合成类胡萝卜素关键中间体十碳烯醛的新方法

对类胡萝卜素关键中间体十碳烯醛的合成方法作出重要改进,新的合成路线包括以反式-1,4-二氯-2-丁烯为起始原料,经格氏反应、缩合反应与酸性水解反应合成2,7-二甲基-2,4,6-辛三烯-1,8-二醛（十碳烯醛）。反应选择性好,副产物少,工艺较简单,操作方便。     

Convenient preparation of picolinyl derivatives from fatty acid esters

It is essential to have simple rapid methods for the determination of fatty acid structures. Traditionally, fatty acids are analysed by gas chromatography using their methyl ester derivatives (FAME). However, their corresponding mass spectra exhibit molecular ions but are usually devoid of ions indicative of structural features and, notably, the position of double bounds on the aliphatic chains [1]. In the most useful approach to structure determination, the carboxyl group is derivatised with a reagent containing a nitrogen atom. Recently, a convenient method for preparing picolinyl esters from intact lipids has been published [2]. However, some problems occurred in our laboratory when this method was used, leading to some modifications and optimisation. Thus, hexane and water have been added while sodium bicarbonate has been removed in order to lower contamination. Temperature and length of the reaction have then been optimised in order to get 100% derivatisation for different kinds of lipids (45 °C and 45 min for FAME). Finally, a comparison of the response factors has confirmed the better sensitivity of the picolinyl derivative against FAME (five times more).     

苯并呋喃甲酰氯的气相色谱分析方法

2,7-二甲基-2,3-二氢-苯并呋喃-6-甲酰氯,(简称苯并呋喃甲酰氯)与无水甲醇反应,生成2,7-二甲基-2,3-二氢-苯并呋喃-6-甲酸甲酯(简称苯并呋喃甲酸甲酯)后,采用气相色谱法,选用5%OV-210/ChromosorbWAW-DMCS(80-100目),Φ3.2mm×1m柱,邻苯二甲酸二乙酯为内标物,分离测定呋喃虫酰肼的重要中间体苯并呋喃甲酰氯的含量。方法的平均标准偏差为0.18,平均变异系数0.22%,平均回收率99.99%。该方法快速、准确,可以实际应用于苯并呋喃甲酰氯的生产监测和质量控制。     

氧芐羟胺盐酸盐的简便合成

氧芐基羟胺盐酸盐可通过苯甲羟肟酸的氧苄醚化、酸水解及氯化氢成盐制得,总收率76%。     

2,5-二(氨基)-1,4-苯醌类化合物的简易合成

报道了一种成本较低的一步合成标题化合物的方法.以对苯二酚为原料,分别与甲胺、二甲胺、乙胺、丙胺、丁胺、苄胺和吗啡啉反应,直接合成7种相应的胺基醌类化合物.目标产物结构经IR、UV、1HNMR、MS确证,并用X-射线衍射法测定2,5-二(二甲氨基)-1,4-苯醌、2,5-二(正丙氨基)-1,4-苯醌和2,5-二(正丁氨基)-1,4-苯醌的晶体结构.     

3,5-二甲基-4-重氮吡唑的合成

以戊二酮和水合肼为起始原料,经过缩合环化、硝化、还原和重氮化4步反应合成了标题化合物,总收率57%。通过红外光谱、核磁共振谱和元素分析等手段确定了其结构,通过结构分析和电子相互作用原理解释了标题化合物在常温下稳定存在的原因。     

2,7-二溴-9,9-二辛基芴的合成工艺改进

以芴、溴素为原料,三氯甲烷为溶剂,铁粉为催化剂,0℃下合成得到2,7-二溴芴,然后以二甲基亚砜为溶剂,四丁基溴化铵为相转移催化剂,室温下与1-溴辛烷反应得到标题化合物,总收率为53.2%。通过1HNMRI、R和元素分析确证了2,7-二溴芴与标题化合物的结构。与目前常用的3种合成方法相比较,该合成工艺具有反应条件温和,后处理简单,收率较高等优点。     

5-取代色胺盐酸盐的微波合成

Fisher吲哚环合法制备5-取代色胺需在加热条件下进行,传统的加热方式反应时间较长,效率不高。选用分子筛为酸催化剂和助滤剂,利用微波辅助合成色胺,可缩短反应时间,提高反应收率,简化后处理操作,减少对环境的污染。     

Copolymerization of isobutene with 2,4,6-octatriene and other triconjugated trienes

Summary The cationic homogeneous Copolymerization at low temperature of 2,4,6-octatriene (OT), 1,3,5-heptatriene (HPT), 2,5-dimethyl-1,3,5-hexatriene (DMH) and alloocimene (AO) with isobutene (I) was performed and the structure of the resulting copolymers examined spectroscopically. OT reacted mainly by 2,7-opening of the triene system yielding soluble copolymers with block character and containing a low amount of cyclized units. Soluble I-HPT copolymers containing 2–4 mol % of conjugated double bonds were obtained. DMH alway gave insoluble copolymers and only traces of conjugated unsaturations were found in I-AO copolymer.     

2,2-二甲基-3-羟基丙酸甲酯的合成研究

以工业甲醛和工业异丁醛为原料,通过羟醛缩合、氧化、酯化合成了2,2 二甲基 3 羟基丙酸甲酯,对其合成温度进行了探讨,反应总产率提高到21.9%,降低成本80%。     

3,5-二甲基-4-羟基苯甲腈的合成研究

以3,5-二甲基-4-羟基苯甲醛和盐酸羟胺为原料,分别在甲酸、乙酸和N,N-二甲基甲酰胺(DMF)中一步反应合成了3,5-二甲基-4-羟基苯甲腈。以DMF为溶剂的反应效果最好,最佳条件下收率达90%以上,粗品含量98%以上。     

对硝基杯芳烃衍生物的合成进展

对硝基杯芳烃是制备功能性杯芳烃重要中间体。从间接硝化和直接硝化两方面系统介绍了对硝基杯芳烃衍生物合成的最新进展，着重讨论了不同硝化方法和硝化试剂的特点。     

Convenient one-pot synthesis of triphenylphosphinecarbomethoxyborane: antitumor activity and structural investigation

The reaction of equimolar quantities of trimethylaminecarbomethoxyborane and triphenylphosphine, in anhydrous 1, 2-dimethoxyethane (monoglyme), produced triphenylphosphinecarbomethoxyborane in 63% yield, via a Lewis-base exchange reaction. The structure of 1 unambiguously shows that the triphenylphosphine moiety coordinates to the boron atom with the C(O)OCH₃ group intact.     

Convenient synthesis of benzoate esters mediated by polymer supported benzoyl chloride

Use of polymeric reagents simplifies routine acylation of alcohols because it eliminates traditional purification. We describe the use of readily available crosslinked poly(N‐benzoyl‐4‐vinylpyridinium)chloride, [P₄VP] COPh, in the solution phase synthesis of esters from alcohols or phenols in the presence of K₂CO₃ in high yields and purity. The products can be obtained by filtration and evaporation of the solvent and the polymeric reagent can be regenerated. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Convenient synthesis of (thiocyanomethyl)-thio heteroaromatics as antifungal agents

Synthesis of some (thiocyanomethyl)-thio heteroaromatic derivatives by reacting metal salts of (mercapto) heteraromatics with chloromethylthiocyanate using methanol or acetone as cosolvent, reported. All the synthesized derivatives were identified by conventional methods, IR-, ¹H NMR and mass spectral data. All the prepared compounds were tested for their antifungal activity. © 1998 SCI     

5,5-二甲基-1,3,2-二氧磷杂环己酰胺衍生物的合成及其应用研究

以新戊二醇、苯甲醛、异丁醛、三氯氧(硫)磷、六水合哌嗪为原料设计并合成了系列化合物，通过元素分析，IR，^1HNMR和MS对其结构进行了表征，对部分化合物进行了热重(TG)和差热(DSC)分析，以评价其热稳定性，并讨论了此类化合物在环氧树脂(E-44)中的阻燃性能。     

Surfactant effect on the catalytic synthesis of 4,4-dimethyl-1,3-dioxane

The main problem of 4,4-dimethyl-1,3-dioxane synthesis is the phase separation arising from the mutual insolubility of the aqueous phase, which contains formaldehyde and an acid catalyst, and the hydrocarbon phase, which contains isobutylene. Isobutylene condensation with formaldehyde has been investigated for the first time in the presence of surfactants with the aim of increasing the efficiency of the process. Surfactant admixtures provide high selectivity and a high reactant conversion, thus allowing the starting material consumption rate to be reduced. The surface and interfacial activities of the admixtures are evaluated. It is assumed that the surfactants cause the formation of microemulsions in the reaction medium and bring about micellar catalysis.     

3,7-二氨基-2,8-二甲基-5-苯基吩嗪盐酸盐合成研究

以邻甲基苯胺、2,5-二氨基甲苯和苯胺为原料,经氧化反应,合成3,7-二氨基-2,8-二甲基-5-苯基吩嗪盐酸盐,讨论了反应条件对反应收率的影响。结果表明,当n(2,5-二氨基甲苯)∶n(2-氨基甲苯)∶n(苯胺)∶(重铬酸钠)=1∶1∶1∶1.945,pH值为6~8,40~45℃反应4 h;98~102℃反应3 h,3,7-二氨基-2,8-二甲基-5-苯基吩嗪盐酸盐的收率为93.6%。     

4,6-二甲基-2-甲磺酰基嘧啶的安全合成

以乙酰丙酮为起始原料,经过环化、甲基化和氧化反应3步合成了4,6-二甲基-2-甲磺酰基嘧啶,总收率61.23％.最后一步氧化,使用oxone氧化剂,反应安全高效.中间体及目标分子结构经核磁共振、红外光谱、质谱、熔点测定确证.     

Electrochemical synthesis of new catechol derivatives

Electrochemical oxidation of catechols (1a-e) has been studied in the presence of 2-acetylcyclopentanone (3) as a nucleophile in aqueous solutions, using cyclic voltammetry and controlled-potential coulometry. The results indicate that the quinones derived from catechols (1a-e), participate in Michael addition reactions with anion of 2-acetylcyclopentanone (3) and via EC mechanism pathway, converted to corresponding catechol derivatives (4a-e). In this work, we derived novel catechol derivatives with good yields based on electrochemical oxidation in aqueous solutions, at carbon electrode in an undivided cell, using environmentally friendly method.