现代化工

现代化工 ›› 2025, Vol. 45 ›› Issue (8) : 90-95. DOI: 10.16606/j.cnki.issn0253-4320.2025.08.017

科研与开发

邻乙酰氨基苯甲醛的合成工艺研究

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Study on synthesis process for 2-acetamidobenzaldehyde

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摘要

以邻甲苯胺为起始原料,经过乙酰化反应制得邻乙酰氨基甲苯,然后合成了一种负载钨杂多酸的MIL-101(Cr)系列MOF材料,并以此为催化剂,通过催化氧化邻乙酰氨基甲苯反应制备邻乙酰氨基苯甲醛。利用XRD、SEM、BET、TG和XPS对催化剂进行表征。考察了反应催化剂种类、物料投料比、反应温度、反应溶剂等因素对催化反应的影响。结果表明,当使用 W2@MIL-101(Cr)作为催化剂,邻甲基乙酰苯胺和双氧水投料摩尔比为1∶4,反应温度75℃,反应溶剂为乙腈时,邻甲基乙酰苯胺转化率可达到73.3%。研究方法操作简单且易于纯化,在最佳反应条件下产物的总收率可达66.1%。

Abstract

o-Methylacetanilide is prepared through acetylation reaction of o-toluidine.Then,MIL-101 (Cr) series MOF materials supported with tungsten-heteropolyacid are synthesized to catalyze the oxidation of o-methylacetanilide to o-acetyl aminobenzaldehyde.The catalysts are characterized by means of XRD,SEM,BET,TG and XPS.The influences of catalyst type,material feed ratio,reaction temperature and reaction solvent on the catalytic reaction are studied.Results show that the conversion rate of o-methylacetanilide can reach 73.3% when W2@MIL-101(Cr) is served as the catalyst,the molar ratio of o-methylacetanilide to hydrogen peroxide is 1∶4,reaction temperature is 75℃,and acetonitrile is served as solvent.The method is simple to operate and easy to purify the product,and total yield of the product can reach 66.1% under the optimal reaction conditions.

Graphical abstract

关键词

邻乙酰氨基苯甲醛 / MOF催化 / 催化氧化反应

Key words

2-acetamidobenzaldehyde / MOF catalysis / catalytic oxidation reaction

Author summay

吕新宇(1977-),男,硕士,高级工程师,研究方向为精细化工工艺研究,lvxinyu@cczu.edu.cn。

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China), AuthorCompanyExt(id=1241416409357447383, tenantId=1226480274814496768, journalId=1226484258170171394, articleId=1240720113269174875, companyId=1241416409344864469, language=CN, country=null, province=null, city=null, postcode=null, companyName=null, departmentName=null, remark=常州大学石油化工学院,江苏常州 213164)])])] 吕新宇,张艳,吕金乌,邱滔. 邻乙酰氨基苯甲醛的合成工艺研究[J]. , 2025, 45(8): 90-95 DOI:10.16606/j.cnki.issn0253-4320.2025.08.017

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邻乙酰氨基苯甲醛是一种重要的有机合成中间体,在医药、染料和农药等领域应用广泛,衍生出的芳香族香料紫罗兰酮和紫罗兰醇具有独特香气,可应用于食品、化妆品、烟草等领域^[1-6]。当前,邻乙酰氨基苯甲醛市场需求量大,该化合物传统的合成方法主要是以邻乙酰氨基苯甲醇为原料^[6-8],但邻乙酰氨基苯甲醇价格偏高且制备工艺繁杂。此外,该方法常用的催化剂为锰、铈等氧化物负载型催化体系和金属卟啉体系^[9-12],皆存在转化率低、催化剂制备困难且难以回收等问题,致使其难以实现工业化生产。因此,探索出更经济环保的邻乙酰氨基苯甲醛合成工艺至关重要。

本文以邻甲苯胺为原料、有机金属框架材料(MOF)为催化剂,通过乙酰化保护和催化氧化两步反应合成邻乙酰氨基苯甲醛,与传统工艺相比,该方法极大地简化了合成工艺,其反应路线如图1。

催化氧化反应采用自制MIL-101(Cr)系列的MOF材料负载含钨杂多酸作为催化剂,利用双氧水氧化,避免了目前催化体系复杂的问题,同时生成的水不污染环境,符合绿色化学的原则,且催化剂用量少又可回收循环利用,符合经济适用性原则。

与传统邻乙酰氨基苯甲醛合成工艺相比,本合成方法很好地解决了氧化过度的问题,简化了合成步骤,提高了收率,且具有工艺稳定、成本低的优点,具有一定的工业应用价值。

1 实验部分

1.1 实验试剂

N,N-二甲基甲酰胺(AR)、硅钨酸水合物(AR)、对苯二甲酸(AR)、乙腈(AR),购自安耐吉化学(安徽泽升科技有限公司)。过氧化氢(AR)、无水乙醇(AR),购自国药集团化学试剂有限公司。钨酸钠二水合物(AR),购自上海麦克林生化科技有限公司。磷钨酸(工业级),购自昆山兴邦钨钼科技有限公司。硝酸铬(Ⅲ)九水合物(AR),购自阿拉丁试剂(上海)有限公司。邻甲基乙酰苯胺、蒸馏水,实验室自制。

1.2 实验过程

催化剂的制备:根据文献[13]的制备方法修改后合成MIL-101(Cr)材料。将3 mL去离子水、5 mL乙醇和10 mL二甲基甲酰胺(DMF)进行混合,然后往上述混合溶液中加入5 mmol的Cr(NO₃)₃·9H₂O和5 mmol的对苯二甲酸进行搅拌。最后将混合溶液转移到密封的聚四氟乙烯作内衬的水热反应釜中,在200℃的烘箱里水热反应5 h。待反应结束将温度降至70℃,直至冷却至室温后,分别用DMF、去离子水和乙醇各洗涤3次过滤得到产物。在真空烘箱中60℃干燥12 h,得到MIL-101(Cr)材料[在混合时加入质量分数为10%的硅钨酸、磷钨酸和钨酸钠,分别记为W1@MIL-101(Cr)、W2@MIL-101(Cr)、W3@MIL-101(Cr)]。

催化氧化反应:向100 mL四口反应瓶中加入邻甲基乙酰苯胺14.9 g(0.1 mol),自制W@MIL-101(Cr)催化剂1.5 g和乙腈50 mL混合后搅拌。待反应温度升至75℃后向上述反应体系中滴加双氧水13.6 g(0.4 mol,30%:45.3 g),滴加完毕保持75℃反应3 h。反应结束后取样进行液相色谱分析,反应转化率为73.3%,邻乙酰氨基苯甲醛选择性为91.6%。粗产物重结晶后得邻乙酰氨基苯甲醛10.7 g(0.07 mol),纯度98.3%(HPLC),总收率66.1%。反应结束后的催化剂通过过滤从反应液中分离出来,依次用DMF、水和无水乙醇洗涤干净干燥后回收套用。

1.3 分析及表征方法

采用Rigol公司液相色谱仪L-3000对邻乙酰氨基苯甲醛进行含量分析,仪器条件为:C18色谱柱,柱温箱40℃,波长254 nm,流动相为乙腈比水20∶80,速度1 mL/min。采用Bruker公司Avance DMX 300 MHz核磁共振仪对化合物进行定性分析。采用日本理学公司D/MAX2500型X射线粉末衍射仪(XRD)测定催化剂的晶态结构。采用德国蔡司公司SUPRA-55场发射扫描电镜(SEM)测定催化剂形貌。采用美国康塔公司Autosorb-iQ2-MP型吸附仪测定催化剂比表面积和孔结构。采用德国耐驰公司TG 209 F3热重分析仪(TGA)测定催化剂于氮气气氛下的热分解能力。采用美国赛默飞世尔公司EscaLab 250Xi X射线光电子能谱仪(XPS)分析催化剂的元素价态。

2 结果与讨论

2.1 氧化催化剂的表征及分析

2.1.1 W@MIL-101(Cr)催化剂的XRD分析

图2为样品MIL-101(Cr)、W1@MIL-101(Cr)、W2@MIL-101(Cr)、W3@MIL-101(Cr)的XRD谱。如图所示,4组不同负载量的MIL-101(Cr)材料[图2(a)]的主衍射峰与文献报道[13]一致,表明成功合成了MIL-101(Cr)材料。将W@MIL-101(Cr)与MIL-101(Cr)进行对比分析,发现W@MIL-101(Cr)催化剂的主要特征衍射峰与文献[13-14]一致,但是,W@MIL-101(Cr)样品比合成的MIL-101(Cr)增多了衍射峰(W的峰),原因可能是负载不均匀。不同负载量的表征结果[图2(b)]表明,随着负载量的增大,MIL-101(Cr)晶体结构会被破坏且影响催化性能。在实验中发现W2@MIL-101(Cr)的催化性能最优,故后续对W2@MIL-101(Cr)进行主要表征。

2.1.2 W@MIL-101(Cr)的SEM分析

图3为样品MIL-101(Cr)与W2@MIL-101(Cr)的SEM照片。如图3(a)所示,MIL-101(Cr)载体材料基本为正八面体形的颗粒体,负载了10%磷钨酸的W2@MIL-101(Cr)催化剂[图3(b)]表面八面体微观形貌无明显的消失,但规整度下降;后续随着磷钨酸负载量达到25%时[图3(c)],颗粒之间发生融合,可能是由于磷钨酸负载量过大造成MIL-101(Cr)晶体基本结构坍塌消失,这与XRD结果相吻合。结合催化剂表征结果,说明磷钨酸的负载及负载量在本催化氧化的实验中起着重要作用。

2.1.3 W2@MIL-101(Cr)与MIL-101(Cr)的比表面积和孔结构分析

图4为样品MIL-101(Cr)与W2@MIL-101(Cr)的N₂吸附-脱附曲线及孔径分布曲线。MIL-101(Cr)与W2@MIL-101(Cr)的N₂吸附-脱附曲线呈现出Ⅳ(H1)型等温线^[15],反映出二者孔径分布较均匀。二者在低压区曲线偏向Y轴,随着压力增大变化逐渐平缓,表明内部存在大量微孔。MIL-101(Cr)和W2@MIL-101(Cr)在p/p₀为0.4~1.0皆出现不明显的回滞环,说明孔径较小。

从表1可知,负载磷钨酸的MIL-101(Cr)比表面积增大,进一步提升催化剂性能,且W2@MIL-101(Cr)拥有更高的微孔和外比表面积,促使双氧水能够及时产生大量·OH。与MIL-101(Cr)相比,W2@MIL-101(Cr)孔径变小,表明负载的磷钨酸造成MIL-101(Cr)微孔被部分堵塞,但更高的外比表面积表明负载的磷钨酸不影响催化剂的表面活性位点,不会影响催化剂利用率。综上,负载10%磷钨酸的W2@MIL-101(Cr)催化剂较适合于本次催化氧化实验。

2.1.4 W2@MIL-101(Cr)与MIL-101(Cr)的热重分析(TG)

图5为样品MIL-101(Cr)与W2@MIL-101(Cr)的热重分析曲线。当温度低于200℃时,两种材料重量均减少3.5%,这是低温下去除催化剂内部的水导致的。200~300℃时重量损失了31.2%,表明已除去羟基和客体分子。300~500℃时,重量损失加剧,表明MIL-101(Cr)结构出现坍塌且晶体形貌发生变化。500~800℃之间,曲线变平缓,材料中碳的氧化使其质量缓慢减少。根据热重分析的结果可知,最后残余质量W2@MIL-101(Cr)比MIL-101(Cr)高10%,进一步证明磷钨酸负载量为10%。

2.1.5 W2@MIL-101(Cr)的XPS分析

图6为W2@MIL-101(Cr)的XPS谱,分析了W2@MIL-101(Cr)中阳离子的化学价态。图6(a)为W2@MIL-101(Cr)的Cr 2p XPS谱,电子结合能位于576.9 eV和586.7 eV处峰分别代表Cr 2p_3/2和Cr 2p_1/2轨道。此外,样品中没有出现其他价态铬,表明铬元素以Cr³⁺的价态存在于W2@MIL-101(Cr)中^[16-18]。图6(b)为W2@MIL-101(Cr)的 W 2p XPS谱,电子结合能为37.4 eV和35.3 eV处分别代表W 2p_1/2轨道和W 2p_3/2轨道,以上两特征峰表明该样品中存在W⁶⁺,钨酸类化合物已被负载于MIL-101(Cr)载体上^[19-21]。

2.2 邻乙酰氨基苯甲醛的合成

2.2.1 催化剂种类对反应的影响

以乙腈为溶剂,在邻甲基乙酰苯胺和双氧水的投料摩尔比为1∶4,体系温度为75℃,搅拌反应3 h的条件下,考察不同催化剂对原料转化率的影响,结果如图7所示。

由图7可以看出,W1@MIL-101(Cr)与W3@MIL-101(Cr)对原料转化率相当,MIL-101(Cr)和磷钨酸对原料转化率只能达到30%左右,原因在于W1@MIL-101(Cr)与W3@MIL-101(Cr)属于负载型催化剂,二者之间的协同效应使得催化氧化效率高于MIL-101(Cr)和磷钨酸。而以W2@MIL-101(Cr)为催化剂,原料转化率可达73.3%,相比于MIL-101(Cr)和磷钨酸等催化剂,W2@MIL-101(Cr)更易于回收。

2.2.2 溶剂对反应的影响

本研究选择5种溶剂,在催化剂为10%的W2@MIL-101(Cr),邻甲基乙酰苯胺和双氧水的投料摩尔比为1∶4,温度75℃,搅拌反应3 h的条件下,研究反应转化率和收率的影响,结果如表2所示。

由表2可以看出,不同的溶剂对反应转化率存在较大影响,在5种反应溶剂中,乙腈对该反应的适用性最优。因此,适合反应溶剂为乙腈。

2.2.3 物料投料比对反应的影响

在以乙腈为溶剂,催化剂为10%的W2@MIL-101(Cr),体系温度75℃,搅拌反应3 h的条件下,研究邻甲基乙酰苯胺与双氧水投料摩尔比对反应转化率和收率的影响,结果如表3所示。

由表3可以看出,邻甲基乙酰苯胺与双氧水投料摩尔比低于1∶4时,原料转化率极低,这是由于75℃下被分解的双氧水过多,无法全部参与到反应中发挥作用。邻甲基乙酰苯胺与双氧水投料摩尔比达到1∶4后,随着双氧水用量的增加,收率趋于稳定。因此,邻甲基乙酰苯胺与双氧水的理想投料摩尔比为1∶4。

2.2.4 体系温度对反应的影响

在以乙腈为溶剂,氧化催化剂为10%的W2@MIL-101(Cr),邻甲基乙酰苯胺和双氧水的投料摩尔比为1∶4,搅拌反应3 h的条件下,研究不同反应温度对原料转化率的影响,结果如图8所示。

由图8可以看出,温度对该反应的影响较大。过低温度使得反应难以进行,过高则会导致双氧水分解过快,从而降低双氧水的利用率。此外,该反应为放热反应,温度过高反而适得其反。综上,最佳反应温度为75℃。

2.3 催化剂的循环

在以乙腈为溶剂,催化剂为10%的W2@MIL-101(Cr),邻甲基乙酰苯胺和双氧水的投料摩尔比为1∶4,反应温度为75℃,搅拌反应3 h的条件下,考察催化剂W2@MIL-101(Cr)的稳定性,结果如图9所示。

从图9可以看出,循环使用5次后邻甲基乙酰苯胺的转化率仍能保持在70%以上,反应生成的邻乙酰氨基苯甲醛选择性未有明显降低。表明W2@MIL-101(Cr)材料具有良好的催化活性与循环使用性能。

对再生的W2@MIL-101(Cr)催化剂进行了XRD测试,结果表明,W2@MIL-101(Cr)的晶体结构在参与氧化反应后保持不变[图10(a)]。与原催化剂相比,再生W2@MIL-101(Cr)的XPS谱依旧存在Cr³⁺[图10(b)],二者的XPS数据并没有明显差异,这说明了双氧水对催化剂表面没有影响。综上,XRD和XPS结果进一步证明W2@MIL-101(Cr)催化材料具有良好的重复使用性和稳定性。

3 结论

本文制备了一种负载钨杂多酸的MIL-101(Cr)系列催化材料,并以此为催化剂,通过两步反应合成了邻乙酰氨基苯甲醛,经过优化催化氧化反应条件,提高邻甲基乙酰苯胺的转化率至73.3%,最终使得总收率达到66.1%。当催化剂为10%wt的W2@MIL-101(Cr),物料投料比为1∶4,反应温度为75℃,反应溶剂为乙腈时,反应转化率和选择性最好。

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