(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

作　　者：谢志鹏 黄道战[1] 黄燕培 黄燕妮 XIE Zhipeng;HUANG Daozhan;HUANG Yanpei;HUANG Yanni(College of Chemistry and Chemical Engineering,Guangxi University for Nationalities,Nanning 530008,Chin)

机构地区：[1]广西民族大学化学与化工学院,广西南宁530008

出　　处：《生物质化学工程》2018年第3期23-28,共6页Biomass Chemical Engineering

基　　金：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)

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H_2O_2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 m L,反应物料比(H_2O_2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。（ 1 S,4 R）-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 m L,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.

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 

分 类 号：TQ35[化学工程]