CN105130962B - 一种四嗪吡唑类杀螨剂 - Google Patents
一种四嗪吡唑类杀螨剂 Download PDFInfo
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- 125000003226 pyrazolyl group Chemical group 0.000 description 1
- DWFZBUWUXWZWKD-UHFFFAOYSA-N pyridaben Chemical compound C1=CC(C(C)(C)C)=CC=C1CSC1=C(Cl)C(=O)N(C(C)(C)C)N=C1 DWFZBUWUXWZWKD-UHFFFAOYSA-N 0.000 description 1
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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
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/713—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with four or more nitrogen atoms as the only ring hetero atoms
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D403/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00
- C07D403/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings
- C07D403/04—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings directly linked by a ring-member-to-ring-member bond
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- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
Abstract
本发明提供一种四嗪吡唑类化合物，其结构如式I所示：
Description
技术领域 本发明属于农药中杀螨剂领域，涉及一种四嗪吡唑类杀螨剂。
背景技术 害螨危害农作物影响农作物正常生长，导致作物减产及品质下降。防治农业害螨的杀螨剂品种繁多，如哒螨灵、霸螨灵、尼索朗、螺螨酯、阿维菌素等。由于害螨极易产生抗药性，众多杀螨剂品种因抗药性已失去原有的高效性，已不能满足现代农业对杀螨剂超高效、长持效及低公害的要求。因此开发新型高活性杀螨剂是当务之急。US4237127及US5455237报道了四嗪类化合物及其在农业防治螨害方面的应用，由此开发出对螨卵高效的杀螨剂品种“四螨嗪”，在螨害治理方面已发挥了重要作用。上世纪90年代匈牙利Chinion公司通过对“四螨嗪”进行结构改造，开发出“四螨嗪”类似物“氟螨嗪”，对各种植食性叶螨均有效，其杀螨卵活性是四螨嗪的四倍，成为杀螨剂领域超高效、长持效、低公害的代表性杀螨剂品种。
虽然氟螨嗪具有很好的触杀性，但是内吸性比较弱，只有中度的内吸性，所以喷雾要均匀；而且在长期的使用过程中也产生了抗药性问题。为了解决上述问题，本发明设计并合成了一种四嗪吡唑类杀螨剂，在现有技术中，如本发明所示的式I化合物用作杀螨剂未见公开。
发明内容 本发明的目的是提供一种结构新颖、生产及使用安全、杀螨效果好、防治成本低的四嗪吡唑类杀螨剂，可用于农业或林业害螨的防治。
本发明的技术方案如下：
一种四嗪吡唑类杀螨剂，结构如式I所示：
式I化合物可通过如下反应制备：
(1)对叔丁基苯甲酸和甲醇反应生成对叔丁基苯甲酸甲酯(化合物Ⅱ)：
(2)化合物Ⅱ和水合肼反应生成对叔丁基苯甲酰肼(化合物Ⅲ)：
(3)4-氯-3-乙基-1-甲基-1H-吡唑-5-羧酸和氯化亚砜反应生成4-氯-3-乙基-1-甲基-1H-吡唑-5-酰氯(化合物Ⅳ)：
(4)化合物Ⅲ和化合物Ⅳ反应生成N-(4-叔丁基-苯甲酰基)-N'-(4-氯-3-乙基-1-甲基-1H-吡唑-5-酰基)肼(化合物Ⅴ)：
(5)化合物Ⅴ和五氯化磷生成N-(4-叔丁基-苯基)氯甲叉基-N’-(4-氯-3-乙基-1-甲基-1H-吡唑基)氯甲叉基肼(化合物VI)：
(6)化合物Ⅵ和水合肼成环生成3-(4-叔丁基-苯基)-6-(4-氯-5-乙基-2-甲基-2H-吡唑基)-1,2-二氢-1,2,4,5-四嗪(化合物Ⅶ)：
(7)化合物Ⅷ用亚硝酸氧化生成化合物I
本发明的优点和积极效果：
本发明化合物(式I)将吡唑环及苯环叔丁基引入四嗪类杀螨剂结构中，具有显著的结构新颖性。本发明化合物对螨卵的抑杀效果，在10ppm达86％，而同浓度下氟螨嗪的杀卵活性只有48％；在1ppm下本发明化合物仍有41％的抑杀率，而氟螨嗪在该浓度下基本无杀卵作用。本发明化合物的杀螨卵活性是氟螨嗪(KC)的5～8倍，表现出超高效性的显著优点。而且本发明化合物为氮环类化合物，具有对有益生物低毒性、易降解、环境相容性好的特点，具有作为创制性杀螨剂新品种产业化的前景。
本发明式I化合物在防治有害螨时，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。
具体实施方式
下列合成实例、生测试验结果可用来进一步说明本发明，但不意味着限制本发明。
合成实例
实例1、式Ⅰ化合物的制备：
(1)化合物Ⅱ的合成：
向250mL三口烧瓶中加入17.8g(0.1mol)对叔丁基苯甲酸，100mL甲醇，冰浴下滴加17.85g(0.15mol)氯化亚砜，搅拌升温至回流，搅拌反应8h。薄层色谱跟踪反应，待原料点消失后，停止反应。减压蒸馏除去溶剂得粗品17.66g，产率92％。
(2)化合物Ⅲ的合成：
向100mL三口烧瓶中加入8.4g水合肼，40mL水，冰浴下滴加17.28g(0.09mol)化合物Ⅱ，搅拌升温至回流，搅拌反应5h。薄层色谱跟踪反应，待原料点消失后，停止反应。减压蒸馏除去低沸物，冷却结晶，抽滤得粗品15.38g，产率89％。
(3)化合物Ⅳ的合成：
向250mL三口烧瓶中加入18.85g(0.1mol)4-氯-5-乙基-2-甲基-2H-吡唑-3-羧酸，100mL甲苯，常温下滴加17.85g(0.15mol)氯化亚砜，搅拌升温至回流，搅拌反应2-3h。薄层色谱跟踪反应，待原料点消失后，停止反应。减压蒸馏除去溶剂，得产品20.7g，产率100％。
(4)化合物Ⅴ的合成：
向250mL三口烧瓶中加入15.36g(0.08mol)化合物Ⅲ，8.9g(0.088mol)三乙胺，100mL乙酸乙酯，常温下下滴加18.22g(0.088mol)化合物Ⅳ，搅拌升温至回流，搅拌反应4h。薄层色谱跟踪反应，待原料点消失后，停止反应。抽滤去除三乙胺盐酸盐，减压蒸馏除去溶剂得粗品24.62g，产率85％。
(5)化合物Ⅵ的合成：
向250mL三口烧瓶中加入18.13g(0.05mol)化合物Ⅴ，80mL甲苯，分批加入20.85g(0.1mol)PCl5，搅拌升温至40℃，搅拌反应10h。薄层色谱跟踪反应，待原料点消失后，停止反应。冷却后蒸去溶剂，残留物在冰水浴中，用稀的氢氧化钠水溶液调节pH至中性，用乙酸乙酯萃取。有机层依次用水、饱和食盐水洗涤，用无水硫酸钠干燥，脱溶后得到紫红色固体15g，收率75％。
(6)化合物Ⅶ的合成：
250mL三口烧瓶中加入12.0g(0.03mol)化合物Ⅵ,甲苯60mL，在40℃时，将2.81g(0.045mol)水合肼滴加到反应液中，滴加完后再保温反应4h。冷却后，加入40mL水，过滤析出的固体，得到产品8.37g，收率77.8％。
(7)化合物I的合成：
100mL三口烧瓶中加入7.17g(0.02mol)化合物Ⅶ,乙酸20mL，搅拌下将0.026mol亚硝酸钠的水溶液(20％)在室温下滴加入反应液中，搅拌过夜。过滤析出的固体，并且用水洗至中性，干燥，得到粗产品。粗产品过层析柱(石油醚:乙酸乙酯＝5:1)，得到紫红色粉末状目标产品5.28g，熔点95.3～98.7℃，收率74.1％。1H NMR(500MHz,DMSO)，δ/ppm：7.998-8.014(2H,Ar-H),7.665-7.682(2H,Ar-H),4.306(3H,NCH3-H),2.615-2.660(2H,CH2-H),1.369(9H,CH3-H),1.204-1.235(3H,CH3-H).
生物活性测试
实例2、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。
表1本发明化合物(式I)杀朱砂叶螨螨卵试验结果
根据测试结果可知，本发明化合物I对朱砂叶螨螨卵抑杀效果显著优于氟螨嗪(KC)。
Claims (2)
1.一种四嗪吡唑类化合物，其特征在于它的结构如下式I所示：
2.根据权利要求1所述的四嗪吡唑类化合物所述的式I化合物在防治农业害螨中的应用。
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