间二氟苯的合成

间二氟苯是生产氟康唑和氟苯水杨酸等药物的中间体。本文介绍以间苯二胺为原料,经重氮化、热分解等反应过程制备间二氟苯,产品纯度达98%以上,收率为30%。     

2,2-二氟苯并[1,3]间二氧杂环戊烯-4-甲醛的合成新工艺

2,2-二氟苯并[1,3]间二氧杂环戊烯-4-甲醛是合成氟咯菌腈的重要中间体,为了进一步提高其收率和纯度,研究了2,2-二氟苯并[1,3]间二氧杂环戊烯-4-甲醛的合成反应条件.以邻甲酚为原料,经“一锅煮”得到中间体3-甲基苯邻二酚,再经醚化、氯化、氟交换和水解5步反应得到2,2-二氟苯并[1,3]间二氧杂环戊烯-4-...     

一种简便的间二氟苯合成方法

１前言 众所周知，在有机化合物中引入氟原子常常能使其表现出特殊的生物和生理活性，因而近年来开发了大量的含氟医药、农药，创造出惊人的社会效益和经济效益。间二氟苯是一个重要的含氟中间体，主要用作合成抗菌药物氟康唑及消炎镇痛药物二氟尼柳的原料，市场需求日益扩大。本文对间二氟苯的合成工艺路线作一简要的概述，对以２，４－二氟苯胺出发的合成方法进行了工艺条件试验，取得较好的结果。２间二氟苯的主要合成方法 文献报道的间二氟苯的合成方法主要有以下几种： １． ｏｔ二 ＣＨＣｌｌ二 ｏｔ＋ ＣＨＣＩＦＺ＋ （－，ｐ－，。…     

从间苯二胺合成间二氟苯的研究

研究了间苯二胺经Ｓｃｈｉｅｍａｎｎ反应来制备间二氟苯，在－１２℃以下低温将间苯二胺的冷盐的酸溶液慢慢滴加到新制备的亚硝酸溶液中，然后加入氟硼酸溶液，能得到９０％收率的间苯二重氮双氟硼酸盐。对上述重氮盐进行热分解可以得到８０％收率的间二氟苯。     

气相色谱法定量分析间－二（三氟甲基）苯合成中的原料及产品

本文介绍了由间－二甲苯合成间－二（三氟甲基）苯过程中间－二甲苯、间－二（三氯甲基）苯、间－二（三氟甲基）苯的气相色谱分析方法，以及对以上三种组分同时进行定性、定量分析的最佳色谱条件。该方法相对误差＜０．８％，相对标准偏差＜０．２％，能准确、快速地对合成中各组分进行定量分析。     

氟咯菌腈的合成

以4-醛基-2,2-二氟苯并-1,3-间二氧杂环戊烯和氰基乙酰胺为原料制得4-(2-氰基)丙烯酰胺-2,2-二氟苯并-1,3-间二氧杂环戊烯(2);以化合物2与TOSMIC(4)经一锅法合成氟咯菌腈。反应总收率46.2%,含量(HPLC)99.8%。     

2,2-二氟苯并[1,3]间二氧杂环戊烯-4-甲醛的合成新工艺

研究了2,2-二氟苯并[1,3]间二氧杂环戊烯-4-甲醛的合成反应条件。以邻甲苯酚为原料,经"一锅煮"得到中间体3-甲基苯邻二酚,再经醚化、氯化、氟交换和水解5步反应得到2,2-二氟苯并[1,3]间二氧杂环戊烯-4-甲醛,在优化的反应条件下,反应总收率为33.2%,目标产物含量99.7%,用IR、1H NMR表征了其结构。     

间二氟苯的合成进展

1前言间二氟苯是许多种含氟医药和农药的关键中间体。例如它是合成2’，4’—二氟—4—羟基—［1，1’—二苯基—3—羧酸］（商品名称：二氯苯水杨酸；Diflubenzuron）的主要原料，此药对关节炎有特效，具有良好的消炎镇痛作用，可用于术后止痛剂。间二氟苯也用于结构环上1位具有2，4—二氟苯基的氟喹诺酮系抗菌剂的合成中，例如：特马沙星（Temafcoxacin）、托磺沙星（Tosulfloxacin）等，此系列抗菌剂通常具有适度的脂溶性和水溶性以及优异的抗菌活性。在农药领域里，可以用间二氟苯合成含氟苯基杀虫剂苯甲酰脲型的Diflubenzuron，该杀…     

2—氯—1,3—二硝基—5—三氟甲基苯用NaI选择性还原脱氯

１,３－二硝基－５－三氟甲基苯（１）和１,３－二氨基－５－三氟甲基苯（２）是制备一些具有特殊光、电及其他性能高分子材料的单体。单体２可以从１还原硝基得到,单体１可以从间硝基三氟甲基苯再硝化得到［１］,但比较方便的途径是这二个单体均可以利用除草剂氟乐灵...     

高温液态水中2,6-二氟苯腈水解反应动力学

为了开发2,6-二氟苯甲酰胺的绿色制备工艺以及探讨高温液态水中腈类物质的水解规律,研究了高温液态水中2,6-二氟苯睛无催化水解反应动力学.系统地研究了不同初始浓度、不同温度下2,6-二氟苯腈、2,6-二氟苯甲酰胺的水解反应动力学以及2,6-二氟苯甲酸的脱羧反应动力学.采用一级串联反应动力学方程拟合2,6-二氟苯腈的水解...     

Separation of ternary system (1,2-ethanediol + 1,3-butanediol +1,3-propanediol) by distillation

A study on separation of system (1,2-ethanediol (1,2-EG) + 1,3-butanediol (1,3-BD) + 1,3-propanediol (1,3-PG)) was conducted in the article. Vapor–liquid equilibria (VLE) behaviors of systems (1,2-EG + 1,3-BD), (1,2-EG +1,3-PG), (1,2-EG + 1,3-BD + 1,3-PG) were studied at 101.3 kPa . A two-column (column C1 and column C2) sequence distillation process at normal pressure was designed and optimized to separate the ternary mixture. The results have shown Wilson model is the most appropriate one to describe the ternary system; product amounts of 1,2-EG, 1,3-BD, and 1,3-PG can be up to 0.970, 0.945, and 0.980, respectively, under optimized conditions.     

Enzymatic synthesis of symmetrical 1,3-diacylglycerols by direct esterification of glycerol in solvent-free system

1,3-Diacylglycerols were synthesized by direct esterification of glycerol with free fatty acids in a solvent-free system. Free fatty acids with relatively low melting points (<45°C) such as unsaturated and medium-chain saturated fatty acids were used. With stoichiometric ratios of the reactants and water removal by evaporation at 3 mm Hg vacuum applied at 1 h and thereafter, the maximal 1,3-diacylglycerol content in the reaction mixture was: 84.6% for 1,3-dicaprylin, 84.4% for 1,3-dicaprin, 74.3% for 1,3-dilinolein, 71.7% for 1,3-dieicosapentaenoin, 67.4% for 1,3-dilaurin, and 61.1% for 1,3-diolein. Some of the system’s parameters (temperature, water removal, and molar ratio of the reactants) were optimized for the production of 1,3-dicaprylin, and the maximal yield reached 98%. The product was used for the chemical synthesis of 1,3-dicapryloyl-2-eicosapentaenoylglycerol. The yield after purification was 42%, and the purity of the triacylglycerol was 98% (both 1,3-dicapryloyl-2-eicosapentaenoylglycerol and 1,2-dicapryloyl-3-eicosapentaenoylglycerol included) by gas chromatographic analysis, of which 90% was the desired structured triacylglycerol (1,3-dicapryloyl-2-eicosapentaenoylglycerol) as determined by silver ion high-performance liquid chromatographic analysis.     

1,3-Dithienium- und 1,3-Dithioleniumsalze. IX. Reaktionen von 1,3-Dithian-2-ylium-tetrafluoroboraten mit C-Nucleophilen

1,3-Dithienium and 1,3-Dithiolenium Salts. IX. Reactions of 1,3-Dithiane-2-ylium Tetrafluoroborates with C-Nucleophiles 1,3-Dithian-2-ylium tetrafluoroborates ( 1 ), which can be easily obtained by variable methods, react in good to excellent yields with variable C-nucleophiles to new geminal disubstituted 1,3-dithianes. The latter compounds are potential precursors of interesting synthetic building blocks. Reactions are described with 2-lithio-1,3-dithianes 2 , sodium cyanide 4 , sodium salts of the nitro alkanes 7 and CH-acids of the type of the 1,3-dicarbonyl compounds 9 . The reduction of 3-oxo-2-(2-phenyl-1,3-dithian-2-yl)-ethoxybutanoat–following a diastereoselective pathway – leads to the Cram product 11 . Further presented is the crystal structure of 2-phenyl-1,3-dithiane-2-ylium tetrafluoroborate ( 1b ).     

Benzazole. XXX. Amidomethylierung von Aromaten mit 1.3-Bis-chlormethyl-benzimidazolon und 1.3-Bis-chlormethyl-benzimidazolthion

Benzazoles. XXX. Amidomethylation of Aromatic Compounds with 1,3-Bis-chloromethyl-benzimidazolone and 1,3-Bis-chloromethyl-benzimidazolthione Aromatic hydrocarbons are amidomethylated on treatment with 1,3-bis-chloromethyl-benzimidazolone 3 or 1,3-bis-chloromethyl-benzimidazolthione 4 in the presence of aluminium chloride, to give 1,3-bis-arylmethyl-benzimidazolones 5–6 and 1,3-bis-arylmethyl-benzimidazolthiones 7–9 , respectively. The amidomethylation of sodium phenates or potassium phenates with 3 and 4 leads to the 1,3-bis-aryloxymethyl-benzimidazolones 10–12 or to the corresponding benzimidazolthiones 13–16 which may be used for the characterization of phenols.     

疏水硅沸石吸附1,3-丙二醇的研究

FX-Ⅱ型沸石对1,3-丙二醇单组分溶液中1,3-丙二醇的静态饱和吸附量达到121.1 mg/g;在1,3-丙二醇和甘油的混合溶液中,研究了甘油质量浓度、吸附时间、吸附温度和盐离子质量浓度对1,3-丙二醇吸附的影响,实验结果表明高的甘油质量浓度对1,3-丙二醇吸附影响较大,吸附时间为14 h时1,3-丙二醇吸附达到平衡,低温及低盐离子质量浓度有利于1,3-丙二醇吸附;对实际发酵液的静态吸附结果表明,增大发酵液pH值可以减少有机酸对1,3-丙二醇的竞争吸附;pH值为7时,1,3-丙二醇吸附量达到102.5 mg/g;筛选了与吸附剂相关的脱附剂,用体积分数50%的乙醇解吸,解吸率达到86%。在此基础上初步研究了沸石对发酵液中1,3-丙二醇的动态吸附,1,3-丙二醇解吸率为82%。与传统的蒸馏法相比,沸石吸附法工艺简单,具有较大的研究和应用前景。     

Zur Reduktion von 1,3-Thiaziniumsalzen; Synthese von 6,6′-Bi-1,3-thiazinylen und 6,6′-Bi-1,3-thiazinylidenen

On the Reduction of 1,3-Thiazinium Salts; Synthesis of 6,6′-Bi-1,3-Thiazinyls and 6,6′-Bi-1,3-Thiazinylidenes 1,3-Thiazinium perchlorates 1 are linked together in a reaction with zinc powder or at a cathode forming 6,6′-bi-1,3-thiazinyls 3 . This reaction proceeds via radical intermediates 2 . Evidence of the existence of the very short-lived radicals is given by means of ring-disk-voltammogrammes as well as by electrochemical luminescence excitation. The 6,6′-bi-1,3-thiazinyls 3 undergo the reverse fission at a platinum anode resulting in thiazinium salts 1 , whereas the dehydrogenation by chloranile yields the violet 6,6′-bi-1,3-thiazinylidenes 6 .     

Crystallization and Polymorphism of 1,3-Acyl-Palmitoyl-<Emphasis Type="Italic">rac</Emphasis>-Glycerols

Crystallization and melting behavior, small-angle X-ray scattering, X-ray powder diffraction and infra-red absorbance were measured for nine 1,3-acyl-palmitoyl-rac-glycerols (1,3-acetoyl-, -butyroyl-, -hexanoyl-, -octanoyl-, -decanoyl-, -lauroyl, -myristoyl- and -oleoyl-palmitoyl-rac-glycerol and 1,3-dipalmitoyl-glycerol). All but one of the prepared 1,3-diacylglycerols (1,3-DAG) were β-stable with 1,3-acetoyl-palmitoyl-rac-glycerol being the exception (β′-stable). Small-angle X-ray scattering indicates that molecules in β-tending diacid 1,3-DAG adopt a herringbone-type configuration similar to monoacid 1,3-DAG. In this configuration acyl chains of the same length associate and regular chain-end matching between terminal methyl groups delineate lamellae. In contrast, molecules in crystalline 1,3-acetoyl-palmitoyl-rac-glycerol are oriented similar to those of 1(3)-monoacylglycerol. Interestingly, DSC curves indicate five of the nine diacid compounds have meta-stable forms—suggesting these forms are quite common for diacid 1,3-DAG. Meta-stable forms are observed in the melting curve when the difference in length between acyl chains is large (1,3-acetoyl-, -butyroyl- and -hexanoyl-palmitoyl-rac-glycerol), and in the crystallization curve when the difference is moderate (1,3-decanoyl- and -lauroyl-palmitoyl-rac-glycerol).     

具有生物活性的1,3-环己二酮类化合物研究评述

综述了1,3-环己二酮类化合物作为杀虫、除草、杀菌和植物生长调节剂研究的进展情况,包括2-酰胺基-1,3-环己二酮类化合物、2-烷基(芳基)-1,3-环己二酮类化合物、乙酰辅酶A抑制剂类1,3-环己二酮化合物和2-酰基-1,3-环己二酮类化合物。     

单质碘催化合成缩醛（酮）

以单质碘为催化剂,对以乙酰乙酸乙酯、环己酮、丁酮、苯甲醛和正丁醛与二元醇(乙二醇,1,2-丙二醇)为原料合成了2-甲基-2-乙氧羰甲基-1,3-二氧环戊烷、2,4-二甲基-2-乙氧羰甲基-1,3-二氧环戊烷、环己酮乙二醇缩酮、环己酮1,2-丙二醇缩酮、丁酮乙二醇缩酮、丁酮1,2-丙二醇缩酮、2-苯基-1,3-二氧环戊烷、4-甲基-2-苯基-1,3-二氧环戊烷、2-丙基-1,3-二氧环戊烷、4-甲基-2-丙基-1,3-二氧环戊烷10个缩醛(酮)的反应条件进行了研究,较系统地研究了醛或酮与二元醇摩尔比、催化剂用量、反应时间诸因素对收率的影响.结果表明,在n(醛或酮):n(乙二醇或1,2-丙二醇)=1:1.3,催化剂的用量占反应物料总质量的0.4%,反应时间为40～60 min条件下,10种缩醛(酮)的收率为45.2%～92.2%.     

Over‐expression of glycerol dehydrogenase and 1,3‐propanediol oxidoreductase in Klebsiella pneumoniae and their effects on conversion of glycerol into 1,3‐propanediol in resting cell system

BACKGROUND: Glycerol dehydrogenase [EC.1.1.1.6] and 1,3‐propanediol oxidoreductase [EC.1.1.1.202] were proved to be two of the key enzymes for glycerol conversion to 1,3‐propanediol in Klebsiella pneumoniae under anaerobic conditions. For insight into their significance on 1,3‐propanediol production under micro‐aerobic conditions, these two enzymes were over‐expressed in K. pneumoniae individually, and their effects on conversion of glycerol into 1,3‐propanediol in a resting cell system under micro‐aerobic conditions were investigated. RESULTS: In the resting cell system, over‐expression of 1,3‐propanediol oxidoreductase led to faster glycerol conversion and 1,3‐propanediol production. After a 12 h conversion process, it improved the yield of 1,3‐propanediol by 20.4% (222.1 mmol L⁻¹ versus 184.4 mmol L⁻¹) and enhanced the conversion ratio of glycerol into 1,3‐propanediol from 50.8% to 59.8% (mol mol⁻¹). Over‐expression of glycerol dehydrogenase in K. pneumoniae had no significant influence both on 1,3‐propanediol yield and on the conversion ratio of glycerol into 1,3‐propanediol in the resting cell system. CONCLUSION: The results were important for an understanding of the significance of glycerol dehydrogenase and 1,3‐propanediol oxidoreductase in 1,3‐proanediol production under micro‐aerobic conditions, and for developing better strategies to improve 1,3‐propanediol yield. Copyright © 2008 Society of Chemical Industry