CN111960936A - 一种选择性合成芳香醛或芳香羧酸的反应方法 - Google Patents
一种选择性合成芳香醛或芳香羧酸的反应方法 Download PDFInfo
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- C07C45/34—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of CHx-moieties in unsaturated compounds
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Abstract
本发明提供了一种选择性合成芳香醛或芳香羧酸的反应方法,以苯环上无取代基或有取代基的甲苯类芳香烃为原料、三价铁的无机盐为催化剂、空气或者氧气为氧化剂、溶剂为乙腈‑水的混合溶液,通过调节催化剂的用量将原料氧化得到芳香醛或芳香羧酸,在紫外光的照射条件下进行10~16h。所述催化剂用量为芳香烃的5~50%mol的情况下得到芳香羧酸为主产物;催化剂用量为芳香烃的70~200%mol得到芳香醛为主产物。本发明提供的合成方法具有原子经济性和高选择性的特征,使用地球含量丰富的金属铁盐催化,具有条件温和,催化剂和溶剂可回收利用等优点。
Description
技术领域
本发明属于化学合成领域,具体的涉及一种选择性合成芳香醛或芳香羧酸的反应方法。
背景技术
芳香醛、芳羧酸是用途广泛的有机中间体。传统的芳甲醛合成方法中,比较有应用价值的方法主要有:二氯苄的水解、苯环甲基的化学氧化剂氧化等。另外,合成芳香族羧酸的一般途径主要有三氯苄的水解、苯环甲基的彻底氧化等。这些传统方法用于合成芳香醛和芳香羧酸都不具有原子经济性,需要大量的物质消耗并产生很多固有的废弃物,易对环境产生不利影响。近年来,绿色化学的兴起,使科学家越来越重视反应的原子经济性。在有机化学领域,碳氢键直接功能化,尤其是使用空气、水等洁净原料和简单过程实现新官能团的引入,得到迅速发展。碳氢键活化功能化中,光催化氧化-功能化是一种实验室非常有效的方法,可以迅速得到芳甲醇、芳醛(酮)或者芳羧酸等高价态产物。尽管这种反应目前仍处于实验室规模,但随着微通道反应器在工业化领域的不断应用和发展,光激活反应的工业化应指日可待。因此化学家们正不断探索光催化下实现各种非活性碳氢键的氧化功能化反应。
Michel Barbier用三氯化铁催化、330nm紫外光照射研究了芳烃侧链的苄位氧化,反应在丙酮中进行,加入少量水可促进反应,但甲苯氧化产物苯甲醛的含量仅达到痕量(Helvetic Chimca Acta 1984,67,866-869)。Akichika Itoh等用溴化锂催化可见光照射条件,甲苯氧化成苯甲酸,收率良好(Synlett,2005,13,2107–2109)。他们用紫外光激发,在四溴化碳及三苯基膦催化下,将甲苯氧化成苯甲酸的分离收率达到99%(TetrahedronLetters,2007,48,9096–9099)。RobertWolf等用蓝光照射,在黄素-钪配合物催化下用空气对甲苯进行氧化,苯甲醛的色谱收率约为70%(Chem.Commun.,2015,51,8425-8428)。2016年,他们跟进报道在蓝光照射及核黄素四醋酸酯及非血红素铁催化剂—[Fe(TPA)-(MeCN)2](ClO4)2)催化下用空气将对氯甲苯氧化成对氯苯甲酸,色谱收率为60%(Angew.Chem.Int.Ed.2016,55,427–430)。Yin Shuangfeng等用花状Bi2WO6微球催化在可见光下对甲苯类底物进行氧化,得到的芳香醛类化合物,其选择性良好,但转化率不超过5%(Chem.Commun.,2016,52,1274-1277)。Kei Ohkubo等研究了用3-氰基-1-癸基喹啉六氟磷酸盐催化,330nm紫外光照射下,用氧气将甲苯氧化成苯甲醛和苯甲醇的动力学行为(RSCAdv.,2016,6,41011–41014)。Lal Dhar S.Yadav等在溴硫盐及NBS催化剂基础上报道用CBr4辅助可见光下氧气氧化甲苯得到芳香醛,分离收率接近90%(RSCAdv.,2016,6,14547–14551)。Thomas J.Meyer报道了在金属锆氧化物薄膜负载黄素单核苷酸型催化剂将对二甲苯氧化成对甲基苯甲醛,NMR收率为72%(Proceedings of the National Academy ofSciences of the United States of America,2017,114(35),9279-9283.)。RajenderS.Varma等用VO@g-C3N4催化实现甲苯的可见光催化氧化,苯甲醛分离收率达90%以上(ACSSustainable Chem.Eng.2016,4,2333-2336)。SunXiaoling等用核黄素四醋酸酯和N-羟基丁二酰亚胺催化可见光激发将甲苯氧化成苯甲酸,但部分取代甲苯主要产物为相应的芳香醛(TetrahedronLetters 59(2018)658–662)。Li Xiaoqing等报道用四溴化碳催化剂可见光激发甲苯类底物氧化成苯甲酸(Synlett,2020,31(3),272-274)。Jiang Zhiyong等研究了三氯化铁催化光照空气氧化乙苯为苯乙酮(Org.Chem.Front.,2018,5,380–385)。
如上所述,光催化氧气或空气氧化苯环侧链反应中,常用催化剂可分为游离基引发剂、光敏活性物质、金属或其负载材料三大类。游离基引发剂、光敏活性物质虽然可能用量较小,但在反应中会被消耗,无法回收。尽管铁盐在很多研究中应用于烷基催化氧化,但应用于芳香烃苄位光催化氧化的报道较少,且多限于微浓度或微量的反应,尤其是甲苯底物的转化率以及芳香醛或者芳香羧酸的选择性和收率都不能令人满意。
发明内容
为克服芳香醛或芳香羧酸传统合成技术中不具有原子经济性、三废多、成本高的缺点,以及现有光催化氧化技术中选择性不高、底物范围窄、催化剂制备繁琐或者昂贵的缺点,本发明提供用硫酸铁作催化剂,在紫外光照射下,用空气氧化高选择性合成芳香醛和芳香羧酸的方法。
本发明采用的技术方案为:一种选择性合成芳香醛或芳香羧酸的反应方法,通过调节催化剂的用量将原料氧化得到芳香醛或芳香羧酸。
进一步地,所述催化剂为铁盐。
进一步地,所述铁盐为三价铁的无机盐,所述三价铁的无机盐为硫酸铁或其水合物。
进一步地,所述催化剂用量为芳香烃的5~50%mol的情况下得到芳香羧酸为主产物;催化剂用量为芳香烃的70~200%mol得到芳香醛为主产物。
进一步地,所述原料为甲苯类芳香烃。
进一步地,所述原料为苯环上无取代基或有取代基的甲苯类芳香烃。
进一步地,所述反应方法在300~400nm波长范围的紫外光的照射条件下进行。
进一步地,所述反应方法使用的氧化剂为空气或者氧气。
进一步地,所述反应方法溶剂为乙腈-水的混合溶液,其中乙腈与水的体积比为1:5~5:1。
进一步地,所述反应条件为常温常压,反应时间为10~16h;所述催化剂和反应溶剂均可回收;所述回收方法为:将反应后的混合液过滤得滤饼S1和滤液,滤液静置分层,得到溶剂层及水层L1,溶剂层用硫酸钠干燥后常压蒸馏回收溶剂,并得剩余物S2;分出的水层L1用乙酸乙酯萃取,得到乙酸乙酯油层和水层,水层L2为回收的催化剂溶液;乙酸乙酯层常压蒸馏得到少量剩余物S3,将S1和S2及S3合并,用柱层析或重结晶纯化得对芳香醛或芳香羧酸。
本发明获得的有益效果为:本发明提供的合成方法具有原子经济性和高选择性的特征,使用地球含量丰富的金属铁盐催化,具有条件温和,催化剂和溶剂可回收利用等优点,并且,一种反应体系只需要改变铁盐用量即可实现芳香醛和芳香羧酸的选择性调节。
(1)催化剂简单、价格低廉,且容易回收;硫酸铁在反应中并不损耗,均溶于水中,反应液经溶剂提取出有机组分后,即可直接进行重复使用,不失活,从而实现催化剂和水的重复使用。(2)同样催化体系,同样反应条件下,改变催化剂用量即可分别获得芳香醛或芳香羧酸,并具有高选择性。(3)甲苯类底物适应性广,并具有良好转化率;除了具有强吸电子基团取代的甲苯之外,都可在反应条件下转变为芳醛或芳羧酸;并且若为二甲苯底物,只氧化一个甲基。对有机溶剂与水层分离后,通过蒸馏或精馏,可实现乙腈的回收。
附图说明
图1为催化剂及溶剂回收流程图。
具体实施方式
下面对本发明实施例中的技术方案进行清楚、完整地描述,显然,所描述的实施例仅仅是本发明一部分实施例,而不是全部的实施例。
一种选择性合成芳香醛或芳香羧酸的反应方法,常温常压下,以苯环上无取代基或有取代基的甲苯类芳香烃为原料、三价铁的无机盐为催化剂、空气或者氧气为氧化剂、溶剂为乙腈-水的混合溶液,通过调节催化剂的用量将原料氧化得到芳香醛或芳香羧酸,在300~400nm波长范围的紫外光的照射条件下进行10~16h。所述催化剂用量为芳香烃的5~50%mol的情况下得到芳香羧酸为主产物;催化剂用量为芳香烃的70~200%mol得到芳香醛为主产物。
实施例1:对氯苯甲醛的光催化合成
在25mL无色透明玻璃试管中,加入0.5mmol对氯甲苯、5mL乙腈、1mmol硫酸铁、5mL水。经由试管口通入空气。在风冷、剧烈搅拌的条件下,使用波长在350~370nm的50W紫外光源照射反应液10h。停止反应,用乙酸乙酯萃取(10mL×3),合并有机层,用硫酸钠干燥,旋转蒸发除去有机溶剂,得到粗产品,由归一面积法气相色谱-质谱联用分析,所含主要物质为:对氯苯甲醇3%,对氯苯甲醛90%,对氯苯甲酸2.5%,对氯甲苯4%。
实施例2:对氯苯甲酸的光催化合成
在25mL无色透明玻璃试管中,加入0.5mmol对氯甲苯、5mL乙腈、0.25mmol硫酸铁、5mL水。经由试管口通入空气。在剧烈搅拌的条件下,通入空气,使用50W波长在350至370nm的紫外光源照射反应液,反应16h,得到乳白色偏黄的固液混合物。将反应液降温,用乙酸乙酯萃取(10mL×3),合并有机层,用硫酸钠干燥,旋转蒸发除去有机溶剂,经柱色谱纯化得对氯苯甲酸0.071g,熔点240℃,产率81%。
实施例3:苯甲醛的合成
在25mL的无色透明玻璃试管中,加入0.5mmol甲苯,1mmol硫酸铁,5mL水,5mL乙腈,经由试管口通入空气。整个反应体系密封以防甲苯挥发导致产率低。在剧烈搅拌的条件下,使用350-370nm波长的50W紫外光源照射反应液12h。反应结束后,使用二氯甲烷(10mL×3)萃取反应液,合并有机层,用无水硫酸钠干燥之后旋转蒸发除去溶剂,经柱色谱分离,得苯甲醛0.041g,产率77%。
实施例4:苯甲酸的合成
在25mL的无色透明玻璃试管中,加入0.5mmol甲苯,0.25mmol硫酸铁,5mL水,5mL乙腈,经由试管口通入氧气。在剧烈搅拌的条件下,使用350-370nm波长的50W紫外光源照射反应液16h。反应结束后,用乙酸乙酯(10mL×3)萃取反应液,合并有机层,用无水硫酸钠干燥,旋转蒸发除去溶剂,经柱色谱分离,得苯甲酸0.056g,产率92%。
实施例5:间甲基苯甲醛的合成
在25mL的无色透明玻璃试管中,加入0.5mmol间二甲苯,1.0mmol硫酸铁,5mL水,5mL乙腈,经由试管口通入氧气。整个反应体系密封以防底物挥发导致产率降低。在剧烈搅拌的条件下,使用350-370nm波长的50W紫外光源照射反应液12h。用乙酸乙酯(10mL×3)萃取反应液,合并有机层,用无水硫酸钠干燥,旋转蒸发除去溶剂,经柱色谱分离,得间甲基苯甲醛0.043g,产率72%。
实施例6:间甲基苯甲酸的合成
在25mL的无色透明玻璃试管中,加入0.5mmol间二甲苯,0.1mmol硫酸铁,5mL水,5mL乙腈,经由试管口通入空气。整个反应体系密封以防底物挥发导致产率降低。在剧烈搅拌的条件下,使用350-370nm波长的50W紫外光源照射反应液16h。反应结束后,使用乙酸乙酯萃取(10mL×3)反应液,合并有机层,用无水硫酸钠干燥,旋转蒸发除去溶剂,经柱色谱分离,得间甲基苯甲酸0.051g,产率75%。
实施例7:3,5-二甲基苯甲醛的合成
在25mL的无色透明玻璃试管中,加入0.5mmol均三甲苯,0.8mmol硫酸铁,5mL水,5mL乙腈,经由试管口通入空气。整个反应体系密封以防底物挥发导致产率降低。在剧烈搅拌的条件下,使用350-370nm波长的50W紫外光源照射反应液12h。反应结束后,使用乙酸乙酯萃取(10mL×3)反应液,合并有机层,用无水硫酸钠干燥,旋转蒸发除去溶剂,经柱色谱分离,得3,5-二甲基苯甲醛0.048g,产率72%。
实施例8:3,5-二甲基苯甲酸的合成
在25mL的无色透明玻璃试管中,加入0.5mmol均三甲苯,0.15mmol硫酸铁,5mL水,5mL乙腈,经由试管口通入空气。整个反应体系密封以防底物挥发导致产率降低。在剧烈搅拌的条件下,使用350-370nm波长的50W紫外光源照射反应液16h。反应结束后,使用乙酸乙酯(10mL×3)萃取反应液,合并有机层,无水硫酸钠干燥,旋转蒸发除去溶剂,经柱色谱分离,得3,5-二甲基苯甲酸0.051g,产率68%。
实施例9:对氯苯甲酸合成中三氯化铁溶液及乙腈的回收
在25mL无色透明玻璃试管中,加入0.5mmol对氯甲苯、5mL乙腈、0.25mmol硫酸铁、5mL水。经由试管口通入空气。在剧烈搅拌的条件下通入空气,使用50W波长在350至370nm的紫外光源照射反应液,反应16h,将反应液降温至0℃,有对氯苯甲酸固体析出。混合液过滤得滤饼S1和滤液。滤液静置分层,得到乙腈层及水层L1。分出的乙腈层用硫酸钠干燥后常压蒸馏,收集的乙腈经检测含水约5.5%(质量百分比),回收率约89%,可直接使用,并得剩余物S2;分出的水层L1用乙酸乙酯萃取(10mL×2),得到乙酸乙酯层和水层。水层L2为三氯化铁溶液,三氯化铁回收率98%以上,可直接回用;乙酸乙酯层常压蒸馏回收并得到少量剩余物S3,将S1和S2及S3合并,用柱层析纯化得对氯苯甲酸,产率80%。
Claims (10)
1.一种选择性合成芳香醛或芳香羧酸的反应方法,其特征在于:通过调节催化剂的用量将原料氧化得到芳香醛或芳香羧酸。
2.根据权利要求1所述一种选择性合成芳香醛或芳香羧酸的反应方法,其特征在于:所述催化剂为铁盐。
3.根据权利要求1所述一种选择性合成芳香醛或芳香羧酸的反应方法,其特征在于:所述铁盐为三价铁的无机盐,所述三价铁的无机盐为硫酸铁或其水合物。
4.根据权利要求1所述一种选择性合成芳香醛或芳香羧酸的反应方法,其特征在于:所述催化剂用量为芳香烃的5~50%mol的情况下得到芳香羧酸为主产物;催化剂用量为芳香烃的70~200%mol得到芳香醛为主产物。
5.根据权利要求1所述一种选择性合成芳香醛或芳香羧酸的反应方法,其特征在于:所述原料为甲苯类芳香烃。
6.根据权利要求5所述一种选择性合成芳香醛或芳香羧酸的反应方法,其特征在于:所述原料为苯环上无取代基或有取代基的甲苯类芳香烃。
7.根据权利要求1所述一种选择性合成芳香醛或芳香羧酸的反应方法,其特征在于:所述反应方法在300~400nm波长范围的紫外光的照射条件下进行。
8.根据权利要求1所述一种选择性合成芳香醛或芳香羧酸的反应方法,其特征在于:所述反应方法使用的氧化剂为空气或者氧气。
9.根据权利要求1所述一种选择性合成芳香醛或芳香羧酸的反应方法,其特征在于:所述反应方法溶剂为乙腈-水的混合溶液,其中乙腈与水的体积比为1:5~5:1。
10.根据权利要求3或9所述一种选择性合成芳香醛或芳香羧酸的反应方法,其特征在于:所述反应条件为常温常压,反应时间为10~16h;所述催化剂和反应溶剂均可回收;所述回收方法为:将反应后的混合液过滤得滤饼S1和滤液,滤液静置分层,得到溶剂层及水层L1,溶剂层用硫酸钠干燥后常压蒸馏回收溶剂,并得剩余物S2;分出的水层L1用乙酸乙酯萃取,得到乙酸乙酯油层和水层,水层L2为回收的催化剂溶液;乙酸乙酯层常压蒸馏得到少量剩余物S3,将S1和S2及S3合并,用柱层析或重结晶纯化得对芳香醛或芳香羧酸。
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CN110563571A (zh) * | 2019-09-11 | 2019-12-13 | 浙江工业大学 | 一种苯甲酸类化合物的合成方法 |
CN110563571B (zh) * | 2019-09-11 | 2022-04-29 | 浙江工业大学 | 一种苯甲酸类化合物的合成方法 |
CN113402376A (zh) * | 2021-06-24 | 2021-09-17 | 武汉理工大学 | 一种基于微通道反应器光催化合成苯甲酸的方法 |
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CN116283518A (zh) * | 2023-03-07 | 2023-06-23 | 中国石油大学(华东) | 一种一步二氯化水解制备醛酮类化合物的方法 |
CN116283518B (zh) * | 2023-03-07 | 2024-06-04 | 中国石油大学(华东) | 一种一步二氯化水解制备醛酮类化合物的方法 |
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