CN104496967A - Substituent N heterozygous aromatic base amide compound and application thereof - Google Patents

Substituent N heterozygous aromatic base amide compound and application thereof Download PDF

Info

Publication number
CN104496967A
CN104496967A CN201510028065.1A CN201510028065A CN104496967A CN 104496967 A CN104496967 A CN 104496967A CN 201510028065 A CN201510028065 A CN 201510028065A CN 104496967 A CN104496967 A CN 104496967A
Authority
CN
China
Prior art keywords
compound
methyl
propyl
general formula
preparation
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.)
Pending
Application number
CN201510028065.1A
Other languages
Chinese (zh)
Inventor
徐凤波
岳军
王文虎
张青青
李庆山
董建兰
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.)
Nankai University
Original Assignee
Nankai University
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 Nankai University filed Critical Nankai University
Priority to CN201510028065.1A priority Critical patent/CN104496967A/en
Publication of CN104496967A publication Critical patent/CN104496967A/en
Pending legal-status Critical Current

Links

Classifications

    • 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
    • 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
    • A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
    • A01N43/60—1,4-Diazines; Hydrogenated 1,4-diazines
    • 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

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)
  • Agricultural Chemicals And Associated Chemicals (AREA)

Abstract

The invention relates to an amide compound and application of the amide compound, in particular to a substituent N heterozygous aromatic base amide compound and application of the substituent N heterozygous aromatic base amide compound, and belongs to the field of insecticide. The substituent N heterozygous aromatic base amide compound is shown as the general formula I in the specification. Compared with a known insecticide compound, the substituent N heterozygous aromatic base amide compound has the advantages that the insecticidal activity is high, composition is easier and more convenient, the substituent N heterozygous aromatic base amide compound is environmentally friendly, and the composition cost is lower.

Description

A kind of N that replaces mixes aromatic base amides and application thereof
Technical field
The present invention relates to amides and application thereof, particularly one replaces N and to mix aromatic base amides and application thereof.Belong to field of pesticides.
Background technology
Due to sterilant in use for some time, insect is understood self and develops immunity to drugs, and therefore, needs to continually develop new type disinsection compounds.Meanwhile, along with people are to the growing demands such as agricultural and animal products and the pay attention to day by day to environment protection, society needs cost is lower, the novel pesticide of environment friendly more.
US2005/0075372A1 reports preparation and the insecticidal activity of following compounds (QS), under the concentration of 50ppm, have high prevention effect to insects such as mythimna separatas:
CN200810116198.4 discloses a kind of 1-substituted pyridyl-pyrazol acid amide compounds and application thereof, reports a class active insecticide, but active compared with the kind " health is wide " of the current widespread use in du pont company, need further optimization.
In the prior art, the mix preparation of aromatic base amides and insecticidal activity thereof of replacement N as representative of the present invention has no open.
Summary of the invention
An object of the present invention is to provide a kind of replacement N of novel structure to mix aromatic base amides, and it can be applicable to the control of the insect pest in agricultural, forestry, has high reactivity, by the field experiment on the ground such as Hainan, Vietnam.
Foregoing invention object of the present invention reaches by the following technical programs:
A kind of N that replaces to mix aromatic base amides, as shown in formula I:
In formula:
W is selected from C or N;
V is selected from N;
R 1be selected from Cl, Br, OH, OCH 2cF 3, C 3-C 6alkene oxygen base, C 3-C 6haloalkene oxygen base, C 3-C 6alkynyloxy group or C 3-C 6halo alkynyloxy group;
R 2be selected from H, F, Cl, Br, OH, CN, methyl, ethyl, sec.-propyl, n-propyl, OCH 3, or it is amino;
R 3be selected from H, F, Cl, Br, OH, cyano group, methyl, ethyl, sec.-propyl, n-propyl, OCH 3, or it is amino;
R 4be selected from H, F, Cl, Br, OH, cyano group, methyl, ethyl, sec.-propyl, n-propyl, OCH 3, or it is amino;
R 5be selected from Cl, Br, cyano group, methyl or CF 3;
R 6be selected from Cl, Br, cyano group, methyl or CF 3;
R 7be selected from H or C 1-C 3alkyl;
R 8be selected from H, methoxyl group, oxyethyl group, propoxy-, C 1-C 6alkyl, C 3-C 6thiazolinyl, C 3-C 6alkynyl or C 3-C 6cycloalkyl, on described alkyl, an optional hydrogen or multiple hydrogen can be replaced by substituents: halogen, hydroxyl, cyano group; Or R 7and R 8the nitrogen formation N methyl piperazine connected together, morpholine, oxazolidine, isoxazole alkyl,
Further illustrate, when W is C atom, when V is atom N:
Work as R 2be selected from F, Cl or CN; R 3be selected from H, F, Cl or CN and R 4when being selected from H, F, Cl, R 8be not selected from H, C 1-C 6alkyl, C 3-C 6thiazolinyl, C 3-C 6alkynyl or C 3-C 6cycloalkyl, other position substituting group is unrestricted.
When W and V is atom N simultaneously: R 1to R 8substituting group is unrestricted.
A kind of optimal technical scheme, is characterized in that: in described formula I:
R 1be selected from Cl, Br, OCH 2cF 3, C 3-C 6alkene oxygen base or C 3-C 6haloalkene oxygen base;
R 2be selected from H, Cl, Br, OH or cyano group;
R 3be selected from H, Cl or Br;
R 4be selected from H, Cl, methyl or ethyl;
R 5be selected from Cl, cyano group, methyl or CF 3;
R 6be selected from Cl or methyl;
R 7be selected from H;
R 8be selected from H, methoxyl group, oxazolidine, isoxazole alkyl, N methyl piperazine or morpholine.
In the definition of the general formula compound provided above, collect term used and be generally defined as follows:
Alkyl refers to straight or branched form, as groups such as methyl, ethyl, propyl group, sec.-propyl, normal-butyl, isobutyl-, sec-butyl, n-pentyl, isopentyl.Cycloalkyl refers to and comprises closed chain form, as groups such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl.Haloalkyl refers to the group that alkyl is optionally substituted with one or more halogen atoms.Thiazolinyl refers to straight or branched thiazolinyl, also comprises polyenoid.Alkynyl refers to straight or branched alkynyl.Alkoxyl group refers to that alkyl end is connected with the group of Sauerstoffatom, as methoxyl group, oxyethyl group, propoxy-etc.Halogenated alkoxy refers to that alkyl is optionally substituted with one or more halogen atoms, and end is connected with the group of Sauerstoffatom.Alkene oxygen base refers to that thiazolinyl end is connected with the group of Sauerstoffatom.Alkynyloxy group refers to that alkynyl end is connected with the group of Sauerstoffatom.Halogen refers to fluorine, chlorine, bromine, iodine.
Another object of the present invention is to provide a kind of above-mentioned replacement N and mixes the preparation method of aromatic base amides.
Above-mentioned purpose of the present invention reaches by the following technical programs:
Above-mentioned replacement N mixes the preparation method of aromatic base amides, and its step is as follows:
General formula II compound and general formula III compound in suitable solvent, temperature reacts 0.5-12 hour obtained target compound I under being 0 DEG C to boiling conditions.
Suitable solvent is selected from: methylene dichloride, chloroform, tetracol phenixin, hexane, benzene, toluene, ethyl acetate, acetonitrile, tetrahydrofuran (THF), dioxane, DMF or dimethyl sulfoxide (DMSO) etc.
Add suitable alkaloids favourable to reaction.Suitable alkali is selected from organic bases as triethylamine, DMA or pyridine etc., or mineral alkali is as sodium hydroxide, potassium hydroxide, sodium methylate, sodium tert-butoxide or potassium tert.-butoxide etc.
The preparation method of general formula compound II is as follows:
Carbonate representated by above formula formula of IV is converted into carboxylic acid cpd representated by general formula V (see T.W.Greene and P.G.M.Wuts by alkaline hydrolysis method; protective material in organic synthesis; 2nd ed.; Johnwiley & Sons; Inc.; the method survey of New York.1991, pp.224-269), the alkali be applicable to comprises the oxyhydroxide of basic metal as lithium, sodium or potassium.
Carboxylic acid cpd representated by general formula V and acyl halide reagent are in solvent, and reflux 1-5 hour obtained general formula II compound; Suitable acyl halide reagent is selected from oxalyl chloride, sulfur oxychloride, phosphorus trichloride, phosphorus tribromide, phosphorus pentachloride or phosphorus pentabromide, and the charged molar ratio of carboxylic acid cpd and acyl halide reagent is 1:1-1:20; Suitable solvent is selected from methylene dichloride, hexane, benzene, toluene, acetonitrile, the acyl halide reagent of dioxane or liquid state.
General formulae IV compound is the important intermediate preparing generalformulaⅰcompound of the present invention, and its structure and physico-chemical property have no report before this.Therefore technical scheme of the present invention also comprises a kind of intermediate preparing generalformulaⅰcompound, shown in general structure IV:
In formula:
W is selected from N;
V is selected from N;
R is selected from H or C 1-C 4alkyl;
R 1be selected from Cl, Br, OH, OCH 2cF 3, C 3-C 6alkene oxygen base, C 3-C 6haloalkene oxygen base, C 3-C 6alkynyloxy group or C 3-C 6halo alkynyloxy group;
R 2be selected from H, F, Cl, Br, OH, cyano group, methyl, ethyl, sec.-propyl, n-propyl, OCH 3, or it is amino;
R 3be selected from H, F, Cl, Br, OH, cyano group, methyl, ethyl, sec.-propyl, n-propyl, OCH 3, or it is amino;
R 4be selected from H, F, Cl, Br, OH, cyano group, methyl, ethyl, sec.-propyl, n-propyl, OCH 3, or it is amino.
Being prepared as follows of general formulae IV compound:
(1) general formulae IV (R 1for OH) preparation of compound
1) general formula Ⅹ (R 1for OH) preparation of compound:
General formula Ⅸ compound and general formula Ⅺ compound react obtained general formula Ⅹ (R under the existence of alkali and solvent 1for OH) compound.Suitable alkali is selected from sodium methylate, potassium methylate, sodium ethylate, potassium ethylate, potassium tert.-butoxide or sodium tert-butoxide etc.Suitable solvent is selected from alcohol as ethanol or methyl alcohol.Temperature of reaction is generally 20 DEG C to boiling point, reaction times general 1-24 hour.Then add organic acid as acetic acid etc. in reaction, or mineral acid hydrochloric acid, sulfuric acid etc. carry out acidifying.
2) general formulae IV (R 1for OH) preparation of compound:
General formula Ⅹ (R 1for OH) compound in the presence of acid in suitable solvent, temperature be 0 DEG C to boiling point under with oxygenant generation oxidizing reaction 1-24 hour obtained general formulae IV (R 1for OH) compound.Suitable oxygenant is selected from hydrogen peroxide, organo-peroxide, Potassium Persulphate, Sodium Persulfate, ammonium persulphate, Potassium peroxysulfate or potassium permanganate.Suitable solvent is selected from tetrahydrofuran (THF), dioxane, ethyl acetate, DMF, acetonitrile etc.The acid used is selected from sulfuric acid, phosphoric acid or acetic acid etc.
(2) general formulae IV (R 1for substituted oxy) preparation of compound
2 of step (1)) middle gained general formulae IV (R 1for OH) compound and halides are in suitable solvent, and temperature reacts 1-24 hour obtained general formulae IV (R under-10 DEG C to boiling point 1for substituted oxy: OCH 2cF 3, C 3-C 6alkene oxygen base, C 3-C 6haloalkene oxygen base, C 3-C 6alkynyloxy group or C 3-C 6halo alkynyloxy group) compound.Suitable solvent is selected from methylene dichloride, chloroform, tetracol phenixin, DMF, acetonitrile, tetrahydrofuran (THF), dioxane or dimethyl sulfoxide (DMSO) etc.Suitable halides such as methyl iodide, allyl bromide 98, propargyl bromide etc. all have commercially available.
(3) general formulae IV (R 1for halogen) preparation of compound
1) general formula Ⅹ (R 1for halogen) preparation of compound
1 of step (1)) middle gained general formula Ⅹ (R 1for OH) compound react with halogenating agent in the presence of the solvent, obtain corresponding general formula Ⅹ (R 1for halogen) compound:
Suitable halogenating agent is selected from trihalophosporus oxide, phosphorus trihalide, phosphorus pentahalides, oxalyl chloride or carbonyl chloride.Suitable solvent is selected from methylene dichloride, chloroform, benzene, dimethylbenzene, chlorinated benzene, tetrahydrofuran (THF), dioxane, ether, acetonitrile, DMF etc.The temperature of reaction is generally react to obtain for 1-24 hour under 20 DEG C to boiling point.Then reactant mineral alkali such as sodium bicarbonate, sodium hydroxide etc. or organic bases such as sodium acetate neutralization obtains target product.
2) general formulae IV (R 1for halogen) preparation of compound
General formula Ⅹ (R 1for halogen) compound in the presence of acid in suitable solvent, temperature be 0 DEG C to boiling point under with oxygenant generation oxidizing reaction 1-24 hour obtained general formulae IV (R 1for halogen) compound.Suitable oxygenant is selected from hydrogen peroxide, organo-peroxide, Potassium Persulphate, Sodium Persulfate, ammonium persulphate, Potassium peroxysulfate or potassium permanganate.Suitable solvent is selected from tetrahydrofuran (THF), dioxane, ethyl acetate, DMF, acetonitrile etc.The acid used is selected from sulfuric acid, phosphoric acid or acetic acid etc.
The preparation method of general formula III compound is as follows:
Synthetic route one:
Carboxylic acid cpd VI and acyl halide reagent are in solvent, and reflux 1-5 hour obtained general formula VII compound; Suitable acyl halide reagent is selected from oxalyl chloride, sulfur oxychloride, phosphorus trichloride, phosphorus tribromide, phosphorus pentachloride or phosphorus pentabromide, and carboxylic acid cpd VI is 1:1-1:20 with the charged molar ratio of acyl halide reagent; Suitable solvent is selected from methylene dichloride, hexane, benzene, toluene, acetonitrile, the acyl halide reagent of dioxane or liquid state.
By general formula VII compound and amine in a solvent, within 1-5 hour, prepare general formula III compound under alkali existence condition.Suitable solvent is selected from methylene dichloride, chloroform, tetracol phenixin, hexane, benzene, toluene, ethyl acetate, acetonitrile, tetrahydrofuran (THF), dioxane, DMF or dimethyl sulfoxide (DMSO) etc.; Suitable alkali is selected from organic bases as triethylamine, DMA or pyridine etc., or mineral alkali is as sodium hydroxide, potassium hydroxide, sodium methylate, sodium tert-butoxide or potassium tert.-butoxide etc.
Synthetic route two:
In a solvent, reflux 1-5 hour obtained general formula VIII compound for carboxylic acid cpd VI and trichloromethylchloroformate or triphosgene; Carboxylic acid cpd VI is 1:1-1:10 with trichloromethylchloroformate or triphosgene charged molar ratio; Suitable solvent is selected from methylene dichloride, chloroform, ethyl acetate, hexane, benzene, toluene, acetonitrile, tetrahydrofuran (THF) or dioxane.
By general formula VIII compound and amine in suitable solvent, reflux and prepare general formula III compound in 1-5 hour.Suitable solvent is selected from methylene dichloride, chloroform, tetracol phenixin, hexane, benzene, toluene, ethyl acetate, acetonitrile, tetrahydrofuran (THF), dioxane, DMF or dimethyl sulfoxide (DMSO) etc.
Table 1 lists structure and the physical properties of partial Formula I compound
Table 1
Compound 1hNMR (400M, DMSO-d 6) data are as follows:
Compound 1:10.39 (br s, 1H), 9.02 (s, 1H), 8.74 (d, 1H), 8.56 (d, 1H), 8.31 (br, 1H), 7.51 (d, 1H), 7.38 (d, 1H), 7.15 (s, 1H), 2.71 (d, 3H), 2.27 (s, 3H).
Compound 2:11.62 (s, 1H), 10.66 (s, 1H), 8.54 (d, 1H), 8.12 (d, 1H), 7.90 (d, 1H), 7.50 (d, 1H), 7.48 (s, 1H), 3.53 (s, 3H).
Compound 3:11.73 (br s, 1H), 10.75 (br s, 1H), 9.05 (s, 1H), 8.76 (d, 1H), 8.63 (d, 1H), 7.98 (d, 1H), 7.53 (d, 1H), 7.25 (s, 1H), 3.63 (s, 3H).
Compound 4:11.58 (s, 1H), 10.42 (s, 1H), 9.06 (s, 1H), 8.75 (d, 1H), 8.57 (d, 1H), 7.57 (d, 1H), 7.35 (d, 1H), 7.14 (s, 1H), 3.64 (s, 3H), 2.30 (s, 3H).
Compound 5:10.43 (br s, 1H), 9.00 (s, 1H), 8.72 (d, 1H), 8.66 (d, 1H), 8.29 (br s, 1H), 7.50 (d, 1H), 7.36 (d, 1H), 7.15 (s, 1H), 2.76 (d, 3H), 2.19 (s, 3H).
Compound 6:11.62 (s, 1H), 10.66 (s, 1H), 8.31 (d, 1H), 8.08 (d, 1H), 7.88 (d, 1H), 7.51 (d, 1H), 7.26 (s, 1H), 3.62 (s, 3H).
Compound 7:11.63 (br s, 1H), 10.66 (br s, 1H), 8.60 (d, 1H), 8.54 (d, 1H), 7.92 (d, 1H), 7.51 (d, 1H), 7.48 (s, 1H), 3.53 (s, 3H).
Compound 8:11.61 (s, 1H), 10.67 (s, 1H), 8.29 (d, 1H), 8.08 (d, 1H), 7.89 (d, 1H), 7.53 (d, 1H), 7.20 (s, 1H), 3.61 (s, 3H), 2.23 (s, 3H).
Compound 9:10.39 (br s, 1H), 8.35 (s, 1H), 8.29 (br s, 1H), 8.06 (d, 1H), 7.90 (d, 1H), 7.50 (d, 1H), 7.15 (s, 1H), 2.76 (d, 3H).
Compound 10:10.41 (br s, 1H), 8.33 (s, 1H), 8.30 (br s, 1H), 8.06 (d, 1H), 7.88 (d, 1H), 7.50 (d, 1H), 7.21 (s, 1H), 2.83 (d, 3H), 2.13 (s, 3H).
Compound 11:10.66 (br s, 1H), 8.32 (br s, 1H), 8.21 (d, 1H), 8.12 (d, 1H), 7.52 (d, 1H), 7.36 (d, 1H), 7.21 (s, 1H), 2.85 (d, 3H), 2.10 (s, 3H).
Compound 12:10.66 (br s, 1H), 8.34 (br s, 1H), 8.22 (d, 1H), 8.09 (d, 1H), 7.90 (d, 1H), 7.51 (d, 1H), 7.28 (s, 1H), 2.87 (d, 3H).
Compound 13:11.58 (s, 1H), 10.42 (s, 1H), 8.24 (s, 1H), 8.12 (d, 1H), 7.57 (d, 1H), 7.35 (d, 1H), 7.14 (s, 1H), 3.64 (s, 3H), 2.30 (s, 3H).
Compound 14:11.67 (s, 1H), 10.44 (s, 1H), 8.23 (s, 1H), 8.16 (s, 1H), 7.90 (d, 1H), 7.51 (d, 1H), 7.25 (s, 1H), 3.67 (s, 3H).
Compound 15:11.50 (br s, 1H), 10.30 (br s, 1H), 8.48 (d, 1H), 8.17 (d, 1H), 8.15 (q, 1H), 7.53 (d, 1H), 7.39 (d, 1H), 7.29 (s, 1H), 3.54 (s, 3H), 2.17 (s, 3H).
Compound 16:11.56 (br s, 1H), 10.34 (br s, 1H), 8.46 (d, 1H), 8.19 (d, 1H), 8.15 (q, 1H), 7.90 (d, 1H), 7.48 (d, 1H), 7.36 (s, 1H), 3.67 (s, 3H).
Compound 17:10.75 (s, 1H), 9.05 (s, 1H), 8.70 (d, 1H), 8.62 (d, 1H), 7.98 (d, 1H), 7.53 (d, 1H), 7.25 (s, 1H), 3.67 (t, 4H), 3.48 (t, 4H).
Compound 18:10.69 (s, 1H), 9.03 (s, 1H), 8.70 (d, 1H), 8.64 (d, 1H), 7.49 (d, 1H), 7.37 (d, 1H), 7.18 (s, 1H), 3.63 (t, 4H), 3.44 (t, 4H).
Compound 19:10.65 (s, 1H), 8.16 (d, 1H), 8.03 (d, 1H), 7.76 (d, 1H), 7.64 (d, 1H), 7.20 (s, 1H), 3.68 (t, 4H), 3.00 (t, 4H), 2.67 (s, 3H).
Compound 20:10.70 (s, 1H), 8.16 (d, 1H), 8.02 (d, 1H), 7.47 (d, 1H), 7.37 (d, 1H), 7.18 (s, 1H), 3.68 (t, 4H), 3.02 (t, 4H), 2.68 (s, 3H).
Compound 21:10.46 (s, 1H), 8.23 (s, 1H), 8.15 (s, 1H), 7.55 (d, 1H), 7.35 (d, 1H), 7.12 (s, 1H), 3.68 (t, 4H), 3.02 (t, 4H), 2.68 (s, 3H).
Compound 22:11.63 (br s, 1H), 10.67 (s, 1H), 8.26 (d, 1H), 8.11 (d, 1H), 7.57 (d, 1H), 7.36 (d, 1H), 7.18 (s, 1H), 4.65 (q, 2H), 3.64 (s, 3H), 2.31 (s, 3H).
Compound 23:11.67 (br s, 1H), 10.62 (s, 1H), 8.25 (d, 1H), 8.11 (d, 1H), 7.91 (d, 1H), 7.53 (d, 1H), 7.15 (s, 1H), 4.62 (q, 2H), 3.66 (s, 3H).
Compound 24:11.65 (br s, 1H), 10.57 (br s, 1H), 8.23 (d, 1H), 8.10 (d, 1H), 7.89 (d, 1H), 7.51 (d, 1H), 7.08 (s, 1H), 5.97 (m, 1H), 5.18 (d, 2H), 4.73 (d, 2H), 3.64 (s, 3H).
Compound 25:11.67 (br s, 1H), 10.55 (br s, 1H), 8.17 (d, 1H), 8.05 (d, 1H), 7.91 (d, 1H), 7.52 (d, 1H), 7.11 (s, 1H), 5.98 (m, 1H), 5.17 (d, 2H), 4.73 (d, 2H), 3.67 (s, 3H).
Compound 26:11.66 (br s, 1H), 10.49 (br s, 1H), 8.53 (d, 1H), 7.99 (d, 1H), 7.56 (d, 1H), 7.37 (d, 1H), 7.16 (s, 1H), 3.65 (s, 1H), 2.12 (s, 3H).
Compound 27:10.64 (s, 1H), 8.54 (d, 1H), 8.32 (brs, 1H), 8.02 (d, 1H), 7.52 (d, 1H), 7.34 (d, 1H), 7.22 (s, 1H), 2.85 (d, 3H), 2.13 (s, 3H).
Compared with known pesticide compound, replacement N of the present invention aromatic base amides of mixing has high insecticidal activity, therefore, the present invention includes the purposes that generalformulaⅰcompound can be used in controlling insect pest.Replacement N of the present invention mixes, and the synthesis of aromatic base amides is more easy, environmental friendliness, and the cost of synthesis is more cheap.Thus the object that more low cost reaches control agricultural insect pest can be met.
The present invention includes with generalformulaⅰcompound is the insect-killing composition of active ingredient.In this insect-killing composition, the weight percentage of active ingredient is between 1-99%.The carrier that agricultural, forestry, health accept also is comprised in this insect-killing composition.
Composition of the present invention can use with the form of preparation.Generalformulaⅰcompound is easier to dispersion when being dissolved or dispersed in carrier as active ingredient or being mixed with preparation to be used as sterilant.As: these chemicals can be made into wettable powder or missible oil.In these compositions, at least add a kind of liquid or solid carrier, and add suitable tensio-active agent when needed.
Technical scheme of the present invention also comprises the method for pest control: be applied on described insect or its growth medium with the effective dose of per hectare 5g to 1000g by insect-killing composition of the present invention.
For some application, such as, one or more other Insecticides (tech) & Herbicides (tech) or fertilizer etc. agriculturally can be added in insect-killing composition of the present invention, additional advantage and effect can be produced thus.
It is clearly understood that, in claim limited range of the present invention, can various conversion and change be carried out.
Embodiment
Following synthesis example, biological activity determination result can be used to further illustrate the present invention, but do not mean that restriction the present invention.
Synthesis example
The preparation of embodiment 1, compound 1
(1) synthesis of the chloro-2 diazanyl pyrazines of 6-
Successively 2,6-dichloropyrazine (4.2g, 28.19mmol), 100ml ethanol, hydrazine hydrate (2.83g, 56.38mmol) are added in reaction flask, return stirring 10h, reaction solution cools, and separates out solid, filters, filtrate is spin-dried for, and obtains yellow solid, yield 80.5%.
1HNMR(400M，DMSO-d 6)：8.48(s，1H)，8.07(d，1H)，7.73(d，1H)，4.02(s，2H)。
(2) synthesis of 1-(6-chloropyrazine-2-base)-3-pyrazolidone-5-carboxylic acid, ethyl ester
200ml dehydrated alcohol is added in reaction flask, add sodium Metal 99.5 (1.03g, 44.97mmol), stirring at room temperature is all dissolved to sodium, add 6-chloro-2-diazanyl pyrazine (5.0g, 34.59mmol), heated and stirred 10min, drip ethyl maleate (5.96g, 34.59mmol).Continue to keep heating temperatures to stir, add glacial acetic acid neutralization reaction to PH=7 ~ 8, mixture 200ml water dilution, is chilled to room temperature, has solid to separate out, filter out solid, use washing with alcohol solid, obtain yellow solid, yield 46%.
1HNMR(400M，CDCl3)：8.20(d，1H)，8.15(d，1H)，5.32(q，1H)，4.36(q，2H)，3.15(m，1H)，2.88(m，1H)，1.32(t，3H)。
(3) synthesis of 1-(6-chloropyrazine-2-base) the bromo-1H-pyrazole-5-ethyl formate of-3-
1-(6-chloropyrazine-2-base)-3-pyrazolidone-5-carboxylic acid, ethyl ester (4.67g is added in reaction flask, 17.25mmol) dry acetonitrile 80ml, add tribromo oxygen phosphorus (4.93g, 17.25mmol), reaction is warming up to 80 DEG C, and TLC detects, be down to room temperature after completion of the reaction, drip saturated sodium hydrogen carbonate solution stopped reaction, concentrated, CH 2cl 2extraction, washing, anhydrous magnesium sulfate drying, then evaporate to dryness methylene dichloride obtains dark oil thing, yield 90.2%.
1HNMR(400M，CDCl 3)：8.18(d，1H)，8.12(d，1H)，5.20(m，1H)，4.19(q，2H)，3.45(m，1H)，3.23(m，1H)，1.23(t，3H)。
(4) synthesis of 1-(6-chloropyrazine-2-base) the bromo-1H-pyrazoles of-3--5-formic acid
1-(6-chloropyrazine-2-base) the bromo-1H-pyrazole-5-ethyl formate of-3-(5.6g is added in reaction flask, 16.79mmol), 90ml water, add sodium hydroxide (1.34g, 33.58mmol), be warming up to 90 DEG C of backflows, TLC detects, stopped reaction, dilute hydrochloric acid regulates about PH=2, separates out yellow solid 2.983g.
1HNMR(400M，DMSO-d 6)：13.06(br s，1H)，8.23(d，1H)，8.09(d，1H)，5.10(q，1H)，3.59(m，1H)，3.35(m，1H)。
(5) synthesis of 1-(6-chloropyrazine-2-base) the bromo-1H-pyrazoles of-3--5-acyl chlorides
1-(6-chloropyrazine-2-base) the bromo-1H-pyrazoles of-3--5-formic acid (0.949g is added in reaction flask, 3.11mmol), add 20ml methylene dichloride, sulfur oxychloride (0.924g, 7.775mmol), add 3 DMF, 65 DEG C of return stirrings, after 5 hours, stop heating, be spin-dried for sulfur oxychloride, obtain reddish-brown oily matter.
The synthesis of chloro-2,4-diketone-1H-benzo [d] [1, the 3] oxazines of (6) 6,8-bis-
3 are added in reaction flask, the chloro-2-benzaminic acid of 5-bis-(1.222g, 5.93mmol), 15ml dioxane, slowly drips the dioxane solution of superpalite (1.173g, 5.93mmol), return stirring, stopped reaction after 2 hours, is spin-dried for solvent and obtains white solid, productive rate 99%.
1HNMR(400M，DMSO-d 6)：11.60(s，1H)，8.09(s，1H)，7.90(s，1H)。
(7) synthesis of the chloro-2-aminobenzamide of N-methoxyl group-3,5-bis-
Add the hydrochloride (0.986g, 11.8mmol) of Vasoxyl in reaction flask, 20ml THF, add 1.65ml triethylamine, stirring at room temperature 2 hours, filter, filtrate is for subsequent use.Chloro-2, the 4-diketone-1H-benzos [d] [1 of 6,8-bis-are added in reaction flask, 3] oxazines (1.37g, 5.905mmol), glacial acetic acid (0.177g, 3.0mmol), 20ml ethyl acetate, drips above-mentioned filtrate, return stirring, TLC detects, after completion of the reaction, extraction into ethyl acetate, washing, anhydrous magnesium sulfate drying, solvent evaporated, obtains yellow solid, productive rate 97.7%.
1HNMR(400M，DMSO-d 6)：11.76(s，1H)，7.56(s，1H)，7.40(s，1H)，6.50(br s，2H)，3.69(s，3H)。
(8) preparation of compound 1
The chloro-2-aminobenzamide (0.235g, 1.0mmol) of N-methoxyl group-3,5-bis-is added, 10mlCH in reaction flask 2cl 2, 0.21ml triethylamine, stirring and dissolving.Drip the dichloromethane solution of 1-(6-chloropyrazine-2-base)-3-bromo-1H-pyrazoles-5-acyl chlorides (0.322g, 1.0mmol) again.Stirred overnight at room temperature, TLC detects, and chromatography over CC, obtains faint yellow solid (0.171g).
1HNMR(400M，DMSO-d 6)：11.62(s，1H)，10.66(s，1H)，8.54(d，1H)，8.12(d，1H)，7.90(d，1H)，7.50(d，1H)，7.48(s，1H)，3.53(s，3H)。
The preparation of embodiment 2, compound 3
(1) synthesis of 2-diazanyl pyrazine
2-chloropyrazine (23.1g, 0.2mol) is added successively, 350ml ethanol, hydrazine hydrate (25g in reaction flask, 0.42mol), be warming up to 80 DEG C of backflows and spend the night, stopped reaction, is down to room temperature, separate out solid, filter and wash to obtain white solid, productive rate 85%.
1HNMR(400M，DMSO-d 6)：8.36(s，1H)，8.31(s，1H)，8.18(d，1H)，8.16(d，1H)，4.30(s，2H)。
(2) synthesis of 1-pyrazine 2-base-3-pyrazolidone-5-carboxylic acid, ethyl ester
Add 340ml dehydrated alcohol in reaction flask, sodium Metal 99.5 (10g, 0.435mol), stirring at room temperature is all dissolved to sodium.Add 2-diazanyl pyrazine (33.2g, 0.30mol), be warming up to 80 DEG C, reaction 10min, drips ethyl maleate (54.24g, 0.315mol), backflow 30min.After completion of the reaction, ice acetic acid stopped reaction, mixture 300ml water dilution, is chilled to room temperature, has solid to separate out, filter out solid, use washing with alcohol solid, obtain brown solid, productive rate 54%.
1HNMR(400M，CDCl 3)：8.38(s，1H)，8.18(d，1H)，8.15(d，1H)，5.35(q，1H)，4.31(q，2H)，3.12(m，1H)，2.87(m，1H)，1.32(t，3H)。
(3) synthesis of the bromo-1H-pyrazole-5-ethyl formate of 1-pyrazine-2-base-3-
Add 1-pyrazine 2-base-3-pyrazolidone-5-carboxylic acid, ethyl ester (5.0g, 0.0212mol) in reaction flask, 80ml acetonitrile, stirring and dissolving, then add tribromo oxygen phosphorus (4.6g, 0.016mol), be warming up to 85 DEG C, backflow.TLC detects, and after reacting completely, adds saturated sodium bicarbonate solution stopped reaction, and washing, dichloromethane extraction, anhydrous magnesium sulfate drying, is spin-dried for methylene dichloride and obtains dark oil thing, productive rate 97.8%.
1HNMR(400M，CDCl 3)：8.69(s，1H)，8.00(d，2H)，4.98(q，1H)，4.21(q，2H)，3.53(m，1H)，3.26(m，1H)，1.24(t，3H)。
(4) synthesis of the bromo-1H-pyrazoles of 1-pyrazine-2-base-3--5-formic acid
Successively by the bromo-1H-pyrazole-5-ethyl formate of 1-pyrazine-2-base-3-(22.0g, 0.074mol), 80ml water, sodium hydroxide (1.15g, 0.085mol) add in reaction flask, be warming up to 60 DEG C, TLC detects, and after reacting completely, regulates about PH=2 with dilute hydrochloric acid, separate out brown-red solid, productive rate 80.4%.
1HNMR(400M，DMSO-d 6)：13.08(br，1H)，8.53(d，1H)，8.14(d，1H)，8.04(d，1H)，4.94(m，1H)，3.78(q，1H)，3.37(q，1H)。
(5) synthesis of the bromo-1H-pyrazoles of 1-pyrazine-2-base-3--5-acyl chlorides
Add 1-pyrazine-2-base-3-bromo-1H-pyrazoles-5-formic acid (0.838g, 3.1mmol) successively in reaction flask, add 20ml methylene dichloride, sulfur oxychloride (0.921g, 7.75mmol), then drip several DMF, 60 DEG C of backflows.React 5 hours, rear stopped reaction, is spin-dried for sulfur oxychloride, obtains khaki color solid.
(6) preparation of compound 3
Add chloro-2 aminobenzamides (0.103g, 0.48mmol) of N-methoxyl group-3-methyl-5 in reaction flask, add 5ml acetonitrile, 0.1ml triethylamine, stirring and dissolving.Drip the 5ml acetonitrile solution of 1-pyrazine-2-base-3-bromo-1H-pyrazoles-5-acyl chlorides (0.138g, 0.48mmol).Stirred overnight at room temperature, washing organic phase, extraction into ethyl acetate, chromatography over CC, obtains yellow solid, productive rate 32.5%.
1HNMR(400M，DMSO-d 6)：11.58(s，1H)，10.42(s，1H)，9.06(s，1H)，8.75(d，1H)，8.57(d，1H)，7.57(d，1H)，7.35(d，1H)，7.14(s，1H)，3.64(s，3H)，2.30(s，3H)。
The preparation of embodiment 3, compound 7
(1) synthesis of the chloro-2 diazanyl pyrazines of 3-
Add 2,3-dichloropyrazine (15.76g, 0.106mol), ethanol 150ml in reaction flask, stirring and dissolving, then add hydrazine hydrate (10.3ml, 0.212mol), be warming up to 80 DEG C, reaction 10h.After cooling, separate out a large amount of yellow solid, washing, dry.Productive rate 83.6%.
1HNMR(400M，DMSO-d 6)：8.30(s，1H)，8.07(d，1H)，7.58(d，1H)，4.36(br s，2H)。
(2) synthesis of 1-(3-chloropyrazine-2-base)-3-pyrazolidone-5-carboxylic acid, ethyl ester
50ml dehydrated alcohol is added in reaction flask, add sodium Metal 99.5 (0.48g, 20.87mmol), stirring at room temperature is all dissolved to sodium, add 3-chloro-2-diazanyl pyrazine (2.32g, 16.05mmol), heated and stirred 10min, drip ethyl maleate (2.77g, 16.05mmol).Continue to keep heating temperatures to stir, add glacial acetic acid neutralization reaction to PH=7 ~ 8, mixture 200ml water dilution, is chilled to room temperature, has solid to separate out, filter out solid, use washing with alcohol solid, obtain red solid, yield 32%.
1HNMR(400M，CDCl 3)：8.16(d，1H)，8.05(d，1H)，5.44(d，1H)，4.25(q，2H)，3.15(m，1H)，2.85(m，1H)，1.27(t，3H)。
(3) preparation of compound 7
The chloro-2-aminobenzamide (0.47g, 2.0mmol) of N-methoxyl group-3,5-bis-is added, 20mlCH in reaction flask 2cl 2, 0.42ml triethylamine, stirring and dissolving.Drip the dichloromethane solution of 1-(3-chloropyrazine-2-base)-3-bromo-1H-pyrazoles-5-acyl chlorides (0.644g, 2.0mmol) again.Stirred overnight at room temperature, TLC detects, and chromatography over CC, obtains faint yellow solid (0.21g).
1HNMR(400M，DMSO-d 6)：11.59(s，1H)，10.68(s，1H)，8.20(d，1H)，8.04(d，1H)，7.90(d，1H)，7.52(d，1H)，7.42(s，1H)，3.56(s，3H)。
The preparation of embodiment 4, compound 15
(1) synthesis of chloro-2 hydrazino pyridines of 3-
Add 2,3-dichloropyridine (115.9g, 0.788mol), 80% hydrazine hydrate (369.2g, 5.9mol), dioxane 80ml in reaction flask, mechanical stirring, return stirring, reaction is spent the night.Cooledly leach solid, obtain white solid, productive rate 89.9%.
1HNMR(400M，DMSO-d 6)：8.06(q，1H)，7.60(br s，1H)，7.58(q，1H)，6.63(q，1H)，3.40(br s，2H)。
(2) synthesis of 1-(3-chloropyridine-2-base)-3-pyrazolidone-5-carboxylic acid, ethyl ester
Add dry ethanol 1.6L in reaction flask, add sodium sheet 26.4g, stirring at room temperature is all dissolved to sodium sheet.Add chloro-2 hydrazino pyridines (137.76g, 0.96mol) of 3-again, after heated and stirred 10min dissolves, drip maleic anhydride diethyl ester (165.3g, 0.96mol), continue to keep heating temperatures reaction.After reacting completely, add glacial acetic acid (76g, 1.27mol) stopped reaction, screw out most of alcohol solvent, add water, separate out a large amount of khaki color product, productive rate 69.6%.
1HNMR(400M，CDCl 3)：8.20(q，1H)，7.68(q，1H)，7.02(q，1H)，5.30(m，1H)，4.26(q，2H)，3.10(q，1H)，2.75(q，1H)，1.27(t，3H)。
(3) synthesis of 1-(3-chloropyridine-2-base) the bromo-1H-pyrazole-5-ethyl formate of-3-
Add 1-(3-chloropyridine-2-base)-3-pyrazolidone-5-carboxylic acid, ethyl ester (105g, 0.391mol), acetonitrile 1000ml, tribromo oxygen phosphorus (91.88g, 0.32mol) in reaction flask, be warming up to 80 DEG C of return stirrings and spend the night.Use saturated sodium carbonate solution stopped reaction, filter out insolubles, acetonitrile wash, merge organic phase, vacuum is spin-dried for acetonitrile and obtains dark oil thing, productive rate 85.6%.
1HNMR(400M，CDCl 3)：8.07(q，1H)，7.65(q，1H)，6.86(q，1H)，5.26(m，1H)，4.20(q，2H)，3.46(q，1H)，3.22(q，1H)，1.20(t，3H)。
(4) synthesis of 1-(3-chloropyridine-2-base) the bromo-1H-pyrazoles of-3--5-formic acid
1-(3-chloropyridine-2-base) the bromo-1H-pyrazole-5-ethyl formate of-3-(105g is added in reaction flask, 0.318mol), sodium hydroxide (20.77g, 0.903mol), water 1000ml, stirring is warming up to 50 DEG C, stir after 5 hours, adding hydrochloric acid regulates PH=3-4 to separate out a large amount of solid, filters to obtain product, productive rate 72.8%.
1HNMR(400M，DMSO-d 6)：13.06(br s，1H)，8.10(q，1H)，7.71(q，1H)，6.88(q，1H)，5.30(m，1H)，3.43(q，1H)，3.26(q，1H)。
(5) preparation of compound 15
The chloro-2 aminobenzamide (10.2g of N-methoxyl group-3-methyl-5 are added in reaction flask, 47.52mmol), acetonitrile 150ml, triethylamine 1.5eq, after stirring perfect solution, drip 1-(3-chloropyridine-2-base) the bromo-1H-pyrazoles of-3--5-acyl chlorides (16g, acetonitrile solution 49.85mmol), stirs 5 hours, and TLC detects, chromatography over CC obtains yellow solid, productive rate 51.2%.
1HNMR(400M，DMSO-d 6)：11.50(br s，1H)，10.30(br s，1H)，8.48(d，1H)，8.17(d，1H)，8.15(q，1H)，7.53(d，1H)，7.39(d，1H)，7.29(s，1H)，3.54(s，3H)，2.17(s，3H)。
The preparation of embodiment 5, compound 17
The synthesis of chloro-2,4-diketone-1H-benzo [d] [1, the 3] oxazines of (1) 6,8-bis-
Add chloro-2 benzaminic acid (3.003g, 14.58mmol) of 3,5-bis-, dioxane 30ml in reaction flask, stirring and dissolving becomes red, transparent solution.The 30ml dioxane solution of slow dropping triphosgene (4.33g, 14.58mmol), return stirring two hours.Filter, filtrate being spin-dried for obtains buff white solid, yield 97.6%.
1HNMR(400M，DMSO-d 6)：11.60(s，1H)，8.09(s，1H)，7.90(s，1H)。
(2) synthesis of the chloro-2-aminobenzamide of N-morpholine-3,5-bis-
Add chloro-2,4-diketone-1H-benzo [d] [1, the 3] oxazines (5g, 21.55mmol) of 6,8-bis-, ethyl acetate 50ml in reaction flask, add acetic acid (10mmol), stir into white suspension.Add morpholine (1.88g, 21.55mmol) again, be warming up to 40 DEG C, along with the carrying out of reaction becomes colorless transparent liquid, TLC detects, and washes after completion of the reaction, extraction into ethyl acetate, is spin-dried for obtain product.Productive rate 69%, colorless oil.
1HNMR(400M，DMSO-d 6)：8.12(d，1H)，7.87(d，1H)，5.03(s，2H)，3.60(t，4H)，3.44(t，4H)。
(3) preparation of compound 17
The chloro-2-aminobenzamide (2.45g, 8.9mmol) of N-morpholine-3,5-bis-, 30ml acetonitrile, triethylamine (1.351g, 13.35mmol) is added, stirring and dissolving in reaction flask.Slowly drip the acetonitrile solution of 1-pyrazine-2-base-3-bromo-1H-pyrazoles-5-acyl chlorides (2.559g, 8.9mmol) again, stirring at room temperature 5 hours.TLC detects, and chromatography over CC, obtains white solid, productive rate 28.6%.
1HNMR(400M，DMSO-d 6)：10.45(s，1H)，9.06(s，1H)，8.78(d，1H)，8.60(d，1H)，8.12(d，1H)，7.84(d，1H)，7.16(s，1H)，3.58(t，4H)，3.47(t，4H)。
The preparation of embodiment 6, compound 19
The synthesis of the chloro-2-amino benzoyl chloride of (1) 3,5-bis-
Add the chloro-2-benzaminic acid (6.8g, 33mmol) of 3,5-bis-in reaction flask, 100ml methylene dichloride, stirring and dissolving, then add sulfur oxychloride (7.852g, 66mmol), 3 DMF.Be warming up to 60 DEG C, stir 5 hours.Revolve evaporate to dryness methylene dichloride, and drain sulfur oxychloride with oil pump, obtain brown solid.
(2) synthesis of the chloro-2-aminobenzamide of N methyl piperazine-3,5-bis-
N methyl piperazine (5g, 49.92mmol) is added, 50ml methylene dichloride, triethylamine (10.1g, 99.84mmol), stirring and dissolving in reaction flask.The 50ml dichloromethane solution of the chloro-2-amino benzoyl chloride (11.21g, 49.92mmol) of slow dropping 3,5-bis-, stirring at room temperature 5 hours.Washing organic phase, dichloromethane extraction, anhydrous magnesium sulfate drying, column chromatography is purified, and obtains faint yellow solid, productive rate 62.3%.
1HNMR(400M，DMSO-d 6)：7.81(d，1H)，7.65(d，1H)，6.41(br s，2H)，3.66(t，4H)，3.03(t，4H)，2.64(s，3H)。
(3) preparation of compound 19
Add the chloro-2-aminobenzamide (2.0g, 6.94mmol) of N methyl piperazine-3,5-bis-in reaction flask, 30ml methylene dichloride, stir, then add triethylamine (1.054g, 10.4mmol), stirring and dissolving.The 30ml dichloromethane solution of slow dropping 1-(3-chloropyrazine-2-base)-3-bromo-1H-pyrazoles-5-acyl chlorides (2.24g, 6.94mmol), stirred overnight at room temperature.Washing organic phase, dichloromethane extraction, anhydrous magnesium sulfate drying, chromatography over CC, obtains yellow solid, productive rate 43.6%.
1HNMR(400M，DMSO-d 6)：10.65(s，1H)，8.16(d，1H)，8.03(d，1H)，7.76(d，1H)，7.64(d，1H)，7.20(s，1H)，3.68(t，4H)，3.00(t，4H)，2.67(s，3H)。
The preparation of embodiment 7, compound 24
(1) synthesis of 1-(6-chloropyrazine-2-base)-3-hydroxyl-1H-pyrazole-5-ethyl formate
1-(6-chloropyrazine-2-base)-3-pyrazolidone-5-carboxylic acid, ethyl ester (10g is added in reaction flask, 36.95mmol), acetonitrile 150ml, 98% sulfuric acid (7.2g, 74mmol), stir after 10 minutes, add Potassium Persulphate (15g, 56mmol), reflux 5 hours.Be cooled to 60 DEG C, suction filtration goes out solid, acetonitrile wash, collects filtrate and washes with dichloro extraction again, and column chromatography purification is dry obtains solid, productive rate 63.2%.
1HNMR(400M，CDCl 3)：9.41(d，1H)，8.45(d，1H)，6.34(s，1H)，4.38(q，2H)，1.35(t，3H)。
(2) synthesis of 1-(6-chloropyrazine-2-base)-3-(allyl group)-1H-pyrazole-5-ethyl formate
1-(6-chloropyrazine-2-base)-3-hydroxyl-1H-pyrazole-5-ethyl formate (5g, 18.61mmol), 30ml DMF, salt of wormwood (5.14g, 37.22mmol) is added in reaction flask, stirring is warming up to 40 DEG C, drips the DMF solution of allyl bromide 98 (3.38g, 27.92mmol), be warming up to 100 DEG C to stir 3 hours, cooling, ethyl acetate is extracted, washing, anhydrous magnesium sulfate drying, chromatography over CC, obtains product, yield 78.3%.
1HNMR(400M，CDCl 3)：8.23(d，1H)，8.15(d，1H)，6.46(s，1H)，6.01(m，1H)，5.28(d，2H)，4.74(d，2H)，4.26(q，2H)，1.28(t，3H)。
(3) synthesis of 1-(6-chloropyrazine-2-base)-3-(allyl group)-1H-pyrazoles-5-formic acid
1-(6-chloropyrazine-2-base)-3-(allyl group)-1H-pyrazole-5-ethyl formate (4.8g is added in reaction flask, 15.55mmol), water 50ml, sodium hydroxide (1.244g, 31.3mmol), be warming up to 40 DEG C of stirring reactions 2 hours, TLC detects, add concentrated hydrochloric acid and regulate PH=2.0, insoluble solids is had to separate out, suction filtration, washing, dry to obtain product, yield 57.3%.
1HNMR(400M，DMSO-d 6)：13.02(br s，1H)，8.23(d，1H)，8.15(d，1H)，6.50(s，1H)，5.98(m，1H)，5.23(d，2H)，4.72(d，2H)。
(4) synthesis of 1-(6-chloropyrazine-2-base)-3-(allyl group)-1H-pyrazoles-5-acyl chlorides
1-(6-chloropyrazine-2-base)-3-(allyl group)-1H-pyrazoles-5-formic acid (3.0g is added in reaction flask, 10.69mmol), 30ml methylene dichloride, sulfur oxychloride (3.178g, 26.73mol), heated and stirred 5 hours, revolve and steam unnecessary sulfur oxychloride, product drained to obtain by oil pump.
(5) preparation of compound 24
N-methoxyl group-3 is added in reaction flask, the chloro-2-aminobenzamide of 5-bis-(2.0g, 8.51mmol), acetonitrile 20ml, triethylamine (1.293g, 12.765mmol), after stirring and dissolving, drip 1-(6-chloropyrazine-2-base)-3-(allyl group)-1H-pyrazoles-5-acyl chlorides (2.80g, 9.361mmol) acetonitrile solution, stirring at room temperature 3 hours, chromatography over CC obtains product, yield 42.3%.
1HNMR(400M，DMSO-d 6)：11.65(br s，1H)，10.57(br s，1H)，8.23(d，1H)，8.10(d，1H)，7.89(d，1H)，7.51(d，1H)，7.08(s，1H)，5.97(m，1H)，5.18(d，2H)，4.73(d，2H)，3.64(s，3H)。
The preparation of embodiment 8, compound 22
(1) synthesis of 1-(6-chloropyrazine-2-base)-3-hydroxyl-1H-pyrazole-5-ethyl formate
1-(6-chloropyrazine-2-base)-3-pyrazolidone-5-carboxylic acid, ethyl ester (10g is added in reaction flask, 36.95mmol), acetonitrile 150ml, 98% sulfuric acid (7.2g, 74mmol), stir after 10 minutes, add Potassium Persulphate (15g, 56mmol), reflux 5 hours.Be cooled to 60 DEG C, suction filtration goes out solid, acetonitrile wash, collects filtrate and washes with dichloro extraction again, and column chromatography purification is dry obtains solid, productive rate 63.2%.
1HNMR(400M，CDCl 3)：9.41(d，1H)，8.45(d，1H)，6.34(s，1H)，4.38(q，2H)，1.35(t，3H)。
(2) synthesis of 1-(6-chloropyrazine-2-base)-3-(trifluoroethyl)-1H-pyrazole-5-ethyl formate
1-(6-chloropyrazine-2-base)-3-hydroxyl-1H-pyrazole-5-ethyl formate (5g is added in reaction flask, 18.61mmol), DMF 100ml, stirring and dissolving, add salt of wormwood (3.86g, 27.92mmol), be warming up to 100 DEG C, drip 2, the DMF solution of 2,2-trifluoro iodoethane, reacts 2 hours.Cooling, extraction into ethyl acetate, washing organic phase, anhydrous magnesium sulfate drying.Chromatography over CC, obtains solid, productive rate 82.6%.
1HNMR(400M，CDCl 3)：8.86(s，1H)，8.26(s，1H)，6.65(s，1H)，4.67(q，2H)，4.32(q，2H)，1.30(t，3H)。
(3) preparation of N-Vasoxyl-3-methyl-5-chloro-2-aminobenzamide
3-methyl-5-chloro anthranilic acid (10g is added in reaction flask, 53.88mmol), add methylene dichloride 100ml, add sulfur oxychloride (16.01g, 134.575mmol) again, 1ml DMF, temperature rising reflux reacts 5 hours, revolve evaporate to dryness methylene dichloride and sulfur oxychloride, obtain 3-methyl-5-chloro o-amino benzoyl chloride, for subsequent use.Vasoxyl (5g, 0.106mol) is added, triethylamine (16.08g in reaction flask, 0.159mol), methylene dichloride 50ml, after stirring and dissolving, add the dichloromethane solution of 3-methyl-5-chloro o-amino benzoyl chloride (27.65g, 0.106mol).Room temperature reaction 5 hours.Washing organic phase, anhydrous magnesium sulfate drying, column chromatography is purified, productive rate 68.7%.
1HNMR(400M，DMSO-d 6)：11.58(s，1H)，7.55(d，1H)，7.37(d，1H)，6.52(br s，2H)，3.64(s，3H)，2.30(s，3H)。
(4) preparation of compound 22
N-Vasoxyl-3-methyl-5-chloro-2-aminobenzamide (2g, 9.32mmol) is added, methylene dichloride 30ml, triethylamine (1.42g, 13.98mmol) in reaction flask.Slowly drip the dichloromethane solution of 1-(6-chloropyrazine-2-base)-3-(trifluoroethyl)-1H-pyrazoles-5-formyl chloride (3.178g, 9.32mmol) again.Room temperature reaction 5 hours, washing organic phase, anhydrous magnesium sulfate drying, chromatography over CC, yellow solid, productive rate 37.6%.
1HNMR(400M，DMSO-d 6)：11.63(br s，1H)，10.67(s，1H)，8.26(d，1H)，8.11(d，1H)，7.57(d，1H)，7.36(d，1H)，7.18(s，1H)，4.65(q，2H)，3.64(s，3H)，2.31(s，3H)。
The preparation of embodiment 9, compound 27
(1) synthesis of 1-(6-chloropyrazine-2-base) the chloro-1H-pyrazole-5-ethyl formate of-3-
1-(6-chloropyrazine-2-base)-3-pyrazolidone-5-carboxylic acid, ethyl ester (10g is added in reaction flask, 36.95mmol), acetonitrile 80ml, phosphorus oxychloride (6.8g, 44.34mmol), return stirring 5 hours, saturated sodium carbonate solution stopped reaction, dichloromethane extraction, washing, anhydrous magnesium sulfate drying, revolves steaming ethyl acetate and obtains oily matter product, yield 80.6%.
1HNMR(400M，CDCl 3)：8.53(d，1H)，7.99(d，1H)，5.05(m，1H)，4.27(q，2H)，3.43(q，1H)，3.26(q，1H)，1.28(t，3H)。
(2) synthesis of 1-(6-chloropyrazine-2-base) the chloro-1H-pyrazoles of-3--5-formic acid
1-(6-chloropyrazine-2-base) the chloro-1H-pyrazole-5-ethyl formate of-3-(6g is added in reaction flask, 20.75mmol), water 50ml, stir, add sodium hydroxide (1.66g, 41.5mmol), heat up 40 DEG C of reactions 3 hours, and concentrated hydrochloric acid regulates PH=2.0, separates out brown solid, suction filtration, washing, obtains product, yield 69.6%.
1HNMR(400M，DMSO-d 6)：13.01(s，1H)，8.21(d，1H)，8.11(d，1H)，5.26(m，1H)，3.52(q，1H)，3.26(q，1H)。
(3) synthesis of 1-(6-chloropyrazine-2-base) the chloro-1H-pyrazoles of-3--5-acyl chlorides
1-(6-chloropyrazine-2-base)-3-chloro-1H-pyrazoles-5-formic acid (4.5g, 17.24mmol), methylene dichloride 50ml, sulfur oxychloride (5.125g, 43.1mmol) is added, heated and stirred 5 hours in reaction flask.Revolve and steam excessive sulfur oxychloride, oil pump is drained, and obtains product.
(4) preparation of compound 27
N-methyl-3-methyl-5-chloro-2-aminobenzamide (2.0g is added in reaction flask, 10.07mmol), acetonitrile 30ml, triethylamine (1.53g, 15.11mmol), after stirring and dissolving, drip 1-(6-chloropyrazine-2-base) the chloro-1H-pyrazoles of-3--5-acyl chlorides (3.055g, 11.01mmol) acetonitrile solution, stirring at room temperature 3 hours, TLC detects, chromatography over CC, obtain faint yellow solid product, productive rate 36.4%.
1HNMR(400M，DMSO-d 6)：10.64(s，1H)，8.54(d，1H)，8.32(brs，1H)，8.02(d，1H)，7.52(d，1H)，7.34(d，1H)，7.22(s，1H)，2.85(d，3H)，2.13(s，3H)。
Bioactive mensuration
The mensuration of embodiment 10, insecticidal activity
According to the solvability of testing compound, former medicinal acetone or dmso solution, then become the liquid 50ml to be measured of desired concn with the tween 80 solution preparation of 1 ‰, acetone or the content of dimethyl sulfoxide (DMSO) in total solution are no more than 10%.
In this insect-killing composition, the weight percentage of active ingredient is between 1-99%.The carrier that agricultural, forestry, health accept also is comprised in this insect-killing composition.
Composition of the present invention can use with the form of preparation.Generalformulaⅰcompound is easier to dispersion when being dissolved or dispersed in carrier as active ingredient or being mixed with preparation to be used as sterilant.As: these chemicals can be made into wettable powder or missible oil.In these compositions, at least add a kind of liquid or solid carrier, and add suitable tensio-active agent when needed.
Technical scheme of the present invention also comprises the method for pest control: be applied on described insect or its growth medium with the effective dose of per hectare 5g to 1000g by insect-killing composition of the present invention.
For some application, such as, one or more other Insecticides (tech) & Herbicides (tech) or fertilizer etc. agriculturally can be added in insect-killing composition of the present invention, additional advantage and effect can be produced thus.
The mensuration of mythimna separate:
Mythimna separata (Mythimna Walker) is the normal population of indoor feeding.Leaf of Semen Maydis punch tool is broken into the leaf butterfly of diameter 1cm, be impregnated in the liquid of the different concns of preparation, 3 ages accessing certain head number after the liquid on blade is done try worm, often process 3 times and repeat.Put into after process 25 DEG C, relative humidity 50-60%, unglazed photograph indoor cultivation, be mainly stomach toxicity, action of contace poison, simultaneously observe examination worm suck phenomenon.72 hours " Invest, Then Investigate " survival borer populations, calculate mortality ratio.
In the compound of part test, following compounds is better to the prevention effect of mythimna separata when concentration 5ppm, mortality ratio more than 60%: 1,3,5,7,8,10,11,12,13,15,16,22,24.
According to the method described above, compound 1,7,8,11,12,13,15,16,22 is chosen and known compound QS (No. 176, the compound in US2005/0075372A1) is that 1ppm carries out mythimna separate contrast in concentration.Result is following as following table 2.
Table 2
Compound 15 sees the following form 3 with the active correlation data that health is wide, compound Q S kills mythimna separata and Pyrausta nubilalis (Hubern). under 0.1ppm concentration.
Table 3
Compound Mythimna separata Pyrausta nubilalis (Hubern).
15 100％ 50％
Kang Kuan 100％ 60％
QS 0％ 0％

Claims (8)

1. replace N to mix an aromatic base amides, it is characterized in that, its structure is as shown in formula I:
In formula:
W is selected from C or N;
V is selected from N;
R 1be selected from C l, Br, OH, OCH 2cF 3, C 3-C 6alkene oxygen base, C 3-C 6haloalkene oxygen base, C 3-C 6alkynyloxy group or C 3-C 6halo alkynyloxy group;
R 2be selected from H, F, Cl, Br, OH, cyano group, methyl, ethyl, sec.-propyl, n-propyl, OCH 3, or it is amino;
R 3be selected from H, F, Cl, Br, OH, cyano group, methyl, ethyl, sec.-propyl, n-propyl, OCH 3, or it is amino;
R 4be selected from H, F, Cl, Br, OH, cyano group, methyl, ethyl, sec.-propyl, n-propyl, OCH 3, or it is amino;
R 5be selected from Cl, Br, cyano group, methyl or CF 3;
R 6be selected from Cl, cyano group, methyl or CF 3;
R 7be selected from H or C 1-C 3alkyl;
R 8be selected from H, methoxyl group, oxyethyl group, propoxy-, C 1-C 6alkyl, C 3-C 6thiazolinyl, C 3-C 6alkynyl or C 3-C 6cycloalkyl, on described alkyl, an optional hydrogen or multiple hydrogen can be replaced by substituents: halogen, hydroxyl, cyano group; Or R 7and R 8the nitrogen formation N methyl piperazine connected together, morpholine, oxazolidine, isoxazole alkyl,
Further, when W is C atom, V is atom N, R 2be selected from F, Cl or CN, R 3be selected from H, F, Cl or CN and R 4when being selected from H, F, Cl, R 8be selected from methoxyl group, oxyethyl group, propoxy-or R 7and R 8the nitrogen formation N methyl piperazine connected together, morpholine, oxazolidine, isoxazole alkyl,
2. compound as claimed in claim 1, is characterized in that, in formula I:
R 1be selected from Cl, Br, OCH 2cF 3, C 3-C 6alkene oxygen base or C 3-C 6haloalkene oxygen base;
R 2be selected from H, Cl, Br, OH or cyano group;
R 3be selected from H, Cl or Br;
R 4be selected from H, Cl, methyl or ethyl;
R 5be selected from Cl, cyano group, methyl or CF 3;
R 6be selected from Cl or methyl;
R 7be selected from H, methoxyl group;
R 8be selected from H, methoxyl group, oxyethyl group, N methyl piperazine, oxazolidine, isoxazole alkyl or morpholine.
3. prepare an intermediate for generalformulaⅰcompound according to claim 1, it is characterized in that, its structure is as shown in general formulae IV:
W is selected from N;
V is selected from N;
R is selected from H or C 1-C 4alkyl;
R 1be selected from Cl, Br, OH, OCH 2cF 3, C 3-C 6alkene oxygen base, C 3-C 6haloalkene oxygen base, C 3-C 6alkynyloxy group or C 3-C 6halo alkynyloxy group;
R 2be selected from H, F, Cl, Br, OH, cyano group, methyl, ethyl, sec.-propyl, n-propyl, OCH 3, or it is amino;
R 3be selected from H, F, Cl, Br, OH, cyano group, methyl, ethyl, sec.-propyl, n-propyl, OCH 3;
R 4be selected from H, F, Cl, Br, OH, cyano group, methyl, ethyl, sec.-propyl, n-propyl, OCH 3, or it is amino.
4. the application of generalformulaⅰcompound in pest control as claimed in claim 1 or 2.
5. an insect-killing composition, is characterized in that, be active ingredient and acceptable carrier in agricultural, forestry or health containing, for example compound shown in the formula I described in claim 1 or 2, in composition, the weight percentage of active ingredient is 1-99%.
6. a prevention and controls for insect pest, is characterized in that, is applied on the medium of insect pest or its growth needing to control by composition according to claim 5 with the effective dose of per hectare 5g to 1000g.
7. replacement N according to claim 1 mixes the preparation method of aromatic base amides, comprises the steps:
General formula II compound and general formula III compound in suitable solvent, temperature reacts 0.5-12 hour obtained target compound I under being 0 DEG C to boiling conditions;
Suitable solvent is selected from: methylene dichloride, chloroform, tetracol phenixin, hexane, benzene, toluene, ethyl acetate, acetonitrile, tetrahydrofuran (THF), dioxane, DMF or dimethyl sulfoxide (DMSO).
8. the preparation method of intermediate according to claim 3, comprises the steps:
(1) general formulae IV (R 1for OH) preparation of compound
1) general formula Ⅹ (R 1for OH) preparation of compound:
General formula Ⅸ compound and general formula Ⅺ compound react obtained R under the existence of alkali and solvent 1for general formula Ⅹ compound of OH;
Described alkali is selected from sodium methylate, potassium methylate, sodium ethylate, potassium ethylate, potassium tert.-butoxide or sodium tert-butoxide;
Described solvent selected from ethanol or methyl alcohol;
Temperature of reaction be 20 DEG C to boiling point, reaction times 1-24 hour; Then add acid such as acetic acid, hydrochloric acid or sulfuric acid in reaction and carry out acidifying;
2) general formulae IV (R 1for OH) preparation of compound:
General formula Ⅹ (R 1for OH) compound in the presence of acid in suitable solvent, temperature be 0 DEG C under boiling point, with oxygenant generation oxidizing reaction 1-24 hour obtained general formulae IV (R 1for OH) compound;
Described oxygenant is selected from hydrogen peroxide, organo-peroxide, Potassium Persulphate, Sodium Persulfate, ammonium persulphate, Potassium peroxysulfate or potassium permanganate;
Described solvent is selected from tetrahydrofuran (THF), dioxane, ethyl acetate, DMF or acetonitrile;
Described acid is selected from sulfuric acid, phosphoric acid or acetic acid;
(2) general formulae IV (R 1for substituted oxy) preparation of compound
2 of step (1)) middle gained general formulae IV (R 1for OH) compound and halides in suitable solvent, temperature be-10 DEG C under boiling point, react 1-24 hour obtained general formulae IV (R 1for substituted oxy: OCH 2cF 3, C 3-C 6alkene oxygen base, C 3-C 6haloalkene oxygen base, C 3-C 6alkynyloxy group or C 3-C 6halo alkynyloxy group) compound;
Described solvent is selected from methylene dichloride, chloroform, tetracol phenixin, DMF, acetonitrile, tetrahydrofuran (THF), dioxane or dimethyl sulfoxide (DMSO);
Described halides is selected from methyl iodide, allyl bromide 98 or propargyl bromide;
(3) general formulae IV (R 1for halogen) preparation of compound
1) general formula Ⅹ (R 1for halogen) preparation of compound
1 of step (1)) middle gained R 1for general formula Ⅹ compound of OH reacts with halogenating agent in the presence of the solvent, obtain corresponding general formula Ⅹ (R 1for halogen) compound:
Described halogenating agent is selected from trihalophosporus oxide, phosphorus trihalide, phosphorus pentahalides, oxalyl chloride or carbonyl chloride;
Described solvent is selected from methylene dichloride, chloroform, benzene, dimethylbenzene, chlorinated benzene, tetrahydrofuran (THF), dioxane, ether, acetonitrile or DMF;
The temperature of reaction, under 20 DEG C to boiling point, reacts 1-24 hour; Then products therefrom sodium bicarbonate, sodium hydroxide or sodium acetate neutralization, obtains target product;
2) general formulae IV (R 1for halogen) preparation of compound
General formula Ⅹ (R 1for halogen) compound in the presence of acid in suitable solvent, temperature be 0 DEG C to boiling point under with oxygenant generation oxidizing reaction 1-24 hour obtained general formulae IV (R 1for halogen) compound;
Described oxygenant is selected from hydrogen peroxide, organo-peroxide, Potassium Persulphate, Sodium Persulfate, ammonium persulphate, Potassium peroxysulfate or potassium permanganate;
Described solvent is selected from tetrahydrofuran (THF), dioxane, ethyl acetate, DMF or acetonitrile;
Described acid is selected from sulfuric acid, phosphoric acid or acetic acid.
CN201510028065.1A 2015-01-20 2015-01-20 Substituent N heterozygous aromatic base amide compound and application thereof Pending CN104496967A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201510028065.1A CN104496967A (en) 2015-01-20 2015-01-20 Substituent N heterozygous aromatic base amide compound and application thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201510028065.1A CN104496967A (en) 2015-01-20 2015-01-20 Substituent N heterozygous aromatic base amide compound and application thereof

Publications (1)

Publication Number Publication Date
CN104496967A true CN104496967A (en) 2015-04-08

Family

ID=52938441

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201510028065.1A Pending CN104496967A (en) 2015-01-20 2015-01-20 Substituent N heterozygous aromatic base amide compound and application thereof

Country Status (1)

Country Link
CN (1) CN104496967A (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20230155447A (en) 2021-03-09 2023-11-10 이시하라 산교 가부시끼가이샤 Method for producing 3-bromo-1-(3-chloropyridin-2-yl)-1H-pyrazole-5-carboxylic acid ester

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1541063A (en) * 2001-08-13 2004-10-27 ��Ļ���Ű˾ Method for controlling particular insects by applying anthranilamide compounds
CN101333213A (en) * 2008-07-07 2008-12-31 中国中化集团公司 1-substituted pyridyl-pyrazol acid amide compounds and use thereof
CN101337959A (en) * 2008-08-12 2009-01-07 国家农药创制工程技术研究中心 2-amino-N-oxybenzamidecompounds with insecticidal activity

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1541063A (en) * 2001-08-13 2004-10-27 ��Ļ���Ű˾ Method for controlling particular insects by applying anthranilamide compounds
CN101333213A (en) * 2008-07-07 2008-12-31 中国中化集团公司 1-substituted pyridyl-pyrazol acid amide compounds and use thereof
CN101337959A (en) * 2008-08-12 2009-01-07 国家农药创制工程技术研究中心 2-amino-N-oxybenzamidecompounds with insecticidal activity

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20230155447A (en) 2021-03-09 2023-11-10 이시하라 산교 가부시끼가이샤 Method for producing 3-bromo-1-(3-chloropyridin-2-yl)-1H-pyrazole-5-carboxylic acid ester

Similar Documents

Publication Publication Date Title
CN110028423B (en) Meta-diamide compound and preparation method and application thereof
CN101333213B (en) 1-substituted pyridyl-pyrazol acid amide compounds and use thereof
EP0264217B1 (en) Aralkylaminopyrimidine derivative, process for producing thereof and insecticide, acaricide and fungicide containing said derivative as active ingredient
KR101693375B1 (en) Halogen-substituted compounds used as pesticides
CA1337525C (en) Alkylaminopyrimidine derivative, process for producing the same, and insecticide, acaricide and fungicide containing the same as active ingredient
CN101659655A (en) Pyrazole amide derivative and application thereof
CN102285963B (en) 3-methoxy pyrazolecarboxamide compound and application thereof
WO2019228289A1 (en) Substituted oxadiazole compound and application thereof
CN105712975A (en) Pyrazole amide compound containing 1,2,3-triazole ring and application of pyrazole amide compound containing 1,2,3-triazole ring
CN104496967A (en) Substituent N heterozygous aromatic base amide compound and application thereof
WO2006080311A1 (en) Anthranilamide compound, method for producing same and pest control agent containing same
CN106831647A (en) A kind of thiadiazoles amides compound and application thereof
CN102285966A (en) 3-fluoro-5-chloropyridyl pyrazolecarboxamide compound and application thereof
CN105732587A (en) 6-substituted pyrimidyl quinazolinone compound and application thereof
CN109574956B (en) Thiadiazole amide compound and application thereof
CN105418590A (en) 6-substituted pyrazolyl quinazolinone compound and use thereof
CN105712973A (en) Pyrazole amide compound and application thereof
CN104206385A (en) Use of amine compound as bactericide
US11390602B2 (en) N-alkyl-N-cyanoalkylbenzamide compound and use thereof
CN104650036A (en) 6-substituented phenyl quinazolinone compound and use thereof
JPH08291149A (en) 4-(2-(trifuluoroalkoxy-substituted phenyl) ethylamino)pyrimidine derivative, its production and pest control agent for agriculture and horticulture
JP3038903B2 (en) Uracil derivatives and pesticides
JPH11116555A (en) 4-anilinopyrimidine derivative and insecticidal, acaricidal and microbicidal agent containing the same and useful for agriculture and horticulture
CN102442969B (en) Butyne ether compound and application thereof
JPH0745481B2 (en) Alkylaminopyrimidine derivative, method for producing the same, and insecticide, acaricide and fungicide containing the derivative as an active ingredient

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
RJ01 Rejection of invention patent application after publication
RJ01 Rejection of invention patent application after publication

Application publication date: 20150408