一种制备(3R,4R)-4,7,7-三甲基-6-氧杂二环[3.2.1]辛烷-3,4-二醇的新方法

doi:10.3969/j.issn.0253-2417.2015.01.002

林产化学与工业 ›› 2015, Vol. 35 ›› Issue (1): 9-15.doi: 10.3969/j.issn.0253-2417.2015.01.002

一种制备(3R,4R)-4,7,7-三甲基-6-氧杂二环[3.2.1]辛烷-3,4-二醇的新方法

黄道战, 朱守记, 蓝虹云, 雷福厚

广西民族大学化学化工学院; 广西林产化学与工程重点实验室, 广西南宁 530008

收稿日期:2013-10-08 出版日期:2015-02-25 发布日期:2015-03-05
作者简介:黄道战(1968-),男,广西横县人,高级实验师,博士,硕士生导师,主要从事林产化工、有机合成研究;E-mail:huangdaozhan@gxun.edu.cn。
基金资助:
广西科学研究与技术开发计划项目(1348006-10); 广西自然科学基金(2011GXNSFA018057);广西民族大学引进人才科研启动项目(2010QD020)

A Novel Method for Preparation of (3R,4R)-4,7,7-Trimethyl-6-oxabicyclo [3.2.1] octane-3,4-diol

HUANG Dao-zhan, ZHU Shou-ji, LAN Hong-yun, LEI Fu-hou

College of Chemistry and Chemical Engineering, Guangxi University for Nationalities;Guangxi Key Laboratory of Chemistry and Engineering of Forest Products, Nanning 530008, China

Received:2013-10-08 Online:2015-02-25 Published:2015-03-05

摘要/Abstract

摘要： 在催化剂过氧磷钨酸十二烷基吡啶盐(Cat-PW₄)的作用下, α-蒎烯与H₂O₂反应生成主要产物(3R,4R)-4,7,7-三甲基-6-氧杂二环[3.2.1] 辛烷-3,4-二醇。不同反应条件对反应转化率和选择性的实验结果表明,最佳反应条件为:12.8 mmol α-蒎烯、5 mL溶剂三氯甲烷、0.2 g催化剂、3.3 mL 30 %H₂O₂,反应温度40 ℃,反应时间3 h,α-蒎烯转化率和产物的选择性分别为94.7 %和39.8 %。反应结束后,该产物存在于水相和有机相中,通过萃取和重结晶分离提纯,得率11 %,纯度达到98 %;其分子结构通过红外光谱、紫外光谱、¹H核磁共振谱、¹³C核磁共振谱、低分辨率质谱及高分辨率质谱确证。

关键词: (3R, 4R)-4, 7, 7-三甲基-6-氧杂二环[3.2.1] 辛烷-3, 4-二醇, α-蒎烯, H₂O₂, 过氧磷钨酸十二烷基吡啶盐

Abstract: (3R,4R)-4,7,7-trimethyl-6-oxabicyclo [3.2.1] octane-3,4-diol was prepared by reaction of α-pinene with 30 % H₂O₂ in presence of dodecyl pyridinium peroxyopolyphosphotungstate catalyst (Cat-PW₄). The effects of different reaction factors on the conversion rate and selectivity were investigated. The optimal conditions are as follows: α-pinene, 12.8 mmol; chloroform as solvent, 5 mL; reaction temperature, 40 ℃; Cat-PW₄ as catalyst, 0.2 g; 30 % H₂O₂, 3.3 mL; reaction time, 3 h. Under these conditions, the conversion rate of α-pinene reached 94.7 %, and the selectivity for the title compound reached 39.8 %. The product existed both in aqueous phase and organic phase and could be isolated from reaction mixtures by extraction and re-crystallization. It was structurally identified by means of IR, UV, ¹H NMR, ¹³C NMR, GC/MS, and HR-ESI-MS. Its yield and purity were 11 % and 98 %, respectively.

Key words: (3R,4R)-4,7,7-trimethyl-6-oxabicyclo[3.2.1] octane-3,4-diol, α-pinene, H₂O₂, dodecyl pyridinium peroxyopolyphosphotungstate

中图分类号:

TQ351

黄道战, 朱守记, 蓝虹云, 雷福厚. 一种制备(3R,4R)-4,7,7-三甲基-6-氧杂二环[3.2.1]辛烷-3,4-二醇的新方法[J]. 林产化学与工业, 2015, 35(1): 9-15.

HUANG Dao-zhan, ZHU Shou-ji, LAN Hong-yun, LEI Fu-hou. A Novel Method for Preparation of (3R,4R)-4,7,7-Trimethyl-6-oxabicyclo [3.2.1] octane-3,4-diol[J]. Chemistry and Industry of Forest Products, 2015, 35(1): 9-15.

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一种制备(3R,4R)-4,7,7-三甲基-6-氧杂二环[3.2.1]辛烷-3,4-二醇的新方法

A Novel Method for Preparation of (3R,4R)-4,7,7-Trimethyl-6-oxabicyclo [3.2.1] octane-3,4-diol

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