CN105968092B - N1(3- substituted pyrazolecarboxylic -5- formoxyls)-substituted benzene oxygen alkyl hydrazine derivative and its application - Google Patents

N1(3- substituted pyrazolecarboxylic -5- formoxyls)-substituted benzene oxygen alkyl hydrazine derivative and its application Download PDF

Info

Publication number
CN105968092B
CN105968092B CN201610380214.5A CN201610380214A CN105968092B CN 105968092 B CN105968092 B CN 105968092B CN 201610380214 A CN201610380214 A CN 201610380214A CN 105968092 B CN105968092 B CN 105968092B
Authority
CN
China
Prior art keywords
substituted
pyrazoles
formoxyls
bases
compound
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Fee Related
Application number
CN201610380214.5A
Other languages
Chinese (zh)
Other versions
CN105968092A (en
Inventor
王威
宁斌科
王列平
李秉擘
毛明珍
薛超
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Xian Modern Chemistry Research Institute
Original Assignee
Xian Modern Chemistry Research Institute
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Xian Modern Chemistry Research Institute filed Critical Xian Modern Chemistry Research Institute
Priority to CN201610380214.5A priority Critical patent/CN105968092B/en
Publication of CN105968092A publication Critical patent/CN105968092A/en
Application granted granted Critical
Publication of CN105968092B publication Critical patent/CN105968092B/en
Expired - Fee Related legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • 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
    • 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

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Agronomy & Crop Science (AREA)
  • Pest Control & Pesticides (AREA)
  • Plant Pathology (AREA)
  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Dentistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Zoology (AREA)
  • Environmental Sciences (AREA)
  • Plural Heterocyclic Compounds (AREA)
  • Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)

Abstract

The invention discloses a kind of N1(3 substituted pyrazolecarboxylic, 5 formoxyl) substituted benzene oxygen alkyl hydrazine derivative, general formula I, R is indicated in Formulas I：Halogen, hydrogen, nitro, methyl, methoxyl group, trifluoromethyl；R1It indicates：Methyl, ethyl, hydrogen；R2It indicates：Trifluoromethyl, chlorine, bromine etc.；R3It indicates：Halogen, hydrogen.Such compound has significant inhibiting effect to 2 insecticide targets of mythimna separata and diamondback moth, can be used as the active ingredient of insecticide.

Description

N1(3- substituted pyrazolecarboxylic -5- formoxyls)-substituted benzene oxygen alkyl hydrazine derivative and its Using
Technical field
The present invention relates to a kind of N1(3- substituted pyrazolecarboxylic -5- formoxyls)-substituted benzene oxygen alkyl hydrazine derivative and its conduct Active component with insecticidal action is used for field of pesticides.
Background technology
In recent decades, heterocyclic compound causes the extensive concern of pesticide worker due to its efficient bioactivity, There is the commercialization pesticide much containing pyrazoles, pyridine heterocycle constantly to be reported out.Such as herbicide azimsulfuron (Azimsulfuron), pyrazolate (Pyrazolate) and pyrrole chlorine grass amine (Nipyraclofen) etc.；Insecticide fenpyroximate (Fenpyroximate), Rynaxypyr (Chlorantraniliprole), nitrile insect amide (Cyantraniliprole) Deng and fungicide pyrazoles Fluoxastrobin (Pyraclostrobin) etc..In addition, the compound of active substructure bishydrazide Often there is good insecticidal activity, also there is extensive research and important application in terms of New pesticides discovery.Such as insecticide Tebufenozide (Tebufenozide), chlorine hydrazides (Halofenozide) and methoxy hydrazides (Methoxyfenozide) etc..
In view of above-mentioned background, principle is spliced using active substructure, by pyrazoles, pyridine and active substructure bishydrazide into Row effectively splicing, to obtain the pesticide candidate variety or lead compound with pesticide activity especially insecticidal activity, undoubtedly It is one of the hot spot of current New pesticides discovery.In addition, due to long-term a large amount of uses of existing insecticide, pest population is to pesticide Sensibility reduces so that the resistance problem that current many insecticide varieties face also becomes increasingly conspicuous, and it is new to develop more structures The insecticide variety of grain husk just becomes an important channel for solving resistance problem.
Invention content
It is a kind of with insecticidal activity the technical problem to be solved by the present invention is in view of the problems of the existing technology, provide N1(3- substituted pyrazolecarboxylic -5- formoxyls)-substituted benzene oxygen alkyl hydrazine derivative and its application, such compound can be used as tool There is the active component of insecticidal action, be used for field of pesticides, and the present invention enriches the type of bishydrazide insecticide, can be with The resistance problems of getting worse are effectively relieved.
The present invention provides a kind of N1(3- substituted pyrazolecarboxylic -5- formoxyls)-substituted benzene oxygen alkyl hydrazine derivative, structure General formula is as shown in I：
In Formulas I, R is indicated：Halogen, hydrogen, nitro, methyl, methoxyl group, trifluoromethyl；R1It indicates：Methyl, ethyl, hydrogen；R2Table Show：Trifluoromethyl, chlorine, bromine；R3It indicates：Halogen, hydrogen.
The N of the present invention1The preparation route of (3- substituted pyrazolecarboxylic -5- formoxyls)-substituted benzene oxygen alkyl hydrazine derivative is as follows Shown in formula：
In formula, R is indicated：Halogen, hydrogen, nitro, methyl, methoxyl group, trifluoromethyl；R1It indicates：Methyl, ethyl, hydrogen；R2Table Show：Trifluoromethyl, chlorine, bromine；R3It indicates：Halogen, hydrogen.
The N of the present invention1The preparation method of (3- substituted pyrazolecarboxylic -5- formoxyls)-substituted benzene oxygen alkyl hydrazine derivative, packet Include following steps：
(1) preparation of 3- substitutions -1- (substituted pyridines -2- bases) -1H- pyrazoles -5- formyl chlorides IV
In three-necked bottle be added 3- substitutions -1- (substituted pyridines -2- bases) -1H- pyrazoles -5- formic acid III and through drying at Toluene, thionyl chloride and the n,N-Dimethylformamide of reason, are to slowly warm up to 50~100 DEG C, keep 3~5h of this thermotonus, Solvent is evaporated off and remaining thionyl chloride obtains 3- substitutions -1- (substituted pyridines -2- bases) -1H- pyrazoles -5- formyl chlorides IV；Wherein, Rate of charge be 10mmol3- substitutions -1- (substituted pyridines -2- bases) -1H- pyrazoles -5- formyl chlorides IV be added 15mL dryings toluene, The N of 6mL thionyl chlorides and 0.03mL, N1Dimethylformamide.
(2)N1The preparation of (3- substituted pyrazolecarboxylic -5- formoxyls)-substituted benzene oxygen alkyl hydrazine I
Substituted benzene oxygen alkyl hydrazine II, triethylamine and dichloromethane are added in three-necked bottle, 3-, which is slowly added dropwise, at 0 DEG C takes The dichloromethane solution of generation -1- (substituted pyridines -2- bases) -1H- pyrazoles -5- formyl chlorides IV, drop finish, and reaction solution is allowed to be gradually increased to 40 DEG C, the reaction was continued 3~5h has a large amount of solids to be precipitated, and organic solvent is evaporated off, then wash 1~2 time through saturated sodium bicarbonate water, until Aqueous solution filters after being in neutrality, and obtained solid obtains N through ethyl alcohol recrystallization1(3- substituted pyrazolecarboxylic -5- formoxyls)-substituted benzene oxygen alkane Base hydrazides I；Wherein, rate of charge is the substituted benzene oxygen alkyl hydrazine II of 10mmol, and triethylamine, the 40mL dichloromethanes of 14mmol is added 3- substitutions -1- (substituted pyridines -2- bases) -1H- pyrazoles -5- formyl chloride IV and 50mL dichloromethane solutions of alkane, 10.2mmol.
The N of the present invention1The application of (3- substituted pyrazolecarboxylic -5- formoxyls)-substituted benzene oxygen alkyl hydrazine derivative is to utilize The method of preliminary virulence test in insecticide room, according to《Pesticide bioactivity evaluates SOP》Activity rating standard, to mythimna separata and 2 targets of diamondback moth check test worm death condition after handling 24 hours and 48 hours, and calculate the death rate, the results showed that have The part of compounds of above structure general formula I has significant inhibiting effect to 2 targets of mythimna separata and diamondback moth, can be used as insecticide Active ingredient.
Beneficial effects of the present invention：Major part N of the present invention1(3- substituted pyrazolecarboxylic -5- formoxyls)-substituted benzene oxygen Alkyl hydrazine derivative has A grades (A grades are 100%-90%) and B grades to 2 targets of mythimna separata and diamondback moth, and (B grades are 90%- 70%) insecticidal activity can be used as the active ingredient of insecticide, and the present invention enriches the type of bishydrazide insecticide, The resistance problems of getting worse can be effectively relieved.
Specific implementation mode
The preparation method of the compound of formula I of the present invention is specifically described below by certain embodiments, these embodiments are only The present invention will be described, rather than limits the invention.
Embodiment 1
Compound I-1：1N- [5- (the bromo- 1- of 3- (3- chloropyridine -2- bases) -1H- pyrazoles)-formoxyl] -4- chlorobenzene oxygen acetyl Hydrazine
(1) take the bromo- 1- of 0.0055mol 3- (3- chloropyridine -2- bases) -1H- pyrazoles -5- formic acid III, 3mL thionyl chlorides and 7mL toluene is added in the three-necked bottle of the 25mL equipped with reflux condensing tube, thermometer, is warming up to 50~80 DEG C of 4~5h of reaction, then Remaining thionyl chloride and toluene is evaporated off, obtains the bromo- 1- of 3- (3- chloropyridine -2- bases) -1H- pyrazoles -5- formyl chloride IV, directly For the next step；
(2) addition (0.005mol) intermediate 4- chlorobenzene oxyalkyls hydrazides II, (0.003mol) in 50mL round-bottomed flasks K2CO3, 10mLTHF and 10mL water.The bromo- 1- of lower dropwise addition intermediate 3- (3- chloropyridine -2- bases) -1H- pyrazoles -5- first is stirred at room temperature Acyl chlorides IV, finishes, and TLC tracking reactions are stirred at room temperature 0.5~3h, filter, washing, the mixed solvent weight of ethyl alcohol or DMF and ethyl alcohol Crystallization, obtains sterling N1[the bromo- 1- of 3- (3- chloropyridine -2- bases) -1H- pyrazoles -5- formoxyls] -4- chlorobenzene oxygen acethydrazides, yield 89%, 111~113 DEG C of fusing point.
Molecular formula：C17H12BrCl2N5O3；
Elemental analysis (%), calculated value：C,42.09；H,2.49；N,14.44；Measured value：C,42.12；H,2.44；N, 14.39；
1H NMR(500MHz,DMSO-d6):δ4.62(s,2H,-CH2 -),6.98-8.52(m,8H,4H-Pyrazole ,3,4,5H-Py, 2,3,5,6H-Ar),10.32(1H),10.78(1H)；
MS:m/z 482.95(M+)
Compound I-2~I-10 is prepared according to method similar compound I-1.
Compound I-2：1N- [5- (the bromo- 1- of 3- (3- chloropyridine -2- bases) -1H- pyrazoles)-formoxyl] -4- chlorobenzene oxygen isopropyls Hydrazides
Yield 90%, 119~121 DEG C of fusing point；
Molecular formula：C18H14BrCl2N5O3；
Elemental analysis (%), calculated value：C,43.31；H,2.83；N,14.03；Measured value：C,43.26；H,2.87；N, 14.08；
1H NMR(500MHz,DMSO-d6):δ 1.43 (d, 3H, J=7.0Hz, CH-CH3 ), 4.82 (q, 1H, J=7.0Hz, CH-CH3),6.96(2H),7.26(s,1H,4H-Pyrazole),7.29-8.51(m,4H,3,4,5H-Py,3,4,5,6H-Ar), 10.34(1H),10.78(1H)；
MS:m/z 496.97(M+)
Compound I-3：1N- [5- (the bromo- 1- of 3- (3- chloropyridine -2- bases) -1H- pyrazoles)-formoxyl] -2,4 dichloro benzene oxygen Acethydrazide
Yield 92%, 118~120 DEG C of fusing point；
Molecular formula：C17H11BrCl3N5O3；
Elemental analysis (%), calculated value：C,39.30；H,2.13；N,13.48；Measured value：C,39.34；H,2.14；N, 13.46；
1H NMR(500MHz,DMSO-d6):δ4.74(s,2H,CH2 ), 7.02 (d, 1H, J=9.0Hz,6H-Ar),7.29 (s,1H, 4H-Pyrazole),7.32-8.51(m,5H,3,4,5H-Py,3,5H-Ar),10.34(1H),10.85(1H)；
13C NMR(125MHz,DMSO-d6):67.16,110.83,115.88,123.12,125.74,127.29, 128.40,129.06,129.89,130.09,137.78,139.81,147.62,148.92,152.92,156.31,166.69；
MS:m/z 516.91(M+)
Compound I-4：1N- [5- (the bromo- 1- of 3- (3- chloropyridine -2- bases) -1H- pyrazoles)-formoxyl] -2,4 dichloro benzene oxygen Isopropyl hydrazides
Yield 88%, 108~110 DEG C of fusing point；
Molecular formula：C18H13BrCl3N5O3；
Elemental analysis (%), calculated value：C,40.52；H,2.46；N,13.12；Measured value：C,40.48；H,2.50；N, 13.09；
1H NMR(500MHz,DMSO-d6):δ 1.48 (d, 3H, J=6.5Hz, CH-CH3 ), 4.87 (q, 1H, J= 3.25Hz,CH-CH3), 7.03 (d, 1H, J=8.5Hz,6H-Ar),7.15(s,1H,4H-Pyrazole),7.17-8.52(m, 5H,3,4,5H-Py, 3,5H-Ar),10.34(1H),10.85(1H)；
MS:m/z 530.93(M+)
Compound I-5：1N- [5- (the bromo- 1- of 3- (3- chloropyridine -2- bases) -1H- pyrazoles)-formoxyl] -3- chlorobenzene oxygen acetyl Hydrazine
Yield 91%, 127~129 DEG C of fusing point；
Molecular formula：C17H12BrCl2N5O3；
Elemental analysis (%), calculated value：C,42.09；H,2.49；N,14.44；Measured value：C,42.13；H,2.46；N, 14.41；
1H NMR(500MHz,DMSO-d6):δ4.65(s,2H,-CH2 -),6.94-8.51(m,8H,4H-Pyrazole ,3,4,5H-Py, 2,4,5,6H-Ar),10.33(1H),10.79(1H)；
MS:m/z 482.95(M+)
Compound I-6：1N- [5- (the bromo- 1- of 3- (3- chloropyridine -2- bases) -1H- pyrazoles)-formoxyl] -3- chlorobenzene oxygen isopropyls Hydrazides
Yield 89%, 112~114 DEG C of fusing point；
Molecular formula：C18H14BrCl2N5O3；
Elemental analysis (%), calculated value：C,43.31；H,2.83；N,14.03；Measured value：C,43.29；H,2.85；N, 14.07；
1H NMR(500MHz,DMSO-d6):δ 1.48 (d, 3H, J=6.5Hz, CH-CH3 ), 4.87 (q, 1H, J=6.5Hz, CH-CH3),6.91-8.52(m,8H,4H-Pyrazole,3,4,5H-Py,2,4,5,6H-Ar),10.35(1H),10.78(1H)；
MS:m/z 496.97(M+)
Compound I-7：1N- [5- (the bromo- 1- of 3- (3- chloropyridine -2- bases) -1H- pyrazoles)-formoxyl] -2- chlorobenzene oxygen acetyl Hydrazine
Yield 91%, 99~101 DEG C of fusing point；
Molecular formula：C17H12BrCl2N5O3；
Elemental analysis (%), calculated value：C,42.09；H,2.49；N,14.44；Measured value：C,42.11；H,2.46；N, 14.49；
1H NMR(500MHz,DMSO-d6):δ4.72(s,2H,-CH2 -),6.96-8.52(m,8H,4H-Pyrazole ,3,4,5H-Py, 3,4,5,6H-Ar),10.32(1H),10.84(1H)；
13C NMR(125MHz,DMSO-d6):67.51,110.82,114.65,122.02,122.81,127.31, 128.65,129.07,130.08,130.57,137.75,139.82,147.63,148.89,153.72,156.32,166.99；
MS:m/z 482.95(M+)
Compound I-8：1N- [5- (the bromo- 1- of 3- (3- chloropyridine -2- bases) -1H- pyrazoles)-formoxyl] -2- chlorobenzene oxygen isopropyls Hydrazides
Yield 90%, 104~106 DEG C of fusing point；
Molecular formula：C18H14BrCl2N5O3；
Elemental analysis (%), calculated value：C,43.31；H,2.83；N,14.03；Measured value：C,43.35；H,2.84；N, 13.99；
1H NMR(500MHz,DMSO-d6):δ 1.49 (d, 3H, J=6.5Hz, CH-CH3 ), 4.85 (q, 1H, J=6.5Hz, CH-CH3),6.95-8.52(m,8H,4H-Pyrazole,3,4,5H-Py,3,4,5,6H-Ar),10.38(1H),10.83(1H)；
13C NMR(125MHz,DMSO-d6):19.16,73.96,110.84,115.71,122.67,122.92, 127.32,128.60,129.07,130.08,130.64,137.81,139.85,147.64,148.90,153.19,156.32, 170.26；
MS:m/z 496.97(M+)
Compound I-9：1N- [5- (the bromo- 1- of 3- (3- chloropyridine -2- bases) -1H- pyrazoles)-formoxyl] -2- fluorobenzene oxygen acetyl Hydrazine
Yield 78%, 87~89 DEG C of fusing point；
Molecular formula：C17H12BrClFN5O3；
Elemental analysis (%), calculated value：C,43.57；H,2.58；N,14.94；Measured value：C,43.61；H,2.55；N, 14.89；
1H NMR(500MHz,DMSO-d6):δ4.72(s,2H,-CH2 -),6.95-8.52(m,8H,4H-Pyrazole ,3,4,5H-Py, 3,4,5,6H-Ar),10.52(1H),10.84(1H)；
MS:m/z 466.98(M+)
Compound I-10：1N- [5- (the bromo- 1- of 3- (3- chloropyridine -2- bases) -1H- pyrazoles)-formoxyl] -2- fluorobenzene oxygen is different Propionyl hydrazine
Yield 83%, 89~91 DEG C of fusing point；
Molecular formula：C18H14BrClFN5O3；
Elemental analysis (%), calculated value：C,44.79；H,2.92；N,14.51；Measured value：C,44.82；H,2.93；N, 14.48；
1H NMR(500MHz,DMSO-d6):δ 1.46 (d, 3H, J=6.5Hz, CH-CH3 ), 4.83 (q, 1H, J=6.5Hz, CH-CH3),6.95-8.52(m,8H,4H-Pyrazole,3,4,5H-Py,3,4,5,6H-Ar),10.38(1H),10.79(1H)；
13C NMR(125MHz,DMSO-d6):19.12,74.09,110.84,116.70,116.83,122.60, 125.13,127.35,128.56,129.06,130.09,133.18,137.81,139.84,145.43,145.51,147.64, 148.93,151.59,153.53,156.30,170.32；
MS:m/z 481(M+)
Embodiment 2
Compound I-11：1N- [5- (the bromo- 1- of 3- (3- chloropyridine -2- bases) -1H- pyrazoles)-formoxyl] -4- fluorobenzene oxygen is different Propionyl hydrazine
(1) the bromo- 1- of 0.0055mol 3- (3- chloropyridine -2- bases) -1H- pyrazoles -5- formic acid III, 5mL thionyl chlorides is taken to add In the three-necked bottle for entering the 25mL equipped with reflux condensing tube, thermometer, 50~80 DEG C of 4~5h of reaction are warming up to, it is extra to be then evaporated off Thionyl chloride, obtain the bromo- 1- of 3- (3- chloropyridine -2- bases) -1H- pyrazoles -5- formyl chloride IV, be directly used in the next step；
(2) addition (0.005mol) intermediate 4- fluorobenzene oxygen isopropyls hydrazides II, (0.006mol) in 50mL round-bottomed flasks Triethylamine, 10mLTHF and 10mL water.The bromo- 1- of lower dropwise addition intermediate 3- (3- chloropyridine -2- bases) -1H- pyrazoles -5- is stirred at room temperature Formyl chloride IV, finishes, and TLC tracking reactions are stirred at room temperature 0.5~3h, filter, washing, the mixed solvent of ethyl alcohol or DMF and ethyl alcohol Recrystallization, obtains N1[3- substitutions -1- (substitution -2- pyridyl groups) -1H- pyrazoles -5- formoxyls] -4- fluorobenzene oxygen isopropyl hydrazides
Yield 81%, 100~102 DEG C of fusing point.
Molecular formula：C18H14BrClFN5O3；
Elemental analysis (%), calculated value：C,44.79；H,2.92；N,14.51；Measured value：C,44.82；H,2.87；N, 14.53；
1H NMR(500MHz,DMSO-d6):δ 1.43 (d, 3H, J=6.5Hz, CH-CH3 ), 4.78 (q, 1H, J=6.5Hz, CH-CH3),6.94-8.52(m,8H,4H-Pyrazole,3,4,5H-Py,2,3,5,6H-Ar),10.32(1H),10.74(1H)；
MS:m/z 481(M+)
Compound I-12~I-18 is prepared according to method similar compound I-11.
Compound I-12：1N- [5- (the bromo- 1- of 3- (3- chloropyridine -2- bases) -1H- pyrazoles)-formoxyl] -4- fluorobenzene oxygen second Hydrazides
Yield 75%, 78~80 DEG C of fusing point；
Molecular formula：C17H12BrClFN5O3；
Elemental analysis (%), calculated value：C,43.57；H,2.58；N,14.94；Measured value：C,43.61；H,2.57；N, 14.98；
1H NMR(500MHz,DMSO-d6):δ4.58(s,2H,-CH2 -),6.97-8.52(m,8H,4H-Pyrazole ,3,4,5H-Py, 2,3,5,6H-Ar),10.32(1H),10.74(1H)；
MS:m/z 466.98(M+)
Compound I-13：1N- [5- (the bromo- 1- of 3- (3- chloropyridine -2- bases) -1H- pyrazoles)-formoxyl] -4- methylenedioxy phenoxies Acethydrazide
Yield 82%, 111~113 DEG C of fusing point；
Molecular formula：C18H15BrClN5O3；
Elemental analysis (%), calculated value：C,46.52；H,3.25；N,15.07；Measured value：C,46.57；H,3.23；N, 15.11；
1H NMR(500MHz,DMSO-d6):δ2.22(s,3H,4-CH3 -Ar),4.54(s,2H,-CH2 -),6.84-8.52 (m,8H, 4H-Pyrazole,3,4,5H-Py,2,3,5,6H-Ar),10.27(1H),10.77(1H)；
MS:m/z 463(M+)
Compound I-14：1N- [5- (the bromo- 1- of 3- (3- chloropyridine -2- bases) -1H- pyrazoles)-formoxyl] -4- methylenedioxy phenoxies Isopropyl hydrazides
Yield 79%, 93~95 DEG C of fusing point；
Molecular formula：C19H17BrClN5O3；
Elemental analysis (%), calculated value：C,47.67；H,3.58；N,14.63；Measured value：C,47.64；H,3.58；N, 14.66；
1H NMR(500MHz,DMSO-d6):δ 1.42 (d, 3H, J=6.5Hz, CH-CH3 ),2.22(s,3H,4-CH3 - ), Ar 4.75 (q, 1H, J=6.5Hz, CH-CH3),6.81-8.52(m,8H,4H-Pyrazole,3,4,5H-Py,2,3,5,6H-Ar), 10.29(1H),10.73(1H)；
13C NMR(125MHz,DMSO-d6):19.15,20.56,73.07,110.82,115.72,127.34,129.06, 130.09,130.26,133.18,137.84,139.83,147.63,148.96,155.44,156.30,170.98；
MS:m/z 477.02(M+)
Compound I-15：1N- [5- (the bromo- 1- of 3- (3- chloropyridine -2- bases) -1H- pyrazoles)-formoxyl] -2- methylenedioxy phenoxies Acethydrazide
Yield 85%, 124~126 DEG C of fusing point；
Molecular formula：C18H15BrClN5O3；
Elemental analysis (%), calculated value：C,46.52；H,3.25；N,15.07；Measured value：C,46.51；H,3.27；N, 15.06；
1H NMR(500MHz,DMSO-d6):δ2.20(s,3H,2-CH3 -Ar),4.60(s,2H,-CH2 -),6.83-8.52 (m,8H, 4H-Pyrazole,3,4,5H-Py,3,4,5,6H-Ar),10.20(1H),10.78(1H)；
MS:m/z 463(M+)
Compound I-16：1N- [5- (the bromo- 1- of 3- (3- chloropyridine -2- bases) -1H- pyrazoles)-formoxyl] -2- methylenedioxy phenoxies Isopropyl hydrazides
Yield 84%, 117~119 DEG C of fusing point；
Molecular formula：C19H17BrClN5O3；
Elemental analysis (%), calculated value：C,47.67；H,3.58；N,14.63；Measured value：C,47.72；H,3.59；N, 14.61；
1H NMR(500MHz,DMSO-d6):δ 1.45 (d, 3H, J=6.5Hz, CH-CH3 ),2.19(s,3H,2-CH3 - ), Ar 4.77 (q, 1H, J=6.5Hz, CH-CH3),6.81-8.52(m,8H,4H-Pyrazole,3,4,5H-Py,3,4,5,6H-Ar), 10.25(1H),10.74(1H)；
MS:m/z 477.02(M+)
Compound I-17：1N- [5- (the bromo- 1- of 3- (3- chloropyridine -2- bases) -1H- pyrazoles)-formoxyl]-benzene oxygen acethydrazide
Yield 81%, 87~89 DEG C of fusing point；
Molecular formula：C17H13BrClN5O3；
Elemental analysis (%), calculated value：C,45.31；H,2.91；N,15.54；Measured value：C,45.33；H,2.94；N, 15.57；
1H NMR(500MHz,DMSO-d6):δ4.57(s,2H,-CH2 -),6.94-8.51(m,9H,4H-Pyrazole ,3,4,5H-Py, 2,3,4,5,6H-Ar),10.15(1H),10.44(1H)；
MS:m/z 448.99(M+)
Compound I-18：1N- [5- (the bromo- 1- of 3- (3- chloropyridine -2- bases) -1H- pyrazoles)-formoxyl]-benzene oxygen isopropyl acyl Hydrazine
Yield 78%, 96~98 DEG C of fusing point；
Molecular formula：C18H15BrClN5O3；
Elemental analysis (%), calculated value：C,46.52；H,3.25；N,15.07；Measured value：C,46.48；H,3.30；N, 15.12；
1H NMR(500MHz,DMSO-d6):δ 1.47 (d, 3H, J=6.5Hz, CH-CH3 ), 4.78 (q, 1H, J=6.5Hz, CH-CH3),6.94-8.51(m,9H,4H-Pyrazole,3,4,5H-Py,2,3,4,5,6H-Ar),10.17(1H),10.34(1H)；
MS:m/z 463(M+)
Embodiment 3
Compound I-19：1N- [5- (3- Trifluoromethyl-1s-(pyridine -2- bases) -1H- pyrazoles)-formoxyl] -4- chlorobenzene oxygen Acethydrazide
(1) 0.0055mol 3- Trifluoromethyl-1s-(pyridine -2- bases) -1H- pyrazoles -5- formic acid III, 5mL protochlorides are taken Sulfone, 6mL toluene are added in the three-necked bottle of the 25mL equipped with reflux condensing tube, thermometer, are warming up to 50~80 DEG C of 4~5h of reaction, Then extra thionyl chloride is evaporated off, obtains 3- Trifluoromethyl-1s-(pyridine -2- bases) -1H- pyrazoles -5- formyl chloride IV, directly For the next step.
(2) addition (0.005mol) intermediate 4- chlorobenzene oxygen acethydrazide II, (0.006mol) in 50mL round-bottomed flasks K2CO3, 15mL water.Lower dropwise addition intermediate 3- Trifluoromethyl-1s-(pyridine -2- bases) -1H- pyrazoles -5- formyl chloride IV are stirred at room temperature, It finishes, TLC tracking reactions are stirred at room temperature 0.5~3h, filter, and washing, ethyl alcohol or DMF and the mixed solvent of ethyl alcohol recrystallize, and obtain N1[3- substitutions -1- (substitution -2- pyridyl groups) -1H- pyrazoles -5- formoxyls] -4- chlorobenzene oxygen acethydrazides.
Yield 76%, 106~108 DEG C of fusing point.
Molecular formula：C18H13ClF3N5O3；
Elemental analysis (%), calculated value：C,49.16；H,2.98；N,15.92；Measured value：C,49.20；H,3.01；N, 15.88；
1H NMR(500MHz,DMSO-d6):δ4.52(s,2H,-CH2 -),6.98-8.52(m,8H,4H-Pyrazole ,3,4,5H-Py, 2,3,5,6H-Ar),10.39(1H),10.81(1H)；
MS:m/z 439.07(M+)
Compound I-20 is prepared according to method similar compound I-19.
Compound I-20：1N- [5- (the bromo- 1- of 3- (pyridine -2- bases) -1H- pyrazoles)-formoxyl] -4- nitrobenzene oxygen acetyl Hydrazine
Yield 80%, 101~103 DEG C of fusing point；
Molecular formula：C17H13BrClN5O3；
Elemental analysis (%), calculated value：C,45.31；H,2.91；N,15.54；Measured value：C,45.29；H,2.92；N, 15.55；
1H NMR(500MHz,DMSO-d6):δ4.62(s,2H,-CH2 -),6.98-8.52(m,8H,4H-Pyrazole ,3,4,5H-Py, 2,3,5,6H-Ar),10.32(1H),10.78(1H)；
MS:m/z 448.99(M+)
The N of the present invention1(3- substituted pyrazolecarboxylic -5- formoxyls)-substituted benzene oxygen alkyl hydrazine derivative insecticidal activity is tested
(1) for examination target and condition of culture：
Mythimna separata, diamondback moth are handled indoors and are placed in culture dish, in 22 ± 3 DEG C of temperature, humidity 60~80% is supported Zooecium is placed.
(2) instrument and equipment and experimental concentration：
Electronic balance (sensibility reciprocal a ten thousandth), 100ml beakers, graduated cylinder, culture dish, para film, sponge, filter paper, pipette, Tweezers, writing brush etc..
Active compound：Aequum is weighed with a ten thousandth electronic balance；Solvent：DMF, 0.2%；Emulsifier：Tween-80, 0.2%；Clear water is added and is diluted to required concentration.
Experimental concentration：
Carrying malicious leaf dish method, accurately 5% test sample acetone soln of preparation is spare using sample.
It is spare that spray-on process accurately prepares 500mg/L using sample.
(3) test method and activity rating：
Reference《Pesticide bioactivity evaluates SOP》.
Dip method：Almost the same, the healthy test worm of Individual Size is chosen, 4 repetitions are often handled, often repeatedly 10 cephalont.It will Leaching worm cage leaching equipped with test worm is into the liquid, is adsorbed on the liquid of polypide surface and surrounding with blotting paper through taking-up in 5 seconds, and set Corresponding organic solvent processing without medicament is as a contrast.
Carry malicious leaf dish method：Using the malicious leaf dish method of load.Use 100 aqueous solutions of 0.01%Tritonix that medicament to be measured is diluted 5 Cabbage leaves are broken into disk by a concentration with the card punch of diameter 1cm, are dropped on blade with 1 μ L micro intravenous drips device points respectively, Mythimna separata uses 1% acetone soln, diamondback moth to use 0.5% acetone soln, waits for that solvent volatilization is dry, is put into 24 orifice plates, per hole 1 Piece, 3 instar larvae of access diamondback moth 1.10 test worms are often handled, 4 repetitions compare drop equivalent acetone treatment blade, are placed in Moisturizing culture under 25 DEG C of temperature condition checks each processing death toll for 24 hours, after 48h, calculates corrected mortality.
The insecticidal activity data of 1 compound I-1~I-20 of table
In table for 24 hours with 48h mortality levels：A grades are 100%-90%；B grades are 90%-70%；C grades are 70%-50%； D grades are 50%-0%；aNT expressions are not tested.

Claims (2)

1. a kind of N1(3- substituted pyrazolecarboxylic -5- formoxyls)-substituted benzene oxygen alkyl hydrazine derivative, it is characterized in that having general formula I institutes The structural formula of expression：
In Formulas I, R is indicated：Halogen, hydrogen, nitro, methyl, methoxyl group, trifluoromethyl；R1It indicates：Methyl, ethyl, hydrogen；R2It indicates： Trifluoromethyl, chlorine, bromine；R3It indicates：Halogen, hydrogen.
2. N described in claim 11The application of (3- substituted pyrazolecarboxylic -5- formoxyls)-substituted benzene oxygen alkyl hydrazine derivative, Be characterized in as to 2 insecticide targets of mythimna separata and diamondback moth have significant inhibiting effect, can be used as insecticide it is effective at Point.
CN201610380214.5A 2016-06-01 2016-06-01 N1(3- substituted pyrazolecarboxylic -5- formoxyls)-substituted benzene oxygen alkyl hydrazine derivative and its application Expired - Fee Related CN105968092B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201610380214.5A CN105968092B (en) 2016-06-01 2016-06-01 N1(3- substituted pyrazolecarboxylic -5- formoxyls)-substituted benzene oxygen alkyl hydrazine derivative and its application

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201610380214.5A CN105968092B (en) 2016-06-01 2016-06-01 N1(3- substituted pyrazolecarboxylic -5- formoxyls)-substituted benzene oxygen alkyl hydrazine derivative and its application

Publications (2)

Publication Number Publication Date
CN105968092A CN105968092A (en) 2016-09-28
CN105968092B true CN105968092B (en) 2018-10-12

Family

ID=57010647

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201610380214.5A Expired - Fee Related CN105968092B (en) 2016-06-01 2016-06-01 N1(3- substituted pyrazolecarboxylic -5- formoxyls)-substituted benzene oxygen alkyl hydrazine derivative and its application

Country Status (1)

Country Link
CN (1) CN105968092B (en)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107954993A (en) * 2017-12-04 2018-04-24 杨子辉 A kind of preparation method of 5- pyrazoles hydrazide kind compound and application
CN114716409B (en) * 2021-01-05 2024-01-12 西北农林科技大学 Diphenyl pyrazole compound and preparation method and application thereof

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2013107867A (en) * 2011-04-21 2013-06-06 Nissan Chem Ind Ltd Pyrazole derivative and pest controlling agent
CN103483313A (en) * 2013-09-03 2014-01-01 南开大学 Novel hydrazide derivatives as well as preparation method and application thereof
CN103641782B (en) * 2013-12-26 2015-01-28 青岛科技大学 Pyrazol acylhydrazone compounds and application thereof
CN104193681B (en) * 2014-08-08 2017-06-27 一帆生物科技集团有限公司 The methyl N of 4 chlorine, 3 ethyl 1 ' (2 substituted benzene oxygen acetyl group) phosphinylidyne hydrazine class compound of 1H pyrazoles 5 preparation and application

Also Published As

Publication number Publication date
CN105968092A (en) 2016-09-28

Similar Documents

Publication Publication Date Title
CN103109816B (en) Thiobenzamide compounds and application thereof
CN105163587B (en) Compositions and methods for controlling pest
Shi et al. Design, synthesis and insecticidal activities of novel anthranilic diamides containing polyfluoroalkyl pyrazole moiety
EP1455579B1 (en) Pyrazoles-pyrimidine fungicides
CN105142403B (en) For the method for pest control
AU2011354895B2 (en) Agri-horticultural pest control compositions comprising 4- (3-butynyl)aminopyrimidine derivatives
CN104955334B (en) The composition and method of pest control
JP2002522526A (en) Trifluoromethylpyrrolecarboxamide
BR112013004835B1 (en) Compounds, fungicidal compositions and method for controlling plant diseases
CN105968092B (en) N1(3- substituted pyrazolecarboxylic -5- formoxyls)-substituted benzene oxygen alkyl hydrazine derivative and its application
WO2012163095A1 (en) Pyrazole formylthiourea derivative, preparation method therefore and use thereof
Zhou et al. Novel phthalamides containing sulfiliminyl moieties and derivatives as potential ryanodine receptor modulators
Lei et al. Design and synthesis of novel 4-hydroxyl-3-(2-phenoxyacetyl)-pyran-2-one derivatives for use as herbicides and evaluation of their mode of action
JP6348568B2 (en) N-, C-disubstituted azoles for nematode pest control
Wu et al. Synthesis and bioactivities study of novel pyridylpyrazol amide derivatives containing pyrimidine motifs
WO2014073622A1 (en) Method for promoting plant growth
CN106543139B (en) Triazolone compound and application thereof
Liu et al. Design, synthesis and insecticidal evaluation of novel pyrazolecarboxamides containing cyano substituted N‐pyridylpyrazole
CN106083838B (en) A kind of bis- substitution -1,3,4- oxadiazole derivatives of 2,5- and its application
CN106831647A (en) A kind of thiadiazoles amides compound and application thereof
WO2014183415A1 (en) Double-amide derivative with optical activity and geometrical isomerism, and preparation and application
AU2013260420B2 (en) Diaminoaryl derivatives substituted by carbamate and pesticidal composition containing same
CN104206385B (en) Use of amine compound as bactericide
WO2016006351A1 (en) Plant resistance inducing control agent, plant resistance inducing control method, plant disease prevention method, insect prevention method, plant growth promoter, microbial infection efficiency promoter, and transgene expression efficiency promoter
CN106478613B (en) 2- [4- (pyridine -2- base oxygroup) phenoxy group] amide derivatives and the preparation method and application thereof

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant
CF01 Termination of patent right due to non-payment of annual fee
CF01 Termination of patent right due to non-payment of annual fee

Granted publication date: 20181012