(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
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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)H_2O_2 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 H_2O_2 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.
( 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)H_2O_2 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 H_2O_2 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.
引文
[1]POWELL J E.6-Oxabicyclo[3.2.1]octane derivatives and compositions and methods for controlling plant growth:US 4486219[P].1984-12-04.
[2]POWELL J E.Trimethyl 6-oxabicyclo[3.2.1]octan-4-ols and 4-ones:US 4536586[P].1985-08-20.
[3]POPOVA L A,BIBA V I,PRISHCHENPENKO V M,et al.Synthesis of monoterpene oxabicyclodiols starting fromα-pinene[J].Journal of General Chemistry of the USSR in English Translation,1992,62(72):1346-1350.
[4]COSTA V V,ROCHA K A,SOUSA L F,et al.Isomerization ofα-pinene oxide over cerium and tin catalysts:Selective synthesis of transcarveol and trans-sobrerol[J].Journal of Molecular Catalysis A:Chemical,2011,345(1/2):69-74.
[5]黄道战,朱守记,蓝虹云,等.一种制备(3R,4R)-4,7,7-三甲基-6-氧杂二环[3.2.1]辛烷-3,4-二醇的新方法[J].林产化学与工业,2015,35(1):9-15.
[6]黄道战,朱守记,蓝虹云,等.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[J].合成化学,2015,23(3):185-190.
[7]ZHAO Z Y,HUANG D Z,LAN H Y,et al.Novel synthesis,crystal structure and herbicidal activity of(3R,4R)-4,7,7-trimethyl-6-oxabicyclo[3.2.1]octane-3,4-diol[J].Chinese Journal of Structure Chemistry,2015,34(12):1819-1824.
[8]SALOMATINA O V,YAROVAYA O I,KORCHAGINA D V,et al.Acid-catalyzed transformations of diepoxy derivatives of terpinolene[J].Russian Journal of Organic Chemistry,2011,47(10):1479-1486.
[9]黄道战,农秀李,黄雪梅,等.过氧磷钼钨酸盐催化一步法合成2-羟基-1,4-桉树脑[J].精细化工,2015,32(10):1185-1189.
[10]ZHAO W,MA B,HUA H,et al.Environmentally friendly and highly efficient alkenes epoxidation system consisting of[π-C5H5N(CH2)11CH3]3PW4O32/H2O2/ethyl acetate/olefin[J].Catalysis Communications,2008,9(14):2455-2459.
[11]SHELDRICK G M.Shelxl-97,Program for X-ray Crystal Structure Refinement[M].Germany:University of G9ttingen,1997.
[12]乌婧,王宝雷,李永红,等.N-苄氧/烷氧苯基-4,6-二取代嘧啶胺类化合物的合成、晶体结构及除草活性[J].高等学校化学学报,2008,29(8):1583-1587.
[13]黄道战,王小淑,朱守记,等.对孟烷-1,2,4-三醇的合成及对水稻稗草的除草活性研究[J].生物质化学工程,2013,47(5):40-44.
[14]BARTON A F M,CLARKE B R,DELL B,et al.Post-emergent herbicidal activity of cineole derivatives[J].Journal of Pest Science,2014,87(3):531-541.
[2]POWELL J E.Trimethyl 6-oxabicyclo[3.2.1]octan-4-ols and 4-ones:US 4536586[P].1985-08-20.
[3]POPOVA L A,BIBA V I,PRISHCHENPENKO V M,et al.Synthesis of monoterpene oxabicyclodiols starting fromα-pinene[J].Journal of General Chemistry of the USSR in English Translation,1992,62(72):1346-1350.
[4]COSTA V V,ROCHA K A,SOUSA L F,et al.Isomerization ofα-pinene oxide over cerium and tin catalysts:Selective synthesis of transcarveol and trans-sobrerol[J].Journal of Molecular Catalysis A:Chemical,2011,345(1/2):69-74.
[5]黄道战,朱守记,蓝虹云,等.一种制备(3R,4R)-4,7,7-三甲基-6-氧杂二环[3.2.1]辛烷-3,4-二醇的新方法[J].林产化学与工业,2015,35(1):9-15.
[6]黄道战,朱守记,蓝虹云,等.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[J].合成化学,2015,23(3):185-190.
[7]ZHAO Z Y,HUANG D Z,LAN H Y,et al.Novel synthesis,crystal structure and herbicidal activity of(3R,4R)-4,7,7-trimethyl-6-oxabicyclo[3.2.1]octane-3,4-diol[J].Chinese Journal of Structure Chemistry,2015,34(12):1819-1824.
[8]SALOMATINA O V,YAROVAYA O I,KORCHAGINA D V,et al.Acid-catalyzed transformations of diepoxy derivatives of terpinolene[J].Russian Journal of Organic Chemistry,2011,47(10):1479-1486.
[9]黄道战,农秀李,黄雪梅,等.过氧磷钼钨酸盐催化一步法合成2-羟基-1,4-桉树脑[J].精细化工,2015,32(10):1185-1189.
[10]ZHAO W,MA B,HUA H,et al.Environmentally friendly and highly efficient alkenes epoxidation system consisting of[π-C5H5N(CH2)11CH3]3PW4O32/H2O2/ethyl acetate/olefin[J].Catalysis Communications,2008,9(14):2455-2459.
[11]SHELDRICK G M.Shelxl-97,Program for X-ray Crystal Structure Refinement[M].Germany:University of G9ttingen,1997.
[12]乌婧,王宝雷,李永红,等.N-苄氧/烷氧苯基-4,6-二取代嘧啶胺类化合物的合成、晶体结构及除草活性[J].高等学校化学学报,2008,29(8):1583-1587.
[13]黄道战,王小淑,朱守记,等.对孟烷-1,2,4-三醇的合成及对水稻稗草的除草活性研究[J].生物质化学工程,2013,47(5):40-44.
[14]BARTON A F M,CLARKE B R,DELL B,et al.Post-emergent herbicidal activity of cineole derivatives[J].Journal of Pest Science,2014,87(3):531-541.