WO2012083550A1 - 吡啶肟醚类衍生物和制备及其应用 - Google Patents
吡啶肟醚类衍生物和制备及其应用 Download PDFInfo
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- WO2012083550A1 WO2012083550A1 PCT/CN2010/080205 CN2010080205W WO2012083550A1 WO 2012083550 A1 WO2012083550 A1 WO 2012083550A1 CN 2010080205 W CN2010080205 W CN 2010080205W WO 2012083550 A1 WO2012083550 A1 WO 2012083550A1
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- arh
- pyrazole
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- 0 Cc1c(**)[n](C)nc1* Chemical compound Cc1c(**)[n](C)nc1* 0.000 description 1
Classifications
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- 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
- C07D401/12—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 linked by a chain containing hetero atoms as chain links
-
- 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
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D405/00—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom
- C07D405/14—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing three or more hetero rings
Definitions
- Patent Publication Document JP 3-240775A JP 3-240775A
- the compounds disclosed in this patent document have good acaricidal and insecticidal activity.
- the molar ratio of the reactant charge is 1:1
- the solvent is an alcohol solvent such as methanol or ethanol
- the reaction is carried out at room temperature
- the reaction time is usually 2 to 10 hours.
- POCl 3 and DMF are made into VilsmeierHaack reagent, and the molar ratio of the reactants may be 1:1 to 10:1, and then the reactant is added thereto to carry out the reaction, and the molar ratio of the reactant to the Vilsmeier Haack reagent may be 1:1 ⁇ 1. :10. Anti 12 small ⁇ °C.
- the molar ratio of reactant to alcohol is 1:1 ⁇ 1:5; the molar ratio of reactant to base is 1 : 1 ⁇ 1:1.5; the base used is NaOH, KOH, K 2 C0 3 , sodium tert-butoxide , potassium t-butoxide, etc., the reaction solvent is alcohol, tetrahydrofuran, etc., the reaction temperature is ° C, the reaction time is 2 ⁇
- ⁇ is N
- X is a halogen
- RR 2 is the same as defined above.
- the molar ratio of reactant to substituted pyridine is 1:1 ⁇ 1:1.5
- the solvent is acetonitrile
- the base is inorganic base: NaOH, KOH, K 2 C0 3, etc.
- the reaction temperature is under acetonitrile reflux
- the reaction time is 2 ⁇ 12 hours.
- the present invention provides pyridinium ether derivatives. Through biological tests, the results showed that several compounds showed high insecticidal and acaricidal activity and could be used as agricultural insecticides and acaricides.
Description
吡 P划亏醚麵生物和制备及其应用
【技术领域】: 本发明涉及肟醚类衍生物, 特别是一种含吡啶肟醚类衍生物和制备 及其应用。
【背景技术】: 许多含吡唑的化合物具有良好的杀虫杀螨活性, 1987年欧洲专利 EP0234045报道了吡 ¾|亏醚类化合物具有杀虫杀螨效果。相继美国专利 US4843068, 日本专利 JP3240775, JP02096568, 欧洲专利 EP0390498、 中国专利 CN1188764 ^ CN1188764以及国际专利 W003086077等专利均报道了吡 亏醚类化合物具有杀虫、 杀螨和杀菌效果, 并介绍了该说系列化合物的合成。
该专利公开的化合物中 Ar为 4-叔丁權基-苯基, 只报导了个另啲吡啶类化合物, 但没有生物活性数据 ¾¾, X和 Y的变化上。 该专利报导 的化合物具有杀螨活性。
专利公开文件 CN1
该专利文件报道的化合物主要集中在 R4的变化上,所报道的化合物具有杀菌活性。
该专利公开的化合物中 Ar为 4-叔丁氧羰基-苯基,只报导了个另啲吡啶类化合 物, 但没有生物活性麵报道, 该专利文献主要集中在 X和 Y的变化上, Y主要 是各种取代的杂环或苯环。 专利所公开的化合物具有杀螨活性。
专利公开文件 JP平 3-240775A :
在专利公开文件 CN1844103中,我们根据本研究小组多年来新农药研究开发的 经验和生物等排的原理,设计合成了系列含吡啶肟醚类化合物,公开的化合物通式 为:
在该专利文件中公开的化合物具有较好的杀螨和杀虫活性。
本发明在专利公开文件 CN1844103的基础上,用氟取代或含氟基团取代的苯氧 基,烷氧基及其它非芳氧基替代吡唑环上的取代苯氧基,设计合成了系列新型的吡 啶肟醚类结构, 生物活性试验表明, 所设计合成的化合物具有比专利文件 和螨都表现出很高的活性。
【发明内容】: 本发明的目的在于提供一种吡啶肟醚类衍生物和制备及其应用。 本 发明以肟醚类杀螨剂的结构为母核' 根据生物等排取代的策略, 密切注意关键原子 间的角度与其周边的电性, 方向性, 立体性等取向, 将新烟碱类杀虫剂中重要的杂 环部分引入其中, 比如取代的吡啶环, 并在肟醚的吡唑环中引入氟取代或含氟基团 取代的苯氧基, 垸氧基及其它非芳氧基的基团, 设计合成了系歹噺型的吡啶肟醚类 结构, 生物活性试验表明, 所设计合成的化合物具有比专利文 #CN1844103公开的 化合物更宽的杀虫谱, 很多化合物对蚜虫、 小菜夜蛾、 甜菜夜 !fe Π螨都表现出很高 的活性。 可以用作农用杀虫杀螨剂使用。
本发明提供的吡啶肟醚
( I )
如上式 ( I )所示, T为 N, 其位置可为 2、 3、 4位。
其中 R1为氟取代的苯基或含氟基团取代的苯基, C^C6的烷基或取代烷基,烯 基或取代烯基,炔基或取代炔基,环己基或取代的环己基,环戊基或取代的环戊基, 环丙基或取代的环丙基; R 为卤素、 COOR3; R3 为。 ^烷基或取 基。
( I )
化合物合成方法如上图所示, 分步简述如下:
反应物投料的摩尔比为 1 :1,溶剂为醇类溶剂,例如甲醇、乙醇的等, 反应于室 温下进行, 反应时间通常为 2〜10小时。
HO. P0C13 Cl、
N
DMF
OHC
首先将 POCl3与 DMF制成 VilsmeierHaack试剂,其投料摩尔比可以为 1 :1〜10: 1, 再将反应物加入其中进行反应, 反应物与 Vilsmeier Haack试剂的摩尔比可以为 1:1〜1 :10。 反 12小 〜 °C。
反应物与醇的投料摩尔比为 1:1〜1:5; 反应物与碱的投料摩尔比为 1 :1〜1 :1.5; 所用碱为 NaOH、 KOH、 K2C03、叔丁醇钠、 叔丁醇钾等等, 反应溶剂为醇、 四氢 呋喃等, 反应温 °C, 反应时间为 2〜
如上所述, 其中 τ为 N, X为卤素, R R2与上文定义相同。 反应物与取代 吡啶投料摩尔比为 1 :1〜1 :1.5, 溶剂为乙腈, 碱为无机碱: NaOH、 KOH、 K2C03 等等, 反应温度于乙腈回流下进行, 反应时间为 2~12小时。
本发明提供吡啶肟醚类衍生物。通过生物测试, 结果显示: 若干化合物显示出 很高的杀虫、 杀螨活性, 可以用作农用杀虫杀螨剂使用。
具体实施方式
下面通过实施例对本发明作进一步说明, 其目的是能更好的理解本发明的内容 及体现本发明的实质性的特点。 因此所举之例不应视为对本发明保护范围的限制: 錢例 1
化合物 D14
(1 )化合物 2的合成
KOC(CH3)3十
1 2
将 1.51g (O.Olmol)化合物 1溶于 10ml无水乙醚中, 于室温在电磁搅拌、 N2 下, 将如上溶液逐滴加入到 40ml无水乙醚与 1.68g (0.015mol)叔丁醇钾的混合物 中, 30分钟左右滴加完, 继续于室温下反应 30分钟左右, 反应结束。 反应液通过 中性 Α12θ3抽滤, 滤夜脱溶得到无色液体产物 0.90g, 收率为 50.3 %。
1H NMR (CDC13) δ Cppm) 300MHz: 1.60 (s, 9H, — COOC(CH3)3), 2.61 (s, 3H, Py— C¾), 7.19-7.22 (d, 1H, Py— H), 8.10—8.13 (d, 1H, Py— H), 9.17 (d, 1H, Py H) o
3
于装有机械搅拌和回流冷凝管的四口瓶中加入 1.93g CO.Olmol)化合物 2, 2.67g (0.015mol) NBS和 O.lg过氧化苯甲酰,加热至回流, 反应 14个小时, 反应结束。 抽滤, 滤液用饱和碳廳内溶液进行洗涤, 有机相用无水 gS04干燥' 60°C—下脱 溶, 柱层析得到产品浅粉色固体粉末 0.90g。
¾NMR (CDC13) δ Cppm) 300MHz: 1.61 (s, 9H, _COOC(CH3)3), 4.60 (s, 2H, Py-CH2), 7.51〜9.12 (m, 3H, Py_H)。
于装有温度计和回流冷凝管的四口瓶中加入 0.472g (2.00mmol) 1.3—二甲基 —环己基氧基一4—吡唑甲醛肟, 0.53g (1.95匪 ol)化合物 3, 0.54g (3.9ηπηο1) 研细的无水 K2C03, 50ml无水乙腈, 电磁搅拌下加热至回流, 反应 8个小时, 反 应结束。 将反应混合物抽滤、 脱溶、 柱层析, 得到目标化合物 0.64g。
根据实施例 1的制备方法, 用不同的原料可制备表中所列的化合物。具体见下
11 收率 C % ) 熔点
la 2-F 93.4 白色固体 73-75 lb 3-F 85.6 纖色油状液体
lc 4-OCF3 77.4 觀色油状液体
Id 76.4 白色固体 69-70 le 5-F2 82.3 白色固体 60-61
If ¾ -F2 91.6 白色固体 69-71
c Me 81.6 白色固体 78-S0
3,4-Fi
d 73.1 白色固体 68-70
2,5-F2
e 79.8 白色固体 112-113
2,4-F2
f 54.0 淡黄色固体 92-93
2-F
a 90.9 淡黄色固体 67-69
3-F
b 78.7 淡黄色固体 81-83
OCF3
c 84.7 黄的油状液体 ― t-Bu
334-F2
d 说 74.4 淡黄色固体 84-85
2,5-Fi
e 77.8 淡黄的油状液体 ―
¾4-F2
f 75.1 淡黄的油状液体 ―a H 86.3 淡黄色固体 97-99b 2-CHj 79.1 淡黄色固体 86-S8c 3-CH3 83.8 淡黄色固体 61^2d 4- H3 77.0
书淡黄色固体 86-87e 3-C1 74.3 淡黄色固体 91-93f 4-C1 85.9 淡黄色固体 126-128g Et 4-F 74.9 淡黄色固体 122-123h 3-Br 64.1 淡黄色固体 88-S9i -COOCH3 96.9 淡黄色固体 4749j 3-CF3 84.0 淡黄色固体 4009-50
00k 2-OCH3 82.3 淡黄色固体 79-811 2,4-Μ¾ 73.3 淡黄色固体 105-106m Et 3,5- M¾ 75.6 淡黄色固体 81-83n 3,4-C 81.3 淡黄色固体 102-103a H 85.8 淡黄色固体 78-79b 2-CHj 63.4 淡黄色固体
c 3-CH3 68.5 淡黄色固体 71-72d -CHj 84.6 淡黄色固体 108-110 l— Pro
e 4-F 97.7 淡黄色固体 123-125f 1 58.4 淡黄色固体 124-125g 3-Br 64.0 淡黄色固体 73-74h -COOCH3 84.8 淡黄色固体 82-83i 2,4-Μ¾ 65.3 淡黄色固体 102-103j 3,4-C 51.7 淡黄色固体 109-110a n-Pro H 82.5 黄色油状液体 -
b 4-C1 74.4 白色固体 81-82c 3-CH3 60.2 黄色油状液体 ―a H 75.1 黄色油状液体 ―b n-Bu CI 80.4 黄色固体 62-64c 3-CH3 73.2 黄色油状液体 ―a H 96.0 淡黄色油状液体 ―b l-Bu -C1 95.0 淡黄色固体 80-82c 说 3-CH3 86.4 淡黄色油状液体 ―a H 75.6 淡黄色固体 61-63b s-Bu -C1 77.3 白色固体 83-84c 3-CH3 64.2 淡黄色固体 44-46 a H 57.3 淡黄色油状液体 ―b l-Pen 1 60.1 淡黄色固体 59^1 c 4- H3 61.7
1c 3-CH3 85.5 淡黄色油状液体 ― a H 50.1 淡黄色油状液体 ―b CI 75.5 淡黄色固体 67-69 c 3-CH3 46. S 淡黄色油状液体 ― a H 57.1 淡黄色油状液体 ―b 4-C1 59.4 淡黄色固体 60-62 c 3-CH3 42.3 淡黄色油状液体 ― 核磁麵
2.24 (s. 3H P iazole-CH3). 3.58 (s. 3H Pyrazole (N)-CH3). 4.86 (s. 2H Py-CH2). la 6.62-6.68 (m, IH, ArH), 6.90-7.19 (m, 4H, ArH& Py-H), 7.45-7.48 (m, IH, Py-H), 7.71 (s, IH, CH=N), 8.21 (d,J= 2.2Hz, IH, Py-H)
2.25 (s, 3H, Pyrazole-CH3), 3.52 (s, 3H, Pyrazole (>¾-CH3), 4.86 (s, 2H, Py-CHj), lb 6.51-6.58 (m, 2H, ArH), 6.73-6.77(m, ΊΗ, ΑτΗ), 7.15-7.19 (m, 2H, ArH& Py-H),
7.44-7.48 (m, IH, Py-H), 7.72 (s, IH, CH=I¾ 8.21 (d,J = 2.1¾ IH, Py-H)
2.34 (s, 3H, Pyrazole-CH3), 3.62 (s, 3H, Pyrazole (Ν>〇¾), 4.94 (s, 2H, Py-CH2), 6.89 (d, lc J = 9.2 Hz, 2H, ArH), 7.18 (d, J = 8.6 ¾ 2H, ArH), 7.27 {d, J = 7.8 ¾ IH, Py-EQ, 7.53-7.57 (m, IH, Py-H), 7.81 (s, IH, CH=I¾ 8.32 (d, J = 2.1¾ IH, Py-H)
2.34 (s, 3H, Pyrazole-CH3), 3.62 (s, 3H, Pyrazole (K)-CH3), 4.97(s, 2H, I>CH2),
Id 6.58-6.62 (m, IH, ArH), 6.71-6.78 (m, l¾ Ar¾ 7.05-7.15 (m, ΙΗ,ΑτΗ , 7.28-7.30 (m, IH, Py-H), 7.54-7.58 (m, IH, Py-H), 7.81 (s, IH, CH=N , 8.31 (d,J = 2.2Hz, IH, Py-H)
/s/u O soiososld osssoiAV
1.43 (t, J = 7.1 Hz, 3H, CH3), 2.32 (s, 3H, Ar-CH3), 2.33 (s, 3H, Pyrazole(C)-CH3), 3.61 (s, 3H, Pyrazole(N)-CH3): 4.43 (q, J = 7.1 1¾ 2H, CH2), 5.16 (s, 2H, Py-CH2), 6.52 (d, Jb = 7.8 ¾ 1¾ ArH), 6.96-7.10 (m, 2¾ ArH), 7.18 (d, J = 6.8 H¾ IH, As , 7.28 (d, J = 2.7 Hz, IH, Py-H), 7.S7 (s, IH, CH=N), 8.19-8.23 (m, IH, Py-H), 9.15 (d, J = 2.0¾ IH,
Py-H).
1.42 (t, J = 7.1 ¾ 3H, CH3), 2.30 (s, 3H, Ar-CH3), 2.31 (s, 3H, Pyrazole(C)-CH3), 3.59c (s, 3H, Pyrazole(N)-CH3)3 4.17 (¾ J = 7.1 Hz, 2H, CH2), 5.19 (s, 2H, Py-CH2), 6.66 (d, J = 7.2 Hz, 2¾ ArH), 6.89 (d, J = 7.6 ¾ IH, ArH), 7.16 (t, J = 7.7Hz, IH, ArH), 7.33 (d, J =8.21¾ IH, Py-¾ 7.92 (s, 1¾ CH=N), S.19-8.23 (m, 1¾ Py-H), 9.14 (s, ¾ Py-H).
1.41 (t, J = 7.1 ¾ 3H, CH3), 2.31 (s, 6H, Ph-CH3& Pyrazole(C)-CH3), 3.59 (s, 3H,d Pyrazole(N)-CH3), 4.41 (q, J = 7.1 H¾ 2H, CH2), 5.18 (s, 2H, Py-CH2), 6.76 (d, J = 8.5 Hz; 2H, ArH), 7.07 (d, J = 8.5 H¾ 2H, ArH), 7.33 (d, J = 7.8 H¾ 1¾ Py-H), 7.91 (s, 1 CH=N), 8.19-8.22 (说m, IH, Py-H), 9.14(4 J = ¾ Py-H).
1.43 (ζ J = 7.1 H¾ 3H, CH3), 2.33 (s, 6H, Ph-CH3& Pyrazole(C)-CH3), 3.62 (s, 3H,e P razole(N)-CH3), 4.43 (¾ J = 7.1 Hz, 2H, CH2), 5.17 (s, 2H, P -CH2): 6.74-6.77 (m, IH, ArH), 6.84-6.89 (m, IH, ArH), 7.03-7.06 (m, IH, ArH), 7.20 (t, J = 8.1 H¾ IH, ArH), 7.30 (d, J = 8.4 ¾ IH, Py-H), 7.94 (s, IH, CH= ), 8.21-8.24 (m, l¾ Py-H), 9.15 (d, J = 2.0H¾ l¾ Py-H).
1.34 (t, J = 7.1 Hz, 3H, CH3), 2.23 (s, 3H, P razole(C)-CH3), 3.53 (s, 3H,f Pyrazole(N)-CH3), 4.35 (q, J = 7.1 Hz, 2H, CH2), 5.08 (s, 2H, P -CH2), 6.70-6.74 (m, 2H, ArH), 7.12-7.16 (m, 2H, ArH), 7.21 (d, J = 6.6 1¾ IH, Py-H), 7.85 (s, IH, CH=N), 8.13-8.16 (m, IH, Py-H), 9.07(4 J= 1.9I¾ IH, Py-H).
1.41 (t, J = 7.1 H¾ 3H, CH3), 2.29 (s, 3H, Pyrazole(C)-CH3), 3.60 (s, 3H, Pyrazole(N)-CH3)5 4.41 (q, J = 7.1 Hz, 2H, CH2), 5书.15 (s, 2H, P -CH2), 6.78-6.81 (m,g
2H, ArH), 6.91-6.95 (m, 2¾ ArH), 7.29 (d, J = 8.1 H¾ 1¾ Py-H), 7.90 (¾ IH, CH=N), 8.19-8.22 (m, IH, Py-H), 9.13 (d, J= 1.9¾ IH, Py-H).
1.42 (ζ J = 7.1 Hz, 3H, CH3), 2.31 (s, 3H, Pyrazole(C)-CH3)3 3.60 (s, 3H,h P razole(N)-CH3), 4.42 (q, J = 7.2 Hz, 2H, CH2), 5.15 (s, 2H, P -CH2): 6.78-6.20 (m, 2H, ArH), 7.30 (&, IH, Py-H), 7.93〔s, IH, CH=1¾ 8.20-8.23 (m, 1¾ Py-H), 9.14 (s, IH, Py-H).
1.42 (t, J = 7.1 ¾ 3H, CH3), 2.32 (s, 3H, Pyrazole(C)-CH3), 3.61 (s, 3H, Pyrazole(N>CH3), 3.91 (s, 3H, 0- CH3), 4.42 (q, J = 7.1 2H, CH2), 5.12 (s, 2H,i I^-CH2), 6.88 (d, J = 9.0 Ήζ, 2Ή, ArH), 7.25 (d, J = 6.6 Hz, IH, Py-H), 7.92 (s, IH, CH= ), 7.96 (d, J = 9.0 Hz, 2H, ArH), 8.17-S.20 (m, IH, Py-H), 9.12 (d, J = 2.0H¾ IH,
Py-H).
1.42 (t, J = 7.1 H¾ 3H, CH3), 2.32 (s, 3H, Pyrazole(C)-CH3), 3.62 (s, 3H, PyrazoleCN)-CH3), 4.42 (q, J = 7.1 ¾ 2H, CH2), 5.11 (s, 2H, Py-CH2), 7.00 (d, J = S.Oj
Hz, 1¾ ArH), 7.18 (s, IH, ArH), 7.23-7.40 (m, 3¾ ArH& Py-H), 7.93 (s, 1¾ CH=N), 8.169-8.20 (m, IH, Py-H), 9.12 (d, J = 1.3Hz, IH, Py-H).
1.41 (t, J = 7.1 Hz, 3H, CH3), 2.29 (s, 3¾ Pyrazole(C)-CH3), 3.63 (s, 3H, Pyrazole(N)-CH3i 3.87 (s, 3H, OCH3), 4.41 ( J = 7.1 ¾ 2H, CH2), 5.16 (s, 2H,k I -CH2), 6.66-6.70 (m, IH, ArH), 6.80-6.85 (m, IH, ArH), 6.92-6.95 (m, 1¾ ArH), 7.02-7.08 (m, IH, ArH), 7.31 (d, J = 8.2 ¾ IH, Py-H), 7.98 (s, IH, CH=N), 8.19-8.23 (m, IH, Py-H), 9.13 (d, J = 1.9Hz, IH, Py-H).
1.35 (t, J = 6.8 Hz, 3H, CH3), 2.19 (s, 3H, Ar-CH3), 2.21 (s, 3H, Ar-CH3), 2.22 (s, 3H, Pyrazole(C)-CH3), 3.52 (s, 3H, Pyrazole(N)-CH3)5 4.34 (q, J = 7.1 ¾ 2H, CH2), 5.09 (s,1 2H, Py-CH2), 6.33 (d, J = 8.2 H¾ IH, ArH), 6.78 (d, J = 7.4 Hz, IH, ArH), 6.90 (s, IH, ArH), 7.22 (d, J = S.6 Hz, IH, Py-H), 7.77 (s, IH, CH=N), S.11-S.14 (m, IH, Py-H), 9.07 (d, J = 2.0Hz, IH, Py-H).
1.41 (t, J = 7.1 ¾ 3H, CH3), 2.26 (s, 6H, Ar-CH3), 2.32 (s, 3H, Pyrazole(C)-CH3), 3.58 (s, 3¾ P razole(N)-CH3), 4.41 (q, J = 7.1 Hz, 2¾ CH2), 5.20 (s, 2H, Py-CH2), 6.46 (s,m 2H, ArH), 6.7 (s, IH, ArH), 7.33 (d, J = 8.1 ¾ IH, Py-H), 7.93 (s, IH, CH=N), 8.19-8.22 (m, IH, Py-H), 9.14 (d, J = 1 4Hz, IH, Py-H).
1.42 (t, J = 7.1 Hz, 3H, CH3), 2.31 (s, 3H, Pyrazole(C)-CH3), 3.61 (s, 3H, Pyrazole(N)-CH3), 4.42 (q, J = 7.1 Hz, 2H, CH2), 5.14 (s, 2H, Py-CH2), 6.68-6.72 (m,n IH, ArH), 6.92 (d = 2.9 ¾ IH, ArH), 7.24 (d, J = 8.3 Hz, IH, Py-H), 7.30 (s, IH, ArH), 7.94 (s, IH, CH=N), 8.20-8.23 (m, IH, Py-H), 9.14 J = 1.9Hz, IH, Py-H).
1.38 (d, J = 6.2 H¾ 6H, CH3), 2.30 (s, 3H, PyrazDle(C)-CH3), 3.61 (s, 3H,
5a P razole(N)-CH3), 5.16 (s, 2H, Py-CH2), 5.29(m, IH, CH), 6.78-6.99 (m, 4H, ArH), 7.27-7.30 (m, 2H, Py-H&ArH), 7.91〔s, 1¾ CH=N), 8.18-8.22 (m, 1 Py-H), 9.13 (d, J = 1.3¾ IH, Py-H).
1.39 (d, J = 6.3 H¾ 6¾ CH3), 2.30 (s, 3¾ ArCH3), 2.32 (s, 3¾ P razole(C)-CH3), 3.60
5b (s, 3H, P razole(N)-CH3), 5.14 (s, 2H, Py-CH2), 5.28(m, IH, CH), 6.51(d, 1 J = 8.1 Hz, ArH), 6.95-7.09 (m ,2 ArH), 7.17(4 J = 7.3 Hz, IH, ArH), 7.29 (s, IH, Py-H), 7.95 (s, lH, CH=N), 8.16-S.20 Cm, lH, Py-H), 9.12(d, J = 2.0¾ IH, Py-H).
1.39 (d, J = 6.3 Hz, 6H, CH3), 2.31 (s, 6H, Pyrazole(C)-CH3&Ar- CH3), 3.59(s, 3H,
5c Pyrazole(N)-CH3)5 5.18 (s, 2H, Py-CH2), 5.28(m, IH, CH), 6.66(4 J = 7.0Hz, 2H, ArH), 6.89(4 J = 7.0Hz, 2H, ArH), 7.13-7.19 (m, IH, ArH), 7.32(d, IH, J = 8.2 Hz, Py-H), 7.92 (s, 1¾ CH=N), 8.17-8.21 (m, l¾ Py-H), 9.12(d, J = 2.0Hz, IH, Py-H).
1.38 (d, J = 6.3 ¾说 6H, CH3), 2.30 (s, 6H, Pyrazole(C)-CH3&Ar-CH3), 3.59 (s, 3H,
5d Pyrazole(N)-CH3)5 5.18 (s, 2H, Py-CH2), 5.28(m, IH, CH), 6.76 (d, J = 6.3 Hz ,2¾ ArH), 7.07 (d, J = 8.2 Hz ,2H, ArH), 7.31 (d, ¾ J = 7.8Hz, Py-H), 7.91 (s, IH, CH=N), 8.18-8.21 (m, IH, Py-H , 9.13 (d, J= 1.4H¾ IH, Py-H).
1.39 (d, J = 6.2 ¾ 6H, CH3), 2.31 (s, 3H, Pyrazole(C)-CH3)5 3.60 (s, 3H,
5e Pyrazole(N>CH3), 5.17 (s, 2H, Py-CH2), 5.28(m, 1¾ CH), 6.86 (d, J = 7.9 Hz ,2¾ ArH), 7.08 (d, J = 7.3 Hz ,2 ArH), 7.31 (d, J = 8.5 ¾ IH, Py-H), 7.92 (s, IH, CH=1¾ 8.18-8.21 (m, IH, Py-H), 9.12 (d, J= 1.3Hz, 1¾ Py-H).
1.39 (d, J = 6.2 Hz, 6H, CH3), 2.30 (s, 3H, Pyrazole(C〕-CH3), 3.60 (s, 3H,
5f P razole(N)-CH3), 5.15 (s, 2H, Py-CH2), 5.28(m, IH, CH), 6.77-6.80〔m ,2H, ArH), 7.12-7.27 (m, 3H, ArH& Py-H), 7.92 (s, IH, CH=N), 8.19-8.22 (m, IH, Py-H), 9.13(4 J = 2.0¾ IH, Py-H). 书
1.38 (4 J = 6.3 6¾ CH3), 2.31 (s, 3H, Pyrazole(C〕-CH3), 3.59 (s, 3H,
¾ Pyrazole(N)-CH3)5 5.14 (s, 2H, Py-CH2), 5.28(m, IH, CH), 6.76-6.79 (m ,1¾ ArH), 6.98 (s, J = 2.1 Hz ,ΙΗ, ArH), 7.09-7.18 (m ,2¾ ArH), 7.26 (d, J = 8.0 Hz, IH, Py-H), 7.92 (s, IH, CH=N), 8.18-8.20 (m, IH, Py-H), 9.1 l(dj = 1.5Hz, IH, Py-H).
1.37 (d, J = 6.3 Hz, 6H, CH3), 2.30(s5 3H, Pyrazole(C)-CH3), 3.59(s, 3H,
5h Pyrazole(N)-CH3)5 3.90 (s, 3H, O- CH3), 5.11 (s, 2H, Py-CH2), 5.26(m, IH, C¾ 6.86-6.89 (m, 2H, ArH), 7.24(d, J = 9.31¾ IH, Py-H), 7.90 (s, IH, CH=N), 7.94-7.96 (m, ¾ ArH): 8.16-8.18 (m, ¾ Py-H), 9.09(d, J = 1.5Hz, IH, Py-H).
1.32 (d, J = 6.2 ¾ 6H, CH3), 2.19-2.23(m, 9H, Pyrazole(C)-CH3&Ar- CH3), 3.52(s,
5i 3H, P razole(N)-CH3), 5.09 (s, 2¾ Py-CH2), 5.21(m, 1¾ CH), 6.33 (d, J = 8.3 Hz, ¾ ArH), 6.7S (d, J = S.3 Hz, IH, ArH), 6.90 (s, IH, ArH), 7.23(s, IH, Py-¾ 7.77 (s, IH, CH= ), 8.10-8.13 (m, IH, Py-H), 9.06(4 J = 1.7Hz, IH, Py-H).
1.39 (d, J = 6.2 Hz, 6H, CH3), 2.31 (s, 3H, Pyrazole(C)-CH3), 3.61 (s, 3H, Pyrazole(N)-CH3)3 5.14 (s, 2H, Py-CH2), 5.29(m, 1 CH), 6.69-6.73 (m, 1¾ ArH),
5j
6.92(d, J = 2.9Hz, 1¾ ArH), 7.21-7.29 (m, IH, ArH& Py-H), 7.94 (s, IH, CH=N), 8.19-8.22 (m, ¾ Py-H), 9.13(d, J = 1.2¾ ¾ Py-H).
1.04 (t, J = 7.4 1¾ 3H, CH3), 1.77-1.84 (m, 2H, CH2), 2.31 (s, 3H, Pyrazole(C)-CH3),
6a 3.60 (s, 3H, Pyrazole(N)-CH3), 4.31 (t, J = 6.7 ¾ 2H, CH2), 5.17 (s, 2H, Py-CH2), 6.86 (d, J = 7.8 Hz, 2H, ArH), 7.08 (t, J = 7.4 Hz; 1 ArH), 7.26-7.33 (m, 3 Py-H&ArH), 7.92 (s, IH, CH=N), 8.19-S.22 (m, IH, Py-H), 9.14 (d, J = 1.5I¾ IH, Py-H).
(t, J = 7.4Hz, 3H, CH3), 1.77-1.87 (m, 2H, CH2), 2.30 (s, 3H, Pyrazole(C)-CH3), 3.60 (s,
6b 3H, P razole(N)-CH3), 4.32 (t, J = 6.7 Hz, 2H, CH2), 5.16 (s, 2H, Py-CH2), 6.79 (d, J = 9.0 H¾ 2¾ ArH), 7.21 (d, J = 9.0 H¾ 2H, ArH), 7.28 (d, J = 6.6 Hz, ¾ Py-H), 7.92 (s, IH, CH=N), 8.20-8.24 (m, IH, Py-H), 9.15 (dj = 1.4¾ IH, Py-H).
0.97 (t J = 7.4 Hz, 3¾ CH3), 1.71-1.78 (m, 2H, CH2), 2.24 (s, 6H, P razole(C)-CH3&Ar-CH3), 3.52 (s, 3H, Pyrazole(N)-CH3), 4.24 ft J = 6.6 Hz, 2H,
6c CH2), 5.12 (s, 2H, Py-CH2), 6.58 (d, J = 7.3 Hz, 2H, ArH), 6.82 (d, J = 7.5 Hz, IH, ArH), 7.09 (t, J = 8.2 Hz, IH, Ar¾ 7.26 (d, J = 8.2 Hz, IH, Py-H), 7.85 (s, IH, CH=N), 8.12-8.16 (m, IH, Py-H), 9.07 (d, J= l .SI¾ IH, Py-H).
0.99 (t, J = 7.3 Hz, 3H, CH3), 1.48 (m, 2H, CH2), 1.77 (m, 2H, CH2), 2.31 (s, 3H, Pyrazole(C)-CH3), 3.60 (s, 3H, Pyrazole(N)-CH3)5 4.36 (t, J = 6.6 Hz, 2H, CH2), 5.17 (s,
7a 2H, P -CH2), 6.86 (d, J = 7.8 H¾ 2¾ ArH), 7.08 (ζ J = 7.4 Hz, IH, ArH), 7.27-7.33 (m, 3H, Py-H&ArH), 7.92 (s, IH, CH=N), 8.18-8.22 (m, IH, Py-H), 9.13 (d, J = 2.0¾ IH,
1.36-1.52 (m, 6H, CH2), 1.78-1.98 (m, 4H, CH2), 2.30 (s, 3H, Pyrazole(C)-CH3), 3.60 (s,b 3H, Pyrazole(¾)-CH3), 5.02-5.08 (m, IH, CH), 5.17 (s, 2H, Py-CH2): 6.7S (d, J = 9.0 Hz, 2H, ArH), 7.21 (d, J = 9.0 H¾ 2¾ ArH), 7.26(4 J = 7.3 Hz, IH, Py-H), 7.91 (s, 1¾ CH= ), 8.20-8.23 (m, IH, Py-H), 9.14 (d, J = l .4Hz, IH, Py-H).
1.40-1.62 (m, 6H, CH2), 1.77-1.96 (m, 4 CH2), 2.30 (s, 6¾ P razole(C)-CH3&Ar-CH3), 3.59 (s, 3H, P razole(N)-CH3): 5.03-5.09 (m, IH, CH),c 5.18 (s3 2H, Py-CH2), 6.66 (d, J = 6.7 Hz, 2H, ArH), 6.89 (d, J = 7.4 Hz, IH, ArH), 7.16 (ζ J = 7.6 ¾ IH, Αήΐ), 7.31 (d, J = 8.1 Hz, IH, Py-H), 7.92 (s, IH, CH=N), 8.18-8.21 (m, ¾ Py-H), 9.14 (d, J = l .4Hz, 1¾ Py-H).
2.31 (s, 3H, Pyrazole(C)-CH3)5 3.60 (s, 3H, Pyrazole(N)-CH3), 3.83 (t, J = 5.7 ¾ 2H, a CH2), 4.61 (t, J = 5.7 Ήζ, 2H, CH2C1), 5.17 (s, 2H, Py-CH2), 6.86 (d, J = 7.8 Ήζ, 2H, ArH), 7.08 (t, J = 7.4 Hz IH, ArH), 7.29-7.35 (m, 3 Py-H&ArH), 7.92 (s, 1 CH=N), 8.20-8.24 (m, IH, P说y-H), 9.16 (d, J= 2.0Hz, IH, Py-H).
2.30 (s, 3H, Pyrazole(C)-CH3), 3.60 (s, 3H, Pyrazole(N)-CH3), 3.83 (ζ J = 5.7 H¾ 2H,b CH2), 4.61 (t, J = 5.7 Hz, 2H, CH2C1), 5.16 (s, 2H, Py-CH2), 6.78 (d, J = 8.9 Hz, 2H, ArH), 7.20 (d, J = 8.9 Hz, 2¾ ArH), 7.29 (d, J = 8.2 H¾ 1¾ Py-H), 7.92 (s, 1¾ CH=N), 8.22-8.25 (m, IH, Py-H), 9.17(4 J= 1.9Hz, IH, Py-H).
2.31 (s, 6H, Pyrazole(g-CH3& AiCH3): 3.59 (s, 3H, PyrazDle(lsl>CH3), 3.83 (t J = 5.6 c Hz, 2H, CH2), 4.61 (t, J = 5.7¾ 2H, CH2C1), 5.19 (s, 2H, Py-CH2): 6.66 (d, J = 7.8 ¾ 2H, ArH), 6.89 (d, J = 7.6 Hz, IH, ArH), 7.16 (t, J = 7.9 Hz, IH, ArH), 7.34 (d, J = 8.2 Hz, IH, Py-E , 7.92 (s, IH, CH=N), 8.21-8.24 (m, IH, Py-H), 9.16 (d, J = 2.0Hz, IH, Py-H).
0.38-0.42 (m, 2H, CHI), 0.62-0.O.68 (m, 2H, CH2), 1.24-0.34 (m, IH, CH),2.33 (s: 3H, Pyrazole(C)-CH3), 3.62 (s, 3H, Pyrazole(N)-CH3), 4.20 (d, J = 7.3 H¾ 2H, CH2), 5.19 a (s, 2H, Py-CH2), 6.SS (d, J = 7.7 Hz, 2H, ArH), 7.08书 (t, J = 7.4 ¾ IH, ArH), 7.30-7.35 (m, 3H, Py-H&ArH), 7.94 (s, 1¾ CH=N), 8.22-8.26 (m, IH, Py-H), 9.17 (d, J = 2.0¾ IH, Py-H).
0.30-0.32 (m, 2H, CH2), 0.54-0. 60 (m, 2H, CHI), 1.14-0.26 (m, IH, CH),
2.23 (s, 3H, P razole(C)-CH3), 3.53〔s, 3H, Pyrazole(N)-CH3), 4.12 (d, J = 7.3 ¾ 2H,b CH2), 5.09 (s: 2¾ P -CH2), 6.71 (d, J = 9.1 ¾ 2H, ArH), 7.14 (d, J = 9.1 Hz, 2H, ArH), 7.21 (d, J = 8.4 Hz, IH, Py-H), 7.85 (s, IH, R=K), 8.17-8.21 (m, IH, Py-H), 9.10 (d, J = 2.1Hz, 1¾ Py-H).
0.30-0.33 (m, 2H, CH2), 0.55-0. 59 (m, 2H, CH2), 0.76-0.81 (m, IH, CH), 2.24 (s, 3H, Pyrazole(C)-CH3), 3.52 (s, 3H, Pyrazole(N)-CH3), 4.12 (d, J = 7.2 ¾ 2H, CH2), 5.12 c (s, 2H, Py-CH2), 6.58 (d, J = 7.5 H¾ 2H, Ar¾ 6.82 (d, J = 7.2 Hz, IH, ArH), 7.09 (t, J = 7.61¾ IH, ArH), 7.26 (d, J = 8.1 ¾ IH, Py-H), 7.85 (s, IH, CH= ), 8.13-8.17 (m, IH, Py-H), 9.09 (s, IH, Py-H).
(s, 3H, PyrazoleCQ-CHj), 3.53 (s, 3H, Pyrazolei ])-CHj)5 3.77 (d, J = 6.3 H¾ 2H, (0>CH2CH), 5.22 s, 2H, Py-CH2), 7.41 (d, J = 8.1 ¾ 1 H, Py-H), S.06 (s, 1H, -CH=N), 8.14 (d, J= 8.1 Hz, 1¾ Py-H), 9.05 (s, l¾ Py-H)
D10 0.84 D, J = 6.9 Hz, 3 H, CH3CH2), 1.23-1.27 (m, 4H, CH^CH^CHB), 1.53 (s, 9H,
1.56-1.61 (m, 2H, CH2CH2CH2), 2.16 (s, 3¾ Pyrazole(C)-CI¾ 3.53 (s, 3H, Pyrazole(N)-CH3): 4.00 (D:J= 6.7¾ 2H, (0)-CH2C¾), 5.23 (s, 2H, Py-C¾), 7.41 (d,J^ 8.1 Hz, 1H, Py-H), 8.07 (s, 1H, -CH= ), 8.17 (dd, = 8.1 Hz, Jj, = 2.1 Hz, 1H, Py-H), 9.05 (d,J= l .S Hz, l ¾ Py-H)
D11 0.83 (d,J = 6.2 ¾ 6H, (CH3)2CH), 1.45-1.50 (m, 2H, CHCH2C¾), 1.53 (s, 9H,
1.60-1.67 (m, 1H, CHfCH:^), 2.16 (s, 3H, PyrazoleCQ-CHj), 3.52 (s, 3H, Pyrazole(N)-CH3)5 4.04 (D, / = 6.7 ¾ 2 H, fo>CH2CH2), 5.23 (s, 2H, P -CH2), 7.41 (d, J = 8.1 Hz, 1H, Py-H), 8.07 (s, 1H, -CH=N), 8.16 (d, J ^ 8.1 Hz; 1H, Py-H), 9.05 (s, ¾
Py-H)
D13 .81 (D, J = 6.3 H说z, 3H, C¾CH2), 1.17-1.28 (m, 6H, (CH2)3CH2), 1.52 (s, 9H, (CHJ)JC)5
1.55-1.59 (m, 2H, CH2CH2), 2.15 (s, 3H, P razol C)-CHs), 3.51 (s, 3H, P razol N)-CH3), 3.99 (D, : 6.6 H¾ 2H, (0)-CH2CH2), 5.21 (s, 2H, Py-C¾), 7.40 (d,J= 8.1 H¾ 1H, Py-H), 8.06 (s, 1H, -CH=:N), 8.15 (d,J= S.l Hz, 1H, Py-H), 9.04 (s, 1H, Py-H)
1.64-1.69 (m, 2H, Cyclohexyl-H), 1.79-1.82 (m, 2H, Cyclohexyl-H), 2.16 (s, 3H, Pyrazole(C)-CH3)5 3.52 (s, 3H, Pyrazole(N)-CHs), 4104.17 (m, 1H, (0> Cyclohexyl-H), 5.22 (s, 2H, Py-CH2), 7.41 (d,J = 8.2 Hz, l¾ Py-H), 8.03 (s, 1H, -CH=N), 8.17(ck = 8.2 Hz,J2= 2.0 ¾ 1H, Py-H), 9.05 (d, J= 1.6 I¾ 1H, Py-H)
D15 0.60-0.69, 1.31-1.42 (m, 5H, Cyclohexyl-H), 0.76, 0.87 (d, J = 6.5 Hz, 5.6 Hz, 3H, CH3), ,
1.53 (s, 9H, (CHs)jC), 1.56-1.61, I.86-1.S8 (m书, 4H, Cyclohexyl-H), 2.17 (s, 3H, Pyrazole(C)-CH3), 3.51, 3.55 (s, 3H, Pyrazole(lSI)-CHj), 4024.10, 4.43444 (m, 1¾ Cyclohe^l-H), 5.24 (s, 2H, Py-CH2), 7.43 (d, J = 8.2 Hz, 1H, Py-H), 8.04〔s, 1H, -CH=N), 8.18 (d, J= 8.2 H¾l¾ Py-H), 9.05 (s, l¾ Py-H
D16 1.51 (s, 9H, (CHj)3C), 2.15 (s, 3H, Pyrazole(C)-CHj), 3.30 (s, 3H, Pyrazole(N>CH3): 5.01
(s, 2H, Py-CH2), 5.23 (s, ¾ Ar-CH2), 7.15-7.17 (m, 2¾ Ar-H), 7.24-7.26 (m, 7H, Ar-H)= 7.38 (d, .7 = 8.1 Hz, 1H, Py-H), 8.05 (s, 1H, -CH=N), 8.11 (d,./ = S. l Hz, 1H, Py-H), 9.02
D17 1.53 (s, 9H, (CHs)sC), 2.16 (s, 3H, Pyrazole(C)-CH3): 3.29 (s, 3H, Pyrazol N)-CH3),
3.45-3.47 (m, 2H, (0)-CH2CH2), 3.55 (s, 3H, (0)-CH3), 4.144.16 (m, 2H, CH2-(0)-Pyrazole), 5.23 (s, 2H, Py-CH2), 7.42 (d, J = 8.1 H¾ 1H, Py-H), 8.06 (s, 1H, -CH=N), 8.18 (dd,Jj = 8.1 ¾ J2 = 2.0 Hz, 1H, Py-H), 9.05 (c = 1.91¾ 1 Py-H)
D18 1.18 (D, J = 7.0 H¾ 3H, C¾CH2), 1.57 (s, 9H, (CH^C), 2.20 (s, 3H, Pyrazole(C)-CH3)5
3.48 (q, J = 7.0 ¾ 2H, C¾CH2)5 3.53-3.55 (m, 2H, (0)-CH2CH2), 3.60 (s, 3H, P razole(N)-C¾), 4.184.20 (m, 2H, C¾<0)-Pyrazole), 5.26 (¾ 2H, Py-C¾), 7.45 (d, J = 8.1 ¾ 1H, Py-H), 8.11 (s, 1H, -CH=N), 8.20 (dd, ^ = 8.1 ¾ J2 = 2.0 ¾ 1H, Py-H), 9.08 (d,./= 1.6 Hz, l¾ Py-H)
Pyrazole(C)-CH3)3 2.17-2.25 (m, 1H, DeDrahydrofuran-IT), 3.56 (s, 3H, Pyrazol )-CH3)3 3.67-3.80 (m, 2H, DeDrahydrofuran-H), 3.88-3.93 (m, 1H, DeDrahydrof ran-H), 3.994.04 (m, 2H, (0)-CH2), 5.23 (s, 2H, Py-C¾), 7.43 (d, J = 8.1 ¾ 1H, Py-H), 8.06 (s, 1H, -CH=N), 8.18 (dd,Jj = 8.1 H¾J2 = 2.0 Hz, 1H, Py-H), 9.05 (d,J= 1.7H¾ 1H, Py-H) 雄例 2
本发明所述化合物的杀虫杀螨活性测试:
1. 对蚕豆蚜的试验:
蚜虫属同翅目 (Homopeera)刺吸式口器害虫,是危害棉花等经济作物的重要害 虫之一。 蚕豆 (A s hburni KalDenbach)是国内有关农药研究单位普遍词养的试 虫。
操作方法: 称取 12mg药样于 lOOmL烧杯中, 加 0.5mLDMF (或其它适合溶
剂), 最多不超过 ImL; 力口乳化剂 Sorpol~560 (或其它适合乳化剂) 1滴, 用玻璃 棒充分搅拌, 使其互相溶解, 再加适量蒸馏水后, 再次充分搅拌, 配成 200ppm的 药液。 将带有若虫的植株在上述药液中浸渍 2-3秒钟, 甩掉多余药液, 将植株扦在 泡沬板上, 加 某油灯灯罩(灯罩上口用纱布、 樣皮圈封口)。 并将试验置于处理 室内。 24h检查结果。 部分化合物测试结果如下表所列:
2. 对朱砂叶螨的试验:
朱砂叶螨 (DeDrmychus cinnabarirms), 非昆虫纲, 属蜘蛛纲叶螨总科, 螨类 害虫代表。 说
操作过程: 称取 12mg药样于 lOOmL烧杯中, 力口 ImL丙酮(或其它适合溶剂)。加 乳化剂 sorpOl~560 (或其它适合乳化剂) 1滴, 用玻璃棒充分搅拌, 使其互相溶解, 再加蒸溜水后, 再次充分搅拌, 配成 200ppm的药液。将带有叶螨的植株在上述药 液中浸渍 5秒钟, 轻轻抖动, 去掉多余的药液, 将植株插入带有方块玻璃盖的水培 缸中, 玻璃盖四周涂以羊毛脂, 防止螨虫逃走。 把试验置于处 ϋ¾内。 24或 48 h 检查结果。 部分化合 则试结果如下表所列:
生测数据 书 目标化合物 la-lfW杀虫活性数据 (200 m^L)
书
200 : 10 0 SO ::: \疆:: 3. il
2b 100 10 0 100 97 83 54 0
2c 100 Ψ ' 97 94 90 68 0
2d 100 10 0 95 88 39 0 0
2e 100 10 0 100 79 13 0 0
2f 100 10 0 100 91 61 0 0
4c 97 9" 1 95 ― ― ― -
4d 90 9C ) 76 ― ― ― -
4f 81 t 73 ― ― ― -
4h S8 11 ί 0 ― ― ― -
4i 91 4i 3 0 ― ― ― ―
4m 74 4 5 0 ― ― ― ―
5a 78 T l 78 ― ― ― -
5b S6 0 0 ― ― ― -
5d 89 7" l 55 ― ― ― ―
5e 84 0 0 - _ - -
5g 82 86 76 ― _ ― ―
6a 100 100 98 91 33 ― ―
6b 96 100 82 35 13 ― -
6c 96 93 55 13 0 ― -
8a 100 93 81 83 75 ― ―
8b 100 95 83 80 77 ― -
8c 100 100 99 92 80 0 0
9a 100 说 100 96 95 92 79 0
9b 100 100 100 96 98 86 12
9c 100 100 95 93 74 0 0
10a 99 96 55 41 31 ― -
10b 86 62 42 0 0 ― ―
10c S8 S7 47 20 0 ― -
11a 100 92 54 37 0 ― - 书
lib 100 S5 81 75 65 ― -
11c 100 96 78 67 0 ― ―
12a 100 100 100 91 34 0 0
12b 100 98 94 89 90 81 19
12c 100 100 97 97 90 0 0 对照化合物
100 100 95 80 50 0 0 (CN1844103公开)
对照化合物
100 90 85 80 75 30 0O (CN1844103公开)
对照化合物
100 95 92 50 22 0 08 (CN1844103公开) 部分化合物对成螨的复筛数据
部分化合物杀红蜘蛛复筛翻书
Claims
1、 一种吡啶肟醚类衍生物, 其特征在于它是具有如下结构式( I ) 的化 合物-
( I )
如上式 ( I ) 所示, T为 N, 其位置可为 2、 3、 4位;
其中 R1为氟取代的苯基或含氟基团取代的苯基, 〜 的烷基或取代烷 基, 烯基或取代烯基, 炔基或取代炔基, 环己基或取代的环己基, 环戊基或 取代的环戊基, 环丙基或取代的环丙基; R2 为卤素、 COOR3; R3 为 (^〜^烷基或取代烷基。
2、 权利要求 1所述的吡啶肟醚类衍生物的制备方法, 其特征在于它是通 过如下的反应步骤合成:
反应物投料的摩尔比为 1 :1, 溶剂为醇类溶剂, 反应于室温下进行, 反应 时间通常为 2〜10小时;
首先将 POCl3与 DMF制成 Vilsmeier Haack试剂, 其投料摩尔比为 1: 1 ~ 10:1, 再将反应物加入其中进行反应, 反应物与 Vilsmeier Haack试剂的摩尔 比可以为 〜1 :10。 反应时间为 3〜12小时, 反应温度为 60〜120°C ;
反应物与醇的投料摩尔比为 1 :1〜1 :5; 反应物与碱的投料摩尔比为 1 :1〜 1 :1.5; 所用碱为 NaOH、 KOH、 K2C03、叔丁醇钠、 叔丁醇钾等等, 反应溶 剂为醇、 四氢呋喃等, 反应温度为 50〜10(TC, 反应时间为 2〜12小时;
于室温下将 1〜1.5
应时间为 1〜3小时; 权 利 要 求 书
如上所述, 其中 T为 N, X为卤素, R R2与上文定义相同; 反应物与 取代吡啶投料摩尔比为 1 :1〜1 :1.5,溶剂为乙腈,碱为无机碱: NaOH、 KOH、 K2C03等等, 反应温度于乙腈回流下进行, 反应时间为 2〜12小时。
3、 按照权利要求 2所述的吡啶肟醚类衍生物的制备方法, 其特征在于所述 的醇类溶剂是甲醇或乙醇。
4、 一种权利要求 1 所述的吡啶肟醚类衍生物的应用, 其特征在于它是用作 农用杀虫杀螨剂。
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Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN104193727A (zh) * | 2014-08-04 | 2014-12-10 | 南通大学 | 含三氟甲基吡啶的吡唑肟醚类化合物的制备和应用 |
WO2015064725A1 (ja) * | 2013-10-31 | 2015-05-07 | 住友化学株式会社 | ピラゾール化合物及びその有害生物防除用途 |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH0296568A (ja) * | 1988-09-30 | 1990-04-09 | Ishihara Sangyo Kaisha Ltd | ピラゾール系化合物、それらの製造方法及びそれらを含有する有害生物防除剤 |
WO2003086077A1 (fr) * | 2002-04-16 | 2003-10-23 | Ishihara Sangyo Kaisha, Ltd. | Compositions anti-tiques ou anti-puces pour les animaux |
CN1844103A (zh) * | 2006-03-22 | 2006-10-11 | 南开大学 | 吡唑肟醚类衍生物和制备及其应用 |
CN101659656A (zh) * | 2009-09-07 | 2010-03-03 | 南开大学 | 吡啶肟醚类衍生物和制备及其应用 |
-
2010
- 2010-12-24 WO PCT/CN2010/080205 patent/WO2012083550A1/zh active Application Filing
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH0296568A (ja) * | 1988-09-30 | 1990-04-09 | Ishihara Sangyo Kaisha Ltd | ピラゾール系化合物、それらの製造方法及びそれらを含有する有害生物防除剤 |
WO2003086077A1 (fr) * | 2002-04-16 | 2003-10-23 | Ishihara Sangyo Kaisha, Ltd. | Compositions anti-tiques ou anti-puces pour les animaux |
CN1844103A (zh) * | 2006-03-22 | 2006-10-11 | 南开大学 | 吡唑肟醚类衍生物和制备及其应用 |
CN101659656A (zh) * | 2009-09-07 | 2010-03-03 | 南开大学 | 吡啶肟醚类衍生物和制备及其应用 |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2015064725A1 (ja) * | 2013-10-31 | 2015-05-07 | 住友化学株式会社 | ピラゾール化合物及びその有害生物防除用途 |
CN104193727A (zh) * | 2014-08-04 | 2014-12-10 | 南通大学 | 含三氟甲基吡啶的吡唑肟醚类化合物的制备和应用 |
CN104193727B (zh) * | 2014-08-04 | 2018-12-04 | 南通大学 | 含三氟甲基吡啶的吡唑肟醚类化合物的制备和应用 |
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