4,4′-联苯二甲酸合成工艺研究
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摘要
以医药中间体合成过程中产生的副产物4,4′-二甲基联苯为原料,经氯代反应生成4,4′-双(三氯甲基)联苯,然后水解制得4,4′-联苯二甲酸;对氯代反应的历程进行了探讨,并通过正交实验考察了反应参数对4,4′-联苯二甲酸收率的影响,得到了优化工艺条件,优化工艺条件下的验证实验表明:反应总收率达到93.40%,纯度达99.20%。采用IR、~1HNMR对产物的结构进行表征,通过HPLC对生成的4,4′-联苯二甲酸的纯度进行测定。该合成工艺具有环境友好、工艺操作简单、转化率及收率高、经济性好等优点,适合工业化大规模生产。
4,4′-diphenyldicarboxylic acid was synthesized by the reaction of chlorination and hydrolysis from the 4,4′-dimethylbiphenyl which was the byproducts of pharmaceutical intermediates.The mechanism of the chlorination reaction was discussed and the effects of reaction parameters on the yield of 4,4′-diphenyldicarboxylic acid were studied via orthogonal experiment.The total yield of the reaction was 93.40%and the purity was 99.20%under the optimized conditions.The structure of the product was characterized by IR and 1 HNMR and the purity of the 4,4′-diphenyldicarboxylic acid was determined by HPLC.The synthetic process had the advantages of environmental friendliness,simple process operation,high conversion rate,high yield and good economic performance,and was suitable for large-scale industrial production.
4,4′-diphenyldicarboxylic acid was synthesized by the reaction of chlorination and hydrolysis from the 4,4′-dimethylbiphenyl which was the byproducts of pharmaceutical intermediates.The mechanism of the chlorination reaction was discussed and the effects of reaction parameters on the yield of 4,4′-diphenyldicarboxylic acid were studied via orthogonal experiment.The total yield of the reaction was 93.40%and the purity was 99.20%under the optimized conditions.The structure of the product was characterized by IR and 1 HNMR and the purity of the 4,4′-diphenyldicarboxylic acid was determined by HPLC.The synthetic process had the advantages of environmental friendliness,simple process operation,high conversion rate,high yield and good economic performance,and was suitable for large-scale industrial production.
引文
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[3]陈旭,宋歌,戴钧明,等.联苯二甲酸共聚改性PET的合成及热性能研究[J].合成纤维工业,2010,33(3):19-21.
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[14]白燕,黄方方,郭鹏涛,等.反相高效液相色谱法测定4,4′-联苯二甲酸[J].福建分析测试,2019,28(1):60-62.
[15]阿布都热西提·阿布力克木,买里克扎提·买合木提,刘丛.合成4,4′-联苯二甲酸的新方法[J].化学试剂,2009,31(3):225-226.
[2]D·R·法格博格.含有4,4′-联苯二甲酸、1,4-环己烷二甲醇和紫外线吸收化合物的共聚聚酯和由其制成的制品[P].CN:1409738A,2003-04-09.
[3]陈旭,宋歌,戴钧明,等.联苯二甲酸共聚改性PET的合成及热性能研究[J].合成纤维工业,2010,33(3):19-21.
[4]郑楠,李煜,叱静,等.由二咪唑和二羧基混合配体构筑的Cu(Ⅱ)配合物[J].河北师范大学学报:自然科学版,2016,(6):514-518.
[5]葛洪玉,马卫兴.4,4′-联苯二甲酸的合成[J].兰州理工大学学报,2007,33(3):69-71.
[6]石林,李翔,刘小成,等.4,4′-联苯二甲酸的合成研究[J].河南化工,2008,25(4):23-24.
[7]Matsuda T,Nakamura T,Sasakawa A et al.Preparation process of biphenyl-4,4′-dicarboxylic acid[P].US:4970338,1990-11-13.
[8]Abiraj K,Srinivasa G R,Gowda D C.Novel and efficient synthesis of symmetrical functionalized biaryls using zinc and triethylammonium formate[J].Synlett,2004,35(33):877-879.
[9]胡国宜,胡锦平,郑建龙.4,4′-联苯二甲酸的制备方法[P].CN:106146286A,2016-11-23.
[10]亓亮,闻永举,吕美云,等.沙坦联苯的合成研究[J].化学研究与应用,2015(1):107-109.
[11]秦海敏,喻宗沅,容如滨,等.2-氰基-4′-甲基联苯的合成进展[J].化学与生物工程,2007(03):5-7.
[12]史达清,陈伟兴.对二甲苯氯化反应的研究[J].江苏师范大学学报(自然科学版),1993(4):41-42.
[13]吴统立,李棋,李长彪.对二甲苯液相连续侧链氯化制备α,α′-二氯对二甲苯的研究[J].云南化工,1985(3):17-25.
[14]白燕,黄方方,郭鹏涛,等.反相高效液相色谱法测定4,4′-联苯二甲酸[J].福建分析测试,2019,28(1):60-62.
[15]阿布都热西提·阿布力克木,买里克扎提·买合木提,刘丛.合成4,4′-联苯二甲酸的新方法[J].化学试剂,2009,31(3):225-226.