine-2,3-dione. Further reaction of this product with copper(II) acetate, zinc(II) acetate and cobalt(II) acetate has led to the metallo derivatives, [octakis(4-biphenyl)-2-seco-2,3-dioxoporphyrazinato] M(II) (M = Cu, Zn, Co). These novel compounds have been characterized by elemental analysis, together with FT-IR, 1H NMR, UV–Vis and mass spectral data. 相似文献
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Compound B (1,1,3,3,3-pentafluoro-2-fluoromethoxy-1-methoxypropane) can be separated by gas chromatography with an extraordinary chiral separation factor on a column coated with Lipodex E (octakis(3-O-butanoyl-2,6-di-O-n-pentyl)-γ-cyclodextrin). The enantioselectivity is greatly reduced when employing the β-cyclodextrin analogue. To further investigate the background of this unusual separation, the complexation between ‘compound B’ and Lipodex E (octakis(3-O-butanoyl-2,6-di-O-n-pentyl)-γ-cyclodextrin) and heptakis(3-O-butanoyl-2,6-di-O-n-pentyl)-β-cyclodextrin were studied by NMR. Association constants of the interaction of the two enantiomers of compound B with Lipodex E and its β-cyclodextrin analogue were determined by NMR chemical shift titration and showed a large difference corroborating earlier GC results. Heteronuclear NOE measurements proved that inclusion complex formation is taking place with compound B situated inside the cavity of the cyclodextrin moiety. Differences between the inclusion complex structures and their connection to association constants are discussed. 相似文献
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Synthesis of octakis({3-glycidoxypropyl}dimethylsiloxy) octasilsesquioxane (G-POSS) was carried out based on a reaction involving the hydrosilylation of allyl glycidyl ether with octakis(dimethylsiloxy) octasilsesquioxane, using Karstedt’s catalyst and toluene. SiO2/POSS hybrid systems were obtained via a method of immobilization by evaporation of the solvent, using hydrated or spherical silica obtained by precipitation in an aqueous or emulsion environment. The surface of the SiO2 was modified using octakis({3-glycidoxypropyl}dimethylsiloxy) octasilsesquioxane (G-POSS). The effectiveness of the modification of the obtained hybrid materials was verified using Fourier transform infrared spectroscopy and nuclear magnetic resonance (29Si and 13C CP MAS NMR). The tests showed that the interactions between the silica support and the modifier are of the nature of chemical adsorption. In addition a mechanism was proposed for the interactions between silica and oligosilsesquioxane. To test the final effect, the hybrid systems were subjected to morphological evaluation (transmission electron microscopy). Parameters of porous structure of the products were also determined: the specific surface area, pore diameter and pore volume. Thermal stability was tested for the pure silsesquioxane cage, the initial silica supports and the resulting systems. Elemental analysis was also carried out to determine the effect of surface modification on the degree of coverage with a particular POSS compound. 相似文献
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《Journal of Coordination Chemistry》2012,65(17):2875-2882
By cyclotetramerization of 3,4-bis(4-tert-butylphenyl)pyrroline-2,5-diimine in the presence of magnesium butanolate, magnesium porphyrazinate with eight (4-tert-butylphenyl) units on the periphery has been synthesized. Its demetalation by the treatment with trifluoroacetic acid resulted in a partially oxidized product, namely, octakis(4-tert-butylphenyl)-2-seco-porphyrazine-2,3-dione. Further reaction of this product with copper(II) acetate, zinc(II) acetate, and cobalt(II) acetate led to the metallo derivatives, [octakis(4-tert-butylphenyl)-2-seco-2, 3-dioxoporphyrazinato]M(II) (M = Cu, Zn, Co). These soluble complexes have been characterized by elemental analysis, FT-IR, 1H NMR, UV-Vis, and mass spectral data. 相似文献
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B3LYP/6-31G(d) calculations find that cubanes, persubstituted with NO2 or BF2 groups, are predicted to undergo near-barrierless, internal disrotations. However, as a consequence of the intrinsically higher energies of eclipsed conformations for threefold than for twofold rotors, the threshold mechanisms for octamethyl-, octakis(trifluoromethyl)-, octakis(trichloromethyl)-, octakis(tribromomethyl)-, octasilylcubane, and octakis(trichlorosilyl)cubane are calculated to be mono- or conrotation. The cubanes with the larger substituents are predicted to be O-symmetric, resolvable, and thus optically active. 相似文献
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Chizhova N. V. Ivanova Yu. B. Rusanov A. I. Khrushkova Yu. V. Mamardashvili N. Z. 《Russian Journal of Organic Chemistry》2019,55(5):655-661
Russian Journal of Organic Chemistry - Zn(II) octakis(4-fluorophenyl)tetraazoporphyrin and Cu(II) octakis(4-fluorophenyl)tetraazorphorphyrin were synthesized by the cyclization of... 相似文献