CN1020606C - Process for producing azole deriv. - Google Patents
Process for producing azole deriv. Download PDFInfo
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- CN1020606C CN1020606C CN88101050A CN88101050A CN1020606C CN 1020606 C CN1020606 C CN 1020606C CN 88101050 A CN88101050 A CN 88101050A CN 88101050 A CN88101050 A CN 88101050A CN 1020606 C CN1020606 C CN 1020606C
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- 0 C*(CC[C@@](C)N=C)CNC Chemical compound C*(CC[C@@](C)N=C)CNC 0.000 description 4
- LBICVBGBKHUMDO-UHFFFAOYSA-N CCCC(C)CC(C)N Chemical compound CCCC(C)CC(C)N LBICVBGBKHUMDO-UHFFFAOYSA-N 0.000 description 1
- LICBBAODDTZAQN-LAXIMJFQSA-N CCCCCCC/C=C(\C)/C[C@@H](C)NCCCC(C)CC(C)CC Chemical compound CCCCCCC/C=C(\C)/C[C@@H](C)NCCCC(C)CC(C)CC LICBBAODDTZAQN-LAXIMJFQSA-N 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D249/00—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms
- C07D249/02—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms not condensed with other rings
- C07D249/08—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles
Abstract
Disclosed herein are an azole derivative represented by the formula (I) wherein R1 and R2 respectively represent a (C1-C5) alkyl group or a hydrogen atom; X represents a halogen atom, a (C1-C5) alkyl group or a phenyl group; n represents an integer of from 0 to 2 and A represents a nitrogen atom or a CH, provided that R1 is not a hydrogen atom when R2 is a hydrogen atom, a process for producing the azole derivative represented by the formula (I), and an agricultural and horticultural composition containing the azole derivative represented by the formula (I).
Description
The present invention relates to a kind of azole derivative, produce the method for this azole derivative, and contain agricultural use and gardening use the composition of this azole derivative as active ingredient with plant disease control activity and plant growth regulating activity.In more detail, the present invention relates to:
1) the represented azole derivative of formula I:
R in the formula
1And R
2Represent (a C respectively
1-C
5) alkyl or hydrogen atom; X represents a halogen atom, (a C
1-C
5) alkyl or phenyl; On behalf of the integer of 0-2 and A, n represent a nitrogen-atoms or CH, and condition is to work as R
2R during for hydrogen atom
1Be not hydrogen atom,
2) method of the azole derivative of production formula I representative, this method comprises the steps:
A) (ⅰ) makes a kind of alkyl ester of 2-oxo-cyclopentane formic acid and the reaction of a kind of substituted benzyl halogen and makes the 1-(substituted benzyl that obtains)-alkyl ester and a kind of (C of 2-oxo-cyclopentane formic acid
1-C
5) the alkylogen reaction; (ⅱ) make a kind of 3-(C
1-C
5Alkyl)-alkyl ester of 2-oxo-cyclopentane formic acid and the reaction of a kind of benzyl halide of replacement; Perhaps (ⅲ) makes the benzyl that 1-(replaces)-3-(C
1-C
5Alkyl)-2-oxo-cyclopentane formic acid and a kind of (C
1-C
5) the alkylogen reaction, thereby the ester derivative of the cyclopentane-carboxylic acid of the formula of obtaining (V) representative:
R in the formula
1And R
2Represent (a C respectively
1-C
5) alkyl or hydrogen atom; R represents (a C
1-C
5) alkyl; X represents a halogen atom, (C
1-C
5) alkyl or phenyl and n be the integer of a 0-2, condition is to work as R
2R when being hydrogen atom
1Not hydrogen atom,
B), thereby obtain the cyclopentanone derivatives of formula IV representative to the decarboxylation that is hydrolyzed of the ester derivative of the cyclopentane-carboxylic acid that obtains thus
（Ⅳ）
R in the formula
1, R
2, X and n be respectively by above-mentioned definition,
When (c) using sulphur inner salt or oxo sulphur inner salt, the cyclopentane derivatives that obtains is thus carried out the oxyethane reaction, perhaps to the derivative of a kind of methylene radical pentamethylene of obtaining from thus obtained cyclopentanone derivatives by witig reaction carry out epoxidation reaction (derivative of described methylene radical pentamethylene is represented by formula III down:
R in the formula
1, R
2, X and n be respectively by above-mentioned definition), thereby make the derivative of cyclopentanone be transformed into the epoxyethane derivative of following formula II representative:
R in the formula
1, R
2, X and n be respectively by above-mentioned definition, then
D) derivative that makes the oxyethane that obtains thus and 1,2 of following formula VI representative, 4-triazole or imidazoles react:
（Ⅵ）
(M represents a hydrogen atom or alkali metal atom in the formula, A represent a nitrogen-atoms or-CH=, thereby obtain down the azole derivative of formula I representative:
R in the formula
1And R
2Represent (a C respectively
1-C
5) alkyl or hydrogen atom; X represents a halogen atom, (C
1-C
5) alkyl or phenyl; N represents the integer of a 0-2; A represents a nitrogen-atoms or CH, and condition is to work as R
2R when being hydrogen atom
1It is not hydrogen atom.
3) have the agricultural usefulness of Fungicidally active and plant growth regulating activity and the composition that gardening is used, said composition contains a kind of azole derivative of formula I representative of significant quantity.
Because the infringement in the crops that various plant diseases cause is huge, and because the environmental pollution that the pharmaceutical chemicals that these plant diseases of control are used causes has brought problem, therefore, that sells has the agricultural of control action kou with requiring people, animal, bird and fish are wanted hypotoxicity with pharmaceutical chemicals with gardening to plant disease, and useful plant wanted hypotoxicity, that is to say, need the pharmaceutical chemicals that agricultural is used and gardening is used that a kind of dispenser is safe, little to environmental influence and plant disease is had good control action kou.
In order to realize this requirement, the sterilant that following agricultural is used and gardening is used has been proposed so far.
(1) triazole of following formula representative or the compound of imidazoles:
R in the formula
1Represent one-CH=CH-X ,-CH ≡ C-X or-CH
2-CH
2-X(wherein X be a hydrogen atom, alkyl, hydroxyalkyl, alkoxyalkyl, cycloalkyl, can substituted substituted aryl, can substituted aralkyl, can substituted aryloxyalkyl group or can substituted heterocyclic radical); R
2Represent an alkyl, cycloalkyl or can substituted aryl; Z represent a chlorine atom, cyano group or-OR
3(R wherein
3Be hydrogen atom, ethanoyl, alkyl, alkenyl or an aralkyl), Y represents a nitrogen-atoms or CH; and the acid salt of described compound and metal complexes thereof [referring to day disclosure pending application application 57-114577(1982), be equivalent to United States Patent (USP) 4507140 and European patent 52424].
(2) triazole of following formula representative or the compound of imidazoles:
R represents a crosslinking group in the formula :-(CH
2) n-(wherein n be 0,1 or 2) ,-CH=CH-,-O-,-S-,-NH-or-C(=O)-; X represents a nitrogen-atoms or CH; Y and Z can be identical or different, represent halogen atom, alkyl, alkoxyl group, halogenated alkoxy, haloalkyl, nitro, phenyl or a phenoxy group respectively, m and p represent 0 respectively, 1,2 or 3, and the acid of described compound, its metal complexes and its functional derivatives [referring to day disclosure pending application application 57-126479(1982), be equivalent to European patent 52425)
(3) derivative of the 1-hydroxyethyl azole of following formula representative:
In the formula R represent an alkyl, can substituted cycloalkyl or can substituted phenyl, X represents a nitrogen-atoms or CH; Y represents one-OCH
2-,-CH
2-CH
2-or-CH=CH-; Z represent a halogen atom, alkyl, cycloalkyl, alkoxyl group, alkylthio, haloalkyl, halogenated alkoxy, halogenated alkylthio, can substituted phenyl, can substituted phenoxy group or can substituted phenylalkyl or can substituted phenyl alkoxyl group (m represents 0,1,2 or 3), its acid salt and its metal complexes [referring to day disclosure pending application application 57-16868(1982), be equivalent to United States Patent (USP) 453241 and European patent 40345].
(4) compound of the cycloaliphatic alcohol of following formula representative:
R in the formula
6Represent a unsubstituted phenyl or be selected from the phenyl that following radicals replaces: halogen atom, amino, nitro, cyano group, phenyl, halogenophenyl, (C by 1～5
1-C
10) alkyl, halo (C
1-C
10) alkyl, (C
1-C
10) alkoxyl group, halo (C
1-C
10) alkoxyl group, (C
1-C
10) alkylthio, (C
1-C
10) alkylene dioxy base, (C
1-C
10) alkylamino and two (C
1-C
10) alkylamino; X represents a hydrogen atom or methyne, ring A is a pentamethylene ring, cyclohexane ring, suberane ring, 1,2-hydrindene ring, tetrahydric naphthalene ring or benzocyclopentane ring, the ring of each this class can not be substituted or phenyl ring is wherein replaced [referring to day disclosure pending application application 58-189171(1983), be equivalent to United States Patent (USP) 4503062 and European patent 94146] by an above-mentioned 1-4 substituting group
(5) triazole compounds or the imidazolium compounds of following formula representative
W is a CH or nitrogen-atoms in the formula; Q is one and replaces or unsubstituted aryl, particularly replaces or unsubstituted phenyl, replace or unsubstituted aralkyl, or replacement or unsubstituted alkyl; R
1, R
2, R
3, R
4, R
5, R
6, R
7And R
8Can be identical or different, represent a hydrogen atom, hydroxyl, alkyl, cycloalkyl, replacement or unsubstituted aralkyl, replacement or unsubstituted phenyl respectively, R
1And R
2, R
3And R
4, R
5And R
6Or R
7And R
8A pair of and adjacent ring carbon atom is represented a carbonyl (C=O) together arbitrarily; R
9And R
10Can be identical or different, represent a hydrogen atom, alkyl, cycloalkyl, replacement or unsubstituted aralkyl or replacement or unsubstituted phenyl respectively, n is 0 or 1, the steric isomer of described compound and its metal complexes [referring to day disclosure pending application application 60-2150674(1985), be equivalent to European patent 153797].
The inventor's result of study, the sterilant that provides a kind of agricultural and gardening to use, its dispenser is safe, little and large-scale plant disease had good control effect to environmental influence, and the inventor has found the azole derivative of following formula representative:
X represents halogen atom, alkyl, haloalkyl, phenyl, cyano group or a nitro respectively in the formula; N represents one 0～5 integer, and A represents a nitrogen-atoms or CH, and condition is that X can be identical or different when n is 1～5 [referring to day disclosure pending application application 62-1429667(1987), be equivalent to UK patent 2180236 A].
For obtain human and beasts hypotoxicity, dispenser is safe and large-scale plant disease is presented the agricultural of good control effect and the sterilant that gardening is used, the inventor has further studied the synthetic of many azole derivatives and its practicality has been measured, found that: the azole derivative of following formula I representative not only has above-mentioned concrete feature, and can be used as plant-growth regulator effectively, just be based on this discovery and just finishing the present invention.
R in the formula
1And R
2Represent (a C respectively
1-C
5) alkyl or hydrogen atom; X represents a halogen atom, (C
1-C
5) alkyl or phenyl; N represents one 0～2 integer, and A represents a nitrogen-atoms or CH, and condition is to work as R
2R when being hydrogen atom
1It is not hydrogen atom.
In other words, the purpose of this invention is to provide a kind of as agricultural and the composition used of gardening, the effective azole derivative of activeconstituents, this azole derivative has plant disease and controls activity and plant growth regulating activity; The present invention also provides the method for producing this azole derivative and contains the composition of using as the agricultural and the gardening of activeconstituents, simultaneously, in the latter demonstrates on a large scale to the good control action kou of plant disease and demonstrate plant growth regulation and hypotoxicity and good dispenser security.
One aspect of the present invention provides down the azole derivative of formula I representative:
R in the formula
1And R
2Represent (a C respectively
1-C
5) alkyl or hydrogen atom; X represents a halogen atom, (C
1-C
5) alkyl or phenyl; On behalf of one 0～2 integer and A, n represent a nitrogen-atoms or CH, and condition is to work as R
2R when being hydrogen atom
1It is not hydrogen atom.
Second aspect present invention provides a kind of azole derivative of formula I representative:
（Ⅰ）
R in the formula
1And R
2Each represents (a C
1-C
5) alkyl or hydrogen atom; X represents a halogen atom, (C
1-C
5) alkyl or phenyl; On behalf of one 0～2 integer and A, n represent a nitrogen-atoms or CH, and condition is to work as R
2R when being hydrogen atom
1It is not hydrogen atom.This method comprises the steps:
A) (ⅰ) makes the benzyl halide reaction of a kind of alkyl ester of 2-oxo-cyclopentane formic acid and a kind of replacement and makes the 1-(substituted benzyl that obtains thus)-alkyl ester and a kind of (C of 2-oxo-cyclopentane formic acid
1-C
5) the alkylogen reaction; (ⅱ) make a kind of 3-(C
1-C
5Alkyl)-alkyl ester of 2-oxo-cyclopentane formic acid and the reaction of a kind of benzyl halide of replacement; Perhaps (ⅲ) makes the benzyl that 1-(replaces)-3-(C
1-C
5Alkyl)-2-oxo-cyclopentane formic acid and a kind of (C
1-C
5) the alkylogen reaction, thereby the ester derivative of the cyclopentane-carboxylic acid of the formula of obtaining (V) representative:
R in the formula
1And R
2Represent (a C respectively
1-C
5) alkyl or hydrogen atom; R represents (a C
1-C
5) alkyl; X represents a halogen atom, (C
1-C
5) alkyl or phenyl and n be the integer of a 0-2, condition is to work as R
2R when being hydrogen atom
1Not hydrogen atom,
B), thereby obtain the cyclopentanone derivatives of formula IV representative to the ester derivative hydrolysis decarboxylation of the cyclopentane-carboxylic acid that obtains thus
（Ⅳ）
R in the formula
1, R
2, R
3, X and n be respectively by above-mentioned definition,
When (c) using sulphur inner salt (sulfonium ylide) or oxo sulphur inner salt, the cyclopentane derivatives that obtains is thus carried out reacting ethylene oxide, perhaps to the derivative of a kind of methylene radical pentamethylene of obtaining from thus obtained cyclopentanone derivatives by witig reaction carry out epoxidation reaction (derivative of described methylene radical pentamethylene is represented by formula III down:
R in the formula
1, R
2, X and n be respectively by above-mentioned definition), thereby make the derivative of cyclopentanone be transformed into the epoxyethane derivative of following formula II representative:
R in the formula
1, R
2, X and n define respectively as above, then
D) derivative that makes the oxyethane that obtains thus and following formula VI represent 1,2,4-triazole or imidazoles react:
M represents a hydrogen atom or alkali metal atom in the formula, and A represents a nitrogen-atoms or CH.
Third aspect present invention provide a kind of agricultural with fungicidal activity and plant growth regulating activity with and the composition used of gardening, the azole derivative that it contains the representative of a kind of formula I down is as active ingredient:
R in the formula
1And R
2Represent (a C respectively
1-C
5) alkyl or hydrogen atom; X represents a halogen atom, (C
1-C
5) alkyl or phenyl; On behalf of the integer of a 0-2 and A, n represent a nitrogen-atoms or CH, and condition is to work as R
2R when being hydrogen atom
1It is not hydrogen atom.
Fourth aspect present invention provides a kind of epoxyethane derivative that is used to produce the azole derivative of formula I representative, and this derivative is represented with time formula II:
R in the formula
1And R
2Represent (a C respectively
1-C
5) alkyl or hydrogen atom; X represents a halogen atom, (C
1-C
5) alkyl or phenyl; N represents the integer of a 0-2, and condition is to work as R
2R when being hydrogen atom
1It is not hydrogen atom.
Fifth aspect present invention provides a kind of methylene radical cyclopentane derivatives that is used to produce the azole derivative of formula I representative, and this derivative is represented (III) with following formula:
（Ⅲ）
R in the formula
1And R
2Represent (a C respectively
1-C
5) alkyl or hydrogen atom; X represents a halogen atom, (C
1-C
5) alkyl or phenyl and n represent the integer of a 0-2, condition is to work as R
2R when being hydrogen atom
1It is not hydrogen atom.
Sixth aspect present invention provides a kind of cyclopentanone derivatives that is used to produce the azole derivative of formula I representative, and this derivative is represented (IV) with following formula:
R in the formula
1And R
2Represent (a C respectively
1-C
5) alkyl or hydrogen atom; X represents a halogen atom, (C
1-C
5) alkyl or phenyl and n represent the integer of a 0-2, condition is to work as R
2R when being hydrogen atom
1It is not hydrogen atom.
Seventh aspect present invention provides a kind of ester derivative of cyclopentane-carboxylic acid of the azole derivative that is used to produce the formula I representative, and this acid is with following formula (V) expression:
R in the formula
1And R
2Represent (a C respectively
1-C
5) alkyl or hydrogen atom; R represents (a C
1-C
5) alkyl; X represents a halogen atom, (C
1-C
5) alkyl or phenyl and n represent the integer of a 0-2, condition is to work as R
2R when being hydrogen atom
1It is not hydrogen atom.
In the accompanying drawings, Fig. 1～76 have provided the infrared absorption spectrum according to the azole derivative shown in the table 1 of the present invention.That is to say that Fig. 1 has shown the infrared absorption spectrum of No. 1 compound in the table 1; Fig. 2 has shown the infrared absorption spectrum of No. 2 compounds in the table 1; Fig. 3 has shown the infrared absorption spectrum of No. 3 compounds in the table 1; Fig. 4～Figure 76 has shown each infrared absorption spectrum of No. 4～No. 76 compounds in the table 1 respectively.
Core of the present invention is the novel azole derivative with the formula I representative:
R in the formula
1And R
2Represent (a C respectively
1-C
5) alkyl or hydrogen atom; X represents a halogen atom, (C
1-C
5) alkyl or phenyl, on behalf of the integer of a 0-2 and A, n represent a nitrogen-atoms or CH, and condition is to work as R
2R when being hydrogen atom
1It is not hydrogen atom; Produce the method for the azole derivative of formula I representative, and each compound that is used as intermediate, be the derivative of ester of the Cyclopentane carboxylic acid of the derivative of cyclopentanone of derivative, formula IV representative of methylene radical pentamethylene of derivative, formula III representative of the oxyethane of formula II representative and formula (V) representative, and contain as the azole derivative of formula I representative and have fungicidal activity and the agricultural of plant growth regulating activity with and the composition used of gardening.
Each intermediate that the physics and the chemical property of the azole derivative of formula I representative and being used to produced above-mentioned azole derivative is shown in table 1～5.
In addition, each of these intermediates all is novel compound.
The nuclear magnetic resonance spectrum of compound is to adopt deuteron magnetic resonance to record as interior mark among the table 1-5.Wherein the symbol implication is as follows:
The s-single line, the d-doublet, the t-triplet, the q-quartet, the m-multiplet, the wide line of b-, the j-coupling constant (unit, hertz).
The every kind of azole derivative infrared absorption spectrum that is recited in the table 1 is shown in accompanying drawing 1-16 respectively.
Based on the consideration of plant disease control activity and plant growth regulating activity, the R in the preferred azole derivative of formula I representative
1Be hydrogen atom or (C
1-C
4) alkyl; R
2Be hydrogen atom or (C
1-C
3) alkyl (R
1And R
2The two can not be a hydrogen atom simultaneously); X is the halogen atom of substituted benzene ring 4-position; N=1, and A is nitrogen-atoms or CH, in addition, as particularly preferred azole derivative, R wherein
1And R
2Represent hydrogen atom or (C separately
1-C
3) alkyl (R
1And R
2The two can not be a hydrogen atom simultaneously); X represents the halogen atom of substituted benzene ring 4-position; N=1, and A represents nitrogen-atoms.
In the compound that table 1 is enumerated, preferred azole derivative is compound 1-3,5, and 9-11,16,18,29-32,37,38,42-45,50,59,62,63,65 and 69.
Azole derivative of the present invention can adopt following method preparation.
Azole derivative shown in the formula I can be by epoxyethane derivative shown in the formula II and 1,2 shown in the following formula VI, and 4-triazole or imidazoles react in thinner and make:
（Ⅵ）
M represents hydrogen atom or alkali metal atom and A represents nitrogen-atoms or CH in the formula.
Can be as epoxyethane derivative shown in the formula II of raw material by following method preparation.
That is to say, cyclopentanone (IV) and sulphur inner salt or oxygen sulphur inner salt such as dimethyl oxygen thiomethyl inner salt or dimethyl sulphide methyl inner salt are reacted in the presence of thinner, adopt " organic synthesis " 49,78(1968) just can obtain the epoxyethane derivative shown in the formula II with method (this method is regarded as the A-method) described in " JACS " (1965) 1353.
In addition, as a kind of and its diverse ways (being called the B-method), can react by Witting [referring to " organic synthesis " 40 66(1966) and " organic chemistry magazine " 28 1128(1963)] the methylene radical pentamethylene shown in the formula III obtained by the cyclopentanone shown in the formula IV, and [close volume the 4th volume referring to " organic synthesis " by epoxidation, 552(1963), 49,62(1969)] obtain the epoxyethane derivative shown in the formula II from the compound that makes.
The reaction formula of above-mentioned A-method and B-method is as follows.
The method for preparing formula II institute formula epoxyethane derivative:
In addition, can prepare the cyclopentanone derivatives shown in the formula IV by following method:
That is to say the R in formula IV
1And R
2The two is identical (C
1-C
5) under the situation of alkyl, make the cyclopentanone compound shown in the formula (VII) be converted into the ester derivative of cyclopentane-carboxylic acid shown in the formula (V) through the dioxane glycosylation reaction, this ester derivative passes through hydrolysis and decarboxylic reaction again, and at R
1And R
2The two one of another is (C for hydrogen atom
1-C
5) under the situation of alkyl, can be with needed benzyl drawing-in system (VIII) thus shown in alkyl cyclopentane carboxylic acid acid ester derivant acquisition formula (V) shown in the ester derivative of cyclopentane-carboxylic acid, this ester derivative passes through hydrolysis and decarboxylic reaction again.Can obtain the cyclopentanone derivatives shown in the formula IV like this.
In addition, if the R in the formula IV
1And R
2Be (the C that differs from one another
1-C
5) alkyl, then with a different (C
1-C
5) ester derivative (R wherein of cyclopentane-carboxylic acid shown in the alkyl introducing-type (V)
1And R
2The two one of be (C
1-C
5) alkyl, and another is a hydrogen atom) afterwards, the ester derivative that makes acquisition just can obtain the required derivative shown in the formula IV through hydrolysis and decarboxylic reaction.
The reaction formula of above-mentioned cyclopentanone is as follows
The synthetic route of formula IV cyclopentanone
By the way, formula (VII) and (VIII) compound are known compound, can pass through " organic chemistry " 29, and 2781(1964) described method is made by the alkyl ester of 2-oxo-cyclopentane formic acid.
As the thinner that is used to prepare azole derivative shown in the formula I of the present invention, can be listed below hydro carbons such as benzene, toluene, dimethylbenzene etc.; Halohydrocarbon such as methylene dichloride, chloroform, tetrahydro-carbon etc.; Pure as methyl alcohol, ethanol etc.; Ethers such as ether, isopropyl ether, tetrahydrofuran (THF) ， diox etc.; And as other kind just like acetonitrile, acetone, dimethyl formamide, methyl-sulphoxide etc.
In addition, in preparing the method for azole derivative of the present invention, be reflected under above-mentioned thinner and alkali or the sour condition that coexists and carry out, the alkali as use herein can be listed below: alkaline carbonate such as yellow soda ash, salt of wormwood etc.; Alkali metal hydroxide such as sodium hydroxide, potassium hydroxide etc.; Alkali metal alcoholate such as sodium methylate, sodium ethylate, potassium tert.-butoxide etc.; Alkalimetal hydride such as sodium hydride, potassium hydride KH etc.; Alkali-metal alkylate such as n-Butyl Lithium etc., other kind are just like triethylamine, pyridine.
As acid, can be listed below: mineral acid example hydrochloric acid, Hydrogen bromide, hydroiodic acid HI, sulfuric acid etc., organic acid such as formic acid, acetate, butyric acid, tosic acid etc.
In order to implement to prepare the method for azole derivative of the present invention, for instance, under the situation of the ester derivative of cyclopentane-carboxylic acid shown in the preparation formula (V), preferred mode is that the compound (being dissolved in thinner) shown in haloalkyl halogen or substituted benzyl halide and formula (VII) or (VIII) is reacted, in case of necessity, under the alkali existence condition, react.Temperature of reaction can be selected to this scope of its boiling point in the solidification value of (using as solvent) thinner as required, is good with 0-100 ℃.
Compound shown in the formula IV can carry out making in decarboxylic reaction 2-24 hour with mineral acid or organic acid under 80-150 ℃ by the ester derivative that makes cyclopentane-carboxylic acid shown in the formula (V), preferably stirs in the reaction.
In order to produce the epoxyethane derivative shown in the formula II, under the situation of using the A-method, preferably will add to by alkali (for example sodium hydride) and mix with iodate trimethylammonium oxygen sulfonium or iodate trimethylsulfonium in the dimethyl oxygen thiomethyl inner salt or dimethyl sulphide methyl inner salt that makes, and these two kinds of compounds are reacted by the ketone shown in the formula IV being dissolved in the prepared solution of thinner (being good with methyl-sulphoxide especially) with equivalent.
Like this, dimethyl oxygen thiomethyl inner salt or dimethyl sulphide methyl inner salt are that the 1.0-2.0 equivalent of cyclopentanone derivatives shown in the formula IV is good.This reaction is preferably in 25-100 ℃ the scope to be carried out 1-40 hour.
In addition, if above-mentioned preparation process adopts the B-method to carry out, then the cyclopentanone derivatives shown in the formula IV must be added to by alkali (for example sodium hydride) and in thinner (being good with methyl-sulphoxide especially), mix in the triphenylphosphine methyl inner salt that makes, these two kinds of compounds were reacted 2-10 hour under 0-100 ℃ of temperature with halogenation Jia base triphenyl phosphonium with equivalent.Isolate thus shown in the formula III that generates behind the methylene radical cyclopentanone derivatives, it is dissolved in thinner, add hydrogen peroxide or organic peracid such as peracetic acid, peroxybenzoic acid, after the metachloroperbenzoic acid etc., make it, preferably-10-80 ℃ of reaction down at-10 ℃-thinner boiling point.
Adopt A-method or B-method by cyclopentanone derivatives obtained shown in the formula II oxirane compound (II), its stereoisomerism structure presents in 1-oxygen spiral shell [2, the 4] heptane of oxirane compound shown in the formula II conformation of ethylene oxide group on the substituted benzyl on the 7-position and 3-position:
For instance, ((the separating of these steric isomers shown in the II-B) can pass through chromatography (thin-layer chromatography, column chromatography, high performance liquid chromatography etc.) finishes formula for II-A) and formula.The structural performance of these steric isomers can be measured by waiting as nuclear magnetic resonance spectrum.
In order to obtain the azole derivative shown in the formula I, can be with the oxirane compound shown in the formula II in the presence of alkali (necessity), add to by azole compounds shown in the formula VI being dissolved in the solution that thinner makes, or in contrast, the an alkali metal salt of azole compounds is added to by oxirane compound being dissolved in the solution that thinner makes, these two kinds of compounds are reacted.Temperature of reaction can be selected to the scope of its boiling point in the solidification point of thinner as required, yet particularly preferably is under this temperature that is reflected at 0-120 ℃, is more preferably to be accompanied by to stir under 60-120 ℃ to carry out 1-10 hour.
After reaction is finished, with the reaction mixture that obtains in ice kind of cooling and with organic solvent such as ethyl acetate, chloroform, methylene dichloride, extractions such as benzene.After isolating organic layer, wash with water and dry scrubber layer, steam the solvent that removes organic layer down in decompression.The resistates that so obtains just can obtain the purpose compound after purification processes.Purification processes can be by carrying out recrystallization to resistates, and the silica gel chromatography separation waits to be finished.
Owing to have formula (II-A) and (two kinds of isomer shown in the II-B) in the oxirane compound as the raw material of azole derivative shown in the formula I, thereby in the azole derivative of purpose shown in the formula I, have following steric isomer, they are by oxirane compound and 1 shown in the formula II, 2, the reaction between 4-triazole or the formula VI imidazoles and making:
-=on paper,
Certainly, for instance, formula (I-A) is with (can finish by chromatography shown in the I-B) by separating of isomer.
Hereinafter set forth the application of azole derivative of the present invention shown in the formula I (azole basic ring pentanol derivatives) as agricultural and gardening active ingredient.
(1) to the fungicidal action of plant disease fungi:
Azole derivative of the present invention demonstrates the effectiveness of preventing and treating the following plants disease in relative broad range.
Pyricularia Oryzae on the paddy rice,
Palace portion cochliobolus on the paddy rice,
Xanthomonas Oryzae on the paddy rice,
Dry thread Pyrenomycetes on the paddy rice,
The bent long spore of wriggling of fork on the paddy rice,
Gibberella fujikuroi on the paddy rice,
White Podosphaera on the apple,
Venturia inaequalis on the apple,
Apple core cup fungi on the apple,
Apple chain lattice spore on the apple,
Apple black skin shell on the apple,
Kikuchi chain lattice spore on the pears,
Pears ball pin shell on the pears,
Pear gymnosporangium on the pears,
Venturia nashicola on the pears,
Grape snag shell on the grape,
Phakopsora ampelopsidis on the grape,
Enclose small cluster shell on the grape,
Standing grain powdery mildew on the barley,
Rye beak spore on the barley,
Puccinia graminis on the barley,
Puccinia triformis on the barley,
Puccinia recondita f. sp. tritici on the wheat,
Wheat septoria on the wheat,
Puccinia triformis on the wheat,
Erysiphe graminis f.sp.tritci on the wheat,
Monofilament shell on the melon,
Curcurbitaceae thorn dish spore on the melon,
Sharp sickle spore on the watermelon,
Sharp sickle sporomorph cucumerinum on the cucumber,
Sharp sickle sporomorph raphani on the Japanese radish,
Two spore powdery mildews on the tomato,
Alternariaspp on the tomato belongs to solani,
Two spore powdery mildews on the eggplant,
Sephaerotheca humuli on grass is mould,
Two spore powdery mildews on the tobacco,
Long handle chain lattice spore on the tobacco,
Buckwheat dish on the sugar beet is given birth to the tail spore,
Alternariaspp on the potato belongs to solani,
Soybean septoria musiva on the soybean,
Kikuchi tail spore on the soybean,
Sclerotinia cinerea on the drupe tree,
Botrytis cinerea on the various crops,
Sclerotinite etc.
In addition, azole derivative of the present invention not only has the effectiveness of prevention and control but also has the effectiveness of treatment some phytopathies.
(2) plant growth regulation:
Be accompanied by with this mechanism of plant hormone coordinate plant growth and obtain explanation, in recent years, in the production field of agricultural and gardening, bring into use the medicine that is called as plant-growth regulator.
For example, produce Zante currant, can promote rooting of cuttings by means of α-Nai Yisuan with Plant hormones regulators,gibberellins, and chlorination 2-chloroethyl TMA (TriMethylAmine) (commodity by name (CCC) can be used as the growth inhibitor of wheat, and this is known by people.
In addition, by adopting this The Application of Technology of plant-growth regulator coordinate plant growth cycle not only to expand farm crop such as cereal to, vegetables, fruit tree etc., and expanded gardening plant such as flowers etc. to and then expanded in a broad sense plant one trees to, the function of plant-growth additive comprises hestening rooting, control is bloomed, the result, fruit is increased, promote growth, control growing and control metabolism.
Therefore, present the use kind and the ever-increasing trend of its consumption of plant-growth additive in recent years, yet in fact, the practical application of plant-growth additive does not reach desired degree.
Azole derivative of the present invention (azole basic ring pentanol derivatives) can show various plant growth regulating activities on a large scale on the growing plants, this characteristic of this material can be listed below.
ⅰ) suppress nourishing and growing of plant, especially suppress the height of tree growth of plant,
ⅱ) the activity of the content of useful component in the increase plant,
ⅲ) the activity in controlling plant ripening stage and flowering period.
As utilizing ⅰ) plant the example of growth inhibitory activity, azole derivative of the present invention can suppress the growth of weeds (demonstrating its weeding effect) and turf; Can prevent easily lodge plant such as paddy rice, barley, wheats etc. lodge; Can realize the mechanized harvest of soybean and cotton by suppressing its height of tree growth; The sprouting that suppresses the association bud can promote the growth of tobacco leaf; Can exempt cut operation by the growth that suppresses hedgerow; Can improve its commercial value by the growth that suppresses ornamental plant, or the like.
For ⅱ) plant the activity that increases useful component content in the plant, the example comprises the raising sugar beet, the sugar degree of sugarcane and citrus; Increase the protein content of cereal and soybean, etc., in addition, cause in ⅲ) plant the activity in controlling plant ripening stage and flowering period, the example comprises and can be used for loading and transporting fresh fruit and fresh flower can make it satisfy seasonable needs again simultaneously.
For azole derivative shown in the formula I is used as mycocide and plant-growth regulator, the mixture of derivative self or derivative and carrier (thinner) composition can be processed into pulvis, wettable pulvis, granule, emulsifiable concentrate, liquid preparation, etc., and the preparation that so makes is suitable for use.
In addition, in case of necessity, can also add other auxiliary such as spreading agent except carrier certainly, emulsifying agent, wetting agent, tackiness agent.
Put off until some time later one in passing, because the azole derivative shown in the formula I contains 1,2,4-triazole ring or imidazole ring, so the form that azole derivative can acid salt comes into operation with mineral acid or organic acid, or with the form use of metal complex.
In addition, in the azole derivative of the present invention shown in the formula I, 1-position on the pentamethylene ring, have the azole ylmethyl respectively on 2-position and the 5-position, (C-C) alkyl and substituted benzyl, thereby may have steric isomer such as suitable, anti-geometrical isomer, so the present invention includes one all kinds of isomer and with arbitrary proportion blended isomer mixture.
Therefore, agricultural of the present invention and gardening composition comprise that those contain a kind of isomer or the isomer mixture composition as active ingredient.
Azole derivative of the present invention shown in the formula I possesses the active and plant adjusting activity of good phytopathy control, and can be used as the active ingredient in agricultural and the gardening composition.
Use azole derivative of the present invention these specific embodiments of active ingredient by showing, can set forth validity of the present invention, yet the following example does not constitute the restriction to essential characteristic of the present invention as agricultural and gardening composition.
[1] production example of azole derivative shown in the formula I and intermediate thereof.
Preparation 1-(4-benzyl chloride base)-3,3-dimethyl-2-oxo-cyclopentane methyl-formiate (midbody compound 156 in the table 5)
5.0 gram sodium hydrides (making by wash 60% oily sodium hydride with dry-out benzene) are added in the 150ml dry-out benzene, in nitrogen atmosphere, stir simultaneously, and then adding 50g 1-(4-benzyl chloride base)-and 2-oxo-cyclopentane methyl-formiate, whole mixture was stirred 40 minutes down in 80 ℃.After being cooled to room temperature, the mixture that dropping 29.4g methyl iodide also will form thus in this reaction mixture stirred 2 hours down in 80 ℃.After it is cooled to room temperature, add 5.0g sodium hydride (1 equivalent), and be placed on 80 ℃ and stirred 30 minutes down.After being cooled to room temperature, in reaction mixture, adding 29.4 gram methyl iodides (monovalent) again, and stirred 8 hours under being placed on 80 ℃.
After thus obtained reaction mixture cooling, with its impouring acetic acid and the formed mixture of frozen water, with the whole mixture of ethyl acetate extraction, produce organic layer, this organic layer elder generation is through sodium bicarbonate aqueous solution and then use the salt water washing, with this organic stratification anhydrous sodium sulfate drying, steam the solvent that removes in the organic layer down in decompression afterwards through washing.
By the resistates underpressure distillation and the purifying that will so obtain, just can obtain 44.8 gram purpose compounds (boiling point: 142-143 ℃ (0.7mm Hg)).
With 5-(4-benzyl chloride base) 2,2-dimethyl-1-cyclopentanone (midbody compound 133 in the table 4)
With 44.8 gram 1-(4-benzyl chloride bases)-3,3-dimethyl-2-oxo-cyclopentane methyl-formiate (compound 156 in the table 5) adds in the Hydrogen bromide of 120ml 47%, and the mixture that so forms was stirred 12 hours down in 100 ℃.
After treating above-mentioned reaction mixture cooling, its impouring frozen water is also used ethyl acetate extraction, obtain organic layer, elder generation uses anhydrous sodium sulfate drying after using salt water washing organic layer again with sodium bicarbonate aqueous solution.Steam the resistates that obtains behind the solvent that removes in the organic layer down in decompression and can obtain 31g purpose compound (boiling point: 124 ℃ (1mmHg)) through underpressure distillation and purifying.
Embodiment 3
Preparation 5-(4-benzyl chloride base)-2,2-dimethyl-1-methylene radical pentamethylene (midbody compound 122 in the table 3)
3.6g sodium hydride (wash 60% oily sodium hydride with dry-out benzene and make) is added in helium-atmosphere in the 150ml anhydrous dimethyl sulfoxide, under 70 ℃, this mixture was stirred 30 minutes, with frozen water with its cooling after, add 53.6g Diethylaminoethyl triphenyl phosphorus, down this mixture was stirred 30 minutes in the frozen water cooling then, this chilled mixture is stirred 10 minutes again under room temperature.After this add 23.6 gram 5-(4-benzyl chloride bases)-2,2-dimethyl-1-cyclopentanone (compound 133 in the table 4), thus it was finished entire reaction course in 30 minutes in 70 ℃ of stirrings again after stirring 1 hour under the room temperature.
After treating the cooling of above-mentioned reaction mixture, obtain an organic layer, use anhydrous sodium sulfate drying again after washing this organic layer with salt brine solution, steam the solvent that removes in the organic layer down in decompression then with its impouring frozen water and with ethyl acetate extraction.
With the oily matter in thus obtained oily of n-hexane extraction and the solid mixture, be purified by separating n-hexane extract with silica gel column chromatography, obtain 22.1 gram purpose compounds.
Preparation 7-(4-benzyl chloride base)-4-dimethyl-1-oxygen spiral shell (2,4) hexane (midbody compound 77 and 78 for preparing with the A-method in the table 2
3g sodium hydride (wash 60% oily sodium hydride with dry-out benzene and make) is added in helium-atmosphere in the 70ml anhydrous dimethyl sulfoxide while stirring, add 27.5g iodate trimethylammonium oxygen sulfonium then.After stirring 30 minutes under the room temperature, in 30 minutes, add again by 23.6g 5-(4-benzyl chloride base)-2, the solution that 2-dimethyl-1-cyclopentanone (the compound sequence number is 133, is shown in table 4) and 20ml anhydrous dimethyl sulfoxide are formed stirs this mixture 2 hours down in 90 ℃.
After treating above-mentioned reaction mixture cooling, it is inclined to frozen water and can obtain an organic layer with ethyl acetate extraction, also use anhydrous sodium sulfate drying with salt brine solution washing organic layer, steam the solvent that removes in the organic layer down in decompression, resulting resistates separates through silica gel column chromatography can obtain 13.95 gram purpose compounds 77 and 1.05 gram purpose compounds 78.
Preparation 7-(4-luorobenzyl)-4,4-dimethyl-1-oxygen spiral shell (2, the 4) heptane (midbody compound 81 and 82 of B-method preparation in the table 2
With 17 gram 5-(4-luorobenzyls)-2, (compound 124 in the table 3, are dissolved in the 170ml chloroform, add 27.1 gram metachloroperbenzoic acids then in 10 minutes, stir this mixture 2 hours under room temperature for 2-dimethyl-1-methylene radical pentamethylene.Secondly, added 25.4 gram calcium hydroxides in introversive this mixture in 10 minutes, and under room temperature, this mixture was stirred 30 minutes.
After leaching solid matter, the chloroform layer in the concentrated filtrate obtains colorless oil, and it is purified with the silica gel column chromatography leafing, obtains 4.5g purpose compound 81 and 86 gram purpose compounds 82.
Preparation C-5-(2, the 4-dichloro benzyl)-2,2-dimethyl-1-(1H-imidazoles-1-ylmethyl)-γ-1-cyclopentanol (compound 15 in the table 1)
996mg sodium hydride (wash 60% oily sodium hydride with dry-out benzene and make) is added in the 18ml anhydrous dimethyl formamide in helium-atmosphere while stirring.Secondly, adding 2.83g 1H-imidazo stirs the mixture till bubbling stops under room temperature.Will be by 5.93g 7-(2, the 4-dichloro benzyl)-4,4-dimethyl-1-oxygen spiral shell (2,4) heptane (compound 83 in the table 2) is dissolved in the formed drips of solution of 10ml anhydrous dimethyl formamide and adds in the top resulting solution, and stirs 2 hours down in 80 ℃.
After treating the cooling of this reaction mixture, incline it to frozen water and use ethyl acetate extraction, obtain an organic layer.
After washing organic layer with water,, and under decompression, steam the solvent that removes in the organic layer with this organic layer of anhydrous sodium sulfate drying.
Resulting residue separates to purify with silica gel column chromatography earlier uses the mixture recrystallization of hexane and ethyl acetate again, and the result obtains 2.7g purpose compound.
Embodiment 7
Preparation t-5-(4-benzyl chloride base)-2,2-dimethyl-1-(1H-1,2,4-triazol-1-yl methyl)-γ-1-cyclopentanol (the compound sequence number 2 in the table 1)
With 5.0 gram 7-(4-benzyl chloride bases)-4,4-dimethyl-1-oxygen spiral shell (2,4) heptane (compound 78 in the table 2) adds in the 30ml anhydrous dimethyl formamide under helium-atmosphere while stirring, and make its dissolving, add 2.2g 1H-1 then lentamente, 2, the sodium salt of 4-triazole (purity: 90%, by Aldrich company production and selling), under 70 ℃, stirred the mixture 2 hours.
After treating the cooling of this reaction mixture, thereby incline it to frozen water and obtain an organic layer with ethyl acetate extraction, wash organic layer with water after, use anhydrous sodium sulfate drying, steam down in decompression then and remove the solvent in the organic layer after the drying.
Resulting resistates obtains the compound of 3.1 gram purposes after silica gel column chromatography separates purification.
Embodiment 8
Preparation 2-(4-benzyl chloride base)-5-methyl isophthalic acid-cyclopentanone (midbody compound 137 in the table 4)
3.04 gram sodium hydrides (wash 60% oily sodium hydride and make with dry-out benzene) are added in the 126ml dry-out benzene, add 18g 3-methyl-2-oxo-cyclopentane methyl-formiate then, after stirring 1 hour under the room temperature, add 21.5 gram 4-chlorobenzyl chlorides again and in 90 ℃ oil bath, this mixture was refluxed 6 hours.
After the cooling of question response mixture, extract with benzene, and wash the benzene layer with salt brine solution.Behind anhydrous sodium sulfate drying benzene layer, steam the solvent that removes in the benzene layer down in decompression, obtain the pale brown look oily 1-(4-benzyl chloride base of 33.6 grams)-3-methyl-2-oxygen cyclopentane-carboxylic acid methyl esters (midbody compound 160 in the table 5).
After adding the Hydrogen bromide of 100ml 47% in the above-mentioned ester of purifying, in 110 ℃ of following vigorous stirring 18 hours.After treating its cooling, use dichloromethane extraction, successively with aqueous sodium carbonate and salt brine solution washing organic layer, use the washed organic layer of anhydrous sodium sulfate drying, and steam the solvent that removes wherein down again in decompression.
By the underpressure distillation resulting resistates of purifying, obtain 17.4 gram purpose compounds.
Preparation 1-(4-benzyl chloride base)-3-ethyl-3-methyl-2-oxo-cyclopentane methyl-formiate (midbody compound 178 in the table 5)
1.7g sodium hydride (wash 60% oily sodium hydride with dry-out benzene and make) is added in helium-atmosphere in the 80ml anhydrous tetrahydro furan while stirring, add 18.2g 1-(4-benzyl chloride base then)-3-methyl-2-oxygen cyclopentane-carboxylic acid methyl esters, under room temperature, stirred this mixture 2 hours.
Secondly, mixture temperature is being remained in 20～30 ℃, dripping the 11.1g iodic ether, under 20～30 ℃ temperature, it was being stirred 1 hour then, stirring 1 hour down at 60 ℃ subsequently.
After treating above-mentioned reaction mixture cooling, its impouring by also using ethyl acetate extraction in frozen water and the formed mixture of acetate, is obtained an organic layer, after the sodium bicarbonate washing, with the salt brine solution washing, steam the solvent that removes in the organic layer down again with the anhydrous sodium sulfate drying organic layer and in decompression.
Resulting resistates is purified through underpressure distillation can obtain 15g purpose compound.
Preparation 4-(4-benzyl chloride base)-7-methyl isophthalic acid-oxygen spiral shell (2,4) heptane (midbody compound 85 in the table 2)
1.44g sodium hydride (wash 60% oily sodium hydride and make with dry-out benzene) is added in helium-atmosphere in the 37ml anhydrous dimethyl sulfoxide while stirring, add 13.2g iodate trimethylammonium oxygen sulfonium again, under room temperature, stirred this mixture 30 minutes then.Secondly, will be by 12.2g 2-(4-benzyl chloride base)-5-methyl isophthalic acid-cyclopentanone (compound 137 in the table 4) formed solution in the 12ml anhydrous dimethyl sulfoxide added in 10 minutes in this mixture, stirred whole mixture 4 hours then under room temperature.
The reaction solution that makes is thus inclined to frozen water, use the dichloromethane extraction mixture, obtain an organic layer, after the salt brine solution washing, use anhydrous sodium sulfate drying again, steam the solvent that removes in the organic layer down in decompression at last.
The resistates that obtains is thus purified through silica gel column chromatography can obtain 6.67g purpose compound.
In addition, also isolate other three kinds of isomer of purpose compound.
That is to say the midbody compound 86 in the 0.15g table 2; 0.16g midbody compound 87 and 0.16g midbody compound 88.
Embodiment 11
Preparation 4-(4-benzyl chloride base)-7-ethyl-1-oxygen spiral shell (2,4) heptane (midbody compound 93,94,95 and 96 in the table 2)
With 8.0 gram 2-(4-benzyl chloride bases)-5-ethyl-1-methylene radical pentamethylene (compound 129 in the table 3) is dissolved in the 100ml chloroform, adds the 11.6g metachloroperbenzoic acid, and stirred 2 hours under room temperature.Secondly, under the frozen water cooling, in this mixture, add 11g calcium hydroxide, under room temperature, stirred the mixture 30 minutes then.
The filtering solid matter, the chloroform layer of concentrated filtrate obtains colorless oil, can obtain 0.7g compound 93 with silica gel column chromatography purification oily matter, 2.4g compound 94,2.2g compound 95 and 2.6g compound 96.
Preparation C-2-(4-benzyl chloride base)-5-methyl isophthalic acid-(1H-1,2,4-triazol-1-yl methyl)-γ-1-cyclopentanol (table 1 compound 16)
Its 630mg sodium hydride (wash 60% oily sodium hydride and make with dry-out benzene) is added to the 10ml anhydrous dimethyl formamide, add 1.8g 1H-1 again, 2, the 4-triazole is then in stirring this mixture under the room temperature till bubbling stops.
Adding is by 3.1g 4-(4-benzyl chloride base)-the 7-methyl isophthalic acid-solution of oxygen spiral shell (2,4) heptane (table 2 compound 85) in the 6.2ml anhydrous dimethyl formamide, under 80 ℃, stirred the mixture 1 hour then.
After treating its cooling,, obtain an organic layer with the dichloromethane extraction mixture with reaction solution impouring frozen water.
After the salt brine solution washing, steam the solvent that removes in the organic layer down with the anhydrous sodium sulfate drying organic layer and in decompression.
Adopt the silica gel column chromatography resulting resistates of purifying, in the n-hexane/ethyl acetate mixture, obtain 2.83g purpose compound behind the recrystallization.
Embodiment 13
Preparation C-2(4-benzyl chloride base)-5-methyl isophthalic acid-(1H-imidazoles-1-ylmethyl)-γ-1-cyclopentanol (table 1 compound 17)
670mg sodium hydride (60% oily sodium hydride makes through washing) is added to the 10ml anhydrous dimethyl formamide, add 1.9g 1H-imidazoles again, and in stirring the mixture under the room temperature till bubbling stops.
Secondly, add by 3.3g 4-(4-benzyl chloride base)-7-methyl isophthalic acid-oxygen spiral shell (2,4) heptane (table 2 compound 85) and the formed solution of 6.6ml anhydrous dimethyl formamide, stirred this mixture 1 hour down in 80 ℃.
After the question response liquid cooling but, its impouring frozen water also can be got an organic layer with dichloromethane extraction.
Behind salt brine solution washing organic layer, use anhydrous sodium sulfate drying again, and remove solvent wherein under reduced pressure.
The resistates that is obtained is purified with silica gel column chromatography, can obtain 3.16g purpose compound in n-hexane/ethyl acetate behind the recrystallization.
The embodiment of (II) preparation agricultural usefulness and garden antifungal composition.
Embodiment 14: dust (powder) agent
With 3 weight parts azole derivative of the present invention (compound 3), 40 weight part potter's clay and 57 weight part talcums mix, and make the fungicide composition that the dust-like agricultural is used and gardening is used through grinding.
Make the method for composition spreading.
Embodiment 15: wettable pulvis
With 50 weight parts azole derivative of the present invention (compound 1), 5 weight part Sulfite lignin, 3 weight part alkylsulfonates and 42 weight part diatomite mix, and make wettable powder through grinding.
The composition that so makes uses as wettable powder after the water dilution.
Embodiment 16: granule
With 5 weight parts azole derivative of the present invention (compound 16), 43 weight part wilkinites, 45 weight part potter's clay and 7 weight part Sulfite lignin uniform mixing; add entry then; it is kneaded together, be machined to particle with the extruding granulating after, drying obtains granular composition.
Embodiment 17: but emulsion concentrate
With 20 weight parts azole derivative of the present invention (compound 13), 10 weight part polyoxyethylene alkylaryl ethers, thereby 3 weight part polyoxyethylene sorbitol acid anhydrides, one lauric acid ester and 67 weight part dimethylbenzene uniform mixing are made the composition of emulsifiable concentrate shape.
(III) application the present invention agricultural uses and garden antifungal composition is treated the embodiment of phytopathy.
Erysiphe graminis f.sp.tritici's on the wheat is anti-| effect test
But every basin is executed the suspension (being diluted with water to predetermined concentration) of the wet powder that 5ml example 15 makes and is applied to (kind .NOR IN64 on the two leaf stage wheat seedling, 3 basins are arranged in the treatment zone, and every basin has 16 strain seedlings) cultivation of these seedling is in the no glaze basin of 10cm at diameter.After treating that diluent is air-dry, the real spore suspension of the Erysiphe grarainis f.sp.tritici that will collect on infected wheat leaf is sprayed in the basin on the seedling, these basins are placed 20～24 ℃ and high humidity following 24 hours, then it is moved into greenhouse.After 9～11 days, detect the occurring degree (disease degree) of seedling, and calculate the controlling valu of fungicidal composition according to following formula according to following examination criteria.
(bioassay standard)
Disease degree disease scope
0 does not have infringement
0.5 disease speck area rate is lower than 10%
1 disease speck area rate is not less than 10%,
Be lower than 20%
2 disease speck area rates are not higher than 20%,
Be lower than 40%
3 disease speck area rates are not less than 40%,
Be lower than 60%
4 disease speck area rates are not less than 60%,
Be lower than 80%
5 disease speck area rates are not less than 80%,
Controlling valu=(1-(treatment zone disease degree)/(check plot disease degree)) * 100(%)
Test-results is shown in table 6.
Table 6
Test compound spray concentration controlling valu
(numbering in the table 1) (ppm) (%)
1 125 100
2 125 100
3 125 95
4 125 100
5 125 100
6 125 100
7 125 95
8 125 95
9 125 100
10 125 100
11 125 100
12 125 90
13 125 100
14 125 100
15 125 95
16 125 100
17 125 95
18 125 100
19 125 100
Table 6(is continuous)
Test compound spray concentration controlling valu
(numbering in the table 1) (ppm) (%)
20 125 50
21 125 100
22 125 100
23 125 100
24 125 100
25 125 100
26 125 100
27 125 100
28 125 100
29 125 100
30 125 100
31 125 100
32 125 100
33 125 100
34 125 100
35 125 100
36 125 100
37 125 100
38 125 100
Table 6(is continuous)
Test compound spray concentration controlling valu
(numbering in the table 1) (ppm) (%)
39 125 100
40 125 100
41 125 100
42 125 100
43 125 95
44 125 100
45 125 100
46 125 95
47 125 100
48 125 100
49 125 100
50 125 100
51 125 100
52 125 100
53 125 75
54 125 100
55 125 100
56 125 100
57 125 100
Table 6(is continuous)
Test compound spray concentration controlling valu
(numbering in the table 1) (ppm) (%)
58 125 100
59 125 100
60 125 100
61 125 100
62 125 100
63 125 100
64 125 100
65 125 100
66 125 100
67 125 100
68 125 100
69 125 100
70 125 100
71 125 100
Table 6(is continuous)
Test compound spray concentration controlling valu
(numbering in the table 1) (ppm) (%)
72 125 100
73 125 100
74 125 100
75 125 100
76 125 100
Commodity Triadim-125 100
ephon
＊
Contrast (being untreated) 0
Annotate
*): commodity Triadimephon has the compound of following formula representative as active ingredient.
Example 19
Cucumber Sphaerotheca fuliginea controls effect test
Cut-off directly is 3 in the no glaze flowerpot of 10cm, and (kind: SAGAMI HAMPAKU), but every basin is executed the emulsion concentrate (being diluted with water to predetermined concentration) of the dilution in 5ml such as the example 15 to every plantation one strain two leaf stage cucumber.After blade after the dispenser dries in air, from sick Folium Cucumidis sativi, the spore brush is descended with the inoculation cucumber, make the cucumber in the greenhouse susceptible with brush.
Inoculation back 9 to 11 days is by the disease degree of following bioassay standard mensuration cucumber plant.The controlling valu of fungicide composition is calculated with following formula:
(bioassay standard)
Disease degree disease scope
0 does not have infringement
0.5 disease speck area rate is lower than 10%
1 disease speck area rate is not less than 10%,
Be lower than 20%
2 disease speck area rates are not higher than 20%,
Be lower than 40%
3 disease speck area rates are not less than 40%,
Be lower than 60%
4 disease speck area rates are not less than 60%,
Be lower than 80%
5 disease speck area rates are not less than 80%,
Controlling valu=(1-(treatment zone disease degree)/(check plot disease degree)) * 100(%)
Test-results is shown in table 7.
Table 7
Test compound spray concentration controlling valu
(numbering in the table 1) (ppm) (%)
1 125 100
2 125 100
3 125 100
4 125 100
5 125 100
6 125 100
7 125 100
8 125 100
9 125 100
10 125 100
11 125 100
12 125 100
13 125 100
14 125 100
15 125 100
16 125 100
17 125 100
Commodity Triadim-125 100
ephon
＊
Contrast (being untreated) 0
Example 20
The control effect test of wheat Puccina recondita
Cut-off directly is 3 in the no glaze flowerpot of 10cm, plants 2 leaf phase wheat seedlings (kind: NOR IN No.64, every basin 16 strains), and every basin sprays the wettable powder suspension (being diluted to predetermined concentration with water) that 5ml such as example 15 make.
When dilute suspension after in air, drying, the suspension of the spore in summer (being collected in the atrophy wheat leaf) of Puccina recondita is sprayed on the wheat seedling in the basin, basin was kept 24 hours at 20-23 ℃ under super-humid conditions, again basin is placed the greenhouse.Inoculate after 3-10 days, measure the disease scopes of 10 strain seedling, calculate the controlling valu of fungicide composition again according to the average disease degree of every leaf with following formula by following bioassay standard:
(bioassay standard)
Disease degree disease scope
0 does not have infringement
0.5 disease speck area rate is lower than 10%
1 disease speck area rate is higher than 10%,
Be lower than 20%
2 disease speck area rates are not less than 20%,
Be lower than 40%
3 disease speck area rates are not less than 40%,
Be lower than 60%
4 disease speck area rates are not less than 60%,
Be lower than 80%
5 disease speck area rates are not less than 80%,
Controlling valu=(1-(treatment zone disease degree)/(check plot disease degree)) * 100(%)
Test-results is shown in table 8
Table 8
Test compound spray concentration controlling valu
(numbering in the table 1) (ppm) (%)
1 125 100
2 125 95
3 125 100
4 125 95
5 125 100
6 125 100
7 125 100
8 125 95
9 125 100
10 125 100
11 125 100
12 125 95
13 125 100
14 125 100
15 125 100
16 125 100
17 125 95
18 125 100
19 125 100
Table 8(is continuous)
Test compound spray concentration controlling valu
(numbering in the table 1) (ppm) (%)
21 125 100
22 125 100
23 125 100
24 125 70
25 125 100
26 125 95
27 125 100
28 125 100
29 125 100
30 125 100
31 125 100
32 125 100
33 125 100
34 125 100
35 125 100
36 125 100
37 125 100
38 125 100
39 125 100
40 125 100
Table 8(is continuous)
Test compound spray concentration controlling valu
(numbering in the table 1) (ppm) (%)
41 125 100
42 125 100
43 125 100
44 125 100
45 125 100
46 125 100
47 125 100
48 125 100
49 125 90
50 125 100
51 125 100
52 125 100
53 125 95
54 125 100
55 125 100
56 125 100
57 125 100
58 125 90
59 125 100
60 125 90
Table 8(is continuous)
Test compound spray concentration controlling valu
(numbering in the table 1) (ppm) (%)
61 125 90
62 125 100
63 125 100
64 125 100
65 125 100
66 125 100
67 125 100
68 125 100
69 125 100
70 125 100
71 125 100
72 125 100
73 125 100
74 125 100
75 125 90
76 125 90
Commodity Triadim-125 95
ephon
＊
Contrast (being untreated) 0
Example 21
Kidney bean is detested grape spore control effect test
With diameter is the no glaze flowerpot plantation Kidney bean of 10cm, when its first leaf period, but the suspension (being diluted with water to predetermined concentration) of the wet powder that sprinkling example 15 makes, every basin 5ml.
After vanes dries in air, with diameter is the middle part that the agar disk (fungi was cultivated 3 days in 20 ℃ the sugaring gelose medium that contains potato decoction in advance) of detesting grape spore fungi containing of 4mm directly sticks to the Kidney bean leaf, and the Kidney bean plant remains on 20-22 ℃ under super-humid conditions.Inoculation back the 3rd day, by of disease speck area and the check plot disease speck area contrast of following bioassay standard,, calculate the controlling valu of Bactericide composition then by following formula to measure the disease degree with treatment zone:
(bioassay standard)
Disease degree disease scope
0 is encroached on
0.5 only at the inoculated fungi that contains agar
Bottom and peripheral part are encroached on
1 disease speck area rate is lower than 20%,
2 disease speck area rates are not less than 20%,
Be lower than 40%
3 disease speck area rates are not less than 40%,
Be lower than 60%
4 disease speck area rates are not less than 60%,
Be lower than 80%
5 disease speck area rates are not less than 80%,
Controlling valu=(1-(treatment zone disease degree)/(check plot disease degree)) * 100(%)
Test-results is shown in table 9
Table 9
Test compound spray concentration controlling valu
(numbering in the table 1) (ppm) (%)
1 500 100
2 500 100
3 500 90
4 500 80
5 500 100
6 500 100
7 500 70
8 500 70
9 500 100
10 500 100
11 500 85
12 500 80
13 500 100
14 500 100
15 500 90
16 500 100
17 500 80
18 500 100
19 500 100
Table 9(is continuous)
Test compound spray concentration controlling valu
(numbering in the table 1) (ppm) (%)
21 500 100
22 500 65
23 500 100
24 500 90
25 500 85
27 500 100
28 500 90
29 500 100
30 500 100
31 500 60
32 500 100
33 500 85
37 500 100
38 500 100
39 500 75
41 500 100
42 500 100
44 500 100
45 500 100
Table 9(is continuous)
Test compound spray concentration controlling valu
(numbering in the table 1) (ppm) (%)
46 500 70
47 500 60
48 500 100
49 500 100
50 500 100
54 500 100
55 500 100
56 500 95
57 500 70
58 500 70
59 500 80
60 500 80
61 500 85
62 500 100
63 500 100
64 500 80
65 500 100
66 500 60
67 500 100
Table 9(is continuous)
Test compound spray concentration system limit value
(numbering in the table 1) (ppm) (%)
68 500 60
69 500 100
70 500 65
71 500 100
72 500 100
73 500 80
74 500 60
75 500 85
76 500 60
Annotate
*): commodity Rovral
Contain the compound represented with following formula as active ingredient.
Example 22
Paddy rice palace portion cochliobolus control effect test
The no glaze flowerpot of cut-off footpath 10cm, 16 paddy rice (kinds: seed SASANIS-HIK I) of every basin sowing, grow into the 4-5 leaf during phase at paddy rice calamity seedling, but the emulsion concentrate (being diluted to predetermined concentration with water) of the dilution in the example 15 is sprayed on the calamity seedling.
After processed vanes dried in air, every basin sprayed thereon (paddy rice palace portion cochliobolus spore is through cultivating in advance) with the suspension of 5ml paddy rice palace portion cochliobolus spore.15 fungal spores are arranged in the visible suspension of 150 times microscopically.
Inoculation finishes, and the flowerpot after handling is placed 25 ℃ and the transfer room of saturated humidity is arranged, and after 2 days, flowerpot moves into the greenhouse is attacked paddy rice.Inoculation back the 5th day, every basin calculates the disease spot number of 10 blades, calculates the controlling valu of fungicidal composition by following formula.
Controlling valu=(1-(treatment zone disease spot number)/(check plot (being untreated) disease spot number)) * 100(%)
Test-results is shown in table 10.
Table 10
Test compound spray concentration controlling valu
(numbering in the table 1) (ppm) (%)
1 125 100
2 125 100
3 125 100
4 125 100
5 125 100
6 125 100
7 125 100
8 125 100
9 125 100
10 125 100
11 125 100
12 125 100
13 125 100
14 125 95
15 125 90
16 125 100
17 125 100
Contrast (being untreated) 0
Example 23
The antibacterial tests of several pathogeny fungies
Present embodiment has shown by the antimycotic characteristic of azole derivative of the present invention to various plant pathogenic fungis
Test method:
Compound of the present invention is dissolved in methyl-sulphoxide, makes predetermined concentration, the solution that in the Erlenmeyer flask of 100ml capacity 0.6ml is prepared thoroughly mixes with 60 ℃ PAS developing medium.In this mixture impouring one glass culture dish, become the flat developing medium that contains The compounds of this invention after the curing.
In addition, be that the punch tool of 4mm will be tested fungi (cultivating in advance) and make small pieces in flat developing medium with diameter, this is contained the developing medium small pieces of testing fungi be inoculated on the flat developing medium that contains The compounds of this invention.After the inoculation, the medium that contains compound and fungi for preparing was cultivated 1-3 days under the temperature that is fit to, made fungal growth.Measure fungi growth with the method for measuring the fungal colony diameter.The comparing of fungi growth and the district of being untreated (developing medium does not contain compound) in the developing medium of so preparation, calculating just can obtain the prevention rate of hypha,hyphae bulk-growth according to the following equation:
R＝（dc-dt）100（%）
R is a mycelial growth prevention rate in the formula, and dc is the diameter of the fungal colony on the flat medium that does not contain compound; Dt is the fungal colony diameter that contains on the flat medium of compound.
The result that calms down is divided into 5 grades by following standard, is shown in table 11.Mycelial growth prevention rate:
5: growth prevention rate is not less than 90 to 100%
4: growth prevention rate is not less than 70%, less than 90%
3: growth prevention rate is not less than 40%, less than 70%
2: growth prevention rate is not less than 20%, less than 40%
1: growth prevention rate is less than 20%
The abbreviation of each fungi is as follows in the table 11:
P.o. paddy rice Pyricularia Oryzae
C.m. spore chamber bacterium is revolved in paddy rice palace portion
G.f. fusarium moniliforme
H.s. paddy rice fork song is grown the spore of wriggling
R.s. paddy rice dry thread Pyrenomycetes
Bo.c. detest the grape spore
S.s. Sclerotinia sclerotirum
F.n. watermelon Fusarium Oxysporum f.niveum
F.c. cucumber Fusarium Oxysporum f.cucumerinum
F.r. Japanese Radix Raphani Fusarium Oxysporum f.raphani
C.l. Curcurbitaceae thorn dish spore
C.b. the beet dish is given birth to the tail spore
S.c. peach Sclerotinia cinerea
V.m. apple tree canker
A.m. apple chain lattice spore
A.k. peach chain lattice spore
G.c. grape encloses small cluster shell
[IV] is with agricultural or the gardening plant-growth regulator example of azole derivative of the present invention as active ingredient
Example 24
The wettable powder form
With 50 parts of (weight) azole derivatives of the present invention (compound 3 of table 1 table), 5 parts of (weight) sulfonated lignin, 3 parts of (weight) alkylsulfonates and 42 parts of (weight) diatomite mixed grindings, make the wettable powder composition, use behind the dilute with water.
Example 25
But emulsification conc forms
25 parts of (weight) azole derivatives of the present invention (compound 20 of table 1 table), 65 parts of (weight) dimethylbenzene are in the same place with 10 parts of (weight) polyoxyethylene alkane aryl oxide uniform mixing, but make the emulsion concentrate composition, use behind the dilute with water.
Example 26
Powder form
8 parts of (weight) azole derivatives of the present invention (compound 11 of table 1 table), 40 parts of wilkinites, 45 parts of (weight) clays and 7 parts of (weight) sulfonated lignin are mixed; after adding water whole mixture is kneaded together; be machined to granularly with the extruding granulating, this saccharoid promptly becomes dust composition after drying.
Example 27
The plant height of paddy rice suppresses effect
At each diameter is in the glass disc of 8.5cm, adds the solution that 10ml contains different compound of the present invention, and concentration is 10ppm.10 rice paddy seed (kinds: SASANISHIKI) of sowing in each dish.Dish is placed its germination of indoor maintenance 7 angels of 27 ℃, measure calamity height of seedling degree then.Data are shown in table 12.
As can be seen from Table 12, each azole derivative of the present invention all shows the growth-inhibiting effect and does not have any phytotoxicity.
Table 12
Compound number height inhibiting rate phytotoxicity
(in the table 1 numbering) (%)
1 84.2 do not have
2 63.8 ″
3 71.8 ″
4 70.0 ″
5 70.0 ″
6 74.6 ″
7 85.9 ″
8 72.3 ″
9 75.7 ″
10 79.7 ″
11 76.8 ″
12 67.2 ″
13 87.0 ″
14 76.8 ″
15 77.4 ″
16 84.2 ″
17 76.8 ″
Claims (3)
1, preparation is by formula I
(R in the formula
1And R
2Each representative-(C
1-C
5) alkyl or hydrogen atom; X represents a hydrogen atom, (C
1-C
5) alkyl or phenyl; N represents the integer of 0-2; A represents a nitrogen-atoms or CH, but must work as R
2R during for hydrogen atom
1Be not hydrogen atom) method of azole derivative of representative, this method comprises formula II
(Ⅱ)
(R in the formula
1, R
2, as above defined of X and n) epoxyethane derivative and the formula IV of representative
(M represents hydrogen atom or alkali metal atom in the formula; A represents nitrogen-atoms or CH) representative 1,2,4-triazole or imidazoles react.
2, method according to claim 1, wherein the preparation method of the epoxyethane derivative of formula II representative comprises:
A) (ⅰ) 2-oxo-cyclopentane alkyl formate and substituted benzyl halogen reaction is with the 1-(substituted benzyl that obtains)-2-oxo-cyclopentane alkyl formate and (C
1-C
5) the alkylogen reaction; (ⅱ) with 3-(C
1-C
5Alkyl)-2-oxo-cyclopentane alkyl formate and the reaction of substituted benzyl halogen; Or (ⅲ) with the 1-(substituted benzyl)-3-(C
1-C
5Alkyl)-2-oxo-cyclopentane formic acid and (C
1-C
5) the alkylogen reaction, the cyclopentane-carboxylic acid ester derivative that obtains thus is with formula (V)
(R in the formula
1And R
2Each representative-(C
1-C
5) alkyl or hydrogen atom; R
2Representative-(C
1-C
5) alkyl; X represents a hydrogen atom, (C
1-C
5) alkyl or phenyl; N represents the integer of 0-2; But must work as R
2R during for hydrogen atom
1Be not hydrogen atom) representative,
B) the cyclopentane-carboxylic acid ester derivative that obtains is hydrolyzed decarboxylation obtains with formula IV
(R in the formula
1, R
2, as above defined of X and n) cyclopentanone derivatives of representative,
(c) cyclopentanone derivatives with above-mentioned gained carries out the oxyethane reaction with sulphur inner salt or oxygen sulphur inner salt, or carries out the oxyethane reaction with the feasible methylene radical cyclopentane derivatives from cyclopentanone derivatives of the uncommon reaction of prestige ladder, and the methylene radical pentamethylene is with formula III
(R in the formula
1, R
2, X and n and above-mentioned person define with) representative, thus cyclopentane derivatives is transformed into epoxyethane derivative, and represents with formula II
(R in the formula
1, R
2, X and n and above-mentioned person define with).
3, method according to claim 1, this method may further comprise the steps:
A) (ⅰ) is with 2-oxo-cyclopentane alkyl formate and the reaction of substituted benzyl halogen, again with the 1-(substituted benzyl that obtains)-2-oxo-cyclopentane alkyl formate and (C
1-C
5) the alkylogen reaction; (ⅱ) with 3-(C
1-C
5Alkyl)-2-oxo-cyclopentane alkyl formate and the reaction of substituted benzyl halogen; Or (ⅲ) with the 1-(substituted benzyl)-3-(C
1-C
5Alkyl)-2-oxo-cyclopentane formic acid and (C
1-C
5) the alkylogen reaction, obtain with formula (V)
(R in the formula
1And R
2Representative-(C respectively
1-C
5) alkyl or hydrogen atom; R representative-(C
1-C
5) alkyl; X represents a hydrogen atom, (C
1-C
5) alkyl or phenyl; N represents the integer of 0-2; But must work as R
2R during for hydrogen atom
1Be not hydrogen atom) representative the cyclopentane-carboxylic acid ester derivative,
B) resulting cyclopentane-carboxylic acid ester derivative is hydrolyzed decarboxylation obtains with formula IV
(R in the formula
1, R
2, X and n define as mentioned above) cyclopentanone derivatives of representative,
(c) with sulphur inner salt or oxygen sulphur inner salt the cyclopentanone derivatives of gained is carried out the oxyethane reaction, the methylene radical cyclopentane derivatives that maybe will derive from cyclopentanone derivatives carry out oxyethaneization with the uncommon reaction of prestige ladder, and the methylene radical cyclopentane derivatives is with formula III
（Ⅲ）
(R in the formula
1, R
2, X and n such as above-mentioned definition) represent it, be about to cyclopentanone derivatives thus and be transformed into formula II
(R in the formula
1, R
2, X and n such as above-mentioned definition) epoxyethane derivative of representative, then
D) with the epoxyethane derivative of gained and with formula VI
(representative one hydrogen atom or the alkali metal atom of M in the formula; A represents a nitrogen-atoms or CH) representative 1,2, the reaction of 4-triazole or imidazoles.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN91109197A CN1044659C (en) | 1987-06-30 | 1991-09-26 | Agricultural and horticultural composition comprising azole derivative |
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP16112687 | 1987-06-30 | ||
| JP161126/87 | 1987-06-30 | ||
| JP271277/87 | 1987-10-27 | ||
| JP62271277A JPH0625140B2 (en) | 1986-11-10 | 1987-10-27 | Novel azole derivative, method for producing the same and agricultural / horticultural drug of the derivative |
Related Child Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN91109197A Division CN1044659C (en) | 1987-06-30 | 1991-09-26 | Agricultural and horticultural composition comprising azole derivative |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1030232A CN1030232A (en) | 1989-01-11 |
| CN1020606C true CN1020606C (en) | 1993-05-12 |
Family
ID=26487374
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN88101050A Expired - Lifetime CN1020606C (en) | 1987-06-30 | 1988-02-27 | Process for producing azole deriv. |
Country Status (15)
| Country | Link |
|---|---|
| KR (1) | KR900003269B1 (en) |
| CN (1) | CN1020606C (en) |
| AR (1) | AR245703A1 (en) |
| CS (1) | CS274740B2 (en) |
| GE (1) | GEP19981269B (en) |
| HU (1) | HU206023B (en) |
| IE (1) | IE74147B1 (en) |
| IL (1) | IL85428A (en) |
| LV (1) | LV10436B (en) |
| MA (1) | MA21204A1 (en) |
| MD (1) | MD422C2 (en) |
| NZ (1) | NZ223444A (en) |
| RU (1) | RU2047605C1 (en) |
| TR (1) | TR26948A (en) |
| UA (1) | UA27101A1 (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EA016291B1 (en) | 2007-04-25 | 2012-03-30 | Басф Се | Fungicide mixtures |
| UA108867C2 (en) * | 2009-12-08 | 2015-06-25 | APPROACHES OF AZOLS, THE METHOD OF THEIR PRODUCTS (OPTIONS), INTERMEDIATES, AGRICULTURAL AND HORTICULTURAL PRODUCTS | |
| CN102067862A (en) * | 2011-02-19 | 2011-05-25 | 陕西美邦农药有限公司 | Ipconazole-containing bactericidal composition |
| CN102077839A (en) * | 2011-03-10 | 2011-06-01 | 陕西美邦农药有限公司 | Antibacterial composition containing ipconazole and triazole compounds |
| JPWO2012165499A1 (en) * | 2011-05-31 | 2015-02-23 | 株式会社クレハ | Triazole compounds and use thereof |
| EP2719693B1 (en) * | 2011-06-07 | 2016-08-10 | Kureha Corporation | Method for manufacturing oxetane compound, method for manufacturing azolylmethylcyclopentanol compound, and intermediate compound |
| US9241488B2 (en) | 2011-06-07 | 2016-01-26 | Kureha Corporation | Azole derivative, method for producing azole derivative, and intermediate compound |
| CA2838586C (en) | 2011-06-07 | 2016-10-11 | Kureha Corporation | Azole derivative, method for producing same, intermediate compound, and agricultural or horticultural chemical agent and industrial material protecting agent |
| JP5881733B2 (en) | 2011-11-25 | 2016-03-09 | 株式会社クレハ | Azole derivatives and uses thereof |
| US20150018560A1 (en) * | 2012-02-10 | 2015-01-15 | BASf ARGO B.V. ARNHEM (NL). ZURICH-BRANCH | Process for preparing cis-5-[1-(4-chlorophenyl)-methylene]-1-hydroxymethyl-2,2-dimethylcyclopentanol |
| UA114458C2 (en) | 2013-12-05 | 2017-06-12 | Куреха Корпорейшн | Agricultural and horticultural chemical, plant disease control method and plant disease control product |
| US9750254B2 (en) | 2013-12-05 | 2017-09-05 | Kureha Corporation | Agricultural or horticultural chemical, method of controlling plant diseases, and product for controlling plant diseases |
| CN104710372B (en) * | 2013-12-13 | 2017-12-15 | 上海交通大学 | Metconazole and preparation method thereof |
| CN106243087B (en) * | 2016-09-12 | 2018-10-09 | 三峡大学 | A kind of triazole pyrrolidones series bactericidal agent, synthetic method and its application |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4863505A (en) * | 1985-09-12 | 1989-09-05 | Kureha Kagaku Kogyo Kabushiki Kaisha | Novel derivative of azole, and agricultural and horticultural composition containing the same as an active incredient |
-
1988
- 1988-02-08 NZ NZ223444A patent/NZ223444A/en unknown
- 1988-02-11 IE IE37588A patent/IE74147B1/en not_active IP Right Cessation
- 1988-02-15 IL IL85428A patent/IL85428A/en not_active IP Right Cessation
- 1988-02-18 CS CS103388A patent/CS274740B2/en not_active IP Right Cessation
- 1988-02-23 AR AR88310141A patent/AR245703A1/en active
- 1988-02-26 KR KR1019880001977A patent/KR900003269B1/en not_active IP Right Cessation
- 1988-02-27 CN CN88101050A patent/CN1020606C/en not_active Expired - Lifetime
- 1988-03-08 MA MA21445A patent/MA21204A1/en unknown
- 1988-03-09 UA UA5052494A patent/UA27101A1/en unknown
- 1988-03-17 TR TR00202/88A patent/TR26948A/en unknown
- 1988-06-04 HU HU88604A patent/HU206023B/en unknown
-
1992
- 1992-08-12 RU SU5052494/04A patent/RU2047605C1/en active
-
1993
- 1993-06-29 LV LVP-93-766A patent/LV10436B/en unknown
- 1993-07-22 GE GEAP19931110A patent/GEP19981269B/en unknown
-
1994
- 1994-09-01 MD MD95-0292A patent/MD422C2/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| CS274740B2 (en) | 1991-10-15 |
| KR900003269B1 (en) | 1990-05-12 |
| HU206023B (en) | 1992-08-28 |
| KR890012981A (en) | 1989-09-20 |
| LV10436B (en) | 1996-08-20 |
| AR245703A1 (en) | 1994-02-28 |
| HUT47254A (en) | 1989-02-28 |
| CN1030232A (en) | 1989-01-11 |
| MA21204A1 (en) | 1988-10-01 |
| LV10436A (en) | 1995-02-20 |
| IE74147B1 (en) | 1997-07-02 |
| CS103388A2 (en) | 1990-12-13 |
| TR26948A (en) | 1994-09-12 |
| MD422C2 (en) | 1997-04-30 |
| IL85428A (en) | 1992-12-01 |
| NZ223444A (en) | 1990-06-26 |
| GEP19981269B (en) | 1998-07-07 |
| RU2047605C1 (en) | 1995-11-10 |
| UA27101A1 (en) | 2000-02-28 |
| IL85428A0 (en) | 1988-07-31 |
| IE880375L (en) | 1988-12-30 |
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