CN111187214A - 氟苯双酰肼唑类化合物及其应用 - Google Patents
氟苯双酰肼唑类化合物及其应用 Download PDFInfo
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- JDTKMFFTJSSMPR-UHFFFAOYSA-N 4-chloro-5-ethyl-2-methylpyrazole-3-carbonyl chloride Chemical compound CCC1=NN(C)C(C(Cl)=O)=C1Cl JDTKMFFTJSSMPR-UHFFFAOYSA-N 0.000 description 1
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Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D231/00—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
- C07D231/02—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings
- C07D231/10—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D231/14—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D231/16—Halogen atoms or nitro radicals
-
- 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
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
- A01N43/56—1,2-Diazoles; Hydrogenated 1,2-diazoles
-
- 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
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
- A01N43/74—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms five-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,3
- A01N43/78—1,3-Thiazoles; Hydrogenated 1,3-thiazoles
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D277/00—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings
- C07D277/02—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings
- C07D277/20—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D277/32—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D277/56—Carbon atoms having three bonds to hetero atoms with at the most one bond to halogen
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
- C07D401/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings
- C07D401/04—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings directly linked by a ring-member-to-ring-member bond
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- Organic Chemistry (AREA)
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Dentistry (AREA)
- Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- Plant Pathology (AREA)
- General Health & Medical Sciences (AREA)
- Wood Science & Technology (AREA)
- Zoology (AREA)
- Environmental Sciences (AREA)
- Pest Control & Pesticides (AREA)
- Agronomy & Crop Science (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
Description
技术领域本发明属于农用杀虫杀螨剂领域,涉及氟苯双酰肼唑类化合物及其应用。
背景技术化学农药是防治农业上病、虫、螨害的主要手段。唑类化合物在杀虫剂、杀螨剂、杀菌剂等农药中有重要应用。含氟农药在性能上相对具有用量少、毒性低、药效高的特点。本发明采用活性基团拼接法合成了一种氟苯双酰肼唑类化合物,在现有技术中,如本发明所述的通式I化合物及其用作农林业杀虫杀螨剂未见公开。
发明内容本发明的目的在于提供一种结构新颖、高效、安全的杀虫、杀螨剂,它可用于农业常见的虫害、螨害的有效防治。
本发明的技术方案如下:
本发明提供了一种氟苯双酰肼唑类化合物,结构如通式Ⅰ所示:
本发明通式Ⅰ化合物可由如下方法制备,反应式中各基团定义同前。
通式Ⅰ化合物及其中间体的具体制法见本发明合成实例。
表1列出了通式Ⅰ化合物的结构和物理性质。
表1化合物Ⅰ的结构和物理性质
本发明的优点和积极效果:
本发明化合物是一种全新结构的芳香双酰肼唑类化合物,在其结构中含有氟原子和氮唑基团,含氟基团增加了脂溶性和渗透性,显著提高了其内吸传导作用,从而提高了其药效;吡唑或噻唑结构增加了作用位点,有益于增加药效和广谱性,受害虫抗性影响小。本发明化合物合成原料易得,合成工艺简单,无需高温高压和特殊设备,生产中产生“三废”少,收率较高,生产成本低。本发明化合物为氮杂环酰肼类化合物,具有对人、畜及有益生物低毒性、易降解、环境相容性好的特点,具有作为创制性杀虫杀螨剂新品种产业化的前景和商品化的潜力。
本发明式I化合物及其盐在防治有害虫、螨时,可单独使用,也可与其它活性物质组合使用,以提高产品的综合性能。
本发明的组合物可以制剂的形式施用。通式Ⅰ化合物作为活性组分溶解或分散于载体或溶剂中,添加适当的表面活性剂配制成乳油、悬浮剂、微乳剂或可湿性粉剂等。
应该明确的是,在本发明的权利要求所限定的范围内,可进行各种变换和改动。
具体实施方式
下列合成实例及生测结果可用来进一步说明本发明,但并不意味着限制本发明。
合成实例:
实例1.化合物Ⅰa的制备:
(1)2,6-二氟苯甲酰氯的合成
在250mL三口烧瓶中,加入2,6-二氟苯甲酸0.2mol(31.62g),加入50mL甲苯溶剂。将0.3mol(35.69g)氯化亚砜放进恒压漏斗中,并加入50mL甲苯将其稀释。加热至回流,边搅拌边缓慢滴加氯化亚砜稀释液。反应过程中使用TLC法进行跟踪检测。反应结束后,将反应混合物减压旋蒸除去溶剂,得产物2,6-二氟苯甲酰氯,用于下步反应。
(2)2,6-二氟苯甲酸-N'-叔丁基-酰肼的合成
在250mL的三口烧瓶中,加入叔丁基肼盐酸盐0.1mol(12.46g),三乙胺0.2mol(20.24g),加入50mL乙酸乙酯作为溶剂。称取2,6-二氟苯甲酰氯0.1mol(17.65g)于恒压滴液漏斗中,并加入50mL乙酸乙酯将其稀释。在冰水浴中,边搅拌边缓慢地将稀释液滴加进反应烧瓶中,滴加完毕后,采用TLC法进行跟踪检测。反应结束后,加水,分液,取有机相,放入冰箱冷藏。等到析出固体后,抽滤,放在烘箱(105℃)烘干。
(3)4-氯-3-乙基-1-甲基-1H-吡唑-5-碳酰氯的合成
在250mL三口烧瓶中加入4-氯-3-乙基-1-甲基-1H-吡唑-5-羧酸0.03mol(5.65g),加50mL甲苯作溶剂。称取0.045mol(5.35g)氯化亚砜于恒压滴液漏斗中,然后加入50mL甲苯进行稀释。加热至回流,边搅拌边缓慢地滴加氯化亚砜稀释液。反应过程中使用TLC法进行跟踪检测。反应结束后,将反应产物减压旋蒸除去溶剂,得产物4-氯-3-乙基-1-甲基-1H-吡唑-5-碳酰氯,用于下步反应。
(4)化合物Ⅰa的合成
在250mL三口烧瓶中,加入2,6-二氟-苯甲酸N'-叔丁基-酰肼0.02mol(4.56g),焦磷酸钾0.01mol(3.3g),加入50mL乙腈为溶剂。称取4-氯-3-乙基-1-甲基-1H-吡唑-5-羧酸0.03mol(6.21g)于恒压滴液漏斗中,并加入50mL乙腈稀释。在常温下边搅拌边缓慢地将稀释液滴加入三口烧瓶中,滴加完毕后继续反应,采用TLC法进行跟踪检测。待反应完毕后,加水和乙酸乙酯萃取分液,取有机层,旋蒸除去溶剂。将所得物放入冰箱冷藏,待析出固体后,抽滤,用石油醚洗涤,将抽滤得到的固体放入烘箱烘干,得产物4.14g,产率52%。化合物Ⅰa的1H NMR(500MHz,DMSO-d6)δ:11.13(s,1H),7.54(tt,J=8.2,6.5Hz,1H),7.15(t,J=8.0Hz,2H),3.72(d,J=1.9Hz,3H),2.54–2.46(m,3H),1.50(d,J=1.5Hz,9H),1.15(q,2H).
实例2.化合物Ⅰb的制备:
(1)2-(3-氯-吡啶-2-基)-5-(2,2-二氟-乙氧基)-2H-吡唑-3-碳酰氯的合成
在250mL三口烧瓶中,加入2-(3-氯-吡啶-2-基)-5-(2,2-二氟-乙氧基)-2H-吡唑-3-羧酸0.03mol(9.10g),用50mL甲苯作溶剂。称取0.045mol(5.35g)的氯化亚砜于恒压滴液漏斗中,并加入50mL甲苯稀释。边搅拌边缓慢滴加氯化亚砜,然后加热至回流状态。采用TLC法进行跟踪检测。待反应完全结束后,旋蒸除去溶剂,制得产物直接进行下一步反应。
(2)化合物Ⅰb的合成
在250mL三口烧瓶中,加入2,6-二氟-苯甲酸N'-叔丁基酰肼0.02mol(4.56g),焦磷酸钾0.01mol(3.3g),加入50mL乙腈为溶剂。称取2-(3-氯-吡啶-2-基)-5-(2,2-二氟-乙氧基)-2H-吡唑-3-碳酰氯0.03mol(9.66g)于恒压滴液漏斗中,于恒压滴液漏斗中,并加入50mL乙腈稀释。在常温下边搅拌边缓慢地将稀释液滴加入三口烧瓶中,滴加完毕后继续反应,采用TLC法进行跟踪检测。待反应完毕后,加水和乙酸乙酯萃取分液,取有机层,旋蒸除去溶剂。将所得物放入冰箱冷藏,待析出固体后,抽滤,用石油醚洗涤,得到黄色固体,烘干,得产物5.55g,产率54%。化合物Ⅰb的1H NMR(500MHz,DMSO-d6)δ:10.99(s,1H),9.98(s,1H),8.42–8.37(m,1H),8.13(dd,J=8.1,1.5Hz,1H),7.64–7.45(m,1H),7.18(t,J=8.2Hz,2H),6.50(t,J=3.6Hz,1H),6.40(t,J=3.5Hz,2H),6.29(t,J=3.6Hz,1H),1.42(s,9H).
实例3.化合物Ⅰc的制备:
(1)2-甲基-4-三氟甲基-噻唑-5-碳酰氯的合成
按实例2步骤(1)的方法,以2-甲基-4-三氟甲基-噻唑-5-羧酸和氯化亚砜反应,可制得2-甲基-4-三氟甲基-噻唑-5-碳酰氯。
(2)化合物Ⅰc的合成
按实例2步骤(2)的方法,以2,6-二氟-苯甲酸N'-叔丁基-酰肼和2-甲基-4-三氟甲基-噻唑-5-碳酰氯反应,可制得化合物Ⅰc,产率52%。化合物Ⅰc的1H NMR(500MHz,DMSO-d6)δ:1H NMR(500MHz,DMSO-d6)δ11.20(s,1H),7.60–7.50(m,1H),7.16(t,J=8.4Hz,2H),2.68(s,3H),1.48(s,9H).
生物活性测定:
实例4、式Ⅰ化合物杀螨卵活性试验
采用浸渍法和统计校正害虫死亡率的方法测定杀螨卵活性。具体过程是:将供试药剂按有效成分分别稀释至所需浓度,在无菌条件下各取50mL药液注入培养皿内,再分别浸入有朱砂螨卵(螨卵按室内标准化方法正常饲养的群体)的叶片,以添加50mL灭菌水的平板做空白对照。将培养皿放在24±1℃恒温培养箱内。48h后调查统计死亡率。每处理3次重复,结果取平均值,见表2。
表2式I化合物对朱砂叶螨卵试验结果
由表2试验数据可见,本发明化合物I具有优异的杀螨卵活性。
实例5、式Ⅰ化合物杀山楂叶螨活性测定:
采用玻片法进行触杀活性测定。玻片法为FAO推荐使用的方法,具体方法为:将1cm宽的双面胶带纸贴在载玻片一端,选取大小一致的健康雌成螨,用零号毛笔将其背面向下成两行固定在胶带纸上,于解剖镜下剔除死螨及不活泼螨后,保证每一载玻片上有成螨30头。在处理液中浸5s后取出,用滤纸轻轻吸掉多余的处理液,12h后观察叶螨的死亡情况。以毛笔尖轻触后,足不动者即视为死亡。计算死亡率。(试验做3次重复,取平均值)。将式I化合物制备成乳油,选取丁醚脲(CK)制备成乳油作平行试验对照,对山楂叶螨的防效试验结果列于表3。
表3杀山楂叶螨活性测定数据
化合物 | 浓度(ppm) | 12h死亡率(%) |
I<sub>a</sub> | 100 | 95.5 |
I<sub>b</sub> | 100 | 98.0 |
I<sub>c</sub> | 100 | 97.2 |
由表3试验数据可见,本发明化合物I具有优异的山楂叶螨活性。
实例6、式Ⅰ化合物杀虫活性试验
杀小菜蛾活性测试方法:本发明化合物对小菜蛾活性测定采用国际抗性行动委员会(IRAC)提出的浸叶法。用配制好的待测药液,用直头眼科镊子浸渍甘蓝叶片,时间3-5秒,甩掉余液,每次1片,每个样品共3片,按样品标记顺序依次放在处理纸上。待药液干后,放入具有标记的10cm长的直型管内,接入3龄小菜蛾幼虫30头,用纱布盖好管口。将试验处理置于标准处理室内,72h检查结果以拔针轻触虫体,不动者为死亡。计算死亡率(试验做3次重复,取平均值)。对小菜蛾的防效试验结果列于表4。
表4式Ⅰ化合物的杀小菜蛾活性测试结果
根据测试结果可知,本发明化合物Ⅰ对小菜蛾有优良杀灭效果。
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