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CN1042528C - 卤代烃催化加氢脱卤反应 - Google Patents

卤代烃催化加氢脱卤反应 Download PDF

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CN1042528C
CN1042528C CN93111071A CN93111071A CN1042528C CN 1042528 C CN1042528 C CN 1042528C CN 93111071 A CN93111071 A CN 93111071A CN 93111071 A CN93111071 A CN 93111071A CN 1042528 C CN1042528 C CN 1042528C
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CN1094022A (zh
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张一平
廖世健
徐筠
余道容
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Dalian Institute of Chemical Physics of CAS
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Abstract

一种温和条件下的卤代烃催化加氢脱卤反应。它是采用负载于含氮配位原子的可溶性高分子载体的钯铬合物为催化剂，在常压、低温醇类溶剂中进行反应。该反应体系简单，催化剂效率高，易制备，活性高，是一种实用的卤代烃脱齿方法。

Description

卤代烃催化加氢脱卤反应
本发明涉及卤代烃的催化加氢-脱卤反应，具体地说是在可溶性含氮配位原子的高分子负载钯催化剂存在下，于常压、低温条件下实现的卤代烃与氢气催化加氢脱卤反应。
卤代烃的脱卤反应不仅是精细有机合成中的重要反应，而且在环保中也有重要用途(用于将难以用常规方法处理的高毒性或引起严重环境污染的卤代烃转化为易处理或可再利用的化合物)。有关这类反应已有许多专利报道。通常是用第八族金属(负载于无机载体上)或配合物作催化剂，用醇、有机酸盐或氢气作氢源，并加入一定量碱(碱金属、碱土金属的氢氧化物或弱酸强碱盐等)。例如欧洲专利(1990,EP352,164)以Pd(OAc)2为催化剂，在Pph3和NEt3存在下，使氯苯与氢气反应生成苯，转化率仅41％。美国专利(1986,US4,618,686)以Pd/C为催化剂，尚需添加磷酸盐，可使多氯代联苯脱卤。反应在50℃、K2CO3存在下进行。美国专利(1971,US3,595,931)用Pd/Al2O3(0.6％)作催化剂，在KOH存在下使2-氯-对二甲苯与氢气进行高温气相反应，生成二甲苯，转化率接近100％。低温时转化率低。目前，常见的脱卤催化体系，当加入碱时不用氢气为氢源而用醇类或有机酸的盐类为氢源。若用氢气为氢源时又不加碱，这样以来二者活性均不高。
本发明的目的是提供具有活性高，稳定性好，简单，易合成，成本低且反应条件温和的脱卤催化剂，实现有机卤化物的加氢脱卤反应。
本发明采用负载于含氮配位原子的可溶性高分子载体(PVP)的钯络合物(PdCl2)为催化剂(以PVP-PdCl2表示)，使卤代烃在常压、低温、醇类溶剂中进行反应，并添加适量碱以中和所生成的HCl。反应可由下式表示：高分子载体(PVP)最佳为聚乙烯吡咯烷酮、聚乙烯醇、聚丙烯酰胺等。催化剂在反应中使用量为5.0×10-2-1.0×10-5M。卤代烃在醇类溶剂(如甲醇、乙醇、正丙醇、异丙醇)中进行的反应温度可控制在20～80℃，反应氢压可控制在常压或高于常压。催化剂中碱或强碱弱酸盐加入量以OH-卤素比为1～5，加入方法可采用一次预先加入，也可分次滴入。催化剂是在醇类溶剂或含有醇的混合溶剂中进行反应。
本发明具有催化剂易制备，钯易回收，活性高，选择性好，反应条件温和，成本低，反应体系简单，原料易得，不需要特殊设备等特点。
这类催化剂对卤代芳烃、苄基卤代物及烯丙基卤化物的脱卤具有很高的活性。如氯苯脱氯反应的最高活性可达100mol Cl/molPd·min。本催化剂在反应中的用量(按Pd计)为5.0×10-2～1.0×10-5M。碱与底物的摩尔比(OH-/X)以1～5为宜。下面通过实例对本发明所述的脱卤反应作详细说明。
实例1氯苯脱氯反应
在50ml玻璃反应瓶中加入无水乙醇5.5ml,PVP-PdCl2的乙醇溶液14.5ml(3.4×10-3M),Mg(OH)20.3g(5mmol)和氯苯0.5ml(5mmol)。反应在常压氢气中进行，反应温度为65℃，经4h反应，氯苯100％转化为苯，无其他副产物生成。
实例2-6
按实例1所述实验条件及步骤进行实例2-6，结果见表1。
表1一些卤代烃的脱卤反应
实例 卤代烃     碱  Pd用量mol/l 反应时间min 转化率％    产物％
 23456 氯苯溴苯苄基氯p-二氯苯m-二氯苯 NaOHMg(OH)2Mg(OH)2Mg(OH)2Mg(OH)2  2.3×10-32.3×10-32.3×10-32.3×10-32.3×10-3  609010180300  10010010095.687.3 苯(100)苯(100)甲苯(100)氯苯(0)，苯(100)氯苯(4,3)，苯(95.7)
由上述实例，当采用本发明提供的PVP-Pdcl2，在常压低温可使卤代烃发生脱卤反应。这种反应不需特殊设备，反应体系简单，催化剂易制备，活性高，是一种经济实用的脱卤方法。

Claims (4)

1．一种卤代烃催化加氢脱卤反应，其特征是采用负载于含氮配位原子的可溶性高分子载体的钯络合物为催化剂，使卤代芳烃和苄基卤代物在常压、20～80℃、醇类溶剂中并加适量碱于氢气存在下进行反应，由下式表示：
Figure C9311107100021
催化剂在反应中使用量为5.0×10-2～1.0×10-5M。
2．按照权利要求1所述的脱卤反应，其特征是所说的高分子载体为聚乙烯吡咯烷酮、聚乙烯醇、聚丙烯酰胺。
3．按照权利要求1所述的脱卤反应，其特征是催化剂中碱或强碱弱酸盐加入量以OH-/卤索比为1～5，加入方法可采用一次预先加入，也可分次滴入。
4．按照权利要求1所述的脱卤反应，其特征是醇类溶剂可选用甲醇、乙醇、正丙醇、异丙醇。
CN93111071A 1993-04-24 1993-04-24 卤代烃催化加氢脱卤反应 Expired - Fee Related CN1042528C (zh)

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CN100465140C (zh) * 2006-12-01 2009-03-04 华南理工大学 催化氢气还原卤代烃脱卤制备烃的方法
CN101475428B (zh) * 2009-01-16 2012-11-21 大连理工大学 氯代芳烃的一种室温下镍催化脱氯方法
CN105503706A (zh) * 2015-12-28 2016-04-20 衢州学院 卤代吡啶类化合物的脱卤降解方法

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Publication number Priority date Publication date Assignee Title
US5068484A (en) * 1989-11-02 1991-11-26 Uop Process for the hydroconversion of a feedstock comprising organic compounds having a tendency to readily form polymer compounds
EP0479116A1 (en) * 1990-10-04 1992-04-08 The Dow Chemical Company Vapor phase hydrogenation of carbon tetrachloride

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5068484A (en) * 1989-11-02 1991-11-26 Uop Process for the hydroconversion of a feedstock comprising organic compounds having a tendency to readily form polymer compounds
EP0479116A1 (en) * 1990-10-04 1992-04-08 The Dow Chemical Company Vapor phase hydrogenation of carbon tetrachloride

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