Horizontal reactive distillation for multicomponent chiral resolution

A novel horizontal reactive distillation apparatus and a new overall process scheme are proposed for continuous multicomponent chiral resolution via reversible enantioselective acylation of a chiral (racemic) substrate by a chiral (racemic) acyl donor. The process enables simultaneous production of up to four enantiomers with enhanced chiral purity. Kinetic studies, miniplant experiments, and process simulation results are described for a model lipase‐catalyzed reaction: (R)‐enantioselective transesterification of (R,S)‐1‐n‐butoxy‐2‐propanol with (R,S)‐1‐methoxy‐2‐acetoxypropane to produce (R)‐1‐n‐butoxy‐2‐acetoxypropane, (R)‐1‐methoxy‐2‐propanol, and the two unreacted (S)‐enantiomers of the (R,S)‐reagents. A horizontal, compartmentalized reactive distillation vessel is specified instead of a conventional reactive distillation column to provide longer liquid‐phase residence time needed for adequate conversion. Low vapor‐traffic pressure drop allows operation under vacuum at reduced temperatures for good enzyme stability and enantioselectivity. The general technology has potential as a means to producing a wide range of chiral synthons used in asymmetric syntheses of chiral pharmaceuticals and other biologically active products. © 2013 American Institute of Chemical Engineers AIChE J, 59: 2603–2620, 2013     

含稠杂环结构聚芳醚酮的合成与表征

以无水ＡｌＣｌ３／ＣｌＣＨ２ＣＨ２Ｃｌ／ＤＭＦ为催化剂／溶剂体系,将（夹）二氧蒽（ＯＤＰ）和吩噻恶（ＯＳＰ）分别与对苯二甲酰氯、间苯二甲酰氯及２,５－二氯对苯二甲酰氯进行亲电缩聚,合成了几种主链含稠杂环结构的聚芳醚酮,用ＩＲ、ＤＳＣ、ＴＧ和ＷＡＸＤ等方法对其进行了分析,研究表明,它们均属非晶态聚合物,其对数比浓粘度均在０．６５以上,具有很高的玻璃化温度（Ｔｇ＝１９０～２５８℃）、优异的耐热性和耐溶     

Structured catalysts for the acylation of aromatics

In the acylation of anisole with octanoic acid, Nafion/silica composites were the most active slurry catalysts, compared to zeolite catalysts. Monolithic structures were coated successfully with Nafion. Tested in the acylation, these structured catalysts exhibited similar high activities, eliminating the disadvantages (attrition, filtration, regeneration) of a slurry system operation. This revised version was published online in June 2006 with corrections to the Cover Date.     

1，1'-二乙酰基二茂铁合成工艺研究

以三氯化铝为催化剂,醋酐为酰化剂,在二氯甲烷中对二茂铁的双酰化进行了研究,讨论了反应温度、催化剂用量、物料摩尔比、投料方式、反应时间对合成工艺的影响,得到了产率较高、反应时间较短的合成l,1'- 二乙酰基二茂铁的工艺条件。     

歧化松香酰化壳聚糖的微波合成及表征

在微波辐射下,以壳聚糖和歧化松香为原料,首次合成了一种新型壳聚糖衍生物———歧化松香酰化壳聚糖(DR-CA),并通过红外、紫外、X射线衍射、扫描电镜、元素分析和热分析等测试手段对产物进行了结构和性能表征。系统研究了溶剂、物料配比(r)、温度、时间和微波功率对取代度(DS)的影响。结果表明,当r为6∶1时,在含吡啶约50%(体积比)的DMF溶液中,微波功率800 W下,100℃反应2.5 h获得了最高取代度的DRCA(DS=0.165)。溶解性试验表明,DRCA具有较好的水溶性,且从DRCA的临界胶束浓度(CMC)(CMC=0.003 g/mL,此时表面张力为σCMC=55.22 mN/m)可知,所合成的DRCA具有一定的表面活性。     

离子液体催化合成2-(4-乙基苯甲酰基)苯甲酸

研究了离子液体催化合成2-(4-乙基苯甲酰基)苯甲酸。并对离子液体中[Bmim]Cl与三氯化铝的摩尔比、原料配比、反应温度和反应时间等工艺条件进行了考察。较优工艺条件为:n(AlCl3)∶n([Bmim]Cl)=1∶3,n(离子液体)∶n(邻苯二甲酸酐)∶n(乙苯)=1∶1∶1,反应温度为50℃,反应时间为4h,在此条件下,[Bmim]Cl-AlCl3催化邻苯二甲酸酐的转化率可达100%,目标产物2-(4-乙基苯甲酰基)苯甲酸的选择性达97.14%,可避免使用有机溶剂。     

磺酰胺类除草剂阔草清的合成研究

以5-氨基-3-巯基-1,2,4-三唑和2,6-二氟苯胺为主要原料,经苄基化、环合、酰化、胺解4步反应合成阔草清,总收率46．5％。该方法可以降低成本,提高反应速度,简化分离步骤,降低能耗和减少污染,是一种较清洁的生产工艺,适合工业化生产。     

酰基化强碱性离子交换纤维制备及其对金属氰络合物吸附性能研究

氰化提金工艺产生的含氰废水中多含有金属氰络离子,其会消耗额外的氰化物,进而影响生产工艺指标.研究以聚丙烯纤维为基体,制备了酰基化强碱性离子交换纤维(ASA-IEF),并考察了其对废水中金属氰络离子的去除性能.ASA-IEF的最优制备条件为反应时间4 h、反应温度30℃、三氯乙酰氯与苯乙烯摩尔比1:1.2.在此条件下,纤...     

黑豆皮花色苷的酶法酰化制备及其稳定性分析

以黑豆皮花色苷矢车菊素-3-O-葡萄糖苷（cyanidin-3-O-glucoside，C3G）为原料，采用月桂酸为酰基供体，经酶法酰化制备具有亲脂性能的花色苷脂肪酸酰化产物。分别以黑豆皮粗提物（C3G含量35.8%）、纯化C3G样品（纯度>80%）、C3G标准品（纯度>98%）为底物进行酰化，通过改进反应溶剂体系，实现了黑豆皮粗提物中花色苷的高效酰化，酰化率达66.59%，产率达到C3G标准品酰化的75%，但工艺更为简单，底物无需纯化；酰化产物矢车菊素-3-O-葡萄糖苷月桂酸酰化物（cyanidin-3-O-glucoside-lauric acid，C3G-La）经液液萃取，纯度可达82.39%；经进一步正相硅胶分离纯化后，产物纯度达97.58%。稳定性试验发现，在pH为中性和酸性环境中，C3G-La的稳定性优于C3G，但二者在碱性和光照条件下稳定性均较差。     

Application of immobilized lipase in production of camptosar (CPT-11)

Lipase fromPseudomonas cepaica (Amano, PS-30) was immobilized on celite and used in organic solvent for the selective acylation of a key alcohol intermediate. The compound was transformed in the synthesis to the anticancer drug Camptosar (CPT-11). Catalyst activity was influenced by the water content and method used to dry the catalyst. This resolution has been conducted on production scale with equal weight of recyclable catalyst.