3-氨基-4-氯苯甲酸十六酯的合成新路线
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摘要
以3-氨基-4-氯苯甲酸和正十六醇为原料,二甲苯为溶剂,对甲苯磺酸为催化剂,通过酯化合成了3-氨基-4-氯苯甲酸十六酯。采用FTIR、~1HNMR对产品的结构进行表征。考察了醇酸物质的量比、催化剂加量、反应物质量分数对酯化率的影响。结果表明∶n(醇)∶n(酸)=1.2∶1,催化剂用量为体系总质量的5%,反应物为体系总质量的65%,反应时间7 h,酯化率达96.20%,单程收率为73.91%。另外,确立了产物提纯、提高单程收率和滤液去除催化剂后回收、重复使用的最佳系统工艺路线,单程收率提至78.90%,总收率为82.62%,产品的纯度高于98.00%。
Hexadecyl 3-amino-4-chlorobenzoate was synthesized by esterification of 3-amino-4-chlorobenzoic and n-hexadecanol using xylene as solvent in the presence of catalyst of p-toluenesulfonic acid. The product was characterized by FTIR and ~1HNMR. The effects of molar ratio of 3-amino-4-chlorobenzoic to n-hexadecanol, amount of catalyst, reactants' mass fraction on the esterification rate were investigated. The optimal conditions were obtained as follows∶ n(n-hexadecanol)∶(3-amino-4-chlorobenzoic)=1.2∶ 1,amount of catalyst being 5% of the total mass of the system, reacants' mass fraction 65% and reaction time7 h. Under the above-mentioned conditions, the esterification rate was 96.20%, and the once-through yield was 73.91%. In addition, the best system route for product purification was established to improve once-through yield and the filtrate recovery and reuse after removal of catalyst. The once-through yield increased to 78.90%, the total yield was 82.62%, and the purity of the product was higher than 98.00%.
Hexadecyl 3-amino-4-chlorobenzoate was synthesized by esterification of 3-amino-4-chlorobenzoic and n-hexadecanol using xylene as solvent in the presence of catalyst of p-toluenesulfonic acid. The product was characterized by FTIR and ~1HNMR. The effects of molar ratio of 3-amino-4-chlorobenzoic to n-hexadecanol, amount of catalyst, reactants' mass fraction on the esterification rate were investigated. The optimal conditions were obtained as follows∶ n(n-hexadecanol)∶(3-amino-4-chlorobenzoic)=1.2∶ 1,amount of catalyst being 5% of the total mass of the system, reacants' mass fraction 65% and reaction time7 h. Under the above-mentioned conditions, the esterification rate was 96.20%, and the once-through yield was 73.91%. In addition, the best system route for product purification was established to improve once-through yield and the filtrate recovery and reuse after removal of catalyst. The once-through yield increased to 78.90%, the total yield was 82.62%, and the purity of the product was higher than 98.00%.
引文
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[6]Kiyohiro Kihara.Method for synthesizing amino alcohol benzoic acid higher alcohol ester:JP9286766[P].1997-11-04.
[7]Chen Zhiping(陈智萍),Wang Shuqing(王树清),Wang Xinran(王歆然),et al.Synthesis of 3,5-di-tert-butyl-4-hydroxybenzoic acid n-hexadecyl ester[J].Advances in Fine Petrochemicals(精细石油化工进展),2014,15(1):50-52.
[8]Lin Dan(林丹).Recent progress in esterification catalysts[J].Energy Chemical Industry(能源化工),2017,38(2):41-45.
[9]Liu Yurong(刘玉荣),Hu Zhiguo(胡志国).Direct synthesis of long-chain alcohols of p-aminobenzoic acid[J].Journal of Henan Normal University(Natural Science)(河南师范大学学报:自然科学版),2008,36(5):174-175.
[10]Guo Jing(郭静),Xu Huanhuan(许欢欢),Xue Qing(薛晴),et al.Synthesis and characterization of a new plasticizer long-chain alcohol ester of p-nitrobenzoic acid[J].Engineering Plastics(工程塑料),2012,40(10):76-79.
[11]Xu Jianfeng(徐剑锋),Wu Libing(吴利兵),Zhang Qingzhan(张庆站).Preparation of hexadecyl 3-amino-4-chlorobenzoate:CN1974543[P].2007-06-06.
[12]Wu Guilong(伍桂龙),Kuang Na(旷娜),Chen Langqiu(陈朗秋),et al.Synthesis of p-nitrophenyl-α-D-mannopyranoside[J].Fine Chemicals(精细化工),2015,32(7):821-826.
[13]Liang Xiaowei(梁晓为),Huang Caihuan(黄才欢),Ou Shiyi(欧仕益),et al.Preparation and antibacterial activity of fourteen and hexadecyl esters of nipagin[J].Food and Fermentation Industries(食品与发酵工业),2016,42(11):53-57.
[14]Hou Yanbing(侯艳冰),Yan Rian(晏日安),Huang Caihuan(黄才欢),et al.Synthesis of long-chain paraben ester preservatives[J].Food Science and Technology(食品科技),2011,(5):238-241.
[15]Yan Rian(晏日安),Liang Shuhua(梁淑华),Huang Xuesong(黄雪松).Study on synthesis of penta esters of parabens[J].Science and Technology of Food Industry(食品工业科技),2006,27(6):148-149.
[16]Determination of acid value and acidity of plasticizer(增塑剂酸值及酸度的测定):GB/T 1668-2008[S].Beijing:China Standard Press(中国标准出版社),2008.
[17]Xing Qiyi(邢其毅).Basic organic chemistry(Ⅲ)[M].Beijing:Higher Education Press(高等教育出版社),2005:452-453.