1,3,5,7-四异氰氧基乙基-1,3,5,7-四甲基环四硅氧烷合成及结构表征

以丙烯酸和1,3,5,7-四甲基环四硅氧烷(D4H)等为初始原料,经酯化、硅氢加成反应制得1,3,5,7-四(三甲基硅氧羰丙基)-1,3,5,7-四甲基环四硅氧烷(2),水解2制得1,3,5,7-四羧丙基-1,3,5,7-四甲基环四硅氧烷(3),3经Staudinger反应和Curtius重排反应制得1,3,5,7-四异氰氧基乙基-1,3,5,7-四甲基环四硅氧烷(4).反应总收率为14.5%,化合物结构经1H NMR,29Si NMR,IR,MS和HRMS确证.     

阴离子聚合法合成PMMA-b-PMTFPS嵌段共聚物

以含缩醛官能团的有机锂为引发剂, 将甲基丙烯酸甲酯(MMA)与含氟硅氧烷单体1,3,5-三甲基-1,3,5-三(3',3',3'-三氟丙基)环三硅氧烷(F3)阴离子嵌段共聚, 获得了窄分子量分布的聚甲基丙烯酸甲酯-b-聚[甲基(3,3,3-三氟丙基)硅氧烷](PMMA-b-PMTFPS)嵌段共聚物, 并用GPC, 1H NMR, FTIR和DSC对嵌段共聚物进行了表征. 研究结果表明, 在THF中利用PMMA-OLi对F3进行阴离子开环聚合时, 单体F3浓度的选择对提高嵌段共聚物产率至关重要.     

紫外光固化聚多氟烷氧丙基甲基硅氧烷的研究

本文报道几种紫外光敏有机硅单体:(γ-甲基丙烯酰氧)丙基甲基二甲氧基硅烷,1,3,5,7-四(γ-甲基丙烯酰氧丙基)四甲基环四硅氧烷和1,3-双(甲基丙烯酰氧甲基)-1,1,3,3-四甲基二硅氧烷的合成,以及它们与αH,αH,ωH-全氟烷氧丙基甲基环四硅氧烷的开环共聚反应,制备了一系列新型光敏聚多氟烷氧丙基甲基硅氧烷.并初步研究了在紫外光辐照下,这类光敏聚多氟烷氧丙基甲基硅氧烷的化学结构对固化速度的影响.     

用哈克流变仪模拟D3F反应挤出阴离子开环聚合反应

采用哈克流变仪模拟1,3,5-三甲基-1,3,5-三(3′,3′,3′-三氟丙基)环三硅氧烷(D3F)阴离子开环聚合的反应挤出试验.通过凝胶渗透色谱法(GPC)测定其绝对分子量,并通过红外光谱(FT-IR)和核磁共振氢谱(1H-NMR)表征其结构.研究表明:在促进剂乙酸乙酯作用下,120 ℃下反应4 min可得到数均分子量为2.45×105的氟硅聚合物,反应温度、时间对制备氟硅聚合物有一定的影响.     

2,4,6-三甲基-2,4,6-叁(3′3′3′-三氟丙基)环三硅氧烷的简便制备法

2,4,6-三甲基-2,4,6-叁(3′3′3′-三氟丙基)环三硅氧烷(D_3~F)是合成氟硅橡胶的单体,一般以硅氢加于烯烃而制得:但因3,3,3-三氟丙烯的沸点为-22℃,需要在加压低温下操作,既不易纯化,又难以控制反应.我们以沸点102℃的甲基三甲氧基硅烷(1)、沸点45.5℃的1,1,1-三氟-3-氯丙烷(2)与镁屑在无溶剂常压下反应.这样既方便又安全,制得的3,3,3-三氟丙基     

特定乙烯基和硅氢键含量聚硅氧烷的可控制备

以1,3,5-三乙烯基-1,3,5-三甲基环三硅氧烷与六甲基环三硅氧烷为共聚单体,四氢呋喃为溶剂,在正丁基锂引发条件下实现可控阴离子开环共聚,制备特定乙烯基含量的聚硅氧烷;同时,以1,3,5,7-四甲基环四硅氧烷与六甲基环三硅氧烷为共聚单体,四氢呋喃为溶剂,在浓硫酸引发条件下实现可控阳离子开环共聚,制备特定硅氢键含量的聚硅氧烷,为制备具有特定乙烯基和硅氢键含量聚硅氧烷国防专用标准物质奠定了基础。     

标准物质RDX、HMX定值的不确定度评估

用建立的非水溶剂电位滴定法测定纯度标准物质1,3,5-三硝基-1,3,5-三氮杂环己烷(RDX)和1,3,5,7-四硝基-1,3,5,7-四氮杂环辛烷(HMX)的含量,用电位滴定曲线准确确定滴定终点。对两种标准物质测定过程和标定过程中不确定度来源进行了分析和计算,得到RDX含量测量结果为(99.710±0.188)%;HMX含量测量结果为(99.703±0.189)%。     

1-(3-氨基丙基)-2,8,9-三氧杂-5-氮杂-1-硅杂双环[3,3,3]十一烷衍生物的合成及其抗肿瘤活性研究

通过1-(3-氨基丙基)-2,8,9-三氧杂-5-氮杂-1-硅杂双环[3,3,3]十一烷与酸反应或1-(3-氯丙基)-2,8,9-三氧杂-5-氮杂-1-硅杂双环[3,3,3]十一烷与胺反应,合成了14种1-(3-氨基丙基)-2,8,9-三氧杂-5-氮杂-1-硅杂双环[3,3,3]十一烷衍生物.体外细胞培养试验结果表明,某些1-(3-氨基丙基)-2,8,9-三氧杂-5-氮杂-1-硅杂双环[3,3,3]十一烷衍生物对艾氏腹水癌细胞具有较好的杀伤活性.     

3,3,3-三氟丙酸的合成

3,3,3-三氟丙酸是一种新型三氟甲基合成切块,在医药、农药、染料及功能材料等精细化工领域有着广泛的应用。以3,3,3-三氟-1-氯丙烷和Cl_2为原料,在紫外光照下经氯化反应合成了3,3,3-三氟-1,1,1-三氯丙烷,再与Oleum试剂经水解反应合成了3,3,3-三氟丙酸,收率47.7%,其结构经~1H NMR,~(13)C NMR和MS确证。并对反应条件进行了优化。     

两种立体构型的1,3,5,-三-α-萘基苯的合成

通过Adole反应和Grigard反应合成了相应的两种立体异构的1,3,5-三-α-萘基苯. 报道了它们的UV, IR, FD-MS和NMR . 论了两种异构体的^1H NMR 和^1^3C NMR的区别.     

Fluorine-containing dialkoxysilanes. The formation of complexes with aminopropyltriethoxysilane and production of transparent films

Three dialkoxysilanes with fluorine-containing groups were synthesized: methyl(3,3,3-trifluoropropyl)dimethoxysilane, methyl(3,3,3-trifluoropropyl)bis(2,2,2-trifluoroethoxy)silane, and methyl(2,2,2-trifluoro-1-trifluoromethylethoxymethyl)bis(2,2,2-trifluoro-1-trifluoro-methylethoxy)silane. It was found by IR and ²⁹Si NMR spectroscopies that (3-aminopropyl)-triethoxysilane forms complexes with the indicated compounds, which are hydrolyzed in the presence of air moisture to form films of high optical quality.     

Nucleophilic substitution of bromine in vicinal bromotrifluoroalkylamines

SecondaryN-(2-bromo-3,3,3-trifluoropropyl)-N-alkylamines cyclize under the action of bases to yield aziridines. TertiaryN-(2-bromo-3,3,3-trifluoropropyl)amines react with S-nucleophiles to give products of bromine substitution.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 5, pp. 955–957, May, 1994.     

Poly(ethylene imine) hybrids containing polyhedral oligomeric silsesquioxanes: Preparation, structure and properties

Both octaglycidyletherpropyl polyhedral oligomeric silsesquioxane and hepta(3,3,3-trifluoropropyl)glycidyletherpropyl polyhedral oligomeric silsesquioxane were synthesized via the hydrosilylation reactions between octahydrosilsesquioxane [and/or hepta(3,3,3-trifluoropropyl)hydrosilsesquioxane] and allyl glycidyl ether. The polyhedral oligomeric silsesquioxane (POSS) macromers were characterized by means of Fourier transform infrared and nuclear magnetic resonance spectroscopy. The inter-component macromolecular reactions between the POSS macromers and poly(ethylene imine) (PEI) were employed to prepare the POSS-containing organic-inorganic PEI hybrids. The inclusion of octaglycidyletherpropyl POSS into PEI results in the formation of the organic-inorganic hybrid networks whereas the introducing hepta(3,3,3-trifluoropropyl)glycidyletherpropyl POSS to PEI affords the linear POSS-grafted PEI copolymers. Differential scanning calorimetry and thermogravimetric analysis show that the POSS-containing PEI hybrids displayed increased glass transition temperatures (T_g’s) and enhanced thermal stability compared to the plain PEI. These PEI hybrid composites can be significantly swollen with water without dissolving, suggesting the formation of hydrogels. The PEI hydrogels containing octaglycidyletherpropyl POSS is in reality the chemically-crosslinked hydrogels whereas the those containing hepta(3,3,3-trifluoropropyl)glycidyletherpropyl POSS displayed the behavior of physical hydrogels. The formation of physical hydrogels is ascribed to the microphase-separated morphology in the hybrids. In addition, the hybrids containing hepta(3,3,3-trifluoropropyl)glycidyletherpropyl POSS exhibited the typical amphiphilicity as evidenced by the increase in surface hydrophobilicity.     

Characterization of degradation products of poly[(3,3,3-trifluoropropyl)methylsiloxane] by nuclear magnetic resonance spectroscopy, mass spectrometry and gas chromatography

Poly[(3,3,3-trifluoropropyl)methylsiloxane] (PTFPMS) was treated with the solvents acetone, ethyl acetate and methanol and its degradation products were analyzed with multiple techniques. ¹H, ²⁹Si and ¹⁹F nuclear magnetic resonance (NMR) spectroscopy were useful for the characterization of the intact polymers and for the determination of cyclosiloxanes. Cyclosiloxanes with a ring size of up to 23 were quantified by gas chromatography. The only degradation products found were TFPmethyl-cyclosiloxanes. 1,3,5,7-Tetrakis(TFPmethyl)-cyclotetrasiloxane was predominant, and (TFPmethyl)cyclotri-, penta- and hexasiloxane could be detected at lower concentrations. The identity of cyclic degradation products with a ring size of up to 6 was unambiguously confirmed by direct infusion mass spectrometry. The TFPmethyl-cyclosiloxanes were successfully ionized by electrospray ionization in the negative mode. None of the techniques applied gave hints to other degradation products such as short linear oligomers. Almost complete degradation of PTFPMS occurred in acetone and methanol, while degradation is distinctly reduced in ethyl acetate.     

Synthesis of 3,3,3-trifluoropropene from vinylidene fluoride

3,3,3-Trifluoropropene is obtained under mild conditions via 3,3,3-trifluoropropyl acetate or 3,3,3-trifluoropropyl methyl ether as key intermediates. The intermediates were prepared by conjugate addition of FCH₂OR (R = COCH₃, CH₃) generated $\text{in situ}$ from HF, paraformaldehyde and HOR to vinylidene fluoride.     

Preparative-scale synthesis of 3,3,3-trifluoropropene oxide

Bromination of 3,3,3-trifluoropropene in 20% oleum, followed by treatment with acetic acid furnishes 2-bromo-3,3,3-trifluoropropyl acetate in quantitative yield, which upon acid hydrolysis and cyclization with alkali affords 3,3,3-trifluoropropene oxide (TFPO) in 63% overall yield.     

A synthesis of the γ-secretase inhibitor BMS-708163

A concise, convergent racemic synthesis of BMS-708163 is reported. Two fragments consisting of N-4-chlorophenylsulfonyl-3,3,3-trifluorpropylglycine and a 1,2,4-oxadiazole derivative of 2-fluorobenzyl alcohol were prepared in separate pots and then coupled together via a Mitsunobu reaction. Since a convenient chiral synthesis of optically pure (d)-3,3,3-trifluoropropyl glycine methyl ester was developed using Schöllkopf reagent alkylation, this methodology can also be adopted for the enantioselective synthesis of BMS-708163.     

Nanostructures and surface dewettability of epoxy thermosets containing hepta(3,3,3-trifluoropropyl) polyhedral oligomeric silsesquioxane-capped poly(ethylene oxide)

Hepta(3,3,3-trifluoropropyl) polyhedral oligomeric silsesquioxane (POSS)-capped poly(ethylene oxide) (PEO) was synthesized via the reaction of hydrosilylation between hepta(3,3,3-trifluoropropyl)hydrosilsesquioxane and allyl-terminated PEO. The POSS-capped PEO was characterized by means of Fourier transform infrared (FTIR) and nuclear magnetic resonance (NMR) spectroscopy. The organic-inorganic amphiphile was incorporated into epoxy resin to prepare the organic-inorganic nanostructured thermosetting composites. The morphology of the hybrid composites was characterized with field emission scanning electronic microscopy (FESEM) and transmission electronic microscopy (TEM). The formation of nanostructures was addressed on the basis of miscibility and phase behavior of the sub-components (viz. POSS and PEO chains) of the organic-inorganic amphiphile with epoxy after and before curing reaction. The static contact angle measurements indicate that the organic-inorganic nanocomposites displayed a significant enhancement in surface hydrophobicity as well as reduction in surface free energy. The atomic force microscopy (AFM) showed that there is significant migration of the POSS moiety at the surface of the thermosets. The improvement in surface properties was ascribed to the enrichment of the POSS moiety on the surface of the nanostructured thermosets, which was evidenced by X-ray photoelectron spectroscopy (XPS).     

Synthesis and structure of diethyl (1-benzyloxycarbonylamino-1-carboranyl-3,3,3-trifluoropropyl)phosphonate

A reaction of C-carboranylmethylmagnesium bromide with diethyl (N-benzyloxycarbonyl-2,2,2-trifluoroethaneimidoyl)phosphonate gave P- and N-protected aminophosphonic acid, an organophosphorus analog of alanine. The phosphonate was characterized by ¹H, ¹⁹F, and ³¹P NMR spectroscopy. X-ray diffraction analysis of diethyl (1-benzyloxycarbonylamino-1-carboranyl-3,3,3-trifluoropropyl)phosphonate showed that the molecules form dimers in crystals due to the intermolecular hydrogen bond.