CN1370162A - Derivatives of trifluoromethylpyri(mi)dine - Google Patents
Derivatives of trifluoromethylpyri(mi)dine Download PDFInfo
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- CN1370162A CN1370162A CN00811841A CN00811841A CN1370162A CN 1370162 A CN1370162 A CN 1370162A CN 00811841 A CN00811841 A CN 00811841A CN 00811841 A CN00811841 A CN 00811841A CN 1370162 A CN1370162 A CN 1370162A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
- C07D401/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings
- C07D401/04—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
- A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
- A01N43/88—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms six-membered rings with three ring hetero atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D413/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms
- C07D413/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings
- C07D413/04—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings directly linked by a ring-member-to-ring-member bond
Abstract
Compounds of formula are described, wherein Z signifies six- or seven-membered, optionally substituted, aromatic or non-aromatic heterocyclyl; X is CH or N; Y is halogen; n is 1, 2 or 3; and m is 0 or 1; and, if appropriate, the E/Z isomers, E/Z isomeric mixtures and/or tautomers thereof, each in free form or in salt form; a method of producing and the use of these compounds, pesticides whose active ingredient is selected from these compounds or from an agrochemically acceptable salt thereof, a method of producing and the use of these compositions, plant propagating material that has been treated with these compositions and a method of controlling pests.
Description
The objective of the invention is following formula: compound:
Wherein Z represents the optional six or seven-first aromatics that replaces or the heterocyclic radical of non-aromatics;
X is CH or N;
Y is a halogen;
N is 1,2 or 3; With
M is 0 or 1; And be its E/Z isomer suitably the time, E/Z isomer mixture and/or its tautomer, the respectively free form or the form of salt naturally; The preparation method of these compounds and application, its activeconstituents are selected from the agricultural chemicals of acceptable salt on these compounds or its agrochemistry, these preparation of compositions methods and applications, the plant propagation material of crossing with these compositions-treated and the method for Pest Control.
In the literature, some pyridine derivate can be used as the activeconstituents of agricultural chemicals.But in field of pest control, it is satisfied fully that the biological property of these known compounds can not make us, and why Here it is needs to produce the compound that other has pesticidal properties, particularly can prevent and treat insect and acarina member's compound; The present invention studies formula (I) compound, thereby has solved this problem.
Formula (I) compound and their suitable tautomers can form salt, for example acid salt.For example form salt with strong inorganic acid, concrete mineral acid for example is sulfuric acid, phosphoric acid or haloid acid; Or form salt with strong organic carboxyl acid, be specially C
1-C
4Alkanoic acid, can be replaced by for example halogen when it is suitable, acetate for example, and for example optional unsaturated dicarboxylic acid, for example oxalic acid, propanedioic acid, toxilic acid, fumaric acid or phthalic acid, hydroxycarboxylic acid and for example, for example xitix, lactic acid, oxysuccinic acid, tartrate or citric acid, or phenylformic acid; Or form salt with organic sulfonic acid, be specially C
1-C
4Alkane or aryl sulfonic acid can be replaced by for example halogen when it is suitable, for example methylsulfonic acid or tosic acid.In the broader sense, formula (I) compound with at least one acidic group can form salt with alkali.Suitable salt such as the metal-salt that forms with alkali, for example basic metal or alkaline earth salt, as sodium, potassium or magnesium salts, or the salt that forms with ammonia or organic amine, for example with morpholine, piperidines, tetramethyleneimine ,-, two-or three-low-grade alkylamine (as ethyl, diethyl, triethylamine or dimethyl propyl amine), or one-, two-or three-hydroxyl low-grade alkyl amine (as one-, two-or trolamine) form salt.Also can form corresponding inner salt in the time of suitably.Free form is preferred.In the salt of formula (I) compound, useful salt is preferred on the agrochemistry.Be understandable that when suitable,, be understandable that perhaps described salt also comprises free formula (I) compound above or hereinafter, free formula (I) compound or its salt also comprises corresponding salt.Same notion also can be used for the tautomer of formula (I) compound and its salt.
Unless otherwise defined, above or hereinafter used general terms and the same meaning that hereinafter provides.
Halogen-itself is as group, or as other group and compound such as haloalkyl, halogenated cycloalkyl, halogenated alkenyl, halo alkynyl group and halogenated alkoxy structural element-it is fluorine, chlorine, bromine or iodine, particularly fluorine, chlorine or bromine mainly are fluorine or chlorine, especially chlorine.
As do not have other definition, and carbon-containing group and compound contain 1-20 separately, preferred 1-18, particularly 1-10, especially 1-6, and more especially 1-4, especially 1-3, particularly 1 or 2 carbon atom, specifically, methyl is preferred.
Alkyl-itself is as group; with as other group and compound such as haloalkyl; alkoxyl group; alkoxyalkyl; halogenated alkoxy; carbalkoxy; alkylthio; halogenated alkylthio; the structural element of alkyl sulphonyl and alkylsulfonyloxy; consider the given number of carbon atom in group or the compound in all cases; it can be straight chain; methyl for example; ethyl; n-propyl; normal-butyl; n-hexyl; n-octyl; positive decyl; dodecyl; n-hexadecyl or Octadecane base; or side chain, for example sec.-propyl; isobutyl-; sec-butyl; the tertiary butyl; isopentyl; neo-pentyl or isohexyl.
Alkenyl and alkynyl group-itself is as group, with as other group and compound such as halogenated alkenyl, halo alkynyl group, alkenyloxy, halo alkenyloxy, chain oxy-acetylene or halo chain oxy-acetylene structural element-it is straight or branched, and contains two or a preferred unsaturated C-C separately.What can be used as example for example has a vinyl, third-2-alkene-1-base, 2-methyl-prop-2-alkene-1-base, but-2-ene-1-base, fourth-3-alkene-1-base, third-2-alkynes-1-base, fourth-2-alkynes-1-base and fourth-3-alkynes-1-base.
Cycloalkyl-for example the structural element of alkyl-it is cyclopropyl as group with as other group and compound for itself, cyclobutyl, cyclopentyl, cyclohexyl, suberyl and ring octyl group.Preferably cyclopentyl and cyclohexyl, particularly cyclopropyl.
The carbon-containing group of halogen-replacement and compound can be partially halogenated or perhalogenation as haloalkyl and halogenated alkoxy, and under polyhalogenated situation, halogenic substituent can be identical or different.The example of haloalkyl-itself as group and as the structural element of other group and compound such as halogenated alkoxy-its by fluorine, chlorine and/or bromine one to trisubstituted methyl, as CHF
2, CF
3Or CH
2Cl; By the ethyl of fluorine, chlorine and/or bromine one to five replacement, as CH
2CF
3, CF
2CF
3, CF
2CCl
3, CF
2CHCl
2, CF
2CHF
2, CF
2CFCl
2, CH
2CH
2Cl, CF
2CHBr
2, CF
2CHClF, CF
2CHBrF or CClFCHClF; By the propyl group or the sec.-propyl of fluorine, chlorine and/or bromine one to seven replacement, as CH
2CHBrCH
2Br, CF
2CHFCF
3, CH
2CF
2CF
3, CF
2CF
2CF
3, CH (CF
3)
2Or CH
2CH
2CH
2Cl; With one of the butyl that is replaced by fluorine, chlorine and/or bromine one to nine or its isomer, as CF (CF
3) CHFCF
3, CF
2(CF
2)
2CF
3Or CH
2(CF
2)
2CF
3
At two-(C
1-C
4-alkyl) in the amine, two alkyl groups are separately independently.
Aryl is meant phenyl or naphthyl especially, preferred phenyl.
Heterocyclic radical is meant 6-or 7-unit, saturated or undersaturated ring, the basic structure bonding of this ring and carbon atom, and this ring preferably has the individual heteroatoms that is selected from N, O or S of 2-4.Preferably have nitrogen-atoms as heteroatoms with two other heteroatomic 6-unit ring is arranged, described two heteroatomss are nitrogen-atoms or Sauerstoffatom preferably, particularly a Sauerstoffatom and a nitrogen-atoms.
According to the possibility that replaces on the heterocyclic radical group, this heterocyclic radical group can have 1-3, preferably have 1 is selected from following substituting group: C
1-C
6-alkyl, C
2-C
6-alkenyl, C
3-C
6-alkynyl group; Halogen, nitro, cyano group ,-OH ,-SH, C
3-C
8-cycloalkyl, halogen-C
3-C
8-cycloalkyl, C
1-C
6-alkoxyl group, halogen-C
1-C
6-alkoxyl group, C
3-C
6-alkenyloxy, C
1-C
4-alkylthio and two-(C
1-C
4-alkyl) amine.
According to the preferred embodiment of the invention, formula (I) compound is:
A) wherein Z is meant the ring of following formula:
At this key U-A, A-M, M-D, D-E, E-G and G-U are singly-bound or two key, condition is two keys that can not occur linking to each other,
A is-O--NR
1-,-S-or-N=;
M is-NR
2-,-O-,-S-,-CR
3R
4-,-N=or-CR
3=;
D is-CR
5R
6-,-NR
7-,-O-,-S-,-N=or-CR
5=;
E is-NR
2-;-O-,-S-or-CR
8R
9-;-N=or-CR
8=; With
G is-O--NR
10-,-S-, or-N=;
U is a carbon;
R
1, R
2, R
7And R
10Represent hydrogen, C separately independently of each other
1-C
20-alkyl, C
3-C
8-cycloalkyl, C
2-C
20-alkenyl or C
3-C
20-alkynyl group; Or one-or polysubstituted C
1-C
20-alkyl, C
2-C
20-alkenyl or C
3-C
20-alkynyl group; By the optional aryl that replaces of one or more substituting groups, this substituting group is selected from: C
1-C
6-alkyl, halogen-C
1-C
6-alkyl, C
2-C
6-alkenyl, C
3-C
6-alkynyl group, halogen, C
1-C
6-alkoxyl group, halogen-C
1-C
6-alkoxyl group, nitro, cyano group, C
3-C
8-cycloalkyl, halogen-C
3-C
8-cycloalkyl, C
3-C
6-alkenyloxy, C
1-C
4-alkylthio and two-(C
1-C
4-alkyl) amine; Or-C (=O)-R
11
R
3, R
4, R
5, R
6, R
8And R
9Represent hydrogen, C separately independently of each other
1-C
6-alkyl, C
3-C
8-cycloalkyl, C
1-C
6-alkoxyl group, C
1-C
6-alkylthio, C
2-C
6-alkenyl, C
3-C
6-alkenyloxy, C
3-C
6-alkynyl group, C
3-C
6-chain oxy-acetylene, aryl, heterocyclic radical, aryloxy, benzyloxy or heterocyclic oxy group; C
1-C
6-alkyl, C
3-C
8-cycloalkyl, C
1-C
6-alkoxyl group, C
1-C
6-alkylthio, C
3-C
6-alkenyl, C
3-C
6-alkenyloxy, C
3-C
6-alkynyl group or C
3-C
6-chain oxy-acetylene, described group is selected from following substituting group and replaces by one or more: halogen, nitro, cyano group ,-OH ,-SH, C
3-C
8-cycloalkyl, halogen-C
3-C
8-cycloalkyl, phenyl and two-(C
1-C
4-alkyl) amine; Or be selected from the following aryl that substituting group replaced: halogen, nitro, cyano group ,-OH ,-SH, COOH, COH, C by one to three
1-C
6-alkyl, C
1-C
6-alkoxyl group, C
1-C
6-alkylthio, halogen-C
1-C
6-alkyl, halogen-C
1-C
6-alkoxyl group, halogen-C
1-C
6-alkylthio, C
3-C
8-cycloalkyl, halogen-C
3-C
8-cycloalkyl and two-(C
1-C
4-alkyl) amine;
Or be together=O or=S;
R
11Expression hydrogen, OH, SH, C
1-C
6-alkyl, C
3-C
8-cycloalkyl, C
1-C
6-alkoxyl group, C
1-C
6-alkylthio, C
2-C
6-alkenyl, C
3-C
6-alkenyloxy, C
3-C
6-alkynyl group, C
3-C
6-chain oxy-acetylene, two-(C
1-C
4-alkyl) amine, aryl, heterocyclic radical, aryloxy, benzyloxy or heterocyclic oxy group; C
1-C
6-alkyl, C
3-C
8-cycloalkyl, C
1-C
6-alkoxyl group, C
1-C
6-alkylthio, C
3-C
6-alkenyl, C
3-C
6-alkenyloxy, C
3-C
6-alkynyl group or C
3-C
6-chain oxy-acetylene, described group is selected from following substituting group and replaces by one or more: halogen, nitro, cyano group ,-OH ,-SH, C
3-C
8-cycloalkyl, halogen-C
3-C
8-cycloalkyl and two-(C
1-C
4-alkyl) amine; Or aryl, heterocyclic radical, aryloxy, benzyloxy or heterocyclic oxy group, described group are selected from following substituting group by one to three and replace: halogen, nitro, cyano group ,-OH ,-SH, COOH, COH, C
1-C
6-alkyl, C
1-C
6-alkoxyl group, C
1-C
6-alkylthio, halogen-C
1-C
6-alkyl, halogen-C
1-C
6-alkoxyl group, halogen-C
1-C
6-alkylthio, C
3-C
8-cycloalkyl, halogen-C
3-C
8-cycloalkyl and two (C
1-C
4-alkyl) amine;
Condition is, if one of M or E, or M and E are-NR simultaneously independently of one another
2,-N=,-O-or-during S-, D represents-CR
5R
6-or-CR
5=.
B) wherein A represents-O-,-NR
1-or-N=; With
R
1Be hydrogen, C
1-C
6-alkyl, C
3-C
8-cycloalkyl, C
2-C
6-alkenyl; Or C
1-C
6-alkyl, C
2-C
6-alkenyl or C
3-C
8-cycloalkyl, described group is selected from following substituting group and replaces by one or more: halogen, nitro, cyano group ,-OH ,-SH, C
3-C
8Cycloalkyl, halogen-C
3-C
8-cycloalkyl, C
1-C
6-alkoxyl group, halogen-C
1-C
6-alkoxyl group, C
3-C
6-alkenyloxy, C
1-C
4-alkylthio, two-(C
1-C
4-alkyl) amine ,-C (=O)-R
12, aryl, aryloxy, arylthio, heterocyclic radical or heterocyclic oxy group; And R
12Be hydrogen, OH, C
1-C
6-alkyl, C
1-C
6-alkoxyl group, two-(C
1-C
4-alkyl) amine, aryl, aryloxy or benzyloxy; Especially wherein R
1Be hydrogen or C
1-C
2-alkyl;
Especially, wherein A be-O-or-N=, most preferably be-O-;
C) wherein M is-NR
2-,-O-,-CR
3R
4-,-N=or-CR
3=;
R
2Be hydrogen, C
1-C
6-alkyl, C
3-C
8-cycloalkyl, C
2-C
6-alkenyl; Or C
1-C
6-alkyl, C
2-C
6-alkenyl or C
3-C
8-cycloalkyl, described group is selected from following substituting group and replaces by one or more: halogen, nitro, cyano group ,-OH ,-SH, C
3-C
8-cycloalkyl, halogen-C
3-C
8-cycloalkyl, C
1-C
6-alkoxyl group, halogen-C
1-C
6-alkoxyl group, two-(C
1-C
4-alkyl) amine ,-C (=O)-R
12, aryl, aryloxy, arylthio, heterocyclic radical or heterocyclic oxy group; And R
12Be C
1-C
6-alkyl or C
1-C
6-alkoxyl group;
R
3And R
4Be hydrogen independently of each other, C
1-C
6-alkyl, C
3-C
8-cycloalkyl, C
1-C
6Alkoxyl group, C
3-C
6-alkenyl or aryl; Or C
1-C
6-alkyl or C
3-C
8-cycloalkyl, described group is selected from following substituting group and replaces by one or more: halogen, nitro, cyano group, C
3-C
8-cycloalkyl, phenyl and two (C
1-C
4-alkyl) amine; Or be selected from the aryl that following substituting group replaces: halogen, nitro, cyano group, C by one to three
1-C
6-alkyl, C
1-C
6-alkoxyl group, C
1-C
6-alkylthio, halogen-C
1-C
6-alkyl, halogen-C
1-C
6-alkoxyl group and two-(C
1-C
4-alkyl) amine;
Or be together=O or=S;
Especially wherein M is-CR
3R
4-or-CR
3=; With
R
2And R
4Be hydrogen independently of one another, C
1-C
6-alkyl, C
3-C
8-cycloalkyl, C
1-C
6-alkoxyl group, C
3-C
6-alkenyl or aryl; Or be together=O or=S;
Especially, wherein M is-CR
3R
4-or-CR
3=; And R
3Be hydrogen or C
1-C
6-alkyl, and R
4Be hydrogen, R especially
3And R
4Be hydrogen, or R
3And R
4Be together=O or=S;
Especially, wherein M is C=O;
D) wherein D is-CR
5R
6-,-NR
7-or-O-,-N=or-CR
5=;
R
5And R
6Be hydrogen independently of one another, C
1-C
6-alkyl, C
3-C
8-cycloalkyl, C
1-C
6-alkoxyl group, aryl or aryloxy; Or be together=O or=S;
R
7Be hydrogen, C
1-C
6-alkyl, C
3-C
8-cycloalkyl, C
3-C
12-alkenyl or C
3-C
20-alkynyl group; Or by halogen one or polysubstituted C
1-C
6-alkyl, or be C
1-C
4-alkoxyl group or phenyl; Aryl; Or-C (=O)-R
11R
11Be hydrogen, OH, C
1-C
6-alkyl, C
1-C
6-alkoxyl group, two-(C
1-C
4-alkyl) amine, aryl, aryloxy or benzyloxy;
Especially wherein D is-CR
5R
6-or-NR
7-; R
5And R
6Be hydrogen or C independently of each other
1-C
2-alkyl, and R
7Be hydrogen, C
1-C
6-alkyl, C
3-C
8-cycloalkyl, phenyl or benzyl; Especially, wherein D is CH
2-or-NR
7-; And R
7Be hydrogen or C
1-C
6-alkyl;
Especially wherein D is-NCH
3-;
E) E is-NR
22-;-O-,-CR
8R
9-;-N=or-CR
8=;
R
8And R
9Be hydrogen or C independently of one another
1-C
6-alkyl, described group is optional to be selected from following substituting group and to replace by one or more: halogen, nitro, cyano group ,-OH ,-SH, C
3-C
8-cycloalkyl, halogen-C
3-C
8-cycloalkyl, phenyl and two-(C
1-C
4-alkyl) amine;
Or be together=O or=S; With
R
22Be hydrogen or C
1-C
6-alkyl, described group is optional to be selected from following substituting group and to replace by one or more: halogen, nitro, cyano group ,-OH ,-SH, C
3-C
8-cycloalkyl, halogen-C
3-C
8-cycloalkyl, C
1-C
6-alkoxyl group, halogen-C
1-C
6-alkoxyl group, C
3-C
6-alkenyloxy, C
1-C
4-alkylthio, two-(C
1-C
4-alkyl) amine and aryl;
Especially wherein E represents-CR
8R
9-, and R
8And R
9Represent hydrogen or C independently of one another
1-C
6-alkyl, or be=O together, especially hydrogen;
F) wherein G represents-O-,-NR
10-or-N=; And
R
10Be hydrogen or C
1-C
20-alkyl;
Especially G represents-N=;
G) wherein X is CH;
H) wherein n is 3;
I) wherein Y is a fluorine;
J) wherein m is 0.
Z preferably has following definitions, at this R
1, R
2, R
22And R
7Definition as mentioned:
According to the present invention, particularly preferably be formula (I) compound of listing in the table 1.
To those skilled in the art, by similar preparation method as can be known the preparation method of formula (I) compound be known.This is particularly related to the method for the following compound of preparation:
X wherein, R
7Define as mentioned with m, A is O or S, and R
3And R
4Be O or S together.Therefore, another object of the present invention is the method for preparation formula (Ia) compound or its salt, wherein
A) in inert solvent, make known or with the following formula: compound that itself is the preparation of known method:
Wherein X is suc as formula the definition of (I), with known or react with the following formula: compound that itself is known method preparation:
To generate following formula: compound or its salt, X wherein, R
7With the definition of m suc as formula (I); With
B) formula (III) compound and carbonyl chloride or sulfo-carbonyl chloride are reacted;
C) be 1 formula (Ia) compound in order to obtain m, making m is that 0 formula (I) compound and oxygenant react, and described oxygenant for example is inorganic peroxide such as Sodium peroxoborate, potassium permanganate or hydrogen peroxide; Or react with mCPBA or organic peracid, described organic peracid for example is peroxybenzoic acid or peracetic acid; Or the mixture of organic acid and hydrogen peroxide, as acetate/hydrogen peroxide;
And/or if desired, make in this way or other method obtains, formula (I) compound that exists with free or salt form changes into different formula (I) compound, available isomer mixture is in this way separated, separate and obtain required isomer, and/or will be in this way or free formula (I) compound that obtains of other method transform salify, will be in this way or the salt of formula (I) compound that obtains of other method change into free formula (I) compound or different salt.
Further, the also available and similar method production of currently known methods of formula (I) compound.For example wherein Z is formula (I) compound of following formula:
Can be by making following formula: compound or its salt:
Wherein X defines as mentioned, at compound N H
2R
7Existence is descended and formaldehyde reacts, and makes thus obtained following formula: compound:
Randomly with formula Q-R
1The compound reaction, wherein Q is leavings group and R
1Definition but is not H as mentioned, and the formula that will so obtain (I) compound (wherein m is 0) is according to said process c) randomly carry out oxidation.
List in above and formula hereinafter (II) and raw material (III) are known or available known method preparations itself, these raw materials can be used to produce formula (I) compound that exists with free form or salt form.The raw material of formula (IV) is new, also is purpose of the present invention therefore.
Above and reaction hereinafter described can carry out in a known manner, for example carry out under the following conditions: do not having, if perhaps suitable, having in the presence of appropriate solvent or thinner or its mixture, under the condition of required room temperature cooling or heating, as at about-80 ℃ boiling temperature to reaction medium, preferably approximately-20 ℃ to approximately+150 ℃ temperature under, be suitable in airtight container at this, under pressure, in inert atmosphere, and/or under non-water condition.Especially favourable reaction conditions is as described in the embodiment.
The process acid that is reflected at a) is carried out under existing, and acid for example is HCl, sulfuric acid or phosphoric acid.
Reaction is preferably carried out under-10 ℃ to+50 ℃ temperature usually at-30 ℃ to+70 ℃.This process is carried out having in the presence of inert solvent or the solvent mixture usually.For this purpose, the example of the solvent that is fit to for example is fat and aromatic hydrocarbon, as benzene,toluene,xylene, sherwood oil, hexane; Halohydrocarbon is as chlorobenzene, methylene dichloride, ethylene dichloride, chloroform, tetracol phenixin, zellon; Ether or ether compound are as dialkyl ether (ether, Di Iso Propyl Ether, t-butyl methyl ether etc.), methyl-phenoxide, diox, tetrahydrofuran (THF); Nitrile is as acetonitrile, propionitrile; Ester is as ethyl acetate (acetate ethyl ester), propyl acetate or butylacetate; Ketone is as acetone, metacetone, methyl ethyl ketone or methyl iso-butyl ketone (MIBK); And the mixture of these solvents and another kind of solvent.
Reaction is under atmospheric pressure carried out, but also can carry out under the condition of pressurize or decompression.
At process b) distortion in, reaction is advantageously in the presence of inert solvent or solvent mixture, in-30 ℃ to+70 ℃, preferably-10 ℃ are extremely carried out under+50 ℃ the temperature.Reaction is preferably carried out in the presence of alkali, for example at organic amine such as trialkylamine (Trimethylamine 99, triethylamine, triisopropylamine or diisopropyl ethyl amine), pyridine (pyridine itself, 4-methylamino pyridine or 4-pyrrolidyl pyridine), morpholine (N-methylmorpholine) or N, N-dialkyl aniline (N, accelerine or N-methyl-N-ethylaniline) carries out under existing.For this purpose, the example of suitable solvent for example is fat and aromatic hydrocarbon, as benzene,toluene,xylene, sherwood oil, hexane; Halohydrocarbon is as chlorobenzene, methylene dichloride, ethylene dichloride, chloroform, tetracol phenixin, zellon; Ether is as dialkyl ether (ether, Di Iso Propyl Ether, t-butyl methyl ether etc.), methyl-phenoxide, diox, tetrahydrofuran (THF); Nitrile is as acetonitrile, propionitrile; Ester is as ethyl acetate (acetate ethyl ester), propyl acetate or butylacetate; And the mixture of these solvents and another kind of solvent.
At process c) distortion in, be reflected at inert solvent or solvent mixture and exist down, in-40 ℃ to+120 ℃, preferably under-20 ℃ to+80 ℃ temperature, carry out more favourable.About solvent, with aforementioned b) distortion in mention those are identical.This process is chosen wantonly in the presence of alkali and is carried out, for example at basic metal or alkaline earth metal hydroxides or as basic metal or alkaline earth metal carbonate or supercarbonate, pyridine, 4-Dimethylamino pyridine, 4-pyrrolidyl pyridine, lutidine, collidine, trialkylamine, N, the non-nucleophilic base of N-dialkyl aniline or dicyclo is as 1,4-diazabicyclo [2.2.2] octane (DABCO), 1,5-diazabicyclo [4.3.0] ninth of the ten Heavenly Stems-5-alkene (DBN) or 1,8-diazabicyclo [5.4.0] 11 carbon-7-alkene (1,5-5) (DBU).
Formula (I) compound that obtains according to method of the present invention or other method can be changed into other formula (I) compound with known method own, it is by with other substituting group of the present invention, replaces according to ordinary method that one or more substituting groups of the initial compounds of formula (I) carry out.
According to the selection to appropriate reaction condition and raw material, in a reactions steps, available another substituting group of the present invention only replaces one of them substituting group, or in same reactions steps, with other substituting group replacement of the present invention several substituting groups wherein.
The salt of formula (I) compound can prepare by currently known methods.For example, can obtain the salt of formula (I) compound and alkali with suitable alkali or with suitable ion-exchange agent treated free cpds.
The salt of formula (I) compound can ordinary method change into free formula (I) compound, for example handles with suitable acid or suitable ion-exchange reagent.
The salt of formula (I) compound can transform other salt of an accepted way of doing sth (I) compound by known method.
Formula (I) compound that exists with free form or salt form can be possible one of isomer form or exist with its mixture, for example according to the number of the unsymmetrical carbon that occurs in the molecule, absolute or relative configuration, and/or according to the configuration of the two keys of the non-aromatics that occurs in the molecule, be pure isomer such as enantiomorph (antipodes) and/or diastereomer, or be isomer mixture such as enantiomeric mixture, as racemic modification, non-enantiomer mixture or raceme mixture.The present invention relates to pure isomer and all possible isomer mixture, and this is understandable by context, even stereochemical details is not illustrated especially in all cases.
According to selection to raw material and method, the mixture of non-enantiomer mixture, raceme mixture and the double bond isomer of formula (I) compound that exists with free form or salt form can be obtained by method of the present invention or other method, available known method, according to the difference on the various component physical-chemical it is separated into pure diastereomer or racemic modification, for example fractional crystallization, distillation and/or chromatography.
To corresponding available enantiomeric mixture as racemic modification, available known method is separated into optically active enantiomorph with it, for example by recrystallization from the optical activity solvent, carry out chromatographic separation as on cellulose acetate, separating with chiral sorbent with high pressure liquid chromatography, in whole compound process, auxiliary with suitable microorganism, by dissociating with special immobilized enzyme, for example use chiral crown ether, in this only a kind of enantiomer by complexing, or by changing into diastereoisomeric salt and separating the non-enantiomer mixture that obtains thus, for example carry out fractional crystallization according to the difference of their solubleness, obtain diastereomer, it can discharge required enantiomer under suitable reagent effect.
According to the present invention, except that the separation of corresponding isomer mixture, diastereo-isomerism selectivity general currently known methods synthetic or that the enantiomerism selectivity is synthetic also can be used for obtaining pure diastereomer or enantiomer, for example, carry out with having corresponding suitable stereochemical educt by method of the present invention.
Separate or higher isomer such as enantiomer or the diastereomer of synthesis of biologically active, or isomer mixture is favourable as enantiomeric mixture or non-enantiomer mixture that condition is that each component has different biological effects.
The formula of free form or salt form (I) compound can also their hydrate forms obtains and/or also can comprise other solvent, and it for example is used for the crystallization of the compound that exists with solid form in case of necessity.
The present invention relates to the form of ownership of described method, in view of the above can by as the intermediate in any stage of initial feed or this method and the compound that obtains begin, and carry out step all or that some lacks, or use, or especially under reaction conditions, generate the raw material of derivative or salt and/or its racemic modification or enantiomeric form.
In the method for the invention, used raw material and intermediate, no matter be free form or salt form, but the preferred compound that uses described production (I) compound or its salt when beginning, they are particularly useful.
The present invention be more particularly directed to the preparation method described in the embodiment P1.
Invention formula (I) compound is the activeconstituents that the value of preventing and/or treating is arranged that is used for pest control, provides good biocidal activity spectrum, even it under lower concentration, also has good tolerance to warm-blooded animal, fish and plant.Activeconstituents of the present invention is to having animal pest normal sensibility and that resistance is arranged, as all or each etap of insect or acarina member all be activated.The desinsection of active substance of the present invention or miticidal effect can directly be used himself, at once or after certain hour as after moult, kill off the insect pests and represent promptly, or represent with the number and/or the hatching rate that kill off the insect pests as reducing ovum that indirectly good effect is with the killing rate of 50-60% (lethality rate) is corresponding at least.
Described animal pest comprises for example European patent application EP-A-736252, page 2, and the 55th walks to and is mentioned in the 6th page of the 55th row.For purpose of the present invention is quoted wherein mentioned insect as a reference.According to compound of the present invention also is to kill as the insect of the nematoda of Filariidae or Setariidae section and the activeconstituents of following insect: the blood lance belongs to (Haemonchus), the hair circle belongs to (Trichostrongylus), mountain region oersted nematode (Ostertagia), Nematodirus (Nematodirus), Gu Bai belongs to (Cooperia), ascarid belongs to (Ascaris), Bunostomum (Bunostumum), esophageal orifice belongs to (Oesophagostonum), summer Bert (Chabertia), the hair tail belongs to (Trichuris), fox hair filaria (Trichuris vulpis) particularly, the circle line belongs to (Strongylus), Trichonema (Trichonema), Dictyocaulus (Dictyocaulus), Hepaticola (Capillaria), the class circle belongs to (Strongyloides), Heterakis (Heterakis), first (Toxocara), particularly dog of belonging to of bow bends first nematode (Toxocara canis), the ascarid type belongs to (Ascaridia), fine stern belongs to (Oxyuris), Agchylostoma (Ancylostoma), particularly ancylostoma caninum (Ancylostoma caninum), hook-type belongs to (Uncinaria), and the bow ascarid belongs to (Toxascaris) and secondary ascarid belongs to (Parascaris); Dirofilaria (Dirofilaria), particularly heart worm (Dirofilaria immitis) are (heartworm); Also particularly to representational Heterodera (Heterodera spp.), beet golden nematode (Heteroderaschachtii) for example, oat golden nematode (Heterodora avenae) and trifolium golden nematode (Heterodora trifolii); Ball Heterodera (Globodera spp.), for example globodera rostochiensis (Globodera rostochiensis); Meloidogyne (Meloidogynespp.), for example Meloidogyne incognita (Meloidogyne incoginita) or javanese root knot nematode (Meloidogyne javanica); Perforation line Eimeria (Radopholus spp.), for example similar similes thorne (Radopholus similis); Pratylenchidae belongs to (Pratylenchus spp.), for example unelected Pratylenchidae (Pratylenchus neglectans) and Cobb root (Pratylenchus penetrans); Pulvinulus sword Turbatrix (Tylenchulus), the nematode (Tylenchulus semipenetrans) of for example partly puncturing; Minute hand nematode (Longidorus), burr nematode (Trichodorus), sword nematode (Xiphinema), Ditylenchus dipsaci (Ditylenchus), aphelenchoides (Aphelenchoides) and Anguina.
Activeconstituents of the present invention is specially adapted to prevent and treat sucking insect, particularly Homoptera insect, is preferred for preventing and treating these insects in vegetables, fruit, rice and the cotton crop.A special advantage of The compounds of this invention is their systemic action.
Use activeconstituents of the present invention; can prevent and treat and appear on the plant; the particularly ornamental plant in crop and agricultural, gardening and forest; or the each several part of plant; insect as type as described on fruit, flower, leaf, stem, stem tuber or the root promptly, makes its Be Controlled or elimination; this provide protection can remain in the certain plants part, after this not regrowth of plant.
Target crop is particularly including cereal, as wheat, barley, rye, oat, paddy, corn or another name for Sichuan Province grain; Beet is as sugar beet or fodder beet; Fruit is as the operatic circle, drupe or mushy fruit, as apple, pears, plum, peach, almond, cherry or berry, as strawberry, rasp berry or blackberry; Leguminous plants is as French beans, root of Szemao crotalaria, pea or soybean; The oil crop is as rape, leaf mustard, opium poppy, olive, Sunflower Receptacle, coconut, Viscotrol C plant, cocoa beans or Semen arachidis hypogaeae; Cucumber plant is as pumpkin, cucumber or muskmelon; Textile plant is as cotton, flax, hemp or jute; Citrus fruit is as orange, lemon, shaddock or oranges and tangerines; Vegetables are as spinach, romaine lettuce, asparagus, wild cabbage, Radix Dauci Sativae, onion, tomato, potato or red pepper; Lauraceae is as avocado, Chinese cassia tree or camphor tree; With tobacco, English walnut, coffee, eggplant, sweet sugarcane, tea, pepper, rattan, hop, banana plant, natural rubber plant and ornamental plant.
The potential Application Areas of other of activeconstituents of the present invention is the stored prod in the health zone and the protection of stored goods and material, particularly protects domestic animal and domestic animal not to be subjected to the harm of the insect of described type.
Therefore, the invention still further relates to agricultural chemicals, but as missible oil, suspension concentrate, existing with existing spray or existing solution, the paste that is used to clad, diluting emulsion with existing dilution, dust, solvable pulvis dispersion powder, wettable powder, pulvis, granule or with the product of polymeric material encapsulation, they are selected according to its intended purposes and concrete environment, and comprise at least a activeconstituents of the present invention.
The described activeconstituents that uses in these compositions is the solid active agent of pure state, for example has specific particle size, or preferably use with the conventional assistant agent that uses of at least a formulation art, this assistant agent is additive for example, as solvent or solid carrier or surface active cpd (tensio-active agent).
For preparation, spendable assistant agent for example is solid carrier, solvent, stablizer, " slowly-releasing " agent, dyestuff, and suitable tensio-active agent.Carrier and assistant agent can be normally used any materials in crop protection agents, particularly control the reagent of slug or snail.Other assistant agent in assistant agent such as solvent, solid carrier, tensio-active agent, nonionogenic tenside, cats product, anion surfactant and the present composition, for example can with EP-A-736, assistant agent described in 252 is identical, and it is incorporated by reference in the present invention.
Rule is, composition contains 0.1-99%, the activeconstituents of 0.1-95% particularly, and 1-99.9%, the particularly at least a solid of 5-99.9% or liquid assistant agent, the tensio-active agent (in all cases, % is meant weight percentage) that may also contain the 0-25%, particularly 0.1-20% of composition as rule.And spissated composition is preferably used as commodity, and rule is, the terminal consumer uses dilute compositions, and these compositions have the activeconstituents of low concentration in fact.Especially, the composition of preferred composition (%=weight percentage) is as follows: missible oil: activeconstituents 1-95%, preferred 5-20% tensio-active agent 1-30%, preferred 10-20% solvent 5-98%, preferred 70-85% pulvis: activeconstituents 0.1-10%, preferred 0.1-1% solid carrier 99.9-90%, preferred 99.9-90% suspension concentrate: activeconstituents 5-75%, preferred 10-50% water 94-24%, preferred 88-30% tensio-active agent 1-40%, preferred 2-30% wettable powder: activeconstituents 0.5-90%, preferred 1-80% tensio-active agent 0.5-20%, preferred 1-15% solid carrier 5-99%, preferred 15-98% granule activeconstituents 0.5-30%, preferred 3-15% solid carrier 99.5-70%, preferred 97-85%
By adding other insect killing substance, the activity of the present composition is substantially enlarged, and be suitable for concrete environment.Other activeconstituents for example is following a few class material: organo phosphorous compounds, nitrophenol and derivative thereof, carbonamidine, acylurea, carbamate, pyrethroid, anabasine and derivative thereof, pyrroles, thiocarbamide and derivative thereof, hydrochloric ether and bacillus thuringiensis (Bacillus thuringiensis) preparation.Particularly suitable component is in this mixture: azoles pyridine phosphorus; Zaprawa enolofos; Cypermethrin; High-cis Cypermethrin (cypermethrin high cis); Fly eradication amine; It is grand to kill mite sulphur; Diazinon; SD-1750; Carbicron; Dicyclanil; ABG-6215; The fluorine fluazuron; Furathiocarb; Isazofos; Iodfenphos TOP; Cover 7; The fluorine third oxygen urea; Methacrifos; Methidathion; Monocrotophos; Phosphamidon; Profenofos; The luxuriant ether of Evil; From bacillus thuringiensis bacterial strain GC91 or the material that from NCTC 11821, obtains; Pymetrozine; Bromopropylate; Entocon ZR 515; Thiodemeton; Resitox; Taufluvalinate; Thiocyclarn; Thiometon; Aldicarb; R-1582; Benfuracarb; Bifenthrin; Buprofezin; Carbofuran; Dibutylamino sulphur (dibutylaminothio); Padan; UC 62644; Chlorpyrifos 94; Cyfloxylate; λ-cyhalothrin; α-Cypermethrin; ζ-Cypermethrin; Deltamethrin; TH-6040; 5a,6,9,9a-hexahydro-6,9-methano-2,4; Benzene worm prestige; Fenitrothion 95; Osbac; Kill the chrysanthemum ester; The peace fruit; Methiocarb; Heptan worm phosphorus; Provado; Isoprocarb; Tamaron; Methomyl; Phosdrin; Thiophos; Parathion-methyl; Zolone; Aphox; Propoxur; Teflubenzuron; Terbufos; Triaxamate; Avermectin; Osbac; RH-5992; Sharp strength spy; β-cyfloxylate; Deinsectization silicon ether; Azoles mite ester; Pyridaben; Fenazaquin; Pyriproxyfen; The pyramine phenylate; Nitenpyram; NI-25; The pyrrole worm is clear; Avermectin (Abamectin); Insecticidal activity extract in the plant; The preparation that includes eelworm-killing activity; The preparation that obtains by subtilis (Bacillus subtilis); The preparation that includes the insecticidal activity fungi; The preparation that includes insecticidal activity virus; AC 303630; Acephate; Fluorine ester chrysanthemum ester; Alanycarb; The nail body Cypermethrin; U-36059; AZ 60541; R-1582 A; R-1582 M; Azoles ring tin; Evil worm prestige; Bensultap; β-cyfloxylate; BPMC; Brofenprox; Bromofos A; Bufencarb; Butocarboxim (butocarboxin); The butyl pyridaben; Cadusafos; Carbaryl; Carbophenothion; Chloethocarb; Earth worm chlorine phosphorus; Chlormephos; The cis Chryson; Clocythrin; Four mite piperazines; Cynock; Cycloprothrin; Cyhexatin; Systox M; Systox S; Methyl-Systox S; Dichlofenthion; Dicliphos; Nialate; Rogor; Dimethylvinphos; Kavadel; Hinosan; Emamectin; Esfenvalerate; Nialate (ethion); Ether chrysanthemum ester; Ethoprop; The oxygen Pyrimithate; Nemacur; Fenbutatin oxide; Fenothiocarb; Fenvalerate; Fenpyrad; Tiguvon; Fluazinam; Flucycloxuron; Flucythrinate; Flufenoxuron; Fluorine third benzyl oxide; Dyfonate; Thiazolone phosphorus; Fubfenprox; HCH; Fluorine bell urea; Hexythiazox; Iprobenfos; Propylamine phosphorus; Karphos; Avermectin; λ-cyhalothrin; Phosphothion; Tick goes out; The first oxydemeton_methyl; Halizan; Meta-tolyl-N-methylcarbamate (MTMC); Milbemycin; Moxidectin; Naled; NC 184; Omethoate; Thioxamyl; Oxydemeton methyl (oxydemethon m); Thiometan; Permethrin; Tsidial; Phorate; R-1504; Volaton; Pirimiphosmethyl M; Pirimiphosmethyl A; Promecarb; Kayaphos; Toyodan; Fac; Pyraclofos (pyrachlophos); Pyrada-phenthion; Anti-Chryson; Pyrethrum; RH 5992; Dioxabenzofos; Cadusafos; Sulfotep; The second Toyodan; Tebufenpyrad; Tebupirimphos; Tefluthrin; Temephos; Terbam; Tetrachlorvinphos; Thiacloprid; Thiamethoxam; Thiafenox; The two prestige of sulphur; Special ammonia fork prestige; Thionazin; Enemy Bei Te; Tralomethrin; Triarthen; Triazophos; Triazuron; Trichlorphon; Desinsection is grand; Trimethacarb; Vamidothion; Xylylcarb; YI 5301/5302; Zetamethrin; DPX-MP062; RH-2485; D2341 and XMC (3,5-xylyl methyl carbamate).
Composition of the present invention also can contain other solid or liquid assistant agent, as stablizer, as vegetables oil, can be epoxidised vegetables oil (as epoxidation Oleum Cocois, rapeseed oil or soybean oil) if desired, foam preventer such as silicone oil, sanitas, viscosity modifier, tackiness agent and/or thickening material, and fertilizer or other activeconstituents are to reach specific effect, as miticide, antiseptic-germicide, anti-mycotic agent, nematocides, invertebrate poison or selective herbicide.
Composition of the present invention can prepare by currently known methods, when not having assistant agent, and for example by grinding, sieve, and/or compacting solid active agent or mixture of active principles, for example become specific granular size; And when at least a assistant agent is arranged, for example by thorough mixing and/or grinding activeconstituents or mixture of active principles and one or more assistant agents.These application that are used to prepare that the method for the present composition and Compound I be used to prepare these compositions also are purposes of the present invention.
Use the method for said composition, promptly prevent and treat the method for described all kinds of insects, for example according to its intended purposes and concrete environment, to select to spray, spray, dust, coating, dressing, sow or topple over, the application of the composition of described various pest controls is another object of the present invention.The concrete concentration of activeconstituents is between 0.1-1000ppm, between the preferred 0.1-500ppm.Use than being generally the 1-2000g/ha activeconstituents preferred 10-1000g/ha, and more preferably 20-600g/ha activeconstituents.
For Crop protection, preferred application process is the leaf (blade face applications) that activeconstituents is applied to plant, the number of times of using with use the degree that is infected by problematic insect than depending on.But, activeconstituents also can be by making it to infiltrate through plant (systemic action) by root with the residing zone of liquid composition dipping plant, or activeconstituents is applied to the residing zone of plant with solid form, in soil, for example with particulate form (solid is used).In paddy rice is cultivated, in the rice field of the measurable adding water filling of granule.
The present composition also is applicable to the protective plant reproductive material; comprise reproductive material by genetic modification; as seed; for example fruit, stem tuber or grain; or the rice shoot of plant is not encroached on by animal pest; described reproductive material available said composition before cultivating is handled, and for example seed carries out dressing prior to seeding.Also activeconstituents of the present invention can be applied to seed (coating), its be by or seed is soaked among the liquid composition, perhaps apply seed with solids composition.Said composition also can be used when reproductive material introduce is cultivated ground, for example planting seed is being used during in the seed ditch dug with a plow.The treatment process of plant propagation material and the reproductive material of so handling also are purposes of the present invention.
With the following examples the present invention is described.They can not constitute any restriction to the present invention.Temperature is degree centigrade that the ratio of solvent is a volume parts in the mixture.Preparation EXAMPLE Example P1: preparation following formula: compound:
P1a): the preparation following formula: compound:
The 20ml acetonitrile is positioned in the flask, feeds the 1.06g hydrogen chloride gas.Be cooled to-40 ℃ then, drip 1,3 of 0.58g, 5-trimethylammonium six hydrogen-1,3,5-triazines.Continue down to stir 10 minutes in-40 ℃, add 4-trifluoromethyl-niacinamide of 2.5g then in batches.Make temperature be increased to room temperature, continuously stirring is spent the night.Add the 40ml t-butyl methyl ether, continue to stir this mixture 15 minutes, and filter.The resistates of filtrate 20ml t-butyl methyl ether washed twice.Obtain the solid of compound (B).P1b): preparation compound (A)
Preparation 3.4g following formula (B) compound and 40ml ethyl acetate are cooled to 0-5 ℃ with them, drip 30% sodium hydroxide solution 5ml.Reaction mixture 20ml ethyl acetate extraction twice, the organic phase dried over sodium sulfate of merging, and concentrated with rotatory evaporator.Resistates mixes with the 20ml glycol dimethyl ether, and in 1 hour, under 0 ℃, it is added drop-wise in the mixture of 6.5g carbonyl chloride and 20ml glycol dimethyl ether.Make the temperature of mixture be increased to room temperature, drip the 2.61g pyridine that is dissolved in the 20ml glycol dimethyl ether then.Reactive material stirred under slowly refluxing spend the night.
Mixture concentrates with rotatory evaporator then, and resistates is dissolved in the 20ml ethyl acetate, with 10ml water washing twice, organic phase dried over sodium sulfate, and uses hexane/ethyl acetate (volume ratio 3/7) purifying resistates on silica gel.The compound that obtains (A) is a viscous oil (compound 1.2).Embodiment P2: all the other compounds of table 1 can be according to method preparation similar to the above.
Table 1: following formula: compound:
Embodiment numbers R
7X A m physics data 1.1 H CH O 01.2 methyl CH O 0 oily 1.3 ethyl CH O, 01.4 n-pro-pyl CH O, 01.5 isopropyl CH O, 0 oily 1.6 normal-butyl CH O, 01.7 phenyl CH O, 01.8 4-Cl-phenyl CH O, 01.9 4-CF3-O-phenyl CH O 01.10 4-CF
3-phenyl CH O 01.11 4-F-phenyl CH O 01.12 benzyl CH O 01.13 cyclopropyl CH O 01.14 cyclohexyl CH O 01.15 methyl CH O 11.16 ethyl CH O 11.17 n-pro-pyl CH O 11.18 isopropyl CH O 1 embodiment numbers R7X A m physical data 1.19 normal-butyl CH O 11.20 phenyl CH O 11.21 4-Cl-phenyl CH O 11.22 4-CF
3-O-phenyl CH O 11.23 4-CF
3-phenyl CH O 11.24 4-F-phenyl CH O 11.25 benzyl CH O 11.26 cyclopropyl CH O 11.27 cyclohexyl CH O 11.28 methyl N O 01.29 ethyl n O 01.30 n-pro-pyl N O 01.31 isopropyl N O 01.32 normal-butyl N O 01.33 phenyl N O 01.34 4-Cl-phenyl N O 01.35 4-CF3-O-phenyl N O 01.36 4-CF
3-phenyl N O 01.37 4-F-phenyl N O 01.38 benzyl N O 01.39 cyclopropyl N O 01.40 cyclohexyl N O 01.41 methyl CH S, 01.42 ethyl CH S, 0 example of formulations (% is percetage by weight) embodiment F 1: missible oil is b a)) c) active component 25% 40% 50% calcium dodecyl benzene sulfonates 5% 8% 6% castor oil polyglycol ether (36 moles of EO) 5%--tributyl phenol polyglycol ethers (30 moles of EO)-12% 4% cyclohexanone-15% 20% xylene mixture 65% 25% 20%
Levigated activeconstituents powder is mixed with assistant agent; Obtain missible oil, obtain the emulsion of desired concn behind its dilute with water. embodiment F 2: solution is b a)) c) d) active component 80% 10% 5% 95% glycol monomethyl methyl ether 20%---polyethylene glycol (400)-70%--NMP-20%--epoxidation coconut oil--1% 5% gasoline (boiling spread: 160-190 ℃)--94%-
Levigated activeconstituents powder is mixed with assistant agent; Obtain solution, it is suitable for using with the form of droplet. embodiment F 3: granule is b a)) c) d) silicic acid 1%-13% 7% attapulgite-90%-18% of active component 5% 10% 8% 21% kaolin 94%-79% 54% high dispersive
Activeconstituents is dissolved in the methylene dichloride, with this spray solution on carrier mixture, vacuum evaporating solvent then.Biological Examples Embodiment B 1: to the effect of Diabrotica balteata larva
The corn rice shoot sprays with aqueous emulsion spray mixing thing, contains the 400ppm activeconstituents in the mixture.After sprayed deposit thing drying, on the corn rice shoot, transplant the second instar larvae of 10 Diabroticabalteata, and be placed in the plastic containers.Estimate after six days.By handling comparing on larva number dead on the plant and those plants of being untreated, measure the percentage ratio (% response value) that group reduces.
In the test, the compound of table 1 has shown good prevention effect to Diabrotica balteata, and particularly the effect of compound 1.2 has surpassed 80%.Embodiment B 2: to the interior suction effect of black peach aphid (Myzus persicae)
Pea seedlings infects with black peach aphid, then root is put into the spray mixing thing that contains the 400ppm activeconstituents, 20 ℃ of hatchings.Estimate after 3 and 6 days.By handling comparing on black peach aphid number dead on the plant and those the untreated plants.
In the test, the compound of table 1 has shown good prevention effect to black peach aphid, and particularly the effect of compound 1.2 has surpassed 80%.
Claims (8)
1. following formula: compound:
Wherein Z represents the optional six or seven-first aromatics that replaces or the heterocyclic radical of non-aromatics;
X is CH or N;
Y is a halogen;
N is 1,2 or 3; With
M is 0 or 1; And be its E/Z isomer suitably the time, E/Z isomer mixture and/or its tautomer, the respectively free form or the form of salt naturally.
2. according to formula (I) compound of claim 1, described compound is a free form.
3. according to formula (I) compound of claim 1 or 2, wherein Z is the ring of following formula:
At this key U-A, A-M, M-D, D-E, E-G and G-U are singly-bound or two key, condition is two keys that can not occur linking to each other,
A is-O--NR
1-,-S-or-N=;
M is-NR
2-,-O-,-S-,-CR
3R
4-,-N=or-CR
3=;
D is-CR
5R
6-,-NR
7-,-O-,-S-,-N=or-CR
5=;
E is-NR
2-;-O-,-S-or-CR
8R
9-;-N=or-CR
8=; With
G is-O--NR
10-,-S-, or-N=;
U is a carbon;
R
1, R
2, R
7And R
10Represent hydrogen, C separately independently of each other
1-C
20-alkyl, C
3-C
8-cycloalkyl, C
2-C
20-alkenyl or C
3-C
20-alkynyl group; Or one-or polysubstituted C
1-C
20-alkyl, C
2-C
20-alkenyl or C
3-C
20-alkynyl group;
By the one or more aryl that following substituting group replaces: C that are selected from
1-C
6-alkyl, halogen-C
1-C
6-alkyl, C
2-C
6-alkenyl, C
3-C
6-alkynyl group, halogen, C
1-C
6-alkoxyl group, halogen-C
1-C
6-alkoxyl group, nitro, cyano group, C
3-C
8-cycloalkyl, halogen-C
3-C
8-cycloalkyl, C
3-C
6-alkenyloxy, C
1-C
4-alkylthio and two-(C
1-C
4-alkyl) amine;
Or-C (=O)-R
11
R
3, R
4, R
5, R
5, R
8And R
9Represent hydrogen, C separately independently of each other
1-C
6-alkyl, C
3-C
8-cycloalkyl, C
1-C
6-alkoxyl group, C
1-C
6-alkylthio, C
2-C
6-alkenyl, C
3-C
6-alkenyloxy, C
3-C
6-alkynyl group, C
3-C
6-chain oxy-acetylene, aryl, heterocyclic radical, aryloxy, benzyloxy or heterocyclic oxy group; C
1-C
6-alkyl, C
3-C
8-cycloalkyl, C
1-C
6-alkoxyl group, C
1-C
6-alkylthio, C
3-C
6-alkenyl, C
3-C
6-alkenyloxy, C
3-C
6-alkynyl group or C
3-C
6-chain oxy-acetylene, described group is selected from following substituting group and replaces by one or more: halogen, nitro, cyano group ,-OH ,-SH, C
3-C
8-cycloalkyl, halogen-C
3-C
8-cycloalkyl, phenyl and two-(C
1-C
4-alkyl) amine;
Or be selected from the following aryl that substituting group replaced: halogen, nitro, cyano group ,-OH ,-SH, COOH, COH, C by one to three
1-C
6-alkyl, C
1-C
6-alkoxyl group, C
1-C
6-alkylthio, halogen-C
1-C
6-alkyl, halogen-C
1-C
6-alkoxyl group, halogen-C
1-C
6-alkylthio, C
3-C
8-cycloalkyl, halogen-C
3-C
8-cycloalkyl and two-(C
1-C
4-alkyl) amine;
Or be together=O or=S;
R
11Expression hydrogen, OH, SH, C
1-C
6-alkyl, C
3-C
8-cycloalkyl, C
1-C
6-alkoxyl group, C
1-C
6-alkylthio, C
2-C
6-alkenyl, C
3-C
6-alkenyloxy, C
3-C
6-alkynyl group, C
3-C
6-chain oxy-acetylene, two-(C
1-C
4-alkyl) amine, aryl, heterocyclic radical, aryloxy, benzyloxy or heterocyclic oxy group; C
1-C
6-alkyl, C
3-C
8-cycloalkyl, C
1-C
6-alkoxyl group, C
1-C
6-alkylthio, C
3-C
8-alkenyl, C
3-C
6-alkenyloxy, C
3-C
6-alkynyl group or C
3-C
6-chain oxy-acetylene, described group is selected from following substituting group and replaces by one or more: halogen, nitro, cyano group ,-OH ,-SH, C
3-C
8-cycloalkyl, halogen-C
3-C
8-cycloalkyl and two-(C
1-C
4-alkyl) amine;
Or aryl, heterocyclic radical, aryloxy, benzyloxy or heterocyclic oxy group, described group are selected from following substituting group by one to three and replace: halogen, nitro, cyano group ,-OH ,-SH, COOH, COH, C
1-C
6-alkyl, C
1-C
6-alkoxyl group, C
1-C
6-alkylthio, halogen-C
1-C
6-alkyl, halogen-C
1-C
6-alkoxyl group, halogen-C
1-C
6-alkylthio, C
3-C
8-cycloalkyl, halogen-C
3-C
8-cycloalkyl and two-(C
1-C
4-alkyl) amine;
Condition is, if one of M or E, or M and E are-NR simultaneously independently of one another
2,-N=,-O-or-during S-, D represents-CR
5R
6-or-CR
5=.
4. according to formula (I) compound of one of claim 1 or 3, wherein A is-O-,-NR
1-or-N=; With
R
1Be hydrogen, C
1-C
6-alkyl, C
3-C
8-cycloalkyl, C
2-C
6-alkenyl; Or C
1-C
6-alkyl, C
2-C
6-alkenyl or C
3-C
8-cycloalkyl, described group is selected from following substituting group and replaces by one or more: halogen, nitro, cyano group ,-OH ,-SH, C
3-C
8-cycloalkyl, halogen-C
3-C
8-cycloalkyl, C
1-C
6-alkoxyl group, halogen-C
1-C
6-alkoxyl group, C
3-C
6-alkenyloxy, C
1-C
4-alkylthio, two-(C
1-C
4-alkyl) amine ,-C (=O)-R
12, aryl, aryloxy, arylthio, heterocyclic radical or heterocyclic oxy group; And R
12Be hydrogen, OH, C
1-C
6-alkyl, C
1-C
6-alkoxyl group, two-(C
1-C
4-alkyl) amine, aryl, aryloxy or benzyloxy.
5. pesticide composition, it contains at least a formula according to claim 1 (I) compound as activeconstituents and at least a assistant agent, and described compound is a free form, or the form of acceptable salt on the agrochemistry.
6. prepare the described method for compositions of claim 5, wherein with activeconstituents and assistant agent thorough mixing.
7. the method for Pest Control wherein will be applied to insect or its habitat as activeconstituents according to formula (I) compound of one of claim 1-4, and described compound is a free form, or optional form for acceptable salt on the agrochemistry.
8. the application of the formula of one of claim 1-4 (I) compound in the described composition of preparation claim 5, described compound is a free form, or optional form for acceptable salt on the agrochemistry.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CH152399 | 1999-08-20 | ||
| CH1523/99 | 1999-08-20 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1370162A true CN1370162A (en) | 2002-09-18 |
Family
ID=4212442
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN00811841A Pending CN1370162A (en) | 1999-08-20 | 2000-08-18 | Derivatives of trifluoromethylpyri(mi)dine |
Country Status (7)
| Country | Link |
|---|---|
| EP (1) | EP1204661A1 (en) |
| JP (1) | JP2003507477A (en) |
| KR (1) | KR20020022817A (en) |
| CN (1) | CN1370162A (en) |
| AU (1) | AU767519B2 (en) |
| BR (1) | BR0013438A (en) |
| WO (1) | WO2001014373A1 (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE102004022897A1 (en) * | 2004-05-10 | 2005-12-08 | Bayer Cropscience Ag | Azinyl-imidazoazines |
| DE102004035134A1 (en) | 2004-07-20 | 2006-02-16 | Bayer Cropscience Ag | Selective insecticides based on Halogenalkylnicotinsäurederivaten, Anthranilsäureamiden or phthalic diamides and safeners |
| DE102008041214A1 (en) | 2008-08-13 | 2010-02-18 | Bayer Cropscience Ag | New N-substituted azinylalkyl-azincarboxamide compounds useful e.g. in plant protection, for combating animal pests, arthropods, nematodes and plant diseases, and for protecting industrial materials against attack and destruction by insect |
| US20170094972A1 (en) | 2015-10-06 | 2017-04-06 | Syngenta Participations Ag | Compounds and Compositions Having Knock-Down Activity Against Insect Pests |
Family Cites Families (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| AR241530A1 (en) * | 1984-12-21 | 1992-08-31 | Ciba Geigy A G Cesionaria De F | Triazole derivates, their preparation and their use as pesticides |
| JPH0733748A (en) * | 1993-05-17 | 1995-02-03 | Nissan Chem Ind Ltd | Pyrimidine derivative and herbicide |
| JPH0873441A (en) * | 1993-11-01 | 1996-03-19 | Nissan Chem Ind Ltd | New 4,5-substituted pyrimidine derivative and herbicide |
| JP3694051B2 (en) * | 1994-07-12 | 2005-09-14 | バイエルクロップサイエンス株式会社 | 1-pyridyltetrazolinone derivatives and herbicides |
| DE19725450A1 (en) * | 1997-06-16 | 1998-12-17 | Hoechst Schering Agrevo Gmbh | 4-Haloalkyl-3-heterocyclylpyridines and 4-haloalkyl-5-heterocyclylpyrimidines, processes for their preparation, compositions containing them and their use as pesticides |
| DE19858193A1 (en) * | 1998-12-17 | 2000-06-21 | Aventis Cropscience Gmbh | 4-Trifluoromethyl-3-oxadiazolylpyridines, process for their preparation, compositions containing them and their use as pesticides |
| AU3730699A (en) * | 1998-05-18 | 1999-12-06 | Sumitomo Chemical Company, Limited | Heterocyclic compound |
| DE19858192A1 (en) * | 1998-12-17 | 2000-06-21 | Aventis Cropscience Gmbh | 4-Trifluoromethyl-3-oxazolylpyridines, process for their preparation, compositions containing them and their use as pesticides |
| DE19858191A1 (en) * | 1998-12-17 | 2000-06-21 | Aventis Cropscience Gmbh | 4-haloalkyl-3-heterocyclylpyridines and 4-haloalkyl-5-heterocyclylpyrimidines and their use as repellents |
-
2000
- 2000-08-18 BR BR0013438-4A patent/BR0013438A/en not_active IP Right Cessation
- 2000-08-18 CN CN00811841A patent/CN1370162A/en active Pending
- 2000-08-18 WO PCT/EP2000/008082 patent/WO2001014373A1/en active IP Right Grant
- 2000-08-18 JP JP2001518704A patent/JP2003507477A/en active Pending
- 2000-08-18 KR KR1020027002158A patent/KR20020022817A/en not_active Application Discontinuation
- 2000-08-18 AU AU72777/00A patent/AU767519B2/en not_active Ceased
- 2000-08-18 EP EP00960488A patent/EP1204661A1/en not_active Withdrawn
Also Published As
| Publication number | Publication date |
|---|---|
| JP2003507477A (en) | 2003-02-25 |
| WO2001014373A1 (en) | 2001-03-01 |
| BR0013438A (en) | 2002-04-30 |
| AU767519B2 (en) | 2003-11-13 |
| EP1204661A1 (en) | 2002-05-15 |
| AU7277700A (en) | 2001-03-19 |
| KR20020022817A (en) | 2002-03-27 |
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