A facile and efficient method for preparation of chiral supported poly(styrene–divinylbenzene) copolymers

A new and efficient method for preparation of optically active poly(styrene–divinylbenzene) copolymers (PS-DVB) is presented here. This is carried out by Friedel–Crafts acylation reaction of chiral N-phthaloyl -leucine acid chloride with PS-DVB beads in the presence of aluminum chloride as Lewis acid catalyst and 1,2-dichloroethane as the solvent at ambient temperature. Reagents’ amounts and reaction conditions are mentioned and four samples with different amounts of functionality have been prepared. Final products were characterized by FT-IR and elemental analysis. The results obtained confirm that the above modification in preparation of chiral supported PS-DVB has been achieved well and in moderate yield.     

1,4,5,8-四氮杂氢化萘（2,3,-6,7）并双呋咱衍生物的合成

由1，4，5，8—四氮杂氢化萘(2，3，-6，7)并双呋咱经羟甲基化、酰化、硝化和叠氮化等反应合成出一系列热稳定的呋咱含能衍生物，并以^1HNMR、IR、MS、元素分析鉴定了其结构。     

The Synthesis of Covalent Triazine-Based Frameworks via Friedel–Crafts Reactions of Cyanuric Chloride with Thienyl and Carbazolyl Derivatives for Fluorescence Sensing to Picric Acid,Iodine and Capturing Iodine

A multifunctional thiophene-based covalent triazine framework (TTPATTh) with triphenylamine as core is synthesized by Friedel–Crafts reaction of cyanuric chloride with thienyl derivative for the first time. The yield of TTPATTh (99.59%) is far higher than that of the carbazole-based CTF (TTPATCz, 47.03%). TTPATTh and TTPATCz possess high BET surface areas with 1235 and 2501 m² g^–1 as well as high pore volumes with 1.60 and 2.23 cm³ g^–1, respectively. TTPATTh and TTPATCz have high thermal stability with high thermal decomposition temperatures of 514 and 598 °C in nitrogen atmosphere. With the introduction of triazine rings, the fluorescence sensing sensitivities of TTPATTh and TTPATCz to picric acid and iodine are improved significantly. Especially for TTPATTh, the K_sv values reach 5.95 × 10⁵ and 1.61 × 10⁴ L mol^–1, and LODs reach 1.02 × 10^–12 and 1.86 × 10^–12 mol L^–1. To the best of the knowledge, this is the most sensitive value among thiophene-based porous organic polymers to PA and I₂. Furthermore, TTPATTh and TTPATCz can also adsorb iodine in vapor phase, cyclohexane solution and aqueous solution, and release iodine by heating or in ethanol solution. The efficiency of controlling the release of iodine is higher than that in ethanol.     

乙氧苯酯的合成工艺改进

以对氨基水杨酸为原料，经酯化、酰化和烃化反应得乙氧苯酯，总收率为８７．４％。讨论了投料比、反应温度和反应时间对收率的影响，并改进了合成工艺。     

Preparation of water‐repellent silks by a reaction with octadecenylsuccinic anhydride

Silk fibers and membranes were acylated with octadecenylsuccinic anhydride (ODSA) at 75°C for different times. Swelling [N,N‐dimethylformamide (DMF) and dimethyl sulfoxide (DMSO)] and nonswelling (xylene) solvent media were used for the reaction. Silk membranes that reacted in DMF or DMSO displayed faster reaction kinetics and attained higher weight‐gain values than fibers. The effect of the solvent on the reaction yield was in the following order: DMSO > DMF ? xylene. The Fourier transform infrared spectra of acylated silk samples showed the characteristic absorption bands of the anhydride at 2990, 2852, 1780–1700, and 1170 cm^?1. The intensity of the latter band, which increased linearly with the weight gain, was used as a marker for evaluating the reaction kinetics of the samples acylated in the nonswelling medium. The moisture regain and water retention of silk fibers acylated with ODSA decreased significantly, regardless of the solvent system used. Accordingly, the water repellency increased. Acylation induced an increase in the thermal stability of the silk fibers and membranes. Fine particles adhering to the surfaces of the silk fibers acylated in xylene were detected by scanning electron microscopy. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 324–332, 2003     

有机碱对莰烯直接乙酰化的影响

研究了在含氮有机碱存在下的莰烯直接乙酰化反应，结果表明，在反应中加入与莰烯等摩尔的六氢吡啶，有利于莰烯乙酰化反应，在反应液中的酰化产物ω－乙酰基莰烯含量最高达到56％，大大超过异构化产物乙酸异冰片酯。     

2-苄基-4-氯苯酚的合成工艺

以非极性溶剂环己烷为介质,以无水氯化锌为催化剂,氯化苄与对氯苯酚在温和条件下合成2-苄基-4-氯苯酚.研究了溶剂、催化剂、反应温度等因素对反应的影响,并对产品进行了表征.结果表明,使用非极性的环己烷为溶剂,对氯苯酚浓度20%,对氯苯酚与氯化苄物质的量比5∶1,无水氯化锌为氯化苄质量的10%,温度30 ℃下反应6 h,产品收率达到78.7%.     

HIV病毒抑制剂中间体5-戊基间苯二酚的合成

以3,5-二甲氧基苯甲酸为起始原料,与LiH在室温下反应5h生成苯甲酸盐,生成的盐再与正丁基锂进行酰化反应得到3,5-二甲氧基苯戊酮,进而在210℃以下进行乌尔夫-黄鸣龙反应将酮还原,生成3,5-二甲氧基戊苯,所得产物与吡啶盐酸盐熔融,于200℃回流2h,脱甲基制得5-戊基间苯二酚,总收率达60.9%,纯度≥98%。     

红色基RL的合成工艺改进

详细研究了红色基RL(对硝基邻甲苯胺,简称RL)的合成工艺,对传统的合成工艺进行了改进,通过用乙酐作氨基保护试剂,混酸硝化,酸性水解等分步操作合成了RL。与传统方法相比,采用乙酐作氨基保护试剂,高温酰化,减少了乙酐用量;用混酸硝化,增强了硝化能力,提高了收率。分别研究了乙酐用量、反应时间、反应温度以及混酸配比对RL收率及熔点的影响规律,得到了反应的较佳条件。采用乙酐酰化分步合成法,RL总收率为56·4%(以邻甲苯胺计),氨基值为91·26%。     

4′-乙酰基缩氨硫脲基苯并-15-冠-5的合成

报道了在多聚磷酸 (PPA )中将冠醚酰化的方法 ,合成了 4′-乙酰基苯并 - 15 -冠 - 5 ,以此为原料 ,在酸性条件下与氨基硫脲作用 ,合成了 4′-乙酰基缩氨硫脲基苯并 - 15 -冠 - 5。经由 IR、MS和元素分析对合成的两种新物质的结构进行了表征