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

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 mmolα-蒎烯、5 m L溶剂三氯甲烷、0.2 g催化剂、3.3 m L 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。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

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.国家自然科学基金资助项目(31460174);广西省自然科学基金资助项目(2011GXNSFA018057);广西省科学研究与技术开发计划资助项目(1348006-10

Efficient Oxidation of 3-Carene to Synthesize 3,4-Epoxycarane Catalyzed by Hexadecyl Pyridinium Peroxoheteropolyoxomolybdotungstate

以过氧磷钼钨酸十六烷基吡啶盐Cat-PMo2W2O24为催化剂,质量分数为30%的H2O2为氧化剂,催化3-蒈烯选择性环氧化合成3,4-环氧蒈烷。考察了溶剂种类、反应温度、催化剂用量、H2O2用量及反应时间对底物转化率与环氧选择性的影响,确定了最佳反应条件为:3-蒈烯12 mmol,溶剂三氯甲烷5 m L,催化剂用量为2.45%(即其质量与3-蒈烯质量的百分数,下同),H2O2与3-蒈烯摩尔比值为1.1,反应温度35℃,反应时间6 h;在最佳条件下,3-蒈烯的转化率和3,4-环氧蒈烷的选择性分别为99.1%和94.8%。Abstract: The oxidation of 3-carene to synthesize 3，4 -epoxycarane catalyzed by hexadecyl pyridinium peroxoheteropolyoxomolybdotungstate( Cat-PMo2W2O24 ) using mass fraction 30% aqueous solution of H2O2 as oxidant has been carried out． The influence of various reaction parameters， including nature of solvent， temperature，catalyst amount，oxidant amount and time on the epoxidation reaction was investigated． Under the optimum conditions( 3-carene 12 mmol; chloroform as solvent 5 mL; reaction temperature 35 ℃; catalyst amount 2. 45%( based on substrate) ; molar ratio of H2O2 to 3-carene，1. 1; reaction time 6 h) ，99. 1% conversion of 3-carene with 94. 8% selectivity towards epoxide 3，4- epoxycarane was achieved．国家自然科学基金(31460174);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

对孟烷-1,2,4-三醇的合成及对水稻稗草的除草活性研究

在1,2-二氯乙烷中,以30%H2O2为氧化剂,过氧磷钨酸季铵盐[π-C5H5N(CH2)11CH3]3PW4O32为催化剂,催化松油烯-4-醇的氧化反应生成对孟烷-1,2,4-三醇;该产物以白色粉末状固体析出,容易通过简单过滤方法分离,其结构经元素分析、红外光谱、1H NMR及13C NMR确证。本实验最佳合成工艺条件为:松油烯-4-醇12.3 mmol,1,2-二氯乙烷5 mL,过氧化氢与松油烯-4-醇的物质的量之比1.25∶1,催化剂用量为2.98%(以松油烯-4-醇的质量分数计),温度50℃,反应时间1.5 h;在此条件下,松油烯-4-醇的转化率和对孟烷-1,2,4-三醇的产率分别达到99.8%和58.0%,纯度达到98%以上。初步除草活性测试表明,对孟烷-1,2,4-三醇对水稻稗草种子萌发后胚根与幼芽的生长具有明显的影响,在10 mmol/L的浓度下,根长抑制率和芽长抑制率分别为100%和81.4%。广西科技攻关项目(1348006-10);广西自然科学基金(2011GXNSFA018057);广西民族大学引进人才科研启