中华医学超声杂志

应用化学 ›› 2010, Vol. 27 ›› Issue (07): 764-768.DOI: 10.3724/SP.J.1095.2010.90672

• 研究论文 • 上一篇    下一篇

酸催化甘油与苯甲醛缩合制备六员环缩醛

王桂敏,单玉华*,张元元,罗娜,汪友谊,蒋志国,李明时   

  1. (江苏工业学院江苏省精细化工重点实验室 常州 213164)
  • 收稿日期:2009-10-16 修回日期:2009-12-02 出版日期:2010-07-10 发布日期:2010-07-10
  • 通讯作者: 单玉华,男,博士,教授; E-mail:yhshan@jpu.edu.cn; 研究方向：可再生资源利用、催化及环保技术开发
  • 基金资助:
    江苏省高校自然科学重大基础研究项目（05KJA43004）江苏省精细石油化工重点实验室开放研究课题(200606)江苏工业学院科技资金资助项目(2005)及江苏工业学院大学生创新资金资助项目(2008)

Acid-Catalyzed Synthesis of Six-Membered Cyclic Acetal from Condensation of Benzaldehyde and Glycerol

WANG Gui-Min, SHAN Yu-Hua*, ZHANG Yuan-Yuan, LUO Na, WANG You-Yi, JIANG Zhi-Guo, LI Ming-Shi   

  1. (Key Laboratory of Jiangsu Fine Chemical Engineering,Jiangsu Polytechnic University,Changzhou 213164)
  • Received:2009-10-16 Revised:2009-12-02 Published:2010-07-10 Online:2010-07-10
  • Contact: shan yu-hua

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摘要：

比较了对甲苯磺酸（PTSA）、磷钨酸（PWA）、KHSO4和FeCl3催化对甘油与苯甲醛的缩合反应收率，及对产物中六元环缩醛5-羟基-2-苯基-1,3-二氧六环(1)与五元环缩醛4-羟甲基-2-苯基-1,3-二氧五环(2)比例的影响。 当以环己烷为带水剂及苯甲醛与甘油的摩尔比为2∶3的情况下，KHSO4为催化剂的缩合产物（1+2）收率较高，为96.8%；PTSA催化的缩合产物中，化合物1的比例最高(m(1)∶m(2)=48.6∶51.4)。 室温下PTSA、PWA、KHSO4和FeCl3均可催化化合物2向化合物1的转化。 在-20 ℃下，只有PTSA能催化化合物2向化合物1的转化。 在-20 ℃，PTSA催化化合物[STHZ]2转化成化合物1a,并以晶体形式从苯（40%）-石油醚（60%）中析出。 母液循环转化3次后，化合物1a的累计收率可达91.1%。

关键词: 羟基苯基二氧六环, 甘油, 苯甲醛, 缩醛, 酸催化缩合

Abstract:

Based on the condensation reaction of glycerol with benzaldehyde, the effects of acid catalysts (p-toluenesulfonic acid(PTSA), phosphotungstic acid(PWA), KHSO4 and FeCl3, respectively) on the yield of the condensation products and the mass ratio of 5-hydroxyl-2-phenyl-1,3-dioxane(1) to 4-hydroxymethyl-2-phenyl-1,3-dioxolane(2) were investigated. Comparison tests indicated that under the conditions of cyclohexane as water entrainer and n(benzalhydehyde)∶n(glycerol)=2∶3, KHSO4 gave the best yield(96.8%) of condensation products(compound 1+2) and PTSA yielded the highest proportion(m(1)∶m(2)=48.6∶51.4) of compound 1 in condensation products(compound 1+2. At room temperature, PTSA, PWA, KHSO4 and FeCl3 all can, but at -20 ℃, only PTSA can catalyze the transformation of compound2 to compound 1. Cis-5-hydroxyl-2-phenyl-1,3-dioxane(1a) was isolated by the catalytic transformation of compound 2 with PTSA at -20 ℃ and crystallized from a mixture of V(benzene)∶V(ligroin)=40∶60. Compound 1a was obtained by recycling the catalytic transformation of compound 2 in the mother liquor three times in a accumulative yield of 91.1%.

Key words: hydroxylphenyldioxane, glycerol, Benzaldehyde, acetals, acid-catalyzed condensation

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