有机化学 ›› 2015, Vol. 35 ›› Issue (11): 2412-2419.DOI: 10.6023/cjoc201505022 上一篇    下一篇

研究简报

3-亚甲基异苯并呋喃-1(3H)-酮及其衍生物合成新方法

王雅珍a, 朱星星b, 林伟a, 郑纯智a, 张继振a   

  1. a 江苏理工学院化学与环境工程学院 常州 213001;
    b 常州大学石油化工学院 常州 213164
  • 收稿日期:2015-05-13 修回日期:2015-06-11 发布日期:2015-07-08
  • 通讯作者: 张继振 E-mail:zhangjizhen_9@aliyun.com

A Novel Synthetic Method of 3-Methyleneisobenfuran- 1(3H)-one and Their Derivatives

Wang Yazhena, Zhu Xingxingb, Lin Weia, Zheng Chunzhia, Zhang Jizhena   

  1. a School of Chemistry and Environmental Engineering, Jiangsu Technology of University, Changzhou 213001;
    b School of Petrochemical Engineering, Changzhou University, Changzhou 213164
  • Received:2015-05-13 Revised:2015-06-11 Published:2015-07-08

报道了3-亚甲基异苯并呋喃-1(3H)-酮及其衍生物简易、高效的合成方法. 其特点是原料易得且价格低廉、反应条件温和、收率高. 该方法以2-甲基苯甲酸及其衍生物为原料, 经过酯化、自由基溴代和三苯基膦发生亲核取代反应合成了2-[(溴三苯基正膦基)甲基]苯甲酸甲酯及其衍生物; 随后发生Wittig反应、羧酸酯碱性条件下水解得到2-乙烯基苯甲酸及其衍生物; 接着和碘(NBS)发生环合反应, 生成3-碘(溴)甲基异苯并呋喃-1(3H)-酮及其衍生物; 最后消除卤化氢得到目标化合物.

关键词: 3-亚甲基异苯并呋喃-1(3H)-酮, 3-碘(溴)甲基异苯并呋喃-1(3H)-酮, 衍生物, 季鏻盐, Wittig反应, 合成

A novel and highly efficient synthesis of 3-methyleneisobenzofuran-1(3H)-one and the corresponding derivatives was reported. The new method was characterized with raw material easy to get, low manufacturing cost, mild reaction conditions and high yields. 2-Methylbenzoic acid and their derivatives were used as starting material, methyl 2-((bromotri- phenylphosphoranyl)methyl)benzoate and their derivatives were synthesized through esterification, free-radical bromination with N-bromobutanimide (NBS) and nucleophilic substitution with triphenylphosphine. After Wittig reaction and hydrolysis of carboxylic esters, 2-vinylbenzoic acid and their derivatives were obtained. Then through cyclization reaction with iodine (NBS), 3-iodo(bromo)methylisobenzofuran-1(3H)-one and their derivatives were obtained, which further react by elimination hydrogen halide with 1,8-diazabicyclo[5.4.0]under-7-ene to afford the target compounds. Eleven intermediates were new compounds.

Key words: 3-methyleneisobenzofuran-1(3H)-one, 3-iodo(bromo)methylisobenzofuran-1(3H)-one, derivatives, quaternary alkylphosphonium salt, Wittig reaction, synthesis