CN105153037B - 一种唑虫酰脲化合物 - Google Patents
一种唑虫酰脲化合物 Download PDFInfo
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- -1 sulfonylurea compound Chemical class 0.000 title claims description 5
- 229940100389 Sulfonylurea Drugs 0.000 title claims 3
- 150000003851 azoles Chemical class 0.000 title claims 3
- 150000001875 compounds Chemical class 0.000 claims abstract description 20
- 241000607479 Yersinia pestis Species 0.000 claims abstract description 7
- 230000000361 pesticidal effect Effects 0.000 claims 1
- 230000000749 insecticidal effect Effects 0.000 abstract description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 241000500437 Plutella xylostella Species 0.000 description 5
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 239000002917 insecticide Substances 0.000 description 4
- CTSLXHKWHWQRSH-UHFFFAOYSA-N oxalyl chloride Chemical compound ClC(=O)C(Cl)=O CTSLXHKWHWQRSH-UHFFFAOYSA-N 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- 241000238631 Hexapoda Species 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- 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 2
- MIDWNRQXTXNCAL-UHFFFAOYSA-N 4-chloro-5-ethyl-2-methylpyrazole-3-carboxamide Chemical compound CCC1=NN(C)C(C(N)=O)=C1Cl MIDWNRQXTXNCAL-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 2
- IDPURXSQCKYKIJ-UHFFFAOYSA-N 1-(4-methoxyphenyl)methanamine Chemical compound COC1=CC=C(CN)C=C1 IDPURXSQCKYKIJ-UHFFFAOYSA-N 0.000 description 1
- NXAIFVHVBHMNJS-UHFFFAOYSA-N 4-chloro-5-ethyl-2-methylpyrazole-3-carboxylic acid Chemical compound CCC1=NN(C)C(C(O)=O)=C1Cl NXAIFVHVBHMNJS-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 240000007124 Brassica oleracea Species 0.000 description 1
- 235000003899 Brassica oleracea var acephala Nutrition 0.000 description 1
- 235000011301 Brassica oleracea var capitata Nutrition 0.000 description 1
- 235000001169 Brassica oleracea var oleracea Nutrition 0.000 description 1
- DPXOFIHEBFBLOG-UHFFFAOYSA-N CCc1n[nH]c(C(N)=O)c1Cl Chemical compound CCc1n[nH]c(C(N)=O)c1Cl DPXOFIHEBFBLOG-UHFFFAOYSA-N 0.000 description 1
- 0 CCc1n[n](*)c(C(N=C=O)=O)c1Cl Chemical compound CCc1n[n](*)c(C(N=C=O)=O)c1Cl 0.000 description 1
- 241001222563 Empoasca onukii Species 0.000 description 1
- 241000973497 Siphonognathus argyrophanes Species 0.000 description 1
- 241001414989 Thysanoptera Species 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 238000003556 assay Methods 0.000 description 1
- 238000004166 bioassay Methods 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000012065 filter cake Substances 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 230000002147 killing effect Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000011272 standard treatment Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 239000008399 tap water Substances 0.000 description 1
- 235000020679 tap water Nutrition 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
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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
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- 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
- A01N47/08—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 the carbon atom having one or more single bonds to nitrogen atoms
- A01N47/28—Ureas or thioureas containing the groups >N—CO—N< or >N—CS—N<
- A01N47/34—Ureas or thioureas containing the groups >N—CO—N< or >N—CS—N< containing the groups, e.g. biuret; Thio analogues thereof; Urea-aldehyde condensation products
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Abstract
本发明公开了一种唑虫酰脲化合物，结构如式I所示：
Description
技术领域 本发明属于农用杀虫剂领域，涉及一种唑虫酰脲化合物及其应用。
背景技术 有害生物的抗性问题是其难以治理的主要根源，开发新型防治药剂是治理抗性的重要途径。US5039693公开了下列化合物(KC)的制备及杀虫活性。该化合物商品名称为唑虫酰胺，对小菜蛾、蓟马及茶小绿叶蝉等害虫有很好的防治效果。
在现有技术中，如本发明所示的唑虫酰脲化合物及其杀虫未见公开。
发明内容
本发明的目的在于提供一种结构新颖、综合性能好、防治成本低的唑虫酰脲化合物，可用于农业或林业主要害虫的防治。
本发明的技术方案如下：
一种唑虫酰脲化合物，结构如式I所示：
本发明化合物可由如下方法制备。
上述两种原料在二氯乙烷溶剂中常温反应即得到式I化合物，上述反应中的吡唑酰基异氰酸酯制备见本发明实施例。
本发明的优点和积极效果：本发明化合物唑虫酰脲继承了唑虫酰胺(KC)杀虫剂的结构特点，又具有脲类杀虫剂的活性基团，与唑虫酰胺具有不同的杀虫机制，对唑虫酰胺业已产生的抗药性的害虫尤为高效。而且本化合物易降解，环境相容性好，具备开发成为超高效绿色环保杀虫剂的潜力。
本发明化合物用于控制虫害用途时，可以单独使用，也可以与其它活性物质组合使用，以提高产品的综合功能。
本发明还包括以化合物I作为活性组分的杀虫组合物，该组合物中活性组分的重量百分含量高为1-95％之间，该杀虫组合物中还包括农业或林业上可以接受的载体。
具体实施方式
下列合成实例及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、化合物I的制备
(1)4-氯-3-乙基-1-甲基吡唑-5-甲酰氯的合成
向250mL反应瓶中加入原料4-氯-3-乙基-1-甲基吡唑-5-甲酸18.85g(0.1mol)，加入甲苯100g，搅拌5min，滴入氯化亚砜23.8g(0.2mol)，缓慢升温至回流。回流反应4h，减压蒸馏除去甲苯及多余氯化亚砜，得棕红色油状物20.70g，收率100％。
(2)4-氯-3-乙基-1-甲基吡唑-5-甲酰胺的合成
向250mL反应瓶中加入80g 40％氨水，冰浴控温0℃以下，滴加4-氯-3-乙基-1-甲基吡唑-5-甲酰氯20.70g(0.1mol)，滴毕，常温反应0.5h，抽滤，滤饼用20mL×2自来水洗涤，得白色固体15g，收率80％。
(3)4-氯-3-乙基-1-甲基吡唑-5-甲酰基异氰酸酯的合成
向250mL反应瓶中分别加入4-氯-3-乙基-1-甲基吡唑-5-甲酰胺18.75g(0.1mol)，二氯乙烷100mL，滴加草酰氯31.75g(0.25mol)，滴毕升温至回流10h，减压蒸馏除去二氯乙烷及多余的草酰氯，得棕色油状物21.35g，收率100％。
(4)化合物I的合成
向100mL反应瓶中加入25g二氯乙烷，2.13g(0.01mol)对甲氧基苄胺，滴加4-氯-3-乙基-1-甲基吡唑-5-甲酰基异氰酸酯2.35g(0.011mol)，滴毕常温反应3h，抽滤得白色固体2.6g，收率61％。熔点：100～103℃。
化合物I的1H NMR(500MHz，DMSO-d6),δ(ppm)：1.153-1.183(t，3H)，2.283(s，3H)，2.525-2.570(q，2H)，3.866(s，3H)，4.375-4.387(d，2H)，6.896-6.913(d，2H)，6.935-6.952(d，2H)，7.175-7.192(d，2H)，7.328-7.345(d，2H)，8.621(s，1H)，10.601(s，1H)。
生物活性测定
实例2杀虫活性测定
杀小菜蛾活性测定：
采用浸叶法。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2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，48h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。结果见表1。
表1 杀小菜蛾活性测定结果
表2结果表明，本发明化合物唑虫酰脲对小菜蛾显著优于对比药剂唑虫酰胺(KC)。
Claims (3)
1.一种唑虫酰脲化合物，结构如式I所示：
2.按照权利要求1所述的一种唑虫酰脲化合物的用途，其特征在于式I化合物用作杀虫剂，防治农作物虫害。
3.一种杀虫组合物，含有权利要求1所述的式I化合物为活性组分和农业或林业上可接受的载体。
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| CN108299409B (zh) * | 2018-04-02 | 2021-01-29 | 青岛科技大学 | 一种苯醚噁二唑类杀虫剂 |
| CN114656402B (zh) * | 2022-04-11 | 2024-01-30 | 青岛科技大学 | 一种含氟烟酰脲类化合物及其用途 |
| CN114805197B (zh) * | 2022-04-11 | 2023-07-11 | 青岛科技大学 | 一种含氟吡啶酰基脲类杀虫杀螨剂 |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5039693A (en) * | 1988-10-14 | 1991-08-13 | Mitsubishi Kasei Corporation | Pyrazole amides and insecticide and miticide containing them as active ingredient |
| CN1183409A (zh) * | 1995-09-08 | 1998-06-03 | 化学工业部沈阳化工研究院 | 用于杀虫杀螨的吡唑类化合物及其制剂 |
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2015
- 2015-09-06 CN CN201510559068.8A patent/CN105153037B/zh active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5039693A (en) * | 1988-10-14 | 1991-08-13 | Mitsubishi Kasei Corporation | Pyrazole amides and insecticide and miticide containing them as active ingredient |
| CN1183409A (zh) * | 1995-09-08 | 1998-06-03 | 化学工业部沈阳化工研究院 | 用于杀虫杀螨的吡唑类化合物及其制剂 |
Non-Patent Citations (3)
| Title |
|---|
| 吡唑酰胺基脲类化合物的合成及除草活性;谭成侠，等;《农药学学报》;20111231;第13卷(第2期);全文 * |
| 新型吡唑甲酰脲类化合物的合成及其生物活性;刘长令，等;《化学研究与应用》;19971231;第9卷(第5期);全文，尤其实验部分 * |
| 新型吡唑甲酰脲类化合物的合成及其生物活性;刘长令，等;《合成化学》;19970430;第5卷(第4期);全文，尤其实验部分 * |
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Denomination of invention: A imidazolyl urea compound Effective date of registration: 20220527 Granted publication date: 20170822 Pledgee: Shandong Zouping Rural Commercial Bank Co.,Ltd. Pledgor: SHANDONG KEDA CHUANGYE BIOTECHNOLOGY Co.,Ltd. Registration number: Y2022980006587 |
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| PC01 | Cancellation of the registration of the contract for pledge of patent right | ||
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Granted publication date: 20170822 Pledgee: Shandong Zouping Rural Commercial Bank Co.,Ltd. Pledgor: SHANDONG KEDA CHUANGYE BIOTECHNOLOGY Co.,Ltd. Registration number: Y2022980006587 |