4,4,4-三苯基-1-丁烯的合成

以烯丙基溴为原料,在N2保护下,乙醚中与镁反应30 m in制得烯丙基溴化镁的乙醚溶液(Ⅰ)。过滤后,将Ⅰ从45℃逐步加热到65℃,蒸出乙醚。然后快速加入四氢呋喃(THF),65℃搅拌20 m in,制得烯丙基溴化镁的THF溶液(Ⅱ)。在冰浴中向Ⅱ缓慢滴加氯代三苯甲烷的THF溶液,搅拌3 h,制得4,4,4-三苯基-1-丁烯(Ⅲ),收率93%。用红外光谱、核磁共振氢谱和碳谱对产物进行了表征。     

三苯基氯甲烷的制备

以无水乙醚为溶剂,溴苯与镁反应制备格氏试剂苯基溴化镁。苯基溴化镁与二苯甲酮反应后,酸性条件下水解,蒸除乙醚,水蒸气蒸馏、抽滤、重结晶,得到三苯甲醇,产率53.7%。三苯甲醇与浓盐酸反应制备三苯基氯甲烷,产率49.4%。     

3-丁炔-1-醇的合成方法研究

介绍了制备的低温金属有机合成法、格氏试剂法和四氢呋喃开环法及其优缺点.采用1种新方法将四氢呋喃开环法中副产物多、产率低的光催化氯代自由基反应设计为原子经济性为100%的加成反应,即以二氢呋喃为原料与氯经加成反应生成二氯二氢呋喃,经消除和开环消除得到3-丁炔-1-醇.实验结果表明,该法中的二氢呋喃氯加成反应收率92.4%.提高了反应的总产率,减少了污染物的产生量,可适于产业化.     

1-正丁基杂氮硅三环的合成及表征

以正溴丁烷和镁屑为原料,制备了正丁基溴化镁;然后与正硅酸乙酯通过格氏反应,合成出正丁基三乙氧基硅烷;再与三乙醇胺在丙酮溶剂中、在氢氧化钠催化下,通过酯交换反应合成出1-丁基杂氮硅三环.研究了溶剂种类、催化剂种类、三乙醇胺与正丁基三乙氧基硅烷的量之比、反应时间对1-正丁基杂氮硅三环产率的影响,并用IR、GC-MS等对产物结构进行了表征.结果表明,格氏反应的平均产率为83.4%;酯交换反应的适宜条件为催化剂氢氧化钠的用量为三乙醇胺质量的2%、三乙醇胺与正丁基三乙氧基硅烷的量之比为2:1、在丙酮回流温度下反应4 h时,在此条件下目标产物的平均产率为73.6%.     

2-己基-4-乙酰氧基四氢呋喃顺反异构体的制备

以烯丙基氯和庚醛为原料通过格氏反应制得1-癸烯-4-醇,产率86%;1-癸烯-4-醇用间氯过氧苯甲酸氧化,得到1,2-环氧-4-癸醇,产率89%;然后,在碳酸钾的作用下1,2-环氧-4-癸醇进行分子内的亲核取代反应,关环得到2-己基-4-羟基四氢呋喃顺反异构体的混合物,产率90%,trans-和cis-异构体比例为53∶47;2-己基-4-羟基四氢呋喃与对硝基苯甲酰氯反应,酯化产物通过柱层析分离,得到trans-和cis-2-己基-4-四氢呋喃对硝基苯甲酸酯,产率分别为52%和40%;分离后的酯化产物的顺反异构体在碱性条件下水解,得到trans-和cis-2-己基-4-羟基四氢呋喃,产率分别为85%和82%;trans-和cis-2-己基-4-羟基四氢呋喃与乙酸酐反应,得到trans-和cis-2-己基-4-乙酰氧基四氢呋喃,产率分别为83%和85%。trans-和cis-2-己基-4-乙酰氧基四氢呋喃经过GC-O进行了评香分析和稀释因子的测定,结果表明,两者具有不同的香气特征和香气强度。     

3-卤-2-卤甲基-1-丙烯合成方法改进

以季戊四醇为原料经卤代、氧化、热分解三步主要反应合成了3-卤-2-卤甲基-1-丙烯.卤代反应中采用不同的卤代剂合成了三卤代新戊醇,在文献基础上加入以二氯甲烷为萃取剂的萃取过程可使三卤(氯)新戊醇产率达72%-98%;再通过氧化反应得到三卤(氯或溴)新戊酸,同样加入萃取过程可使酸的产率达到63%-80%,最后热分解脱卤化氢和二氧化碳制备3-卤-2-卤甲基-1-丙烯时(卤素为氯和溴),在文献基础上加入吡啶作催化剂可使热分解温度降至200 ℃(原分解温度为260 ℃),总产率可达45%-72%.在制备3-碘-2-碘甲基-1-丙烯时避光搅拌,可降低产物分解,产率为60%.所有的化合物经过了IR和1HNMR的确认.     

5,5′-二甲基-3,3′-二(三甲基硅基)联苯的合成

采用3,5-二溴甲苯(Ⅰ)为原料,与镁屑及三甲基氯硅烷(TMSCl)按n(Ⅰ)∶n(Mg)∶n(TMSCl)=4.5∶4.9∶6.9的比例在四氢呋喃(THF)中制得三甲基硅基(-TMS)单保护的5-甲基-3-溴-三甲基硅基苯(Ⅱ),产率为85%.以此为中间体与镁屑按n(Ⅱ)∶n(Mg)=6.5∶6.6的比例制成格氏试剂后,与等物质的量的芳基烷(Ⅱ)在质量分数为5%的无水氯化镍(NiCl2)催化下偶联合成了5,5′-二甲基-3,3′-二(三甲基硅基)联苯(Ⅲ),偶联产率为78%.     

3-羟基-4-苯基-2-丁酮的合成

分别以(E)-1-苯基-1-丁烯-3-酮和4-苯基-2-丁酮为起始原料合成了3-羟基-4-苯基-2-丁酮。以(E)-1-苯基-1-丁烯-3-酮为起始原料,经过环氧化和还原两步反应得到产物;第1步环氧化反应,用双氧水作氧化剂,产率64%;第2步α,β-环氧酮在Pd/C催化作用下用甲酸还原,得到产物3-羟基-4-苯基-2-丁酮,产率67%;该路线总产率为43%。以4-苯基-2-丁酮为起始原料,经过烯醇硅醚中间体氧化得到产物;4-苯基-2-丁酮在六甲基二硅胺作用下与三甲基碘硅烷反应得到4-苯基-2-丁烯-2-基三甲基硅醚,产率为75%;第2步烯醇硅醚用间氯过氧苯甲酸氧化,得到产物3-羟基-4-苯基-2-丁酮,产率达71%;该路线总产率为53%。以(E)-1-苯基-1-丁烯-3-酮为起始原料的合成路线总产率略低,但操作简单,试剂价廉易得,是更为实用可行的合成路线。     

5,5,5-三苯基-1,2-环氧戊烷的合成

以三苯基甲基氯为原料,采用环氧化合物取代法经3步反应得到标题化合物,产率61%。探讨了影响反应的多种因素,并找到了较好的合成条件。     

2-氯-3-氰甲基吡啶的合成及表征

对2-氯-3-氰甲基吡啶(Ⅳ)的合成进行了研究。首先,起始原料2-氯烟酸和SOCl2在甲苯中回流酰化,再加入甲醇酯化,得到2-氯烟酸甲酯(Ⅰ),产率94%。Ⅰ在NaBH4-MeOH/THF还原体系中,于70℃反应生成2-氯-3-羟甲基吡啶(Ⅱ),产率93%。Ⅱ和SOCl2在二氯甲烷中,0℃反应生成2-氯-3-氯甲基吡啶(Ⅲ),产率92%。最后,Ⅲ和NaCN在DMSO和水体系中,100℃时发生氰基取代,生成2-氯-3-氰甲基吡啶(Ⅳ),产率86%。该合成路线的总收率达70%。中间产物和目标化合物经元素分析,FTIR和1HNMR进行了表征。     

“一锅法”合成14-O-[(2-氨基-1, 1-二甲基乙基)硫甲羰基]目特林

以截短侧耳素、对甲苯磺酰氯和二甲基半胱胺盐酸盐为主要原料,以乙醚为溶剂,采用一锅法合成沃尼妙林中间体14-O-[(2-氨基-1,1-二甲基乙基)硫甲羰基]目特林。最佳工艺条件为:n(截短侧耳素)∶n(对甲苯磺酰氯)∶n(二甲基半胱胺盐酸盐)=1∶1.1∶1.1;相转移催化剂为四丁基溴化铵,用量为1.6 g;反应温度为30℃;反应时间为2.5 h;目标产物收率达91%。并用正交设计法对主要工艺条件进行了优化,结果与单因素实验结果相同。产品结构通过核磁共振波谱、红外光谱进行了表征,测定了产物的熔点。     

Highly efficient ring-opening polymerization of tetrahydrofuran by anhydrous ferric chloride

Poly(tetramethylene ether glycol) (PTMG), widely used as a precursor in the fabrication of commodity polymers, is typically produced byacid-catalyzed polymerization of tetrahydrofuran (THF). Herein, we report a detailed investigation of the cationic ring-opening polymerization of THF catalyzed by ferric chloride (FeCl₃), which can be considered as a strong Lewisacid. The polymerization reactions were performed in the presence of acetic anhydride at 20°C with FeCl₃, which readily produced poly(tetramethylene ether glycol diester) (PTMG_DE). A maximum yield of 79.2% was obtained within 30 min using a FeCl₃ to acetic anhydride molar ratio of 5:4. The resulting polymers generally exhibited low molecular weights and a narrow polydispersity index and could be easily converted into PTMG using aqueous NaOH. In contrast with the FeCl₃-acetic anhydride system, other iron-based catalysts such as FeCl₂ and FeCl₃·6H₂O did not show any noticeable activity in the polymerization of THF. The proposed mechanism involves initiation of the acetyl cation generated by FeCl₃, propagation by nucleophilic addition of THF, and termination by the acetate anion, accounting for the high activity of the FeCl₃ catalyst for THF polymerization. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47999.     

5-烷基-2-(4-氰基苯基)-1,3-二噁烷的合成

对 5 烷基 2 (4 氰基苯基 ) 1,3 二 口恶烷的合成进行了研究 ,以 5 戊基 2 (4 氰基苯基 ) 1,3 二口恶烷的合成为例 ,论述了以溴代烷和丙二酸二乙酯为初始原料 ,采用相转移催化烃基化反应合成了 2 戊基丙二酸二乙酯 ,收率 91 7% ;进而以四氢铝锂和硼氢化钠为还原剂于 0～ 2 0℃在四氢呋喃溶剂中合成了 2 戊基丙二醇 ,收率≥ 80 % ;再与对氰基苯甲醛在催化剂氯化钙存在下反应合成了 5 戊基 2 (4 氰基苯基 ) 1,3 二 口恶烷 ,收率≥ 90 %。并通过核磁共振氢谱和红外光谱证实了其结构     

Phase diagrams for oil/methanol/ether mixtures

One-phase transmethylations of vegetable oils with methanol to form methyl esters occur considerably faster than conventional two-phase reactions. Addition of simple ethers is an efficient method for producing a single phase. Ternary phase diagrams have been determined at 23°C for oil/methanol/ether mixtures; these are useful when applying the one-phase method across a wide range of conditions. Soybean, canola, palm, and coconut oils were used in combination with five ethers, namely, tetrahydrofuran (THF), 1,4-dioxane (DO), diethyl ether (DE), diisopropyl ether (DI), andtert-butyl methyl ether (TBM). All five ethers can produce miscibility for all methanol/oil compositions. The ether/methanol volumetric ratios required for miscibility at a methanol/soybean or canola oil volumetric ratio of 0.20 (5.4 molar ratio) at 23°C are: THF, 1.15; DO, 1.60; DE, 1.38 DI, 1.57; and TBM, 1.57. For THF, this results in one-phase mixtures that contain 65 vol% oil. Soybean and canola oil form identical diagrams. Palm oil requires slightly less ether at the lower methanol concentrations, but coconut oil requires considerably less across the whole concentration range. Acid-catalyzed reactions, when performed at the boiling point of the most volatile component, require less ether than predicted from the diagrams.     

1-甲氧基-9,10-双(苯乙炔基)蒽的合成

由１－硝基蒽醌与甲酸钠作用生成１－甲氧基蒽醌,收率７５％。１．甲氧基蒽醌与苯乙炔基溴化镁在ＴＨＦ中回流２４ｈ,水解后的混合物不经分离直接与氯化亚锡的乙酸溶液反应３０ｍｉｎ,一步法合成了题示化合物,收率４６％。     

溴化聚苯乙烯中溴、氯含量连续测定方法

提出了一种连续测定溴化聚苯乙烯中溴、氯含量的新方法。用四氢呋喃作溶剂溶解样品．加入联苯钠脱有机卤素,然后加水稀释,用稀硝酸调节pH值,采用ZD-2电位滴定仪测定等当点．从而确定溴、氯含量。检测范围溴含量在40％-70％,氯含量在0．5％～5％。该方法简单、快速、准确。     

Ethylene carbonate/ether mixed solvents electrolyte for lithium batteries

Conductivities and Li charge—discharge efficiencies for LiClO₄ethylene carbonate (EC)/ether mixed solvents systems were studied, compared with those for propylene carbonate (PC)/ether and EC/PC/ether mixed solvents electrolytes, for use in nonaqueous lithium secondary batteries. As the ethers, tetrahydrofuran (THF), 1,2-dimethoxyethane, diethoxyethane and 1,3-dioxolane were used. Conductivities for EC/ether mixed systems were higher than those for both EC/PC/ether and PC/ether mixed systems, due to the high dielectric constant for EC and low viscosity for ethers. Conductivities showed maximum values around EC/ether mixing volume ratio = 1/1 and at about 1 M solute. For example 1 M LiClO₄EC/THF (1/1) showed approximately 40% higher conductivity, 14 × 10^?3 S cm^?1, than for PC/THF. Li charge—discharge efficiencies for EC/ether mixed systems also increased more than those for EC/PC/ether and PC/ether. This seems to be due to adsorption of less Li reactive ether and EC than PC, around deposited Li. In the same solute—solvents systems, Li cycling efficiencies for EC/eether mixed systems tended to increase Li cycling efficiency of 92%. This value was approx. 10% higher than for PC/THF.     

新法制备氯苯和对二氯苯格氏试剂

在无任何引发剂存在下,以普通镁屑（ 粉） 、氯苯、对二氯苯、无水四氢呋喃或无水乙醚等为原料,制备了氯苯、对二氯苯的格氏试剂,其收率均在９０％ 以上。与传统制备方法相比,反应更易引发,反应条件更易控制,收率较高。     

Fractionation of commercial frying oil samples using sep-pak cartridges

Commercial frying oil samples were fractionated by column chromatography on hydrated silicic acid according to the standardized DGF-IUPAC-AOAC method. The non-polar fraction was isolated using a mixture of petroleum ether:diethyl ether (87:13), while the polar fraction was eluted by diethyl ether. These used frying oil samples were also fractionated using Sep-Pak cartridges. The non-polar fraction was eluted with 20 ml of a mixture of petroleum ether:diethyl ether (92:8), while the polar fraction was eluted with methanol. The purity of each fraction was studied by thin layer chromatography (TLC) and by the Iatroscan TLC/FID system using a mixture of hexane:tetrahydrofuran:acetic acid (97:3:1) as solvent system. The Sep-Pak and the standardized methods gave similar results. This indicates that the state of degradation of a frying oil (detection of polar components) could be studied using Sep-Pak cartridges, which is less time- and solvent-consuming than column chromatography.