CN1061967A - Isothiazolcarboxylicacid acid derivatives contains the rice blast control agent of these derivatives and uses the rice blast of these control agent to prevent and treat method - Google Patents
Isothiazolcarboxylicacid acid derivatives contains the rice blast control agent of these derivatives and uses the rice blast of these control agent to prevent and treat method Download PDFInfo
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Abstract
In the paddy cultivation, containing rice blast (pyriculariaoryzae) is shown that the rice blast control agent of a kind of Isothiazolcarboxylicacid acid derivatives of excellent activity is applied on the water surface in rice field, make the paddy crop absorb this derivative by root, thereby strengthen the resistance against diseases of paddy crop, the structural formula of this derivative is as follows:
R wherein
1And R
2Represent hydrogen or halogen atom or specific group independently of one another, and Y represents an OR
3Base (R
3Be hydrogen or alkali metal atom or a special groups), a NHR
4Base (R
4Be a hydrogen atom or a special groups), or a morpholino base.
Description
The present invention relates in the paddy cultivation, show the Isothiazolcarboxylicacid acid derivatives that rice blast (Pyricularia oryzae) is had excellent activity, contain of the rice blast control agent of these derivatives, and use the rice blast of these control agent to prevent and treat method as activeconstituents.
The prevention and control of plant diseases, pest control plays an important role in the paddy cultivation.Rice blast (Pyricularia oryzae) is a kind of disease of especially severe, has therefore developed and has used multiple mycocide and prevented and treated method.Yet, can not think that these prevent and treat method or mycocide is in full force and effect.In fact, they include, and one or more still need overcome, as the shortcoming of prevention effect aspect.In the open NO.1995/1968 of Japanese Patent, disclose some Isothiazolcarboxylicacid acid derivatives and had fungicidal and Bactericidal activity, wherein described Isothiazolcarboxylicacid acid ester class and amine salt class the tomato disease that is caused by Xanthomonas vesicatoria, the soybean diseases and the wildfire that are caused by Uromyces phaseoli var typica are demonstrated prevention effect.But this patent disclosure is not mentioned the effect of these medicaments to rice blast.
In addition, U.S. Pat 3,341 547(1967) discloses isothiazole carbonization acid amides and has had the weedkiller effect.
But, can not be owing to judging that they effectively draw the conclusion that specified disease is had special-effect to other diseases.Also prove by the known fact or empirical law, herbicidal effect can not be discussed in a similar fashion and the control of specific disease.For example, agricultural streptomycin is used to the crop pest of preventing and treating wildfire and being caused by Xanthomonas, but it demonstrates rice blast and does not have effect fully.On the contrary, be widely used as rice blast and prevent and treat the Fujione of agent, pyrochelon etc., showing does not have any effect to other diseases.
Rice blast is a kind of disease that causes the rice field grievous injury.Thereby, tested the various method of preventing and treating so far.Recently.The chemical agent of some kind is used as the mycocide of control rice blast.Yet their aspect a lot (as fungicidals) are not have enough effects.
Usually, can test the validity or the ineffectivity of mycocide in vitro.Effect at experiment desk research mycocide is easy.This is because mycocide directly acts on the corresponding fungi.Yet, the disease that some does not have the chemical agent of fungicidal effect but can prevent and treat crop in vitro.But this class indirect effect can not be tested in test tube under many occasions, therefore is difficult for studying them.
In order to overcome the existing problem of above-mentioned conventional control medicament, the inventor studies in the possible effect aspect the control rice blast different compounds.As a result, found that some special Isothiazolcarboxylicacid acid derivatives has good prevention effect to rice blast, therefore caused of the present invention finishing.
Although these derivatives itself do not present significant anti-mycotic activity to pyricularia oryzae, they have can be to paddy generation effect, thereby strengthens the special performance of the ability of paddy opposing rice blast.
Thereby, the invention provides a kind of rice blast control agent, this control agent contains a kind of Isothiazolcarboxylicacid acid derivatives of being represented by following formula I as activeconstituents:
R wherein
1Represent a hydrogen or halogen atom or C
1-4Alkyl or C
1-3Alkoxyl group, R
2Represent hydrogen or halogen atom or nitro or C
1-4Alkyl, Y are represented an OR
3Base (R
3Be hydrogen or alkali metal atom, C
1-4Alkyl or a NHR
5R
6R
7Base, R
5, R
6And R
7Be a hydrogen atom or C
1-4Alkyl), NHR
4Base (R
4Be a hydrogen atom, the C of a straight or branched
1-16Alkyl, C
5-7Cycloalkyl, cyclohexenyl, dimethylamino or furfuryl group, or by one or more C
1-8Alkoxyl group, C
1-3Alkyl sulfide, the C that phenyl and/or halogenophenyl replace
1-4Alkyl), or the morpholino base, the present invention also provides the method for preparing this derivative, contains the rice blast control agent of this derivative as activeconstituents, and uses the rice blast of this control agent to prevent and treat method.
When using this control agent by submergence manipulation rice field, this derivative is absorbed in the paddy crop, therefore its resistance against diseases is significantly strengthened.
Although the included Isothiazolcarboxylicacid acid derivatives of some above-mentioned formula I is known compound, its amide derivatives is new compound.Having known does not so far have a kind ofly on any practical level rice blast is had prevention effect in these compounds.
Compound of the present invention has very unique effect, although they do not have significant anti-mycotic efficiency to pyricularia oryzae, even or have anti-mycotic efficiency also very a little less than, they demonstrate the good prevention effect to rice blast.Can think, any rice blast control agent of the present invention is applied to the paddy crop all can promotes in paddy is made object, to generate a kind of antimycotic material, as phytoalexin, therefore make plant that the infringement that disease causes is produced resistivity, pyricularia oryzae and avoid development of disease protects from infection.By the neither effect that can find that these are unique of any anti-microbial test that carries out usually so far (as the culture dish test).
Embodiment among the open NO.1995/1968 of Japanese Patent has described the tomato disease of Isothiazolcarboxylicacid acid ester class to being caused by Xanthomonas Vesicatoria, soybean diseases that is caused by Uromyces phase oli var.typica and wildfire demonstrate prevention effect and to the fungi of some kind, as Aspergillus niger, Penicillium expansum and Alternaria solani etc. has anti-mycotic efficiency.
Found now derivative of the present invention to effective rice blast different fully with above-mentioned disease, it is a kind of infectious disease of paddy that makes.Even consider example in the past, also quite clear, at all can not be according to other disease effective chemical medicaments are derived above-mentioned disease effective chemical medicament.For example, the disease that agricultural streptomycin can be used for wildfire or caused by Xanthomonas, but the disease that is caused by pyricularia oryzae is not demonstrated any effect.On the contrary, be widely used as the Fujione of rice blast control agent, pyroguilon etc. show without any effect other diseases.
In the compound of being represented by formula I, those compounds that can demonstrate better rice blast prevention effect are Isothiazolcarboxylicacid acid derivatives, and wherein Y is by OR
5Representative, and R
3Be hydrogen or alkali metal atom, or by NHR
4Representative, and R
4Be the C of a hydrogen atom or a straight or branched
1-16Alkyl.It is more effective as the rice blast control agent of activeconstituents to contain them.
Although some included compound of formula I is hitherto known compound, the Isothiazolcarboxylicacid acid amide derivatives of being represented by following formula II is new compound.
R wherein
1Represent a hydrogen or halogen atom or C
1-4Alkyl or C
1-3Alkoxyl group, R
2Represent a hydrogen or halogen atom or nitro or C
1-4Alkyl, Y
1Represent a NHR
4Base (R
4Be straight or branched C
1-16Alkyl, C
5-7Cycloalkyl, cyclohexenyl, dimethylamino or furfuryl group, or by one or more C
1-8Alkoxyl group, C
1-3The C that alkyl sulfide, phenyl and/or halogenophenyl replaced
1-4Or the morpholino base alkyl).
Energy shows that the new compound of better rice blast prevention effect can comprise the Isothiazolcarboxylicacid acid amide derivatives of formula II, wherein Y
1Represent a NHR
4Base, R
4Be a hydrogen atom or straight or branched C
4-16Alkyl.
Can prepare the represented compound of formula II according to following reaction formula 1,2 and 3 pointed methods according to open NOS.1995/1968 of Japanese Patent and 21432/1968 disclosed mode.
Be not known compound by the included formula I compound of formula II.Wherein Y represents one-O
-+NHR
5R
6R
7Base, these compounds can make according to following reaction scheme 4:
Reaction scheme 4
Relevant to preparation new compound of the present invention the represented reaction of reaction scheme 3, will be discussed in more detail below.
With thionyl chloride isothiazole-5-carboxylic acid derivative (4) is changed into carboxylic acid chloride (7) by method well known in the prior art.Even though isothiazole-5-carboxylic acid derivative (4) is mixed simply with thionyl chloride and heat, reaction also can successfully be carried out, react and in benzene, toluene or other inert solvents, carry out mostly.It is following after 1-3 hour to be reflected at backflow, removes excessive thionyl chloride with distillation method.Interpolation such as benzene or toluene equal solvent are removed thionyl chloride fully with distillation method subsequently.Residue can be used as the carboxylic acid chloride in the subsequent step.
With a kind of compound reaction of resulting chloride of acid (7), can obtain isothiazole-5-carboxylic acid amide derivative (8) thus then with amine.Conventional acid amides synthetic method all can be used for this amidation.Hereinafter will introduce a kind of representational method.Chloride of acid is dissolved in a kind of inert solvent; as benzene,toluene,xylene, tetrahydrofuran (THF), dioxan, ethyl acetate, chloroform or dimethyl formamide etc.; with the equivalent that is equivalent to or slightly surpasses carboxylic acid chloride (7) to wherein adding a kind of alkali, as triethylamine or pyridine.The mixture that is obtained is cooled off on ice-water bath, under 5-10 ℃, add amine gradually.Although this reaction can be carried out under many occasions instantaneously, usually reaction mixture is stirred under identical temperature additional 30 minutes to 1 hour so that react completely.Can use 2 equivalents or more the amine of volume replace alkali, carry out this reaction as triethylamine or pyridine.
After reacting completely, add a large amount of water, add solvent subsequently, as ethyl acetate, benzene or toluene to carry out extracting operation.Wash organic solvent with hydrochloric acid, sodium bicarbonate aqueous solution and water successively, use dried over sodium sulfate then.Adopt the solvent distillation method can obtain the straight product of isothiazole-5-carboxylic acid amide derivative (8).If desired, can make high purity product by recrystallization or column chromatography.
The preparation method of the Isothiazolcarboxylicacid acid derivatives that formula II is represented can be summarized as follows:
Prepare a kind of method by the Isothiazolcarboxylicacid acid amide derivatives that descends formula II to represent:
R wherein
1Represent a hydrogen or halogen atom or C
1-4Alkyl or C
1-3Alkoxyl group, R
2Represent hydrogen or halogen atom or nitro or C
1-4Alkyl, Y
1Expression NHR
4Base (R
4Be a hydrogen atom, straight or branched C
4-16Alkyl, C
5-7Cycloalkyl, cyclohexenyl, dimethylamino or furfuryl group, or by one or more C
1-6Alkoxyl group, C
1-3The C that alkyl sulfide, benzene and/or halogenophenyl replaced
1-4Alkyl), or a morpholino base, this method comprises the chloride of acid of representing by following formula III
(R wherein
1And R
2Definition the same) with a kind of amine reaction of representing by following formula IV:
(R wherein
4Represent a hydrogen atom, a straight or branched C
4-16Alkyl, C
5-7Cycloalkyl, cyclohexenyl, dimethylamino or furfuryl group, or by one or more C
1-6Alkoxyl group, C
1-3The C that alkyl sulfide, phenyl and/or halogenophenyl replace
1-4Alkyl), or with the morpholino radical reaction.
Can be with agricultural fungicidal agent of the present invention and agrochemicals medicament, be mixed with mixed preparation as other mycocides, sterilant, weedkiller and plant-growth regulator, soil improvement agent or fertilizer material and use, combine jointly with them and just used let alone.
Although compound of the present invention can use separately, be preferably it and carrier, comprise that the form that solid or liquid filling agent are mixed into composition uses.Term used herein " carrier " is meant synthetic or natural, inorganic or organic material, add them to strengthen the characteristic that the present invention prevents and treats agent, promptly help to absorb this derivative by the paddy crop root, when submergence is used, just give the ability of paddy crop disease-resistant evil thus, also help simultaneously to store, transport and manage as the compound of activeconstituents.
Suitable solid carrier comprises that for example clay if you would take off stone, kaolin and wilkinite; Inorganic substance are as diatomite, terra alba, talcum, vermiculite, gypsum, lime carbonate, silica gel and ammonium sulfate; Plant organic matter matter is as Semen sojae atricolor pulp, sawdust and wheat-flour; And urea.
Suitable liquid vehicle comprises, arene for example is as toluene, dimethylbenzene and isopropyl benzene; Paraffin-type is as kerosene and mineral oil; Halogenated hydrocarbon is as tetracol phenixin, chloroform and ethylene dichloride; Ketone is as acetone and methyl ethyl ketone; Ethers is as diox, tetrahydrofuran (THF) and diethylene glycol dimethyl ether; Alcohols is as methyl alcohol, ethanol, propyl alcohol and glycol ether; Dimethyl formamide; Methyl-sulphoxide; And water.
In addition,,, and consider factors such as preparation method and employed farmland, can separately or be used in combination those auxiliarys as described below according to purpose in order to strengthen the effect of The compounds of this invention.
For emulsification, dispersion, distribution, wetting, bonding or purpose such as stable, can add following auxiliary: anion surfactant, as lignosulfonic acid salt, alkyl benzene sulfonate, alkylsurfuric acid salt, polyoxy alkylidene alkylsurfuric acid salt and polyoxy alkylidene alkyl phosphate class; Nonionic surface active agent is as polyoxyalkylene alkyl ether class, polyoxy alkylidene alkaryl ethers, polyoxy alkylidene alkyl amine, polyoxy alkylidene alkylamide, polyoxy alkylidene alkyl sulfide ethers.Polyoxy alkylidene fatty acid ester, glycerol fatty acid ester class, fatty acid esters of sorbitan class, polyoxy alkylidene fatty acid esters of sorbitan class and polyoxy propylidene-polyoxyethylene block copolymer; Lubricant is as calcium stearate and paraffin; Stablizer is as phosphoric acid hydrogen isopropyl ester; Methylcellulose gum; Carboxymethyl cellulose; Casein; Gum arabic or the like.Must point out that auxiliary is not limited to above-named those materials.
The significant quantity of all cpds of the present invention is 0.5-20%(weight usually in pulvis), in emulsion 5-50%(weight), but be 9-90%(weight in wet-milling), be 0.1-20%(weight in granular preparation), and be 9-90%(weight in mobile preparation).On the other hand, the amount of carrier is 60-99%(weight usually in pulvis in various preparations), but be 9-90%(weight in wet-milling), be 80-99%(weight in granular preparation), be 40-95%(weight in emulsion), and be 9-90%(weight in mobile preparation).In addition, the total amount of auxiliary is 0.1-20%(weight usually in pulvis), be 1-20%(weight in emulsion), but be 0.1-20%(weight in wet-milling), be 0.1-20%(weight in granular preparation), and be 0.1-20%(weight in mobile preparation).
Rice blast of the present invention control agent available and it in the paddy cultivation, exist the whole growth stage of pyricularia oryzae potentially dangerous all to demonstrate fabulous prevention effect.
When they are used to, before for example in cultivation usually, transplanting during the rice seedling bed in cultivation stage, be every case (40-80g of 60cm * 30cm), or when being expressed as 0.2-2g activeconstituents/case with the amount of activeconstituents, they can demonstrate its effect at rate of application.During rice field after they are applied to transplanting, can be next to and transplant the back and use them and be the 0.5-5kg/10 are in during wearing this whole section in boots (Booting), or they can demonstrate its activity when being shown the 25-250g/10 are with the scale of activeconstituents at rate of application.
Certainly, do not adopt transplanting, for example adopting in the method that directly sowing is cultivated, also can use similar processing.
By this application process, it can promote to form a kind of antimycotic material in paddy is made object, and this material plays opposing pyricularia oryzae, thereby strengthens the resistivity to disease.
Thereby each control agent of the present invention need expend some times and could show its prevention effect after using, and this is not directly act on pyricularia oryzae because of this control agent, but the resistivity of enhancing paddy itself.Thereby what meet the requirements is that the control agent can take place near expection before time of rice blast to use in 2-50 days.Although this control agent is compared with the agent of used those control so far, its effect can keep the much longer time, and frequency of utilization is generally per season 1-3 time.
Below the preparation method of some Isothiazolcarboxylicacid acid derivatives of formula I of the present invention will be described by following embodiment.
Embodiment 1
Synthesizing of 3-methyl-5-Isothiazolcarboxylicacid acid (compound N O.1)
5-cyano group-3-methyl-isothiazole (10.5g) in 100ml 2N aqueous sodium hydroxide solution, was heated 2 hours down in refluxing.Formed homogeneous solution is cooled to room temperature, and further uses ice-cooled.With concentrated hydrochloric acid its PH is transferred to 3-4 then.With the crystallization of filtration method collecting precipitation,, obtain 10.1g 3-methyl-5-Isothiazolcarboxylicacid acid (productive rate: 83.4%) thus then under reduced pressure in 60 ℃ of dryings.Fusing point 203-204 ℃.
Embodiment 2
3,4-two chloro-5-Isothiazolcarboxylicacid acids (compound N is O.2) synthetic
1) 5-cyano group-3,4-two chloroisothiazoles synthetic
Sodium cyanide (49.0g) is added in the 500ml dimethyl formamide, then under agitation in one hour, drip 76.1g dithiocarbonic anhydride in room temperature.Owing to making the temperature of reaction mixture, heat release reaches 30 ℃.After dropwising, at room temperature stirred this mixture one hour and 60 ℃ of restir 3 hours.Reaction mixture was at room temperature kept 12 hours, have a large amount of crystalline deposits to come out during this period.The crystallization that obtains so under agitation is dispersed in the reaction mixture, chlorine is spurted in the reaction mixture.When making internal temperature reach 70 ℃, reaction mixture put in the water-bath cool off owing to originally heat release.When internal temperature is reduced to 65 ℃, remove water-bath.This operation was carried out 2.5 hours, and the amount of chlorine that adjusting simultaneously sprays into is to remain on temperature 60-65 ℃.Make reaction continue again to weaken until exothermic effects in 30 minutes, and at this moment internal temperature is reduced to 35 ℃.At room temperature spray nitrogen 1 hour then so that remaining chlorine is disposed.
When under high degree of agitation, being added dropwise to reaction mixture in the 1500ml water, being settled out crystallization and following heat release and foaming.At this moment cool off so that water temperature remains in the 35-60 ℃ of scope.After dropwising, reduce to till 5 ℃ until the temperature of mixture in ice-cold following mixture that obtains stirring.Be dissolved in the 500ml ethyl acetate with the precipitation of filtration method collection generation and with it then.After insoluble substance is filtered out, make the filtrate drying with anhydrous magnesium sulfate.After under reduced pressure distilling solvent, obtain orange-yellow plate crystal.These crystallizations are placed the methyl alcohol recrystallization of trying one's best few, obtain 5-cyano group-3 thus, 4-two chloroisothiazoles, productive rate are 87.6%.Fusing point 84.5-85 ℃.
2) 3,4-two chloro-5-Isothiazolcarboxylicacid acids synthetic
With 19.6g at embodiment 2-1) in the 5-cyano group-3 of gained, 4-two chloroisothiazoles place 400ml 2N aqueous sodium hydroxide solution, in the heating down 2 hours that refluxes.Reaction mixture is chilled to 5 ℃, adds concentrated hydrochloric acid then the pH value of mixture is transferred to 3-4.Put recrystallization in the boiling water with the crystallization of filtration method collecting precipitation and with it, obtain 18.8g white crystals (fusing point 178-179 ℃) (productive rate: 86.5%) thus.
Infrared spectra (cm
-1, directrix):
2982-2751，2754，1733，1513，1502，1419，1377，1344，1315，1225，1111，968，856，832，702
Ultimate analysis:
C??H??N??Cl??S
Calculated value (%) 24.36 0.51 7.07 35.81 16.16
Measured value (%) 23.38 0.59 7.49 34.95 16.06
The data of ultimate analysis and infrared spectra show that white crystals is 3,4-two chloro-5-Isothiazolcarboxylicacid acids.
Embodiment 3
Synthesizing of N-normal-butyl-3-methyl-5-Isothiazolcarboxylicacid acid acid amides (compound 19)
3-methyl-5-Isothiazolcarboxylicacid acid (2.3g) is dissolved in the 40ml ethyl acetate.After adding the 2g triethylamine, the mixture that obtains is cooled off and dropping 1.5g n-Butyl Amine 99 under 5-10 ℃ with ice-water bath.After dripping end, continue to stir 30 minutes.Use sodium bicarbonate aqueous solution and water washing reaction mixture successively.After with dried over sodium sulfate, distillation removes and desolvates, and the result obtains 2.60g buttery N-normal-butyl-3-methyl-5-Isothiazolcarboxylicacid acid acid amides.
Embodiment 4
3,4-two chloro-N-n-pentyls-5-Isothiazolcarboxylicacid acid acid amides (compound N is O.29) synthetic
Thionyl chloride (6ml) is added 0.60g 3, in the 4-two chloro-5-Isothiazolcarboxylicacid acids, refluxed subsequently 30 minutes.After excessive thionyl chloride was removed in distillation, the adding benzo under reduced pressure distills removed low-boiling point material.Tetrahydrofuran (THF) (15ml) and triethylamine (0.5g) are added in the residue, drip the solution of 0.38g n-amylamine in tetrahydrofuran (THF) in 5-10 ℃ down ice-cooled subsequently.Obtaining mixture stirring at room 30 minutes, then with this mixture impouring substantially in ponding.The aqueous solution that is obtained with the 100ml ethyl acetate extraction is handled with the method that is similar to synthetic example 3 subsequently then.Obtain a kind of buttery 3,4-two chloro-N-n-pentyls-5-Isothiazolcarboxylicacid acid acid amides (output: 0.75g).
The preparation method of ester class, alkaline metal salt and amine salt class will be described below.
Embodiment 5
3,4-two chloroisothiazoles-5-carboxylic acid isopropyl acid ester (compound N is O.6) synthetic
Thionyl chloride (20g) is added 1.5g 3, in 4-two chloroisothiazoles-5-carboxylic acid and under refluxing with the mixture heating up that obtained 1 hour.Excessive thionyl chloride is removed in distillation under reduced pressure, adds a small amount of benzo then and under reduced pressure distills solvent once more to remove the thionyl chloride of trace.In residue, add anhydrous diethyl ether (10ml), obtain acyl chloride solution thus.
2-propyl alcohol (0.54g) and triethylamine (0.92g) are dissolved in the anhydrous diethyl ether, under ice-cooled, to wherein being added dropwise to the above-mentioned acyl chloride solution that makes.Make it 30 ℃ of reactions 30 minutes then, and remove by filter insolubles, filtrate is concentrated, then (normal hexane: ethyl acetate=9: 1) purify, obtain the 1.02g title compound on silicagel column by chromatogram.
Embodiment 6
3,4-two chloroisothiazoles-5-carboxylic acid potassium (compound N is O.7) synthetic
The potassium hydroxide (0.27g) that will be dissolved in the 3ml water adds 3, and 4-two chloroisothiazoles-5-carboxylic acid (0.95g) is in 4ml alcoholic acid solution.Distillation under reduced pressure removes desolvates.Crystallization with small amount of ethanol washing gained.
Embodiment 7
3,4-two chloro-5-Isothiazolcarboxylicacid acid acid amides (compound N is O.4) synthetic
The vitriol oil (10ml) is added 1.0g 5-cyano group-3, in 4-two chloroisothiazoles.When after heating 20 minutes under 110 ℃, isothiazole compounds dissolves fully.With reaction mixture with ice-cooled, and with the crystallization of filtration method collecting precipitation.Then obtaining crystallization is placed the mixed solvent of 1: 1 second alcohol and water to carry out recrystallization.
Embodiment 8
Synthesizing of 3-methyl-Isothiazolcarboxylicacid acid triethyl ammonium salt (compound N O.8)
3-methyl-5-Isothiazolcarboxylicacid acid (1.0g) is dissolved in the 10ml anhydrous tetrahydro furan, under agitation in room temperature to wherein dripping the solution of 0.72g triethylamine in the 5ml anhydrous tetrahydro furan.At room temperature with the mixture restir that obtains 30 minutes, distillation under reduced pressure removed and desolvates then, and the result obtains the 1.71g(stoichiometric quantity) title compound.
Embodiment 9
Synthesizing of 3-methyl-5-Isothiazolcarboxylicacid acid sec.-propyl ammonium salt (compound N O.9)
3-methyl-5-Isothiazolcarboxylicacid acid (1.0g) is dissolved in the 10ml anhydrous tetrahydro furan, under agitation in room temperature to wherein dripping the solution of 0.41g Isopropylamine in the 5ml anhydrous tetrahydro furan.Carrying out along with dripping forms white crystals simultaneously.At room temperature the reaction mixture restir after 30 minutes, is collected crystallization also with a small amount of anhydrous tetrahydro furan washing with filtration method.Under reduced pressure in 40 ℃ with crystallizing and drying 3 hours, the result obtains 1.20g title compound (productive rate: 85%).
Embodiment 10
3,4-two chloro-5-Isothiazolcarboxylicacid acid triethyl ammonium salts (compound N is O.10) synthetic
With the 1.0g 3 of embodiment 2 gained, 4-two chloro-5-Isothiazolcarboxylicacid acids are dissolved in the 10ml anhydrous tetrahydro furan, drip the solution of 0.52g triethylamine in the 5ml anhydrous tetrahydro furan subsequently.At room temperature with the mixture restir of gained 30 minutes, distillation under reduced pressure removed and desolvates then, and the result obtains the 1.51g(stoichiometric quantity) title compound.
Embodiment 11
3,4-two chloro-5-Isothiazolcarboxylicacid acid sec.-propyl ammonium salts (compound N is O.11) synthetic
With the 1.0g 3 of embodiment 2 gained, 4-two chloro-5-Isothiazolcarboxylicacid acids are dissolved in the 10ml anhydrous tetrahydro furan.At room temperature stir the mixture that is obtained, drip the solution of 0.30g Isopropylamine in the 5ml anhydrous tetrahydro furan simultaneously.Carrying out along with dripping forms white crystals simultaneously.At room temperature, collect crystallization with filtration method, then with a small amount of anhydrous tetrahydro furan washing with the mixture restir that obtains 30 minutes.Under reduced pressure in 40 ℃ with crystallizing and drying 30 minutes, the result obtains 1.10g title compound (productive rate: 85%).
According to the foregoing description, can be by using easily synthetic other compounds of the present invention of already known processes.Representative compounds (compound that comprises the foregoing description) is shown in table 1.
Although can use these pure compounds, use more effective with dosage form it.The example of preparation will be described below.Must point out that the example of following preparation is that the mode by embodiment provides.All " parts " or " umber " all is meant " weight part or umber " or " %(weight) " among the following embodiment.
Example of formulations 1(granular preparation)
With 5 parts of 3-methyl isothiazole-5-carboxylic acids (compound N is O.1), 22 parts of wilkinites, 70 parts of talcums, 3 parts of " Sorpol (sorpol) 5060 " (tensio-active agents; The trade(brand)name that Toho chemical Industry Co.Ltd. produces) and a small amount of defoamer be mixed into homogeneous material, granulate by basket nodulizer, drying then, the result has obtained granular preparation.
Example of formulations 2(granular preparation)
With 5 part 3,4-two chloroisothiazoles-5-carboxylic acid (compound N is O.2), 60 parts of wilkinites, 31 parts of talcums, 1 part of Sodium dodecylbenzene sulfonate, 1 part of polyoxyethylene alkyl aryl ether and 2 parts of sodium lignosulfonates mix.In this mixture, add suitable quantity of water and mixing.With obtaining material pelletization and with method drying well known in the prior art, the result obtains 100 parts of granular preparations with nodulizer.
Example of formulations 3(granular preparation)
With 5 part 3,4-two chloroisothiazoles-5-carboxylic acid amide (compound N is O.4), 35 parts of wilkinites, 57 parts of talcums, 2 parts of sodium lignosulfonates and 1 part of Sodium dodecylbenzene sulfonate mix.In mixture, add suitable quantity of water and mixing.With obtaining material pelletization and with method drying well known in the prior art, the result obtains 100 parts of granular preparations with nodulizer.
Example of formulations 4(granular preparation)
With 5 part 3,4-two chloroisothiazoles-5-carboxylic acid potassium (compound N is O.5), 60 parts of wilkinites, 31 parts of clays, 2.5 parts of sodium alkyl benzene sulfonates and 0.5 part of polyvinyl alcohol grind and are mixed into uniform mixture.In this mixture, add suitable quantity of water and mixing.With obtaining material pelletization and with method drying well known in the prior art, the result obtains 100 parts of granular preparations with nodulizer.
Example of formulations 5(granular preparation)
With 2 parts of 3-methyl-N-n-octyl isothiazole-5-carboxylic acid amide (compound N is O.23), 94.7 parts of clays, 0.2 part of dialkyl sulfosuccinate, 0.1 part of sodium alkyl sulfate and 3.0 parts of poly carboxylic acid sodium grind and are mixed into uniform mixture.In this mixture, add suitable quantity of water and mixing.With obtaining material pelletization and with method drying well known in the prior art, the result obtains 100 parts of granular preparations with nodulizer.
Example of formulations 6(granular preparation)
3 parts of N-n-heptyls-3-methyl isothiazole-5-carboxylic acid amide (compound N O.22), 93.5 parts of clays, 0.5 part of dialkyl sulfosuccinate and 3 parts of carboxymethyl celluloses are ground and are mixed into uniform mixture.In this mixture, add suitable quantity of water and mixing.With obtaining material pelletization and with method drying well known in the prior art, the result obtains 100 parts of granular preparations with nodulizer.
But example of formulations 7(wet-milling)
With 50 parts of N-normal-butyls-3-methyl-5-Isothiazolcarboxylicacid acid acid amides (compound N O.19), 40 parts of lime carbonate, 5 parts " solpol 5039 " (mixture of anion surfactant and white carbon; The trade(brand)name that Toho Chemical Industry Co.Ltd. produces) but and 5 parts of white carbon mix equably and grind to form wet-milling.
But example of formulations 8(wet-milling)
With 70 parts of N-n-pentyls-3-methyl-5-Isothiazolcarboxylicacid acid acid amides (compound N is O.20), 25 parts of kaolin, 3 parts " solpol 5039 " but and 2 parts of white carbon mix equably and grind to form wet-milling.
But example of formulations 9(wet-milling)
With 50 parts of N-n-hexyls-3-methyl-5-Isothiazolcarboxylicacid acid acid amides (compound N is O.21), 40 parts of lime carbonate, 5 parts " solpol 5039 " but and 5 parts of white carbon mix equably and grind to form wet-milling.
But example of formulations 10(wet-milling)
With 70 parts of N-n-heptyls-3-methyl-5-Isothiazolcarboxylicacid acid acid amides (compound N is O.22), 25 parts of kaolin, 3 parts " solpol 5039 " but and 2 parts of white carbon mix equably and grind to form wet-milling.
But example of formulations 11(wet-milling)
At 40 part 3,4-two chloro-N-n-hexyls-5-Isothiazolcarboxylicacid acid acid amides (compound N is O.30), 5 portions of " solpol3353 " (nonionogenic tensides; The trade(brand)name that Toho Chemical Industry Co.Ltd produces), 5 part of 1% xanthan gum solution among 40 parts of water and the 10 parts of 1,2 ethylene glycols, is combined into uniform solution with the composition beyond the activeconstituents earlier.Add compound of the present invention then.By after stirring, in sand mill with this mixture wet-milling, but the result has obtained wet-milling.
Example of formulations 12(emulsion)
With 20 part 3,4-two chloro-N-n-octyls-5-Isothiazolcarboxylicacid acid acid amides (compound N O.32), 55 parts of dimethylbenzene, 20 parts of N, dinethylformamide and 5 parts of " solpol2680 " (tensio-active agents, the trade(brand)name that Toho Chemical Industry Co., Ltd. produce) is uniformly mixed into emulsion.
The mobile preparation of example of formulations 13()
40 parts of N-n-heptyls-3-methyl-5-Isothiazolcarboxylicacid acid acid amides (compound N O.22), 5 parts " solpol3353 ", 5 part of 1% xanthan gum solution, 40 parts of water and 10 part 1, among the 2-ethylidene glycol, earlier the composition beyond the activeconstituents is mixed into homogeneous solution.Add compound of the present invention then.After stirring, with this mixture wet-milling, the result obtains mobile preparation in sand mill.Example of formulations 14(pulvis)
10 fens N-n-octyl-3-methyl-5-Isothiazolcarboxylicacid acid acid amides (compound N O.23), 90 parts of clays are mixed equably, and the result obtains a kind of pulvis.
Example of formulations 15(pulvis)
With 5 part 3,4-two chloro-N-n-heptyls-5-Isothiazolcarboxylicacid acid acid amides (compound N O.31), 40 parts of clays and 55 parts of talcums grind and mixing, and the result obtains a kind of pulvis.
The good rice blast prevention effect that will be produced in the time of will describing use rice blast control of the present invention agent specially by following test below.
Test 1(rice blast prevention effect test-processing rice seedling bed)
In each test, handle in the rice seedlings field bed (rice seedling (kind: Mangetsu Mochi of cultivating among the 30cm * 60cm) with every seedbed rate of utilization of being scheduled to the granular preparation of example of formulations 2 gained; Two leaf stage).After three days, be transplanted to rice seedling among 1/5000 are of Wa Shi (Wagner) jar and in the greenhouse, cultivate.Transplanted back 30 days, injection pyricularia oryzae spore suspension is also cultivated on the paddy crop.Make then the paddy crop under high humidity in 25 ℃ the growth 1 week, calculating foci numbers then.Calculate the control value according to following formula.The result of three revision tests is summarized in the table 2.
Control value (%)=1-(handling the focus number in the jar)/(the focus number in the jar that is untreated) * 100
Table 2-1
* control compounds A: thiabendazole [3-allyloxy-1,2-benzisothiazole-1,1-dioxide]
Table 2-2
* control compounds
Table 2-3
* control compounds
Test 2(rice blast prevention effect test-immersion method is used test)
In each test, with rice seedling (kind: Mangetsu Mochi; 3 leaf phases) migrate in 1/10000 are of Wa Shi jar, then 1 week of cultivation in the greenhouse.On the water surface, handle rice seedling by prepared granular preparation in the use example of formulations 2 with every are of predetermined rate of utilization.After 30 days, injection pyricularia oryzae spore suspension is also cultivated on the leaf of paddy crop.Make then the paddy crop under high humidity in 25 ℃ the growth 1 weeks, with 1 weekly interval calculating foci number.The results are shown in Table 3 with three revision tests.
Table 3-1
Table 3-2
* control compounds
Test 3(is to the anti-mycotic activity of pyricularia oryzae)
In each test, the pyricularia oryzae of a bacterium colony dish (diameter 6mm) is inoculated in the PDA substratum that contains the 100ppm compound.This substratum after 5 days, is detected the mycelial growth degree 25 ℃ of cultivations.The results are shown in Table 4.
Table 4-1
From testing 1,2 and 3 result can find out, compare with thiabendazole (used contrast mycocide in the jar test of the paddy crop of practical application), these Isothizole derivatives do not show the significant anti-mycotic activity to pyricularia oryzae, but it has been shown higher prevention effect.Thereby they are effective to control pyricularia oryzae in paddy cultivation.
Although described the present invention, should be understood that to those skilled in the art various changes and modifications all are conspicuous with preferable embodiment.These changes and improvements all considered to be within the authority and scope of claims.
Claims (8)
1, a kind of rice blast control agent, it contains a kind of as activeconstituents, the Isothiazolcarboxylicacid acid derivatives of being represented by formula I down:
(Ⅰ)
R wherein
1Represent a hydrogen or halogen atom or C
1-4Alkyl or C
1-3Alkoxyl group, R
2Represent hydrogen or halogen atom or nitro or C
1-4Alkyl, and Y represents an OR
3(R
3Be hydrogen or alkali metal atom, C
1-4Alkyl or NHR
5R
6R
7Group; R
5, R
6And R
7Be a hydrogen atom or C
1-4Alkyl), NHR
4Base (R
4Be a hydrogen atom, a straight or branched C
1-16Alkyl, C
5-7Cycloalkyl, cyclohexenyl, dimethylamino, or furfuryl group, or by one or more C
1-6Alkoxyl group, C
1-3The C that alkyl sulfide, phenyl and/or halogenophenyl replace
1-4Or a morpholino base alkyl).
2, the reagent of claim 1, wherein Y represents an OR
3Base, R
3Be hydrogen or alkali metal atom, or represent a NHR
4Base, R
4Be hydrogen or straight or branched C
1-16Alkyl.
3, a kind of Isothiazolcarboxylicacid acid amide derivatives of representing by following formula II:
（Ⅱ）
R wherein
1Represent a hydrogen or halogen atom or C
1-4Alkyl or C
1-3Alkoxyl group, R
2Represent hydrogen or halogen atom or nitro or C
1-4Alkyl, and Y
1Represent a NHR
4Base (R
4Be straight or branched C
4-16Alkyl, C
5-7Cycloalkyl, cyclohexenyl, dimethylamino or furfuryl group, or by one or more C
1-6Alkoxyl group, C
1-3The C that alkyl sulfide, phenyl and/or halogeno-benzene group replace
1-4Or a morpholino base alkyl).
4, the derivative of claim 3, wherein Y ' represents a NHR
4Base, R
4Be straight or branched C
4-16Alkyl.
5, a kind of method for preparing the Isothiazolcarboxylicacid acid amide derivatives, this derivative is represented by following formula II:
（Ⅱ）
R wherein
1Represent a hydrogen or halogen atom or C
1-4Alkyl or C
1-3Alkoxyl group, R
2Represent hydrogen or halogen atom or nitro or C
1-4Alkyl, and Y ' represents a NHR
4Base (R
4Be a hydrogen atom, a straight or branched C
4-16Alkyl, C
5-7Cycloalkyl, cyclohexenyl, dimethylamino or furfuryl group, or by one or more C
1-8Alkoxyl group, C
1-3The C that alkyl sulfide, phenyl and/or halogenophenyl replace
1-4Alkyl), or a morpholino base, this method comprises a kind of chloride of acid of representing by following formula III:
(R wherein
1And R
2Identical with above-mentioned definition), react with the amine of representing by following formula IV:
(R wherein
4Represent a hydrogen atom, a straight or branched C
4-16Alkyl, C
5-7Cycloalkyl, cyclohexenyl, dimethylamino or furfuryl group, or by one or more C
1-6Alkoxyl group, C
1-3The C that alkyl sulfide, phenyl and/or halogenophenyl replace
1-4Alkyl), or with morpholine react.
6, a kind of method of preventing and treating rice blast, this method comprise that the rice blast of the Isothiazolcarboxylicacid acid derivatives that contains claim 1 or 3 is prevented and treated agent is applied to paddy crop or paddy crop field.
7, a kind of method of preventing and treating rice blast, this method comprise the rice blast control agent of the Isothiazolcarboxylicacid acid derivatives that contains claim 1 or 3 is applied to rice seedling with the ratio of 4-40g activeconstituents/10 are before transplanting.
8, a kind of method of preventing and treating rice blast, this method comprise the rice blast control agent of using the Isothiazolcarboxylicacid acid derivatives that contains right requirement 1 or 3 with the ratio of 25-250g/10 are.
Applications Claiming Priority (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP24862390 | 1990-09-20 | ||
| JP248623/90 | 1990-09-20 | ||
| JP123454/91 | 1991-05-28 | ||
| JP15131291 | 1991-06-24 | ||
| JP151312/91 | 1991-06-24 |
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| Publication Number | Publication Date |
|---|---|
| CN1061967A true CN1061967A (en) | 1992-06-17 |
| CN1029189C CN1029189C (en) | 1995-07-05 |
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ID=26480606
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 91109765 Expired - Fee Related CN1029189C (en) | 1990-09-20 | 1991-09-20 | Isothiazolecarboxylic acid derivatives, rice blast control agents containing same as active ingredients, and rice blast control method applying control agents |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101437806B (en) * | 2006-05-08 | 2011-01-19 | 组合化学工业株式会社 | 1,2-benzoisothiazole derivative, and agricultural or horticultural plant disease-controlling agent |
| CN102421765A (en) * | 2009-05-01 | 2012-04-18 | 庵原化学工业株式会社 | Method for producing isothiazole derivative |
| CN102030718B (en) * | 2009-09-28 | 2012-09-05 | 湖北成宇制药有限公司 | Preparation method of 3,4-dichloro-5-cyan-isothiazole |
| CN102942565A (en) * | 2012-11-06 | 2013-02-27 | 江西天人生态股份有限公司 | 3,4-dichloro isothiazole derivatives, their preparation method and application |
| CN102361559B (en) * | 2009-02-03 | 2013-11-06 | 拜尔农作物科学股份公司 | Use of sulfurous, heteroaromatic acid analogs as bactericides |
| CN104649996A (en) * | 2014-12-17 | 2015-05-27 | 南开大学 | Isothiazole oxime ether derivatives as well as preparation method and application thereof |
| CN105454252A (en) * | 2007-12-11 | 2016-04-06 | 拜耳知识产权有限责任公司 | Active Compound Combinations |
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1991
- 1991-09-20 CN CN 91109765 patent/CN1029189C/en not_active Expired - Fee Related
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101437806B (en) * | 2006-05-08 | 2011-01-19 | 组合化学工业株式会社 | 1,2-benzoisothiazole derivative, and agricultural or horticultural plant disease-controlling agent |
| CN105454252A (en) * | 2007-12-11 | 2016-04-06 | 拜耳知识产权有限责任公司 | Active Compound Combinations |
| CN102361559B (en) * | 2009-02-03 | 2013-11-06 | 拜尔农作物科学股份公司 | Use of sulfurous, heteroaromatic acid analogs as bactericides |
| CN102421765A (en) * | 2009-05-01 | 2012-04-18 | 庵原化学工业株式会社 | Method for producing isothiazole derivative |
| CN103709117A (en) * | 2009-05-01 | 2014-04-09 | 庵原化学工业株式会社 | Method for producing isothiazole derivative |
| CN102421765B (en) * | 2009-05-01 | 2014-04-23 | 庵原化学工业株式会社 | Method for producing isothiazole derivative |
| CN103709117B (en) * | 2009-05-01 | 2015-09-16 | 庵原化学工业株式会社 | The preparation method of Isothizole derivatives |
| CN102030718B (en) * | 2009-09-28 | 2012-09-05 | 湖北成宇制药有限公司 | Preparation method of 3,4-dichloro-5-cyan-isothiazole |
| CN102942565A (en) * | 2012-11-06 | 2013-02-27 | 江西天人生态股份有限公司 | 3,4-dichloro isothiazole derivatives, their preparation method and application |
| CN102942565B (en) * | 2012-11-06 | 2016-01-27 | 江西天人生态股份有限公司 | One class 3,4-dichloro Isothizole derivatives and its production and use |
| CN104649996A (en) * | 2014-12-17 | 2015-05-27 | 南开大学 | Isothiazole oxime ether derivatives as well as preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1029189C (en) | 1995-07-05 |
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