双官能单萜氧杂二环二醇乙酸酯类衍生物的合成及其除草活性

Synthesis and Herbicidal Activities of Bifunctional Acetic Acid Ester Derivatives of Monoterpene Oxabicyclodiol

以(3R,4R)-4,7,7-三甲基-6-氧杂二环[3,2,1]辛烷-3,4-二醇(1)和乙酰氯(2)为原料,经"一锅法"制得混合物Ⅰ;Ⅰ经分离纯化得4个新型的双官能单萜氧杂二环二醇乙酸酯类衍生物(3a^3d),其结构经1H NMR,13C NMR,FT-IR和HR-MS表征。考察了物料比r[n(2)∶n(1)]和反应时间对3a^3d相对浓度的影响。结果表明,在反应条件[1 5 mmol,r=7,回流反应7 h]下,3a^3d的相对浓度分别为21.6%,15.6%,37.9%和24.9%;在反应条件[1 5 mmol,r=4,回流反应7 h]下,3a^3d的相对浓度分别为50.7%,36.6%,7.84%和4.86%。用培养皿法测试了1和3a^3d的除草活性。实验结果表明,1和3a^3d均能显著抑制一年生黑麦草胚根与胚芽生长;在用药浓度为5 mmol·L-1时,1和3a^3d对根长抑制率分别为55.1%,86.0%,84.2%,91.3%和97.5%;对芽长抑制率分别为55.1%,76.5%,92.8%,94.8%和98.4%。

Four novel acetic acid ester derivatives（3a-3d） were synthesized by the reaction of （3R, 4R） -4,7,7-trimethyl-6-oxabicyclo [ 3.2.1 ] octane-3,4-diol （ 1 ） with acetyl chloride （2） by one-pot method and then purified. The structures were characterized by 1H NMR, 13C NMR, FF-IR and HR-MS. Effects of material ratio { r[ n（2） ： n（1） ] } and reaction time on the relative concentration of 3a -3d were investigated. The resluts showed that the relative concentration of 3a - 3d were 21.6%, 15.6%, 37.9% and 24.9% under the condition of 1 5 mmol, r=7 and reflux for7 h. The relative concentra- tion of3a -3d were 55.1%, 86.0%, 84.2%, 91.3% and 97.5% under the condition of 1 5 mmol, r =4 and reflux for 7 h. The herbicidal activities of 1 and 3a -3d were tested by dish dipping method. The results showed that 1 and 3a - 3d exhibited obvious inhibition activities against the growth of annual ryegrass root and shoot. The inhibition rate of 1 and 3a - 3d against root growth at 55 mmol·L^-1 were 55.1%, 86.0%, 84.2%, 91.3% and 97.5%, respectively. The inhibition rate of 1 and 3a -3d against shoot elongation at 5 mmol ·L^-1 were 55.1%, 76.5%, 92.8%, 94.8% and 98.4%, respectively.