CN112645815A - 一种基于低共熔溶剂催化合成肉桂酸甲酯的制备方法 - Google Patents
一种基于低共熔溶剂催化合成肉桂酸甲酯的制备方法 Download PDFInfo
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- 230000005496 eutectics Effects 0.000 title claims abstract description 25
- CCRCUPLGCSFEDV-BQYQJAHWSA-N methyl trans-cinnamate Chemical compound COC(=O)\C=C\C1=CC=CC=C1 CCRCUPLGCSFEDV-BQYQJAHWSA-N 0.000 title claims abstract description 25
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- 238000006243 chemical reaction Methods 0.000 claims abstract description 39
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- WBYWAXJHAXSJNI-VOTSOKGWSA-M .beta-Phenylacrylic acid Natural products [O-]C(=O)\C=C\C1=CC=CC=C1 WBYWAXJHAXSJNI-VOTSOKGWSA-M 0.000 claims abstract description 18
- WBYWAXJHAXSJNI-SREVYHEPSA-N Cinnamic acid Chemical compound OC(=O)\C=C/C1=CC=CC=C1 WBYWAXJHAXSJNI-SREVYHEPSA-N 0.000 claims abstract description 17
- 229930016911 cinnamic acid Natural products 0.000 claims abstract description 17
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- WBYWAXJHAXSJNI-UHFFFAOYSA-N methyl p-hydroxycinnamate Natural products OC(=O)C=CC1=CC=CC=C1 WBYWAXJHAXSJNI-UHFFFAOYSA-N 0.000 claims abstract description 17
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- C—CHEMISTRY; METALLURGY
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- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/08—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0215—Sulfur-containing compounds
- B01J31/0225—Sulfur-containing compounds comprising sulfonic acid groups or the corresponding salts
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- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
- B01J31/0235—Nitrogen containing compounds
- B01J31/0239—Quaternary ammonium compounds
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Abstract
本发明公开了一种基于低共熔溶剂催化合成肉桂酸甲酯的制备方法。以氯化胆碱与对甲苯磺酸混合制得的低共熔溶剂为反应的催化剂和溶剂,采用肉桂酸和甲醇作为反应原料进行酯化反应并经过相分离、中和、结晶干燥等工艺获得肉桂酸甲酯。本发明所用的低共熔溶剂在制备过程中原子利用率为100%,与传统质子酸催化剂相比,反应条件温和,反应时间短,不易腐蚀设备,可循环使用,符合绿色催化反应工艺的要求。通过对反应条件的调节控制,能在较低的成本下获得较高收率。
Description
技术领域
本发明属于有机化工合成领域,涉及一种基于低共熔溶剂催化合成肉桂酸甲酯的制备方法。
背景技术
肉桂酸甲酯常用于制作香料,可用于化妆品产品如高级香水中,也能够用于非化妆品产品,如家用清洁剂和洗涤剂。除此之外肉桂酸甲酯可以添加到香烟烟丝中,用作增香剂和香味补偿剂。由于肉桂酸甲酯具有杀幼虫、驱避或杀虫活性,被认为是安全的合成农药替代品。同时作为一种亲水活性优异的羧酸类物质,肉桂酸甲酯接枝多元共聚物与其它有效助剂复配的新型减水剂,可用于建筑领域。此外,近年来,在医学方面已被证明具有抗脂肪生成和血管舒张活性作用,能够预防由乙酸诱导的体内损伤引起的结肠炎。
传统肉桂酸甲酯的合成工艺多以质子酸如浓硫酸为催化剂,不但反应时间长,易腐蚀反应设备,使设备老化,而且催化剂或反应过程中使用的溶剂回收困难,造成严重的环境污染。实现可持续和环境友好的化工生产过程是科学研究不断追求的目标。基于此,寻找环保、易回收、对反应设备腐蚀性小的催化剂是取代传统工艺的关键。
低共熔溶剂通常由氢键受体组分和氢键供体组分在一定的摩尔比下形成。它们的原料廉价易得,制备过程简单,不会产生废物或有毒有害物质,原子经济性高。这些类型的溶剂由于其极低的蒸汽压而被认为有可能用于聚合物化学和合成有机化学(Journal ofCleaner Production, 2014, 65: 246)。
在合成肉桂酸酯的研究中,中国专利CN1117066C和CN111689855A主要研究使用不同反应物提高制备肉桂酸甲酯转化率的方法,俞善信等(香料香精化妆品, 1995,(2): 12)使用三氯化铁催化制备肉桂酸甲酯,效果不低于硫酸,然而醇的用量较大,催化剂不可回收,不利于工业化生产;陈卓等(贵州科学, 2007(02): 43)研究了在多种1,3-二烷基咪唑离子液体和适量三氯化铝构成的催化反应体系中合成肉桂酸甲酯的酯化反应,其中新型杂多酸苯并噻唑离子液体表现优异但其制备过程复杂,价格昂贵。本发明提出的氯化胆碱基低共熔溶剂催化合成肉桂酸甲酯的制备方法中采用三种配比的低共熔溶剂氯化铵胆碱-对甲苯磺酸(ChCl-PTSA)作为催化剂与溶剂,它不仅拥有媲美于离子液体良好的反应性能,而且价格低廉,绿色环保,制备方法简单,对设备腐蚀性小,反应条件温和,易回收,符合环境保护和人类可持续发展的要求,同时具有工业化应用潜能。
发明内容
本发明的目的是针对现有技术的不足,通过调节工艺条件,提供一种绿色高效的基于低共熔溶剂催化合成肉桂酸甲酯的制备方法。该方法在反应过程中无需加入其他溶剂溶解反应原料,操作简单,在一定的反应工艺条件下能够获得不错的效果。
本发明的方法包括如下步骤:
(1)首先制备氯化胆碱基低共熔溶剂,按照1:1~3的摩尔比分别称取适量氯化铵胆碱和对甲苯磺酸,将两者分别在50℃下真空干燥30 min,再将两者在60℃下混合搅拌至澄清透明溶液,反应所得产物即为氯化胆碱基低共熔溶剂催化剂ChCl-PTSA,将制得的低共熔溶剂密封后放置在硅胶干燥箱中,备用;
(2)按照一定摩尔比分别称取适量的肉桂酸和无水甲醇,将两者均加入三口烧瓶中,搅拌加热至指定温度后,再向三口烧瓶中加入适量步骤(1)所制的低共熔溶剂后反应1~3 h;
(3)反应结束后,将反应液趁热经分液漏斗分为水相和有机相;
(4)将步骤(3)中的水相在60℃下真空干燥1h以回收催化剂,供循环使用;
(5)将步骤(3)中的有机相倒入烧杯中并将烧杯置于40~50℃水浴锅中,在不断搅拌下加入适量的4%碳酸钠溶液至弱碱性pH=7~8,以除去未反应的肉桂酸和催化剂中的酸,然后静置分层,除去水相,保留有机相;接着在不断搅拌下将有机相倒入约为其三倍体积的5~10℃去离子水中以析出结晶,然后抽滤并用去离子水洗涤至滤液为中性得到白色或淡黄色固体,干燥后得目标产物肉桂酸甲酯。
所述的肉桂酸与甲醇的摩尔比为1: 2~3,所述的催化剂用量为反应物总质量的10%~30%。
所述步骤(2)的反应温度为64~76℃。
本发明的创新点在于使用低共熔溶剂ChCl-PTSA作为肉桂酸酯化反应的催化剂,原料廉价易得,制备方法简单,对设备腐蚀性小,反应条件温和,易回收能够进行循环使用,符合绿色环保和人类可持续发展的要求,具有较大的应用前景。
具体实施方式
低共熔溶剂催化剂ChCl-PTSA催化剂的制备
称取6.98g(0.05mol)氯化胆碱和8.61g(0.05mol)对甲苯磺酸,将两者分别在50℃下真空干燥30 min,再将两者混合并在60℃下搅拌至形成澄清透明溶液,反应所得产物即为低共熔溶剂催化剂CAT1;
重复上述步骤,分别将对甲苯磺酸质量变更为17.22g(0.10mol)和25.82g(0.15mol),依次可得低共熔溶剂催化剂CAT2和CAT3;
将所制备的三个低共熔溶剂催化剂密封并放置在硅胶干燥箱中,备用。
实施例1
分别称量14.82g(0.1mol)肉桂酸和9.61g(0.3mol)甲醇于三口烧瓶中,搅拌加热至64℃后,再向三口烧瓶中加入4.89g(20%)催化剂CAT3并在该温度下反应2h。反应结束后,将反应液趁热经分液漏斗分为水相和有机相。水相在60℃下真空干燥1h以回收催化剂,供循环使用;有机相倒入烧杯中并将烧杯置于40℃水浴锅中,在不断搅拌下加入适量的4%碳酸钠溶液至弱碱性pH=7~8,然后静置分层,除去水相,保留有机相;接着在不断搅拌下将有机相倒入三倍体积的10℃去离子水中以析出结晶,然后抽滤并用去离子水洗涤至滤液为中性得到白色或淡黄色固体,干燥后得目标产物肉桂酸甲酯,其收率为84.37%。
实施例2
分别称量14.82g(0.1mol)肉桂酸和6.41g(0.2mol)甲醇于三口烧瓶中,搅拌加热至76℃后,再向三口烧瓶中加入2.13g(10%)催化剂CAT1并在该温度下反应3h。反应结束后,将反应液趁热经分液漏斗分为水相和有机相。水相在60℃下真空干燥1h以回收催化剂,供循环使用;有机相倒入烧杯中并将烧杯置于50℃水浴锅中,在不断搅拌下加入适量的4%碳酸钠溶液至弱碱性pH=7~8,然后静置分层,除去水相,保留有机相;接着在不断搅拌下将有机相倒入三倍体积的5℃去离子水中以析出结晶,然后抽滤并用去离子水洗涤至滤液为中性得到白色或淡黄色固体,干燥后得目标产物肉桂酸甲酯,其收率为80.46%。
实施例3
分别称量14.82g(0.1mol)肉桂酸和9.61g(0.3mol)甲醇于三口烧瓶中,搅拌加热至76℃后,再向三口烧瓶中加入6.11g(25%)催化剂CAT2并在该温度下反应1h。反应结束后,将反应液趁热经分液漏斗分为水相和有机相。水相在60℃下真空干燥1h以回收催化剂,供循环使用;有机相倒入烧杯中并将烧杯置于45℃水浴锅中,在不断搅拌下加入适量的4%碳酸钠溶液至弱碱性pH=7~8,然后静置分层,除去水相,保留有机相;接着在不断搅拌下将有机相倒入三倍体积的7℃去离子水中以析出结晶,然后抽滤并用去离子水洗涤至滤液为中性得到白色或淡黄色固体,干燥后得目标产物肉桂酸甲酯,其收率为90.48%。
实施例4
分别称量14.82g(0.1mol)肉桂酸和9.61g(0.3mol)甲醇于三口烧瓶中,搅拌加热至70℃后,再向三口烧瓶中加入4.89g(20%)催化剂CAT3并在该温度下反应2h。反应结束后,将反应液趁热经分液漏斗分为水相和有机相。水相在60℃下真空干燥1h以回收催化剂,供循环使用;有机相倒入烧杯中并将烧杯置于50℃水浴锅中,在不断搅拌下加入适量的4%碳酸钠溶液至弱碱性pH=7~8,然后静置分层,除去水相,保留有机相;接着在不断搅拌下将有机相倒入三倍体积的7℃去离子水中以析出结晶,然后抽滤并用去离子水洗涤至滤液为中性得到白色或淡黄色固体,干燥后得目标产物肉桂酸甲酯,其收率为89.23%。
实施例5
分别称量14.82g(0.1mol)肉桂酸和9.61g(0.3mol)于三口烧瓶中,搅拌加热至76℃后,再向三口烧瓶中加入7.32g(30%)催化剂CAT3并在该温度下反应为1h。反应结束后,将反应液趁热经分液漏斗分为水相和有机相。水相在60℃下真空干燥1h以回收催化剂,供循环使用;有机相倒入烧杯中并将烧杯置于45℃水浴锅中,在不断搅拌下加入适量的4%碳酸钠溶液至弱碱性pH=7~8,然后静置分层,除去水相,保留有机相;接着在不断搅拌下将有机相倒入三倍体积的5℃去离子水中以析出结晶,然后抽滤并用去离子水洗涤至滤液为中性得到白色或淡黄色固体,干燥后得目标产物肉桂酸甲酯,其收率为92.55%。
实施例6
分别称量14.82g(0.1mol)和8.01g(0.25mol)甲醇于三口烧瓶中,搅拌加热至76℃后,再向三口烧瓶中加入4.57g(20%)催化剂CAT3并在该温度下反应2h。反应结束后,将反应液趁热经分液漏斗分为水相和有机相。水相在60℃下真空干燥1h以回收催化剂,供循环使用;有机相倒入烧杯中并将烧杯置于40℃水浴锅中,在不断搅拌下加入适量的4%碳酸钠溶液至弱碱性pH=7~8,然后静置分层,除去水相,保留有机相;接着在不断搅拌下将有机相倒入三倍体积的10℃去离子水中以析出结晶,然后抽滤并用去离子水洗涤至滤液为中性得到白色或淡黄色固体,干燥后得目标产物肉桂酸甲酯,其收率为87.66%。
实施例7
分别称量14.82g(0.1mol)肉桂酸和9.61g(0.3mol)甲醇于三口烧瓶中,搅拌加热至70℃后,再向三口烧瓶中加入实施案例5中回收的催化剂反应2h,反应结束后,将反应液趁热经分液漏斗分为水相和有机相。水相在60℃下真空干燥1h以回收催化剂,供循环使用;有机相倒入烧杯中并将烧杯置于40℃水浴锅中,在不断搅拌下加入适量的4%碳酸钠溶液至弱碱性pH=7~8,然后静置分层,除去水相,保留有机相;接着在不断搅拌下将有机相倒入三倍体积的5℃去离子水中以析出结晶,然后抽滤并用去离子水洗涤至滤液为中性得到白色或淡黄色固体,干燥后得目标产物肉桂酸甲酯,收率为 91.74%。
Claims (3)
1.一种基于低共熔溶剂催化合成肉桂酸甲酯的制备方法,其特征在于包括以下步骤:
(1)首先制备氯化胆碱基低共熔溶剂,按照1:1~3的摩尔比分别称取适量氯化铵胆碱和对甲苯磺酸,将两者分别在50℃下真空干燥30 min,再将两者在60℃下混合搅拌至澄清透明溶液,反应所得产物即为氯化胆碱基低共熔溶剂催化剂ChCl-PTSA,将制得的低共熔溶剂密封后放置在硅胶干燥箱中,备用;
(2)按照一定摩尔比分别称取适量的肉桂酸和无水甲醇,将两者均加入三口烧瓶中,搅拌加热至指定温度后,再向三口烧瓶中加入适量步骤(1)所制的低共熔溶剂后反应1~3 h;
(3)反应结束后,将反应液趁热经分液漏斗分为水相和有机相;
(4)将步骤(3)中的水相在60℃下真空干燥1h以回收催化剂,供循环使用;
(5)将步骤(3)中的有机相倒入烧杯中并将烧杯置于40~50℃水浴锅中,在不断搅拌下加入适量的4%碳酸钠溶液至弱碱性pH=7~8,以除去未反应的肉桂酸,然后静置分层,除去水相,保留有机相;接着在不断搅拌下将有机相倒入约为其三倍体积的5~10℃去离子水中以析出结晶,然后抽滤并用去离子水洗涤至滤液为中性得到白色或淡黄色固体,干燥后得目标产物肉桂酸甲酯。
2. 根据权利要求1所述的方法,其特征在于所述的肉桂酸与甲醇的摩尔比为1 : 2~3,所述的催化剂用量为反应物总质量的10%~30%。
3.根据权利要求1所述的方法,其特征在于所述步骤(2)的反应温度为64~76℃。
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