(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

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。

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

(1S,4R)-4,7,7-trimethyl-6-oxabicyclo3.2.1]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.