CN111909003B - 一种制备公斤级新型联苯四酚的氧化偶联方法及其催化剂 - Google Patents

一种制备公斤级新型联苯四酚的氧化偶联方法及其催化剂 Download PDF

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CN111909003B
CN111909003B CN202010084223.6A CN202010084223A CN111909003B CN 111909003 B CN111909003 B CN 111909003B CN 202010084223 A CN202010084223 A CN 202010084223A CN 111909003 B CN111909003 B CN 111909003B
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张润通
彭江华
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Guangdong Oukai New Material Co ltd
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Abstract

本发明公开了一种制备新型联苯四酚的氧化偶联合成方法及其催化剂。该类新型联苯四酚具有如通式I所示的结构。在铜、铁、镍、锰、钴、铬、镁、钠、钾等金属化合物、金属配合物或碱式金属配合物，以及酸性溶液或含氧的有机碱性溶液的作用下，用烷氧基苯、烷基苯酚或烷氧基苯酚碳碳键氧化偶联反应得到通式I。

Description

一种制备公斤级新型联苯四酚的氧化偶联方法及其催化剂
技术领域
本发明涉及一种制备公斤级新型联苯四酚的氧化偶联方法及其催化剂，包括氧化偶联条件以及催化剂筛选。
背景技术
偶联反应，是由两个有机化学单位进行某种化学反应而得到一个有机分子的过程，其中包括自由基偶联反应，过渡金属催化偶联反应。经典的偶联反应如Suzuki、Heck、Sonogashira、Stille、Kumada、Negishi和Hiyama是有机金属试剂与预活化的卤代烃之间的偶联反应。而卤代烃则需要提前制备，增加了反应步骤和实验流程。此外，贵金属钯的配位化合物Pd(PPh3)4是此类反应最常用的催化剂，其他催化剂包括PdCl2(PPh3)2、PdCl2(MeCN)2等。
氧化偶联反应是指反应物中的低价态的碳原子转化为高价态的碳原子化合物的一类氧化反应，该反应必须在氧化剂的存在下，直接将两个亲核试剂(Nucleophile)进行偶联，能够对烯、炔和芳烃等的C-H键直接进行活化和官能团化。氧化偶联反应的核心部分是催化金属源与氧化剂，常见的氧化剂有氧气、活性二氧化锰、重铬酸钾、高锰酸钾、二价铜盐及其氧化物、双氧水、TBHP、臭氧等。相对于传统的偶联反应，氧化偶联反应具有缩短反应步骤和原子经济性等优点。氧化偶联反应在医药、农药、化工和材料等有机中间体的合成中发挥着日益重要的作用。
廉价金属催化的氧化偶联反应可以追溯到1869年，Glaser报道了可以利用末端炔烃自身氧化偶联制备共轭二炔烃。使用CuCl做为催化剂，在氨水和乙醇的混合溶剂中，在空气中以苯乙炔为原料得到了1,3-二炔。Albert于1953年研究了在K2Cr2O7/H2SO4催化下，各种3,4,6-三烷基苯酚类的氧化偶联反应，得到了不同类型的联苯二酚，产率介于23～76％。在不同氧化剂(K2Cr2O7、过氧化苯甲酰、MCPBA/FeCl3)与反应条件下，
Figure BDA0002381463010000011
等人报道了对羟基苯丙酸酯、3-叔丁基-4-羟基苯丙酸酯等一系列市售化合物的氧化偶合，收率达到22～32％。1962年Hay以O2作为氧化剂用催化量的TMEDA和CuCl来催化端基炔的偶联。Noji用CuCl(OH)TMEDA作催化剂，在二氯甲烷溶液中空气氧化2-萘酚得到了联萘二酚，化学产率为90～96％；Deuβen将2-萘酚和FeCl3在四氢呋喃中回流，产率为54％。此外，还有大量专利文献如US3210384、US481589、WO99/46227A1、WO9946227、JP2002069022、US4101561、US4070383、J.Chem.Soc.C 1971,2967、J.Org.Chem.1983,48,4948等报道了Cu/O2配合物催化的各种烷基取代苯酚氧化偶联制备联苯二酚的反应，产率在35～95％左右。
本发明中发展的一种制备新型联苯四酚的氧化偶联方法以及催化剂具有反应步骤短、原子经济性高、操作简便易于放大合成、收率较高、催化剂价格低廉易得且容易制备等特点。本发明对比了KMnO4、K2Cr2O7、MnO2、CrO3、FeCl3等传统的金属氧化剂与Cu(TMEDA)Cl2/O2、Cu(Et3N)Cl/O2、K3[Fe(CN)6]/O2等金属配合物氧化剂催化下，间苯二酚氧化偶联制备公斤级新型联苯四酚反应结果，并对氧化偶联条件和催化剂进行了优化和筛选。
发明内容
本发明目的是为了开发一种新型联苯四酚及其衍生物骨架的高效氧化偶联合成方法。其特点是：金属廉价易得、金属氧化剂或配合物制备相对简单、后处理步骤少、四酚骨架偶联收率较高和可以放大合成。
本发明所述的新型联苯四酚是一种制备新型联苯四齿亚磷酸酯配体的重要中间体原料。该四酚化合物的其中一种结构表达式，即：2,2’,6,6’-四羟基-3,3’,5,5’-四叔丁基-1,1’-联苯(结构式2)表示如下：
Figure BDA0002381463010000021
合成结构式2的起始原料为：4,6-二叔丁基间苯二酚，分别使用酸性和碱性的氧化偶联方法，合成路线如下：
酸性体系制备方法
Figure BDA0002381463010000031
碱性体系制备方法
Figure BDA0002381463010000032
具体实施方式
下面通过实施例对本发明的以上路线进行具体的描述，有必要指出的是，本实施例只用于对本发明作进一步说明，但并不对本发明构成任何限制。该领域的技术人员可以根据本发明的内容作出一些非本质的改进和调整。
实施例1
酸性体系制备方法
在公斤级合成通风房内，向10L装有防爆式机械搅拌桨、滴液漏斗、防爆式高低温循环、温度探针、回流冷凝器和下泄放料阀门等装置的双层玻璃夹套反应釜中加入4,6-二叔丁基间苯二酚(4.5mol)，酸性溶液(3.8L)，搅拌至溶解后，向反应釜中滴入定量的金属氧化剂(0.45–6.75mol)和水的澄清溶液(2L)。滴加期间，反应釜有局部放热现象，需用防爆式高低温循环控制好釜内温度。滴加完后，在额定温度(-20–50℃)下搅拌反应1～12小时。反应完成后，当釜内有大量固体颗粒析出时，用布氏漏斗或离心机分批次过滤所得滤饼即为氧化偶联产物，即：2,2’,6,6’-四羟基-3,3’,5,5’-四叔丁基-1,1’-联苯(结构式2)；当没有固体析出时，用防爆式旋转蒸发仪旋干溶剂得到粘稠状粗产品，往粗产品中加入一定比例的水或甲醇和水的混合溶液，用机械搅拌桨进行打浆直至析出固体颗粒，过滤后得到产品。两种后处理反应方法产率接近，介于15～75％之间。
表1
Figure BDA0002381463010000041
Figure BDA0002381463010000042
实施例2
碱性体系制备方法
在公斤级合成通风房内，向10L装有防爆式机械搅拌桨、滴液漏斗、防爆式高低温循环、温度探针、气体导管、回流冷凝器和下泄放料阀门等装置的双层玻璃夹套反应釜中依次加入部分反应溶剂(3L)、碱性化合物(0.0225–0.9mol)和定量的金属化合剂(0.0225–0.45mol)，在室温下均匀搅拌0.5～1个小时；在搅拌期间，往反应液面以下不间断地通入氧气或压缩空气(可由鼓泡判别)。待金属-有机碱配合物形成后，用滴液漏斗往反应釜内缓慢滴加已溶解好的4,6-二叔丁基间苯二酚溶液(4.5mol，3.8L)，并一直保持通入氧气或空气。滴加完后，反应溶液在额定温度(25～40℃)下搅拌反应24～48小时。在此期间，由气体所带出的溶剂损耗通过补充溶剂来补偿。反应完成后，当釜内有大量固体颗粒析出时，用布氏漏斗或离心机分批次过滤所得滤饼即为氧化偶联产物，即：2,2’,6,6’-四羟基-3,3’,5,5’-四叔丁基-1,1’-联苯(结构式2)；当没有固体析出时，用防爆式旋转蒸发仪旋干溶剂得到粘稠状粗产品，往粗产品中加入一定比例的水或甲醇和水的混合溶液，用机械搅拌桨进行打浆直至析出固体颗粒，过滤后得到产品。两种后处理反应方法产率接近，介于55～92％之间。
表2
Figure BDA0002381463010000051
Figure BDA0002381463010000052
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Claims (3)

1.一种联苯四酚的氧化偶联合成方法，其特征在于：所述联苯四酚的结构如下式2所示，合成路线和反应条件如下：
Figure FDA0004162216590000011
所述金属化合物为[Cu(MeCN)4][PF6]，氧源为氧气或空气，所述溶剂为甲醇、乙醇、异丙醇、正丁醇、叔丁醇。
2.如权利要求1中所述的合成方法，其特征在于，所述氧化偶联反应的金属化合物与原料的摩尔比介于0.005～0.1，在25～40℃温度下均匀搅拌24～48小时。
3.如权利要求1中所述的合成方法，其特征在于：反应完成后，停止通入气体，当有大量固体颗粒析出时，过滤所得滤饼即为氧化偶联产品；当没有固体析出时，旋干溶剂得到粘稠状粗产品，使用水或甲醇和水混合液对粗产品进行打浆或重结晶，析出固体颗粒，过滤后得到产品。
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