CN108530293B - 一种高纯度氯代2-羧基二苯甲酮的制备方法 - Google Patents
一种高纯度氯代2-羧基二苯甲酮的制备方法 Download PDFInfo
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Abstract
本发明公开了一种高纯度氯代2‑羧基二苯甲酮的制备方法，将氯取代或非取代的邻氯甲苯制备成格式试剂后与邻氯苯甲酰氯反应，制备得到氯代2‑甲基二苯甲酮；再将氯代2‑甲基二苯甲酮在催化剂和氧化剂存在下发生氧化反应，制得氯代2‑羧基二苯甲酮。本发明合成步骤简单，成本低廉，工艺环保，所得产品纯度高，可直接应用于微电子等领域。
Description
技术领域
本发明属于有机合成领域，具体涉及一类高纯度氯代二苯甲酮的合成新工艺。
背景技术
二苯甲酮类物质属于化学物质世界中的一大家族，被广泛应用于医药、农药、染料、塑料、涂料、日用化工、电子化学品等领域。如二苯甲酮衍生物作为非甾体抗炎药药效基团，成为一类用途广泛的药物中间体。二苯甲酮类光引发剂由于其引发的量子效率高等优点，成为目前产量最大的光引发剂。在电子工业中，氨基二苯甲酮类具有良好的半导体倍频功能。在所有领域中，应用较为广泛的一类为紫外线吸收剂，在化妆品工业中可用于防晒油或者防晒膏的制备。羧基二苯甲酮类化合物作为二苯甲酮家族中的一员，也受到越来越多的重视和应用。关于2-羧基二苯甲酮类化合物的合成在国内外所见报道不多。2-羧基二苯甲酮有一些合成方法报道(Journal of the American Chemical Society,36,732-7；1914)，此类方法主要用苯与苯酐的傅克反应得到，但是对于芳环上有取代基的二苯甲酮化合物，如氯代2-羧基二苯甲酮的合成则没有涉及。该类化合物常应用于微电子领域，对纯度要求非常高，因此，开发新的高纯度的氯代2-羧基二苯甲酮的制备工艺，具有很强的经济及社会效益。
发明内容
本发明针对现有技术不足，提供了一种低成本、安全性高、工艺环保的高纯度氯代2-羧基二苯甲酮的制备方法。
本发明具体技术方案如下：
一种氯代2-羧基二苯甲酮的制备方法，包括如下步骤：
(1)将氯取代或非取代的邻氯甲苯制备成格式试剂；
(2)将步骤(1)制得的格式试剂与邻氯苯甲酰氯反应，制备得到氯代2-甲基二苯甲酮；
(3)将氯代2-甲基二苯甲酮在催化剂和氧化剂存在下发生氧化反应，制得氯代2-羧基二苯甲酮。
本发明所述氯代2-羧基二苯甲酮优选具有如下结构：
本发明所述的制备方法，步骤(1)所述格式试剂是由氯取代或非取代的邻氯甲苯与镁粉在无水乙醚或四氢呋喃中反应制得。
本发明所述的制备方法，步骤(2)反应条件为0-150℃反应1-36小时，反应溶剂选自四氢呋喃、乙醚、石油醚、环己烷、苯、甲苯、乙苯中的一种或几种。
本发明所述的制备方法，步骤(2)所述格式试剂与邻氯苯甲酰氯的摩尔比为1:0.6-1.6。
本发明所述的制备方法，步骤(3)所述催化剂选自醋酸钴、醋酸锰、醋酸镍、醋酸铜、溴素、溴化钠、溴化钾、溴化钴中的一种或几种，所述氧化剂为空气或氧气。所述催化剂的量相当于氯代2-甲基二苯甲酮0.001-5％摩尔量。
本发明所述的制备方法，步骤(3)反应条件为20-150℃下反应2-48小时，反应溶剂选自醋酸、丙酸、丁酸、异丁酸、戊酸、异戊酸中的一种或几种。
本发明所述的制备方法，步骤(3)之后，反应物趁热过滤，冷却，析出产物，然后用任意体积比的甲苯-乙醇混合溶剂重结晶，高纯度氯代2-羧基二苯甲酮。上述制备方法优选甲苯-乙醇混合溶剂中甲苯与乙醇的体积比为3:1～7，上述重结晶试剂能够得到纯度大于99.5％的产物，当甲苯与乙醇的体积比为1:1时，产物的纯度能够达到99.9％以上。
本发明一个具体的技术方案，包括以下步骤：
(1)在装有金属镁屑(粉)的圆底烧瓶中，通入干燥的热氮气，30分钟后冷却。加入甲基氯苯、少量四氢呋喃或者甲苯、引发剂碘，加热引发。向反应瓶中滴加溶剂控制反应温度，反应4小时，冷却，所得格式试剂备用。
(2)将格式试剂溶于溶剂中，冰浴条件下缓慢滴入邻氯苯甲酰氯的溶液中，格式试剂与邻氯苯甲酰氯的摩尔比为1:0.6-1:1.6，继续在0-150℃反应1-36小时，反应完毕，蒸去溶剂。反应物倒入冰的稀盐酸中，甲苯萃取，减压蒸去甲苯得到氯代2-甲基二苯甲酮；
(3)将氯代2-甲基二苯甲酮溶于醋酸中，加入相当于氯代2-甲基二苯甲酮0.001-5％摩尔量催化剂，通入空气或者氧气，20-150℃下反应2-48小时，反应完毕，自然冷却至室温，析出固体，然后过滤，用任意体积比的甲苯/乙醇混合溶剂重结晶，真空干燥，即得到纯度大于99.9％的氯代2-羧基二苯甲酮。
本发明优点：合成步骤简单，成本低廉，工艺较为环保，所得产品纯度高，可直接应用于微电子等领域。
具体实施方式
以下通过实施例说明本发明的具体步骤，但不受实施例限制。
在本发明中所使用的术语，除非另有说明，一般具有本领域普通技术人员通常理解的含义。
下面结合具体实施例并参照数据进一步详细描述本发明。应理解，该实施例只是为了举例说明本发明，而非以任何方式限制本发明的范围。
在以下实施例中，未详细描述的各种过程和方法是本领域中公知的常规方法。
下面结合具体实施例对本发明进一步说明。
本发明所述的制备方法反应路线如下：
以2-氯-6-(2-氯苯甲酰基)苯甲酸(化合物A)和6-(2-氯苯甲酰基)苯甲酸(化合物B)为例说明本发明技术方案，
实施例1化合物B(6-(2-氯苯甲酰基)苯甲酸)的制备
(1)格式试剂的制备
取48克(2.0M)镁粉，放入四口圆底烧瓶中，通入干燥的热氮气，30分钟后冷却。加入邻甲基氯苯、少量乙醚、碘，加热引发反应。向反应瓶中滴加乙醚使总溶剂量为1000毫升，控制反应温度，反应4小时，冷却，所得格式试剂备用。
(2)中间体6-(2-氯苯甲酰基)甲苯的制备
将格式试剂的乙醚溶液(浓度2.0M)1000毫升，冰浴条件下缓慢滴入含有420.0克(2.4M)邻氯苯甲酰氯的二甲苯溶液中，继续回流反应36小时，反应完毕，减压蒸掉溶剂。反应物倒入1000毫升冰的稀盐酸中，1000毫升甲苯萃取两次，合并甲苯。无水硫酸镁干燥，减压蒸掉甲苯，得到中间体6-(2-氯苯甲酰基)甲苯425.6克，产率92.5％。
(3)化合物B(6-(2-氯苯甲酰基)苯甲酸)的制备
将230克中间体中间体6-(2-氯苯甲酰基)甲苯溶于500毫升丁酸中，加入3.46克醋酸钴，通入空气，在50℃下反应6小时，反应完毕，自然冷却至室温，析出固体，然后过滤，将得到的滤渣真空干燥，产物溶于热的500毫升体积比为1:1的甲苯-乙醇溶剂中重结晶，真空干燥，即得到氯代2-羧基二苯甲酮222.5克，纯度99.92％，产率85.4％。
Claims (4)
1.一种高纯度氯代2-羧基二苯甲酮的制备方法，所述氯代2-羧基二苯甲酮具有如下结构：
，其中R代表H或Cl，其特征在于包括如下步骤：
（1）将氯取代或非取代的邻氯甲苯制备成格式试剂；
（2） 冰浴条件下将步骤（1）制得的格式试剂缓慢滴入邻氯苯甲酰氯的溶液中，制备得到氯代2-甲基二苯甲酮，反应条件为0-150℃反应1-36小时，反应完毕，蒸去溶剂，反应物倒入冰的稀盐酸中，甲苯萃取，减压蒸去甲苯得到氯代2-甲基二苯甲酮，反应溶剂选自四氢呋喃、乙醚、石油醚、环己烷、苯、甲苯、乙苯中的一种或几种，所述格式试剂与邻氯苯甲酰氯的摩尔比为1:0.6-1.6；
（3）将氯代2-甲基二苯甲酮在催化剂和氧化剂存在下发生氧化反应，制得氯代2-羧基二苯甲酮，所述催化剂选自醋酸钴，所述氧化剂为空气或氧气，所述催化剂的量相当于氯代2-甲基二苯甲酮0.001-5%摩尔量，反应条件为20-150℃下反应2-48小时，反应溶剂选自醋酸、丙酸、丁酸、异丁酸、戊酸、异戊酸中的一种或几种。
2.如权利要求1所述的制备方法，其特征在于步骤（1）所述格式试剂是由氯取代或非取代的邻氯甲苯与镁粉在无水乙醚或四氢呋喃中反应制得。
3.如权利要求1或2所述的制备方法，其特征在于步骤（3）之后将反应物趁热过滤，冷却，析出产物，然后用任意体积比的甲苯-乙醇混合溶剂重结晶，即得到高纯度氯代2-羧基二苯甲酮。
4.如权利要求3所述的制备方法，其特征在于所述甲苯-乙醇混合溶剂中甲苯与乙醇的体积比为3:1～7。
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