(1S,4R)-4,7,7-三甲基-6-氧杂二环[3.2.1]辛烷-1,4-二醇的一步催化合成及其除草活性

doi:10.3969/j.issn.1673-5854.2018.03.004

生物质化学工程 ›› 2018, Vol. 52 ›› Issue (3): 23-28.doi: 10.3969/j.issn.1673-5854.2018.03.004

(1S,4R)-4,7,7-三甲基-6-氧杂二环[3.2.1]辛烷-1,4-二醇的一步催化合成及其除草活性

谢志鹏, 黄道战, 黄燕培, 黄燕妮

广西民族大学化学与化工学院, 广西南宁 530008

收稿日期:2017-09-22 出版日期:2018-05-30 发布日期:2018-05-31
通讯作者: 黄道战,副教授,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。 E-mail:huangdaozhan@gxun.edu.cn
作者简介:谢志鹏(1992-),男,湖北红安人,硕士生,主要从事林产化工、有机合成研究
基金资助:
国家自然科学基金资助项目（31460174）；广西研究生教育创新计划项目（gxun-chxzs2016113）

One-step Catalytic Synthesis and Herbicidal Activity of (1S,4R)-4,7,7-Trimethyl-6-oxabicyclo[3.2.1] octane-1,4-diol

XIE Zhipeng, HUANG Daozhan, HUANG Yanpei, HUANG Yanni

College of Chemistry and Chemical Engineering, Guangxi University for Nationalities, Nanning 530008, China

Received:2017-09-22 Online:2018-05-30 Published:2018-05-31

摘要/Abstract

摘要： 以过氧磷钼钨酸十六烷基吡啶盐（HPP）为氧化-酸双功能相转移催化剂，30%（质量分数）的H₂O₂为氧化剂，催化异松油烯一步转化合成（1S，4R）-4，7，7-三甲基-6-氧杂二环[3.2.1]辛烷-1，4-二醇（2）。优化后的反应条件为异松油烯用量4 mmol，催化剂HPP的用量7.35%（以异松油烯质量计），溶剂氯仿用量0.8 mL，反应物料比（H₂O₂与异松油烯物质的量比）值为3，35℃反应6 h，此条件下异松油烯的转化率高达100%，化合物2的产率达到29%。红外光谱、核磁共振谱及单晶X衍射表征结果表明成功合成了化合物2。初步的除草活性实验结果表明：化合物2能抑制黑麦草根和芽的生长，在120 mmol/L浓度下，对黑麦草根和芽生长的抑制率分别高达91.8%和80.7%，与已报道的1，8-桉树脑相比，化合物2对黑麦草的抑制作用更好。

关键词: 单萜氧杂双环二醇, 一步催化合成, 异松油烯, 过氧杂多酸盐, 除草活性

Abstract: (1S,4R)-4,7,7-trimethyl-6-oxabicyclo[3.2.1]octane-1,4-diol(2) was synthesized from terpinolene by using hexadecyl pyridinium peroxo heteropolyoxomolybdotungstate(HPP) as redox-acid bifunctional catalyst and 30%(mass fraction) H₂O₂ as oxidant. The optimal conditions for the reaction were terpinolene 4 mmol, HPP catalyst 7.35%(calculated by the mass of terpinolene), solvent chloroform 0.8 mL, the reaction material ratio(molar ratio of H₂O₂ and terpinolene) 3, reaction temperature 35℃, reaction time 6 h. Under these conditions, the conversion rate of terpinolene reached 100% and the yield of compound 2 reached 29%. The molecular structure was identified by means of IR, NMR and single crystal X-ray diffraction. The preliminary herbicidal activity assay indicated that compound 2 showed excellent inhibitory effect against the root growth and shoot elongation of ryegrass(Lolium rigidum); the inhibition rates against the root growth and shoot elongation were up to 91.8% and 80.7%, respectively, at the concentration of 120 mmol/L. Compared with the reported 1, 8-cineole, compound 2 had better inhibitory effect on ryegrass.

Key words: monoterpene oxabicyclodiol, one-step catalytic synthesis, terpinolene, peroxypolyoxometalate, herbicidal activity

中图分类号:

TQ35

谢志鹏, 黄道战, 黄燕培, 黄燕妮. (1S,4R)-4,7,7-三甲基-6-氧杂二环[3.2.1]辛烷-1,4-二醇的一步催化合成及其除草活性[J]. 生物质化学工程, 2018, 52(3): 23-28.

XIE Zhipeng, HUANG Daozhan, HUANG Yanpei, HUANG Yanni. One-step Catalytic Synthesis and Herbicidal Activity of (1S,4R)-4,7,7-Trimethyl-6-oxabicyclo[3.2.1] octane-1,4-diol[J]. bce, 2018, 52(3): 23-28.

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(1S,4R)-4,7,7-三甲基-6-氧杂二环[3.2.1]辛烷-1,4-二醇的一步催化合成及其除草活性

One-step Catalytic Synthesis and Herbicidal Activity of (1S,4R)-4,7,7-Trimethyl-6-oxabicyclo[3.2.1] octane-1,4-diol

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