两种溴碘代苯新合成方法的研究

设计报道一种在温和条件下，以溴代苯胺为原料，经叠氮化、碘甲烷碘代，合成功能单体3，5-二溴-1-碘代苯和4-溴-1-碘代苯的新方法。     

溴代苯酐的制备

以邻苯二甲酸酐为原料，在金属铁作用下，与液溴发生溴代反应，制得溴代苯酐，运用正交试验研究了反应的主要影响因素，得到了较佳制备条件，收率达75.3%。用红外光谱及紫外光谱对产品结构进行了表征。     

溴化苯乙烯的合成研究

为了提高合成聚溴化苯乙烯的溴含量,实验对聚溴化苯乙烯的单体溴化苯乙烯进行了研究。首先对β-溴乙基溴代苯进行研究,主要以β-溴乙基苯为原料,利用溴素作为溴化剂,铁粉作为催化剂进行合成。然后以β-溴乙基溴代苯为原料,在醇钠的作用下进行合成了溴化苯乙烯单体。实验主要探究了催化剂用量、反应温度、保温时间对合成β-溴乙基溴代苯的影响以及醇的选用、反应温度、反应时间对合成溴化苯乙烯的影响。实验结果表明采用铁粉作为催化剂,催化剂用量3%,反应温度为30℃,保温时间为120 min合成β-溴代苯乙烷效果较好;选择异丙醇为溶剂,控制反应温度在4℃、保温4 h合成溴化苯乙烯单体效果较好。     

醛,酮α—溴代反应的研究—过溴型聚合物试剂的合成及应用

研究了过溴型聚合物试剂的合成及其在醛、酮α-溴代反应中的应用。探讨了α-溴代反应的动力学及反应条件。此合成方法可使醛、酮的α-溴代物获得良好的产率:α-溴丁醛达93.7%;α-溴庚醛98%;α-溴代环己酮98%。这些产率都大大高于文献值。     

对溴甲基苯甲酸合成工艺研究

以对甲基苯甲酸为原料,单质溴为溴代试剂,研究了对溴甲基苯甲酸的合成工艺路线。分别探索了单质溴和双氧水联用进行溴代的影响条件,如溶剂种类、反应温度、原料配比、引发剂种类等。提高了溴原子的利用效率,确定了最优反应条件,以较高的收率得到了对溴甲基苯甲酸。     

5-溴阿魏酸的合成研究

研究了标题化合物的合成工艺。以N-溴代丁二酰亚胺为溴代试剂,对香草醛进行溴化反应合成5-溴香草醛;以石油醚替代苯作为反应溶剂,5-溴香草醛与丙二酸进行Knoevenagel缩合反应制备标题化合物。二氯甲烷为最佳反应溶剂,通过正交试验确定5-溴香草醛的最佳反应条件:n(香草醛)∶n(NBS)=1∶1.5,CH2Cl2为溶剂,反应时间1.0 h,反应温度为室温。5-溴阿魏酸的总产率75.2%。该方法具有产率高、反应条件温和、时间短、试剂价格低廉及副产物丁二酰亚胺可回收利用等优点。     

1,2-二(溴甲基)-4-氟苯的合成路线研究

以3,4-二甲基苯胺为原料,经重氮化和溴代合成标题化合物.溴代反应以液溴为溴化剂,操作简便、收率较高.考察了原料配比、反应时间和温度对反应的影响,优化出一条较为理想的工艺条件.所得产品结构通过GC.MS、1HNMR进行了表征.     

新方法合成α-溴代苯乙酮类化合物

报道了一种以双(二甲乙酰胺基)三溴化氢为溴化剂,以苯乙酮类化合物为原料,合成了5种α-溴代苯乙酮化合物的新方法。最佳的合成条件为:n(苯乙酮)∶n(溴化剂)=1∶1,甲醇中20℃反应2 h,α-溴代苯乙酮类化合物收率达82%~94%。该合成方法操作简单,副产物可回收利用,适合大规模生产。     

溴代烷烃的清洁合成及表征

以工业副产品溴化钾为溴源,水为溶剂,在溴化钾0.1mol,醇0.08mol,浓硫酸5～8mL,水2.5～4.5mL,回流反应4h条件下,合成了12种溴代烷烃,包括直链溴代烷烃、支链溴代烷烃、溴代环烷烃。经折光率、1HNMR、IR、元素分析对其结构进行了表征。水相经生石灰简单处理后,达到环保排放要求。讨论了合成条件对不同结构溴代烷烃收率的影响,考察了该工艺的放大及重复使用稳定性。     

4-溴代百里香酚的合成

以百里香酚为原料,通过溴取代反应合成4-溴代百里香酚。采用FTIR、¹H NMR等手段对产物进行了表征,确定了产物结构。探讨了溶剂种类、溴代剂种类和用量、反应时间、反应温度和微波加热功率对产物得率的影响,得到适宜的工艺条件为:以N-溴代丁二酰亚胺为溴代剂,n(百里香酚):n(N-溴代丁二酰亚胺)=1:1.5,溶剂为乙酸,反应温度为20℃,反应时间15min,微波反应功率500W。在上述条件下,4-溴代百里香酚的得率为65.1%。     

Use of trifluoromethanesulfonic acid as catalyst for the cyclization of polyisoprene

In this study, trifluoromethanesulfonic acid was employed as catalyst for the cyclization of polyisoprene. From ¹H nuclear magnetic resonance spectroscopy and gel permeation chromatography investigations, cyclization was confirmed, and the molecular structure variation of polyisoprene during cyclization reaction was determined. With the comparison to that catalyzed by other strong acids (methanesulfonic acid), polyisoprene was cyclized with much higher efficiency, using trifluoromethanesulfonic acid as catalyst. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 3666–3669, 2006     

三氟甲磺酸催化1-己烯齐聚反应的研究

使用三氟甲磺酸作催化剂对1-己烯齐聚反应进行研究。考察三氟甲磺酸催化剂用量、反应温度和反应时间等工艺条件对产物聚α-烯烃收率的影响。确定了最佳工艺条件：催化剂用量1.0 mL，反应温度50 ℃，反应时间3 h，此条件下，1-己烯转化率约为90%，产物主要是二聚物、三聚物、四聚物和五聚物，没有裂解产品。为进一步工业化开发聚α-烯烃合成油提供了基础数据。     

三氟甲磺酸催化便捷高效合成2,4-滴丁酯除草剂

以2,4-二氯苯氧乙酸与正丁醇为原料,三氟甲磺酸为催化剂,催化合成2,4-滴丁酯,考察了醇酸摩尔比、反应时间及催化剂用量等对反应的影响。结果表明,合成2,4-滴丁酯的最佳反应条件是:正丁醇与2,4-二氯苯氧乙酸的摩尔比为3∶1,催化剂用量为0.2%(占2,4-二氯苯氧乙酸摩尔量),回流反应8 h,在此条件下,酯化率达97.1%。     

三氟甲磺酸催化合成柠檬酸酯

利用一种新型高效绿色催化剂三氟甲磺酸(CF3SO3H)合成绿色增塑剂柠檬酸三丁酯,结果表明该催化剂用量少(占柠檬酸的0.1%),反应时间短(5 h)。研究了该催化剂合成乙酰柠檬酸酯的一体化工艺,实现了无须精制柠檬酸三丁酯,直接从柠檬酸出发制得乙酰柠檬酸三丁酯,产率高(两步87.1%),纯度高(99.1%),大幅简化了生产工艺和成本且环保,适合工业化。同时,研究了CF3SO3H催化合成丙酰、丁酰柠檬酸酯类产品的一体化工艺。     

Superacidic Trifluoromethanesulfonic Acid-Induced Cycli-Acyalkylation of Aromatics

Superacidic trifluoromethanesulfonic acid-induced synthesis of 1-indanone and 1-tetralone derivatives through Friedel-Crafts cycli-acyalkylation of aromatics with unsaturated carboxylic acids was achieved. Depending on the reactant used, different substituted indanones and tetralones were obtained in moderate to good yields.     

Effect of acid/hydrocarbon ratio,temperature and contact time on the isobutane-isobutylene alkylation with trifluoromethanesulfonic acid

The effect of the acid-hydrocarbon ratio and temperature on the isobutane-isobutylene alkylation with trifluoromethanesulfonic acid was studied over the temperature range of 40CT–80C. The effect of acid/hydrocarbon ratios and temperature passes through a maximum giving high quality alkylate of approximately 70% branched C₈ products at –30C, with a catalyst/hydrocarbon ratio of 0.5. The optimum reaction conditions also depend on the induction period and the effect of secondary reactions influenced by contact time. TFSA is a readily recyclable acid without the need for any purification or regeneration.     

sp3‐sp2 C‐C Bond Formation via Brønsted Acid Trifluoromethanesulfonic Acid‐Catalyzed Direct Coupling Reaction of Alcohols and Alkenes

A novel and efficient trifluoromethanesulfonic acid‐catalyzed sp³‐sp² C C bond formation reaction through the direct coupling of alcohols with alkenes has been realized under mild conditions. The present protocol provides an attractive approach to a diverse range of polysubstituted olefins in good to excellent yields with high stereo‐ and regioselectivities.     

Bromine — containing polyurethane ionomers

Summary Polyurethane ionomers with reduced flammability were obtained by incorporating a brominated chain extender (dibromoneophentyl glycol-DBNPG) into the ionomers based on isophoronediisocyanate, polyoxytetramethylene glycol and 2,2-bis(hydroxymethyl)propionic acid. To examine the influence of brominated diol on the characteristics of the synthesized polymers, model polyurethane compounds containing various amounts of brominated and nonbrominated chain extenders (1,4-butanediol and neopenthyl glycol) were prepared, as well. The products were studied by FTIR, DSC and TGA methods. Hydrolytic stability of the ionomers in water was controlled by FTIR; their flammability was examined by oxygen index measurements.     

Efficient synthesis of 1,3-dioxanes catalyzed by trifluoromethanesulfonic acid using formalin as formaldehyde source

Prins cyclizations of styrene derivatives were smoothly conducted in a water solution of formaldehyde using trifluoromethanesulfonic acid (TfOH) as catalyst. While excellent yield was obtained in the Prins cyclization of styrene in the presence of TfOH, low yields or no reaction were observed when other traditional minimal acids catalysts were used.     

氨基磺酸催化合成乙酰水杨酸的研究

以水杨酸和乙酸酐为原料,采用氨基磺酸作催化剂合成乙酰水杨酸。考察了影响反应的因素。结果表明,酰化反应的优化条件为：n（水杨酸）∶n（乙酸酐）∶ n（氨基磺酸）＝1∶ 1.5 ∶0.006 1,反应时间25 min,反应温度（81～85） ℃,产率可达93.34%。