CN105660667A - 一种高效农业除草剂 - Google Patents
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
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- A01N35/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having two bonds to hetero atoms with at the most one bond to halogen, e.g. aldehyde radical
- A01N35/06—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having two bonds to hetero atoms with at the most one bond to halogen, e.g. aldehyde radical containing keto or thioketo groups as part of a ring, e.g. cyclohexanone, quinone; Derivatives thereof, e.g. ketals
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Abstract
本发明公开了一种高效农业除草剂,该除草剂中含有异丙隆以及一种从王不留行中提取分离得到的结构新颖的化合物,该化合物为首次报道。本发明还提供了该化合物的制备方法,包括将干燥的蚌兰叶粉碎、乙醇热回流提取、溶剂液液萃取、乙酸乙酯萃取物用大孔树脂除杂、正相硅胶和反相硅胶分离等步骤。试验结果表明,本发明提供的除草剂可以选择性地抑制麦田菵草、日本看麦娘等一年生禾本科杂草和繁缕、牛繁缕等阔叶杂草的生长。
Description
技术领域
本发明属于农业领域,具体涉及一种高效农业除草剂。
背景技术
小麦、大米、玉米等是我国最重要的几种粮食作物,粮食产量的高低直接关系到国家粮食安全、社会稳定与和谐。对于小麦这一北方主要的农作物品种,硬草、看麦娘、日本看麦娘、罔草等恶性杂草的无序增长严重影响小麦产量。其中近年来日本看麦娘和罔草的为害面积和严重度逐年加大,少数地区的个别田块小麦产量损失高达2~3成,最严重的田块形成草荒,解决这两种杂草的危害已经迫在眉睫,成为小麦病虫害防止领域最主要的问题之一。
目前,针对小麦禾本科杂草所应用的药剂主要有炔草酯、精恶唑禾草灵、绿麦隆、异丙隆及异丙隆·绿麦隆等,经生产应用的实践证明,这些药剂对麦田硬草、普通看麦娘防除效果较好,对日本看麦娘和罔草的防除效果仅有30-40%较差。从目前已经上市的除草剂品种看来,迄今为止还没有一个对麦田菵草、日本看麦娘具有优良防效的单剂或复配剂产品,由于缺乏此类除草剂,导致麦农在田间除草时只能根据自身经验对不同的除草剂进行随意搭配混用,缺乏科学性,防除效果不稳定,时常发生药害造成小麦减产。
在现有技术中,也有人尝试使用多成分复方除草剂解决上述问题,例如中国专利201210009678.7公开了一种三组分复方复合除草组合物,由于对各成分用量的不科学调配以及三种不同分子结构的化学成分出现了一定的抵触,导致其实际应用时除草效果未如预料的理想,同时三种成分复配使用大大增加了实际的应用难度和成本。中国专利201010617746.9也公开了一种除草剂,同样存在与上述方案类似的问题。
发明内容
本发明的目的在于提供一种高效农业除草剂,该除草剂可以选择性地抑制麦田菵草、日本看麦娘等一年生禾本科杂草和繁缕、牛繁缕等阔叶杂草的生长。
上述目的是通过下面的技术方案得以实现的:
一种高效农业除草剂,含有异丙隆和如下结构所示的化合物(Ⅰ),
进一步地,所述的高效农业除草剂中所述化合物(Ⅰ)与异丙隆的物质的量之比为3~5:1。
所述的化合物(Ⅰ)的制备方法,包含以下操作步骤:(a)将王不留行的干燥成熟种子粉碎,用80~90%乙醇热回流提取,合并提取液,浓缩至无醇味,依次用石油醚、乙酸乙酯和水饱和的正丁醇萃取,分别得到石油醚萃取物、乙酸乙酯萃取物和正丁醇萃取物;(b)步骤(a)中乙酸乙酯萃取物用大孔树脂除杂,先用10%乙醇洗脱6个柱体积,再用75%乙醇洗脱10个柱体积,收集75%乙醇洗脱液,减压浓缩得75%乙醇洗脱物浸膏;(c)步骤(b)中75%乙醇洗脱浸膏用正相硅胶分离,依次用体积比为80:1、55:1、30:1、15:1和1:1的二氯甲烷-甲醇梯度洗脱得到5个组分;(d)步骤(c)中组分4用正相硅胶进一步分离,依次用体积比为20:1、15:1和10:1的二氯甲烷-甲醇梯度洗脱得到3个组分;(e)步骤(d)中组分2用十八烷基硅烷键合的反相硅胶分离,用体积百分浓度为75%的甲醇水溶液等度洗脱,收集8~10个柱体积洗脱液,洗脱液减压浓缩得到化合物(Ⅰ)。
进一步地,所述大孔树脂为AB-8型大孔吸附树脂。
进一步地,所述用乙醇热回流提取采用的乙醇浓度为85%。
所述的化合物(Ⅰ)在制备农业除草剂方面的应用。
本发明的有益效果:
本发明提供的除草剂可以选择性地抑制麦田菵草、日本看麦娘等一年生禾本科杂草和繁缕、牛繁缕等阔叶杂草的生长。
具体实施方式
下面结合实施例进一步说明本发明的实质性内容,但并不以此限定本发明保护范围。尽管参照较佳实施例对本发明作了详细说明,本领域的普通技术人员应当理解,可以对本发明的技术方案进行修改或者等同替换,而不脱离本发明技术方案的实质和范围。
实施例1:化合物(Ⅰ)分离制备及结构确证
试剂来源:乙醇、石油醚、乙酸乙酯、正丁醇、二氯甲烷为分析纯,购自上海凌峰化学试剂有限公司,甲醇,分析纯,购自江苏汉邦化学试剂有限公司。
制备方法:(a)将王不留行的干燥成熟种子(1kg)粉碎,用85%乙醇热回流提取,合并提取液,浓缩至无醇味,依次用石油醚、乙酸乙酯和水饱和的正丁醇萃取,分别得到石油醚萃取物、乙酸乙酯萃取物和正丁醇萃取物;(b)步骤(a)中乙酸乙酯萃取物用AB-8型大孔树脂除杂,先用10%乙醇洗脱6个柱体积,再用75%乙醇洗脱10个柱体积,收集75%乙醇洗脱液,减压浓缩得75%乙醇洗脱物浸膏;(c)步骤(b)中75%乙醇洗脱浸膏用正相硅胶分离,依次用体积比为80:1(8个柱体积)、55:1(8个柱体积)、30:1(6个柱体积)、15:1(8个柱体积)和1:1(5个柱体积)的二氯甲烷-甲醇梯度洗脱得到5个组分;(d)步骤(c)中组分4用正相硅胶进一步分离,依次用体积比为20:1(8个柱体积)、15:1(10个柱体积)和10:1(6个柱体积)的二氯甲烷-甲醇梯度洗脱得到3个组分;(e)步骤(d)中组分2用十八烷基硅烷键合的反相硅胶分离,用体积百分浓度为75%的甲醇水溶液等度洗脱,收集8~10个柱体积洗脱液,洗脱液减压浓缩得到化合物(Ⅰ)(2.3g)。
结构确证:白色粉末,HR-ESIMS显示[M+H]+为m/z303.2284,结合核磁特征可得分子式为C20H30O2,不饱和度为6。核磁共振氢谱数据δH(ppm,CDCl3,500MHz):H-2(1.65,m),H-3(1.59,m),H-3(2.21,m),H-4(1.92,dd,J=7.1,17.3Hz),H-4(2.31,m),H-7(2.21,m),H-7(2.26,m),H-8(2.01,d,J=13.2Hz),H-8(2.57,dt,J=4.6,13.2Hz),H-10(5.02,s),H-12(3.37,s),H-14(5.61,dd,J=2.4,12.2Hz),H-15(1.97,d,J=15.6Hz),H-15(2.82,ddd,J=6.6,12.2,15.6Hz),H-16(0.87,s),H-17(0.97,s),H-18(1.73,s),H-19(3.97,d,J=11.6Hz),H-19(4.22,d,J=11.6Hz),H-20(1.63,s);核磁共振碳谱数据δC(ppm,CDCl3,125MHz):37.8(C,1-C),42.5(CH,2-C),27.2(CH2,3-C),31.6(CH2,4-C),127.5(C,5-C),136.4(C,6-C),26.5(CH2,7-C),38.4(CH2,8-C),145.8(C,9-C),136.1(CH,10-C),196.8(C,11-C),58.4(CH2,12-C),129.2(C,13-C),134.3(CH,14-C),33.7(CH2,15-C),24.6(CH3,16-C),33.1(CH3,17-C),22.2(CH3,18-C),60.3(CH2,19-C),18.9(CH3,20-C)。红外波谱表明该化合物含有羟基(3335cm-1),羰基(1755cm-1)和烯烃(1612cm-1)基团。13C-NMR、DEPT和HSQC谱中显示有20个碳信号,包括四个甲基δC24.6,33.1,22.2,18.9;七个亚甲基(一个连氧碳)δC27.2,31.6,26.5,38.4,58.4,33.7,60.3;三个次甲基(两个烯烃碳)δC42.5,136.1,134.3;以及六个季碳(一个羰基碳,四个烯烃碳)δC37.8,127.5,136.4,145.8,196.8,129.2。HMBC谱中H2-7与C-6;H2-12与C-13;H-14与C-12和C-13;Me-16与C-1,C-2,C-6和C-17;Me-17与C-1,C-2,C-6和C-16;Me-18与C-4,C-5和C-6;H2-19与C-13和C-14;Me-20与C-8,C-9和C-10的相关性以及1H-1HCOSY谱中H-14与H2-15,H-2,H2-3和H2-4;以及H2-7与H2-8的相关性表明该化合物是由环己烯与环十二碳二烯酮通过C-1,C-2与C-6位连接形成的桥环化合物。综合氢谱、碳谱、HMBC谱和NOESY谱,以及文献相关类型核磁数据,可基本确定该化合物如下所示,立体构型进一步通过ECD试验确定,理论值与实验值基本一致。
实施例2:除草剂的制备和除草效果
取适量溶剂DMSO将异丙隆和化合物(Ⅰ)溶解,再用自来水稀释,异丙隆的摩尔浓度为80μg/ml,化合物(Ⅰ)的摩尔浓度为320μg/ml。化合物(Ⅰ)的摩尔浓度为异丙隆摩尔浓度的3~5倍。
使用方法:一个星期喷洒两次。
以对麦田菵草、日本看麦娘、繁缕、牛繁缕的抑制率为考察指标,分别设置试验组一和试验组二,试验组一喷洒本发明提供的除草剂,试验组二的除草剂中仅含有与试验组一浓度相同的异丙隆。试验期限为1个月。结果见下表。
麦田菵草抑制率 | 日本看麦娘抑制率 | 繁缕抑制率 | 牛繁缕抑制率 | |
试验组一 | 96% | 99% | 98% | 98% |
试验组二 | 45% | 38% | 42% | 40% |
结果表明,本发明的除草剂中,化合物(Ⅰ)对除草效果发挥了非常重要的作用,说明本发明提供的除草剂可以选择性地抑制麦田菵草、日本看麦娘等一年生禾本科杂草和繁缕、牛繁缕等阔叶杂草的生长。
上述实施例的作用在于说明本发明的实质性内容,但并不以此限定本发明的保护范围。本领域的普通技术人员应当理解,可以对本发明的技术方案进行修改或者等同替换,而不脱离本发明技术方案的实质和保护范围。
Claims (6)
1.一种高效农业除草剂,其特征在于:含有异丙隆和如下结构所示的化合物(Ⅰ),
2.根据权利要求1所述的高效农业除草剂,其特征在于:所述化合物(Ⅰ)与异丙隆的物质的量之比为3~5:1。
3.权利要求1或2所述的化合物(Ⅰ)的制备方法,其特征在于包含以下操作步骤:(a)将王不留行的干燥成熟种子粉碎,用80~90%乙醇热回流提取,合并提取液,浓缩至无醇味,依次用石油醚、乙酸乙酯和水饱和的正丁醇萃取,分别得到石油醚萃取物、乙酸乙酯萃取物和正丁醇萃取物;(b)步骤(a)中乙酸乙酯萃取物用大孔树脂除杂,先用10%乙醇洗脱6个柱体积,再用75%乙醇洗脱10个柱体积,收集75%乙醇洗脱液,减压浓缩得75%乙醇洗脱物浸膏;(c)步骤(b)中75%乙醇洗脱浸膏用正相硅胶分离,依次用体积比为80:1、55:1、30:1、15:1和1:1的二氯甲烷-甲醇梯度洗脱得到5个组分;(d)步骤(c)中组分4用正相硅胶进一步分离,依次用体积比为20:1、15:1和10:1的二氯甲烷-甲醇梯度洗脱得到3个组分;(e)步骤(d)中组分2用十八烷基硅烷键合的反相硅胶分离,用体积百分浓度为75%的甲醇水溶液等度洗脱,收集8~10个柱体积洗脱液,洗脱液减压浓缩得到化合物(Ⅰ)。
4.根据权利要求3所述的化合物(Ⅰ)的制备方法,其特征在于:所述大孔树脂为AB-8型大孔吸附树脂。
5.根据权利要求3所述的化合物(Ⅰ)的制备方法,其特征在于:所述用乙醇热回流提取采用的乙醇浓度为85%。
6.权利要求1或2所述的化合物(Ⅰ)在制备农业除草剂方面的应用。
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