乙酰基二茂铁的合成

以三氯化铝为催化剂,乙酰氯为酰化剂,在二氯乙烷中对二茂铁酰化得到了产率较高的乙酰基二茂铁。研究了反应温度、加料方式和反应物摩尔比对反应的影响。     

DFT方法研究无水AlCl_3催化剂对二茂铁乙酰化反应的影响

通过DFT方法理论研究无水AlCl_3催化剂对二茂铁乙酰化反应的影响。反应物、产物、中间体和过渡态的几何构型在B3LYP/6-31G*水平上进行优化和振动分析,过渡态正确性用内禀反应坐标(IRC)计算进行确认。在b2plypd3/def2tzvp级别进行单点能量计算。利用极化连续介质模型(IEF-PCM)考虑整体溶剂化效应。结果表明,无水AlCl_3催化剂大大降低了反应的吉布斯自由能垒,是保证反应可以发生的关键。     

二茂铁酰化反应研究

以二茂铁为起始原料,分别与乙酸酐、酰氯、氯乙酰氯,在质子酸或Lew is酸作用下发生Friedel-Crafts酰基化反应生成乙酰基二茂铁,二乙酰基二茂铁,氯乙酰基二茂铁(2 a~2 c),在制备的过程中我们对(2 a~2 c)合成工艺进行优化,以68.9%~98.6%的收率得到三种常见的酰化产物,与文献相比收率都有所提高。     

二茂铁—优良的燃料燃速催化剂

根据国内外有关资料，提出了人造液化气，炉用燃料柴油（煤油）车用汽油柴油节能消烟添加剂的配比，重点介绍二茂铁燃速催化剂。     

二茂铁硅烷接枝的丁羟燃速催化剂

皮特辛(BUTACENE)是由Fe(CH_2)_4SiH(CH_3)_2与低分子HTPB的接枝共聚物。接枝可以H_2PtCl_6·H_2O为硅氢化反应的催化剂,在60℃下进行。皮特辛推进剂具有良好的工艺和力学性能以及老化性能,推进剂加工更安全。含皮特辛的推进剂配方燃速可达70～80mm/s。     

二茂铁及其衍生物的应用

综述了二茂铁及其衍生物在添加剂、燃速催化剂、医学、液晶材料、感光材料以及二茂铁有机磁体等方面的应用和最新研究进展。     

对乙基苯甲酸的合成

以苯和乙酸乙酯为原料，无水三氯化铝为催化剂，合成了对乙基苯乙酮，继而合成了对乙基苯甲酸，研究了反应条件对反应的影响。在最佳条件下，对乙基苯甲酸的总收率达到46．0％。     

二茂铁二羧酸双(二乙二醇)酯合成研究

以二茂铁、乙酰氯、溴、二乙二醇等为原料,合成出中间体二乙酰二茂铁、二茂铁二羧酸、二茂铁二羧酸二甲酯,再采用酯交换工艺,通过提高二乙二醇比例,选用低毒溶剂油,并利用甲醇/溶剂油易于分层、准确控制反应终点,合成出了高质量分数的目标产物二茂铁二羧酸双(二乙二醇)酯。该方法与直接酯化法相比收率提高至80%,目标产物质量分数为93%,相比酰氯法避免了使用剧毒的草酰氯、氯化亚砜,是低成本规模化制备目标产物的优化方法。     

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.     

Boron trifluoride etherate as a catalyst in acylation of ferrocene

Ferrocene was acylated in acetic or propionic anhydride, in presence of boron trifluoride etherate giving acetyl ferrocene ( 1 ) (in quantitative yields) or propionyl ferrocene ( 2 ) (in high yields). A more general procedure is based on the reaction between ferrocene and carboxylic anhydrides or acyl halides in presence of ascorbic acid. Acetyl, propionyl, benzoyl, anisoyl and 3-phenyl propionyl ferrocenes ( 1 – 5 ) were obtained in moderate to high yields.     

Friedel-Crafts酰基化催化剂的研究进展

Friedel-Crafts酰基化反应在有机合成研究与现代工业生产中有着非常重要的作用,其催化剂主要有 Lewis酸、超强酸/盐、离子液体、沸石类以及负载型催化剂。本文分别介绍了上述五类催化剂在F-C酰基化反应中的发展沿革与目前应用情况,分析评价了各类催化剂在该反应中的优缺点,并重点综述了沸石类催化剂和负载型催化剂的研究现状。最后从绿色化学、可持续发展的角度出发,指出沸石类和负载型两类催化剂具有较好的综合催化性能和工业化应用前景,值得进一步研究。     

Cerium-containing MCM-41 materials as selective acylation and alkylation catalysts

The synthesis of Ce–MCM-41, Al–MCM-41 and Ce–Al–MCM-41-type mesoporous materials was carried out hydrothermally by refluxing the gel with magnetic stirring under atmospheric pressure for 24–36 h. The samples were characterized thoroughly in order to obtain the structural and textural properties, which reveal the presence of well-ordered M41S-type materials. The Ce–MCM-41 samples were used for catalytic acylation of alcohols, thiols, phenols and amines show good activity and selectivity including high chemoselectivity towards selective monofunctional acylation of bifunctional compounds. Quite importantly the acylation of bulky molecules such as cholesterol, ergesterol and β-sitosterol could be achieved using Ce–MCM-41 as solid catalyst. The presence of Ce along with Al in Ce–Al–MCM-41 was found to have synergistic effect as Ce–Al–MCM-41samples were more active catalysts for alkylation of naphthalene compared to either Ce–MCM-41 or Al–MCM-41 with comparable Si/Al or Si/Ce molar ratio.     

Influence of solvent on degree of acylation in the formation of sucrose esters

Sucrose palmitates were prepared by the interesterification of sucrose and methyl palmitate in different solvents. The ratio of methyl palmitate to sucrose in dimethylformamide (DMF) solution was varied so that the effect on yield and ester composition could be evaluated. When sucrose esters were prepared in DMF, the palmitoyl groups approximated a random distribution when only penta- and lower esters were formed. When the proportion of palmitoyl groups was increased, hexa- through octaesters were formed, but the yield was less than that calculated for a random distribution. The interesterification of sucrose and methyl palmitate in solvents other than DMF, but under otherwise identical reaction conditions, yielded different reaction products. Only traces of sucrose esters were produced in hexamethylphosphoramide and formylmorpholine. Reactions in dimethylsulfoxide and N-methyl-2-pyrrolidinone yielded larger percentages of higher esters than were obtained in DMF. However the distribution was far from random. Presented at the AOCS Meeting, New Orleans, April 1970. S. Market. Nutr. Res. Div., ARS, USDA.     

制备方法对催化剂性质的影响

以活性氧化铝为载体，以硝酸钴为钴源考察了制备方法对催化剂物化性质的影响，采用浸渍法分别用慢速干燥法和快速干燥法制备不同钴含量的Co／Al2O3催化剂。表征结果表明：不同干燥方法制得的F-T合成催化剂的性质具有比较大的差异。     

Influence of ferrocene addition on the morphology and structure of carbon from petroleum residue

Nano-sized iron particle/carbon composites have been synthesized from a petroleum residue by heating at 420 °C with ferrocene under pressure. The morphologies and structural features of the composites were investigated using TEM, HREM and XRD measurements. The effect of ferrocene addition on the development of turbostratic carbon from the petroleum residue was discussed. It was found that, by increasing the amount of ferrocene added from 3% to 20%, the size of the nano-iron particles tended to increase from 20–80 nm to 30–180 nm. The iron particles pyrolyzed from ferrocene mainly exist in the forms Fe–O and Fe_1−xS when the ferrocene content was low (3% and 6%), and α-Fe when ferrocene contents were high (10% and 20%). Upon further heat treatment in the range 500 to 900 °C, the iron particles tended to aggregate and Fe–O and Fe_1−xS were transformed into α-Fe and austenite. In comparison with the carbon formed without ferrocene addition, the resulting carbon exhibited a turbostratic structure as shown by HREM, in which the d₀₀₂ spacing decreased with the increase of ferrocene loading and increasing temperature, suggesting the carbonization was promoted by the catalysis of the nano-iron particles.     

Influence of catalysts on the combustion of ammonium bichromate

The influence of inorganic and organic catalysts on the combustion of ammonium bichromate has been investigated at pressures ranging from 1 to 1000 atm. The maximum catalytic action of additives has been found to occur at atmospheric pressure, with the combustion rate for the most effective additives decreasing by a factor of four to five. The influence of the same additives on the combustion of other ammonium salts studied earlier is compared. Institute of Chemical Physics, Russian Academy of Sciences, 117977 Moscow. Translated from Fizika Goreniya i Vzyrva, Vol. 31, No. 6, pp. 28–36, November–December, 1995.