催化氢化法制备醋酸甲脒的研究

采用以活性炭为载体负载Pd、In制备的催化剂，在醋酸存在条件下，将氰胺加氢合成醋酸甲脒。考察了催化剂组成（Pd-In/C）、反应温度、氰胺和醋酸的物质的量的比对反应速率的影响。结果表明，最佳反应条件为温度10 ℃，氰胺和醋酸的物质的量的比1∶1.1～1∶1.2。催化剂回收处理后可重复使用8次。     

1,8-辛二醇单边乙酰化合成工艺研究

研究了1,8-辛二醇在四氢呋喃溶剂中,吡啶为缚酸剂和乙酸酐进行单边乙酰化反应制备8-乙酰氧基-1-辛醇。通过改变反应温度、反应时间、反应物配比和吡啶的用量等因素研究了1,8-辛二醇单边乙酰化的最佳制备工艺条件:溶剂为二氯甲烷、反应温度为0℃、反应时间为4.5 h、乙酸酐和1,8-辛二醇的摩尔比为0.95:1、傅酸剂吡啶的用量为乙酸酐1.2倍量(摩尔比)。在最佳工艺条件下,气相分析单边乙酰化的收率为82.7%。     

Isolation,identification, and bioassay of chemicals affecting nonpreference carrot-root resistance to carrot-fly larva

Roots of the carrot cultivars Vertou L.D. (resistant) and Long Chantenay (susceptible) were subjected to detailed chemical analysis to identify extracts and compounds influencing larval host-finding (preference/non-preference) behavior and to compare concentrations of these compounds in resistant and susceptible cultivars. Vertou yielded threefold less volatile material in headspace extracts of pureed roots. Extracts of chopped root in methanol, steam, hexane, and chloroform were inactive in behavioral assays. However, ether extracts were active and their hydrocarbon and carbonyl-rich fractions contained potent attractants. The principal constituent of the carbonyl-rich fraction of each cultivar was the carotatoxin complex comprising the neurotoxin falcarinol (carotatoxin), falcarindiol, and falcarindiol monoacetate, the latter compound here reported for the first time from carrot. Falcarinol (50 and 100 g) was active in a behavioral assay, and all three ingredients of the complex were potent electrophysiological stimuli, eliciting maximum single unit responses to source concentrations of 10 ng. Furthermore, the complex was more abundant by about 1000 g/root in Long Chantenay. As this comprised extra amounts of 70, 862, and 110 g of falcarinol, falcarindiol, and falcarindiol monoacetate, respectively, the observed differences seem both behaviorally and physiologically relevant. It is generally accepted that coevolution has transformed the role of many toxins into host-location cues, but this seems a relatively rare example of a neurotoxin (falcarinol) evincing, in decreased concentrations, nonpreference host resistance. This evolved response to a toxin present in large concentrations is contrasted with that totrans-2-nonenal, which paralyses and kills the larva and is present in only trace amounts in the root.     

气相色谱法测定1,4-丁二醇及其酯化产物含量

以醋酸正丁酯为内标物,采用毛细管气相色谱内标法测定1,4-丁二醇及其酯化产物的含量。结果表明:1,4-丁二醇、1,4-丁二醇单醋酸酯、1,4-丁二醇双醋酸酯的相对校正因子曲线分别在0.7090~41.30mg·mL-1、0.5980~41.82mg·mL-1、0.5429~39.10mg·mL-1范围内呈现良好的线性关系(R2≥0.9994),平均加标回收率为94.53%~103.20%,RSD≤4.72%。该方法操作简便、精密度高、重现性好、结果稳定可靠,可用于1,4-丁二醇及其酯化产物的含量测定。     

氢醌单乙酸酯的合成

本文采用易于制备的负载型碱K2CO3－AI2O3合成了氢醌单乙酸酯。实验结果表明氢醌与乙酸酐在极性溶剂中反应的产率较高,在乙酸乙酯中反庆氢醌单乙酸酯产率达58．9％,而在非极性溶剂甲苯中反应氢酯单乙酸酯产率较低。     

乙酸氧乙基化催化反应动力学研究

研究了以三价铝盐为催化剂的乙酸氧乙基化反应的动力学规律，得到了描述该反应过程的动力学数学模型：ｒ＝｛ｅｘｐ［（１．８３±１８０）－（８３３７－７００）／Ｔ］＋ＣＫｅｘｐ［（１１７．６４±０．８０）－（５９９６±４８３）／Ｔ］｝Ｃｃ２Ｈ４Ｏ     

乙二醇乙酸酯合成的研究

研究了以乙二醇和乙酸为原料，在三氯化铁催化剂和醋酸丁酯共沸脱水剂作用下合成乙二醇单乙酸酯工艺。结果表明：n(乙二醇)：n(乙酸)=2，脱水剂用量15％(占原料总量)，催化剂用量0．6％(占原料总量)，乙二醇乙酸酯的产率达82%。     

MgO/APT催化剂酸碱性质对1,4-丁二醇单醋酸酯转化反应的影响

以Mg(NO3)2为镁源,采用等体积浸渍法制备系列镁改性凹凸棒土催化剂Mg O/APT,利用XRD、BET、FT-IR和TPD对催化剂进行表征。结果表明,Mg O/APT催化剂具有与凹凸棒土相同的晶相结构;随着Mg O负载量的增加,Mg O/APT的碱强度和碱含量显著增加,较强酸量明显减少,弱酸酸位增加。在固定床反应装置上,考察催化剂气相催化转化1,4-丁二醇单醋酸酯反应性能。结果表明,催化剂表面的酸碱性对1,4-丁二醇单醋酸酯气相转化反应的产物分布有显著影响。酸性为主的催化剂APT上有利于1,4-丁二醇单醋酸酯发生分子内酯交换环化反应生成四氢呋喃;而适量酸-碱活性位有助于实现1,4-丁二醇单醋酸酯发生脱水-水解反应,生成3-丁烯-1-醇及3-丁烯-1-醇醋酸酯,过多碱性位有助于1,4-丁二醇单醋酸酯发生酯水解反应生成1,4-丁二醇。     

对苯二酚单乙酸酯的合成研究

以D001树脂为催化剂,用对苯二酚分别与乙酸酐和乙酸进行了反应实验并得到了对苯二酚单乙酸酯。结果表明：这两种方法均有较高的收率和选择性,采用乙酸酐为原料具有反应快,反应温度低的优点,但成本较高;以乙酸乙酯为溶剂对苯二酚与乙酸酐在80℃左右反应1h,对苯二酚单乙酸酯的收率为41．4％,采用乙酸为原料所需反应时间较长,但成长低,以甲苯为溶剂对苯二酚与过量的乙酸在110℃左右反应8h,对苯二酚单乙酸酯的收率为51．6％。