CN102838566A - Preparation of 4-methyl-1,2,3-thiadiazolyl-5-formate derivatives with plant activated anti-disease activity - Google Patents
Preparation of 4-methyl-1,2,3-thiadiazolyl-5-formate derivatives with plant activated anti-disease activity Download PDFInfo
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Abstract
The invention relates to water/oil-soluble 4-methyl-1,2,3-thiadiazolyl-5-formate derivatives with plant activated anti-disease activity and salts thereof, of which the general formulae (I, II) are disclosed in the specification, wherein X represents oxygen atom, nitrogen atom or sulfur atom; n=0,1,2,3,4,5... or (CH2)n represents alkyl group with branched chain; Y represents Cl<->, Br<->, F<->, I<->, AcO<->, acetylsalicylate group, citrate group, salicylate group, p-toluenesulfonate group, hydrogen sulfate group or any other anion; R1 represents C1-6 alkyl group, C1-6 alkoxy group, C1-6 alkenyl group or aryl group; R2 represents C1-6 alkyl group, C1-6 alkoxy group, C1-6 alkenyl group or aryl group; or R1 and R2 are selected from the following structures.
Description
Technical field
The present invention relates to the 4-methyl isophthalic acid, 2, the preparation of 3-thiadiazoles-5-formate ester verivate and plant are activated anti-disease activity.
Background technology
Thiadiazoles derivative is important medicine and pesticide intermediate, particularly contains 1,2, and the compound of 3-thiadiazole heterocyclic has wide biological activity.Have 3 compounds to belong to this class formation in the commercial Pesticidal products in the whole world, Acibenzolar (BTH) is a benzo [1,2; 3]-and thiadiazoles-7-carboxylic acid sulfo-methyl esters and tiadinil (TDL) i.e. 3 '-chloro-4,4 '-dimethyl--1,2; 3-thiadiazoles-5-formylaniline and TDZ (N-phenyl-N '-1; 2,3-thiadiazoles-5-urea), wherein BTH and TDL all have the characteristics of inducing plant generation to pathogen resistance; It is typical plant activator; But the immunity system of plant activator inducing plant and be created in wide spectrum on physics, chemistry and the Physiology and biochemistry defense mechanism, system lasting and that lag behind obtains disease resistance, is " environment friendly agricultural " truly, is the key areas and the direction of plant protection from now on and Pesticide Science research.BTH is the product of Syngenta Co.,Ltd; Be the most successful, the best compound of induced activity of exploitation at present; TDL is the sterilant of the novel rice field control rice blast that can develop of Japanese agricultural chemicals strain formula, and the research of this compound induced activity is confirmed the expression that this compound can evoking tobacco plant resistant gene and produces the resistance to TMV.
When nineteen ninety-five, Switzerland's vapour clung to the discovery BTH of a Jia Ji company (at present being Novartis Co.,Ltd); And its structure activity relationship studied; Find that thiadiazoles partly is that the performance anti-disease activity is necessary among the BTH; This greatness is found to be the synthetic new diazosulfide class plant activator of design and prepares, and the successful exploitation of such medicament has broken through the traditional understanding of people to the novel pesticide initiative.
Chinese patent CN 101250166 has reported 1,2, and the 3-thiadiazoles derivative specifically is meant the 4-methyl isophthalic acid, 2, and most of all abilities evoking tobacco produces the resistance to TMV in 3-thiadiazoles-5-carboxamides derivatives, and the induced activity of part of compounds and BTH and TDL are suitable; CN 101250168 has reported the 4-methyl isophthalic acid; 2, part of compounds has bacteriostatic action in various degree to the part pathogenic fungi of measuring in the verivate of 3-thiadiazoles imines, and part of compounds ability evoking tobacco produces the resistance of anti-TMV; The induced activity and the TDL that have are suitable, but all are lower than BTH; CN 101544633 has reported N-(5-methyl isophthalic acid, 3-thiazol-2-yl)-4-methyl isophthalic acid, 2, and 3-thiadiazoles-5-methane amide is that N-(5-methyl-1,3-thiazole-2-yl)-4-methyl-1,2,3-thiadiazole has the disease-resistant and germ-resistant activity of inducing plant equally; CN 101591308 reported and contained 1,2, and the part of compounds in the bishydrazide compounds of 3-thiadiazoles reactive group has the activity of desinsection, the antibacterial and anti-TMV of evoking tobacco.We learn the 4-methyl isophthalic acid through above report, 2, and reactive group is 1,2 in the 3-thiadiazoles derivative, 3-thiadiazoles ring, this is synthetic new 1,2 of higher sterilization, the antibacterial and inducing anti-disease activity that have for we design, and 3-thiadiazole verivate provides the guide.But they have significant disadvantages this compounds of patent documentation report: promptly the water-soluble of them all is not very desirable, makes that its speed of action is slower, need make various preparations; Like tiadinil (TDL) and benzo [1; 2,3] thiadiazoles-7-carboxylic acid etc. is water insoluble, is slightly soluble in organic solvent; Need make emulsion to it, suspension agent.
The tradition pesticide formulation are main with missible oil, wettable powder, pulvis and granule; Be accompanied by the development and the exploitation of pesticides new formulation; Following can the development towards directions such as aqua, aqueous emulsion and microemulsions; From this development trend; This just has higher requirement to the novel pesticide molecule that is about to succeed in developing, not only want efficient, low toxicity, safety and and environmental friendliness, it is certain water-soluble to hope also that simultaneously drug molecule has; If drug molecule has good water-solubility and just can be made into aqua and directly use, so not only can reduce production costs but also can reduce when drug molecule is made into certain preparation to add the environmental pollution that high amounts of solvents, tensio-active agent, auxiliary agent and permeate agent etc. are brought.From this respect, the drug molecule good water-solubility has very important significance.Simultaneously, have certain water-soluble and fat-soluble drug molecule, it is necessary also to be that medicine effectively passes microbial film.
No matter medicine is that epidermis absorbs or other approach absorb, and all need pass barrier membranes with the form of molecule.Medicine needs at first dissolving, and if medicine have ideal biopharmacy characteristic, it is diffused into the zone of lower concentration from the zone of high density, stride across cytolemma and enter into the recycle system.All microbial films contain lipid as major ingredient.Active molecule all has and contains phosphatic high polar end structure in the biofilm structure, and, in most of the cases, two highly hydrophobic hydrocarbon chains.Microbial film has bilayer structure, and the hydrophilic chain end structure is towards the water zone of both sides.Very hydrophilic medicine can't pass biomembranous lipid layer and very hydrophobic medicine because the similar reason that mixes stops wherein as a biomembranous part, thereby can not effectively get into inner tenuigenin.
The objective of the invention is to make them can reach a good balance, reduce the outer loss of organism, thereby improve the utilization ratio of medicine through improving the water-soluble and fat-soluble of phenylpropyl alcohol thiadiazole verivate.The novel cpd of these phenylpropyl alcohol thiadiazole verivates has two identical constructional features: they have part (oil soluble part) and the one-level that protonated form exists under physiology PH condition of a close ester property; Secondary, or tertiary amine group (water-soluble portion).Water-soluble-molten balance of oil like this is that medicine effectively passes microbial film institute necessary [Susan Milosovich, et al.J.Pharm.Sci., 82,227 (1993)].The amino that has positive charge has increased the solubleness of medicine greatly.This point can be seen from experimental implementation: in the product aftertreatment, the compound that does not become positive ion is dissolved in methylene dichloride and is water insoluble, add the hydrogen ion salify after, compound is dissolved in water layer, also is dissolved in methylene dichloride.As a rule, the solubleness of medicine is the step of the slowest and maximum speed limit in the absorption process.When these novel cpds are made medicament, in its molecule amino can with the phosphoric acid salt end group bonding of cytolemma.Therefore, thus very high these medicines that help of the partial concn of medicine in the microbial film outside through the zone of area with high mercury to lower concentration.After these drug molecules entered into microbial film, hydrophilic parts can promote the tenuigenin that medicine enters into the concentrated aqueous solution of semi liquid state.
Summary of the invention
The purpose of this invention is to provide the 4-methyl isophthalic acid, 2, the compound method of 3-thiadiazoles-5-formate ester verivate and salt thereof, this compounds has excellent plant inducing anti-disease activity.
The 4-methyl isophthalic acid, 2, shown in (I and II series), table 1 and table 2 represented to see in the chemical structural formula that part is concrete to the chemical structure of general formula of 3-thiadiazoles-5-formate ester verivate and salt thereof as follows:
Wherein:
X represention oxygen atom, nitrogen-atoms, sulphur atom; N=0,1,2,3,4,5 ... Or (CH
2)
nRepresentative has the alkyl of side chain; Y represents Cl
-, Br
-, F
-, I
-, AcO
-, acetylsalicylate, citrate, salicylate, tosic acid root, bisulfate ion, or other negative ions.R
1Represent the alkyl of 1-6 carbon atom, the alkoxyl group of a 1-6 carbon atom, the thiazolinyl or the aryl of a 1-6 carbon atom; R
2Represent the alkyl of 1-6 carbon atom, the alkoxyl group of a 1-6 carbon atom, the thiazolinyl or the aryl of a 1-6 carbon atom; Or R
1, R
2Be selected from following structure:
The comparatively preferred compound of the present invention is:
N=1～4; X represents N, O, S; Y represents Cl
-, Br
-, F
-, I
-, AcO
-, acetylsalicylate, citrate, salicylate, tosic acid root, bisulfate ion, or other negative ions; R
1, R
2Be selected from H, C
1-C
4Alkyl or R
1=R
2Be selected from following structure:
General formula compound of the present invention (I, II) following method preparation:
Reaction path is following:
Thiadiazoles formic acid and SOCl
2, PCl
3Or oxalyl chloride is dissolved in The suitable solvent, dioxane for example, benzene, toluene, ETHYLE ACETATE; THF, normal hexane, tetracol phenixin, chloroform or methylene dichloride; With organic bases such as pyridine, triethylamine is a catalyzer with DMF, temperature be 0 ℃ to boiling point down reaction made corresponding acyl chlorides in 1-24 hour.
The acyl chlorides that last step makes and (n+1)-(dialkyl group) amino-1-(mercaptan, amine) alcohol (preparing), in The suitable solvent, temperature is 0 ℃ and reacts down to boiling point and to make product (I) in 1-24 hour.Solvent can be dioxane, benzene, toluene, ETHYLE ACETATE, THF, acetone, normal hexane, tetracol phenixin, chloroform or methylene dichloride etc.Add alkaline matter, like pyridine, triethylamine, sodium hydroxide, Pottasium Hydroxide, yellow soda ash, sodium hydrogencarbonate, salt of wormwood or saleratus etc. are to reacting favourable.
Product (I) and diluted acid YH can be dissolved in product (I) in the The suitable solvent, add diluted acid YH, and temperature is 0 ℃ and reacts down to boiling point and to make product (II) in 1-24 hour.Solvent can be dioxane, benzene, toluene, ETHYLE ACETATE, THF, acetone, normal hexane, tetracol phenixin, chloroform or methylene dichloride etc.
The present invention can also explain with the compound of listing in table 1, the table 2, but not limit the present invention.
Table 1: the The compounds of this invention of part shown in general formula I
Table 2: the The compounds of this invention of part shown in general formula I I
(I, II) compound has plant activation anti-disease activity, the infringement of the fine prevention phytopathogen of ability to general formula of the present invention.Compare with existing similar compound, this compounds shows better water-solubility and anti-disease activity.
The present invention comprises that also (I, II) compound is the fungicide compsn of active ingredient with general formula.The weight percentage of active ingredient is 1-99% in this sterilant component.Comprise also in this fungicide compsn that agricultural goes up acceptable carrier.
General formula (I of the present invention; II) compound and can process several formulations as the fungicide compsn of active ingredient and use, especially general formula (II) can directly be made into aqua and use; Both reduced with an organic solvent the pollution of environment, be more conducive to absorption and the conduction of plant again.In these compsns, also can add the liquid or solid carrier, and add an amount of tensio-active agent and come compounding application.
Other embodiment of the present invention is the method for control germ, and this method comprises compound of the present invention and compsn thereof are applied on the surface of said plant or its growth medium.Amount of application is generally per hectare 100 and restrains 500 grams, and preferred significant quantity is that per hectare 100 restrains 300 grams.In addition, also can add one or more other sterilant in compound of the present invention and in the active composition, can produce thus more efficient, the effect of wide spectrum.
(I, II) compound both can use separately as plant activation antiviral agents and also can cooperate other known sterilant, sterilant, plant-growth regulator or fertilizer to be mixed together use general formula of the present invention.
Should be clear and definite be in claim scope of the present invention, can carry out various changes and conversion as required.
Embodiment
The following example is tested the plant activation anti-disease activity that the result can further be used for explaining compound of the present invention with giving birth to test, but does not mean that restriction the present invention.
Synthetic embodiment
The preparation of compound 1
1,4-methyl isophthalic acid, 2,3-thiadiazoles-5-formic acid synthetic
In the 250ml round-bottomed flask, add 17.22g (0.1mol) 4-methyl isophthalic acid, 2, the methanol solution of the 3mol/LNaOH of 3-thiadiazoles-5-ethyl formate and 40ml; Stirring at room 24h; Remove methyl alcohol then under reduced pressure and get the light brown solid, this solid, is dissolved in this solid in the 100ml water then through the dry yellowish brown solid that gets with the ether washing then; Be acidified to PH=2 with Hydrogen chloride; Suction filtration gets the milk yellow solid again with normal hexane washing 3 times and the dry Off-white solid 12.5g of getting, 192～194 ℃ of mp, productive rate 87.5%.
1H?NMR(403MHz，DMSO)δ：2.86(s，3H，thiadiazole-C
H 3)。
2,4-methyl isophthalic acid, 2,3-thiadiazoles-5-formyl chloride synthetic
In the 100ml round-bottomed flask, add 7.2g (0.05mol) 4-methyl isophthalic acid, 2,3-thiadiazoles-5-formic acid and 55ml sulfur oxychloride; Reflux 8h cools off then, and following unnecessary sulfur oxychloride of first condition of normal pressure steams; Decompression steams product 2000Pa, 78 ℃ of faint yellow cut 6.61g, productive rate 87.5% then; This product is very active, should be kept at this product sealing in the vacuum drier with subsequent use.
3, compound 1:2 '-N, N-dimethyl--4-methyl isophthalic acid, 2,3-thiadiazoles-5-ethyl formate synthetic
In the 100ml round-bottomed flask, add 4.32g (0.03mol) 4-methyl isophthalic acid, 2,3-thiadiazoles-5-formic acid and 30ml sulfur oxychloride; Reflux 8h then; Cooling, following unnecessary sulfur oxychloride of first condition of normal pressure steams, and decompression steams product 2000Pa then; 78 ℃ of faint yellow cut 3.85g, productive rate: 79%.
In this 100ml reaction flask, add the 30ml methylene dichloride then, induction stirring slowly drips 2.11g N for a moment then under cryosel is bathed; The mixed solution of N-dimethylethanolamine, 3.6ml triethylamine and 20ml methylene dichloride; Drip off afterreaction liquid and become flaxen turbid solution, stirred overnight at room temperature then, the TLC detection reaction was complete in second day; So transfer to reaction solution in the beaker of 200ml, with saturated NaHCO
3Neutralization reaction liquid is to PH=7.5～8.5, and (3 * 30ml), organic layer anhydrous sodium sulfate drying 4h, precipitation get 3.85g weak yellow liquid compound 1, productive rate 75.6% with the washing organic phase then.
1H?NMR(400MHz，CDCl
3)δ：2.27(s，6H，C
H 3)，2.89(s，3H，thiadiazole-C
H 3)，2.66(t，2H，J
H＝5.6Hz，C
H 2)，4.39(t，2H，J
H＝5.6Hz，C
H 2)；HRMS：calc?for?C
8H
13N
3O
2S；(M+H)
+216.0801；found216.0809。
The preparation of compound 2
Compound method and post-treating method get orange fluid cpds 2, productive rate 71.14% with compound 1.
1H?NMR(400MHz，CDCl
3)δ：0.99(t，6H，J
H＝6.8Hz，C
H 3)，2.55(q，4H，J
H＝6.8Hz，C
H 3)，2.76(t，2H，J
H＝6.4Hz，C
H 2)，2.90(s，3H，thiadiazole-C
H 3)，4.35(t，2H，J
H＝6.4Hz，C
H 2)；HRMS：calc?for C
10H
17N
3O
2S；(M+H)
+244.1144；found?244.1113。
Synthesizing of compound 3
The method for preparing acyl chlorides is the same, in this 100ml reaction flask, adds the 40ml methylene dichloride then, and induction stirring for a moment; Slow Dropwise 5 .03gN under cryosel is bathed then, the mixed solution of N-diisopropyl ethanolamine, 5.2ml triethylamine and 20ml methylene dichloride drips off afterreaction liquid and becomes flaxen turbid solution; Stirred overnight at room temperature with dichloromethane extraction water layer twice, merges organic layer and uses anhydrous sodium sulfate drying 4h then then; Precipitation gets 8.65g compound 3, thick productive rate 79.8%.
1H?NMR(400MHz，CDCl
3)δ：1.02(d，12H，J
H＝6.0Hz，C
H 3)，3.96(q，2H，J
H＝6.0Hz，C
H)，2.77(t，2H，J
H＝5.6Hz，C
H 2)，2.96(s，3H，thiadiazole-C
H 3)，4.29(t，2H，J
H＝5.6Hz，C
H 2)；HRMS：calc?for?C
12H
21N
3O
2S；(M+H)
+272.1427；found?272.1425。
Synthesizing of compound 6
Compound method and post-treating method be with compound 1, productive rate 75%.
1H?NMR(400MHz，CDCl
3)δ：2.57(t，4H，J
H＝4.0Hz，C
H 2)，2.77(t，2H，J
H＝5.6Hz，C
H 2)，3.71(t，4H，J
H＝4.0Hz，C
H 2)，2.96(s，3H，thiadiazole-C
H 3)，4.79(t，2H，J
H＝5.6Hz，C
H 2)；HRMS：calc?for?C
10H
15N
3O
3S；(M+H)
+258.0907；found?258.0908。
Synthesizing of compound 15
Yield 49.0%.
1H?NMR(400MHz，CDCl
3)δ：1.02(d，12H，J
H＝6.0Hz，C
H 3)，3.96(q，2H，J
H＝6.0Hz，C
H)，2.77(t，2H，J
H＝5.6Hz，C
H 2)，2.96(s，3H，thiadiazole-C
H 3)，4.29(t，2H，J
H＝5.6Hz，C
H 2)；HRMS：calc?for?C
12H
21N
3O
2S；(M+H)
+272.1427；found?272.1425。
Compound 1-H's is synthetic
In the four-hole round-bottomed flask of 25mL, add 2 '-N, N-dimethyl--4-methyl isophthalic acid; 2, the methylene dichloride that 3-thiadiazoles-5-ethyl formate 0.43g (0.002mol) and 10ml handled is under the induction stirring; Under ice bath, slowly feed exsiccant HCl gas then; TLC detects and finishes until reaction, and precipitation gets white solid compound 1-H 0.50g, yield 99.4%.mp?184～185℃；?
1H?NMR(400MHz，D
2O)δ：2.93(s，6H，C
H 3)，2.84(s，3H，thiadiazole-C
H 3)，3.58(t，2H，J
H＝4.8Hz，C
H 2)，4.68(t，2H，J
H＝4.8Hz，C
H 2)；HRMS：calc?for?C
8H
14N
3O
2SCl；M
+216.0801；found216.0800。
Compound 2-H's is synthetic
The same 1-H of compound method gets milk yellow solid 2-H, yield 100%.mp?148～150℃；
1H?NMR(400MHz，D
2O)δ：1.27(t，6H，J
H＝7.2Hz，C
H 3)，3.27(q，4H，J
H＝7.2Hz，C
H 3)，3.59(t，2H，J
H＝4.8Hz，C
H 2)，2.83(s，3H，thiadiazole-C
H 3)，4.67(t，2H，J
H＝4.8Hz，C
H 2)；HRMS：calc?for?C
10H
18N
3O
2SCl；M
+244.1144；found?244.1110。
Compound 3-H's is synthetic
Yield 100%.
1H?NMR(400MHz，D
2O)δ：1.32(t，12H，J
H＝6.4Hz，C
H 3)，3.74(m，2H，C
H)，?3.57(t，2H，J
H＝4.8Hz，C
H 2)，2.82(s，3H，thiadiazole-C
H 3)，4.62(t，2H，J
H＝4.8Hz，C
H 2)；HRMS：calc?for?C
12H
22N
3O
2SCl；M
+272.1427；found?272.1432。
Compound 6-H's is synthetic
Yield 100%.mp：124～126℃；
1H?NMR(400MHz，D
2O)δ：3.29(br，2H，C
H 2)，3.57(br，2H，C
H 2)，3.82(br，2H，C
H 2)，4.06(br，2H，C
H 2)，3.64(t，2H，J
H＝4.8Hz，C
H 2)，2.83(s，3H，thiadiazole-C
H 3)，4.73(t，2H，J
H＝4.8Hz，C
H 2)；HRMS：calc?for?C
10H
18N
3O
2SCl；M
+258.0907；found?258.0902。
Compound 15-H's is synthetic
Yield 99.8%.
1H?NMR(400MHz，D
2O)δ：2.90(s，6H，C
H 3)，3.35(t，2H，J
H＝6.0Hz，C
H 2)，3.73(q，2H，J
H＝6.0Hz，C
H 2)，2.71(s，3H，thiadiazole-C
H 3)，HRMS：calc?for?C
8H
15N
4OSCl；M
+215.0961；found?215.0965。
Other compound all can obtain through similar approach in table 1, the table 2.
Give birth to and survey instance:
For new synthetic 4-methyl isophthalic acid; 2; The biological activity of 3-thiadiazoles derivative has only been tested infecting the anti-intensity that lures of botrytis cinerea (Botrytis cinerea per.), and the preparation of these two serial target compound medicaments all is to be that biological activity test is direct water-soluble test through adding directly that water processes; Wherein 2% kasugamycin wettable powder is the contrast medicament, and botrytis cinerea liquid is only inoculated in the clear water contrast.
Target compound to the concrete TP of the prophylaxis effect of graw mold of tomato is: tomato seedling 4～5 leaves of selecting uniformity; Adopt air to connect and blow spray painting head spray liquid; Leave dual sides evenly is sprayed onto; Treat the soup seasoning, behind 48h, adopt hand-held plastics atomizer that the blade tow sides are evenly sprayed botrytis cinerea liquid.When spraying medicine (bacterium) liquid, be covered with the blade face pros and cons but do not drip with droplet and be advisable.After the inoculation plant is placed 25 ℃, relative humidity is in 90% the environment greenhouse of preserving moisture.Inoculate 8 days " Invest, Then Investigate "s and all inoculate the disease index of blade.
0 grade: no scab; 1 grade: lesion area accounts for below 5% of whole leaf area; 3 grades: lesion area accounts for 6～10% of whole leaf area; 5 grades: lesion area accounts for 11～25% of whole leaf area; 7 grades: lesion area accounts for 26～50% of whole leaf area; 9 grades: lesion area accounts for more than 50% of whole leaf area;
Disease index=∑ (the sick number of sheets * relative progression) * 100/ (investigating total number of sheets * 9)
Control effect (%)=(the contrast disease refers to-handle that disease refers to) * 100/ contrast disease refers to
General formula I I compound directly adds water, does not add any tensio-active agent and auxiliary agent, is made into aqua and lures the activity resistent test.
Part of compounds test result such as following table:
Thiadiazoles series of parts compound is to luring the activity resistent result in seedling stage of graw mold of tomato
Z
11 *: 4-methyl-[1,2,3]-5-formic acid
*The contrast medicament
Claims (5)
1.4-methyl isophthalic acid, 2,3-thiadiazoles-5-formate ester verivate and salt thereof, as general formula (I, II) shown in:
Wherein:
X represention oxygen atom, nitrogen-atoms, sulphur atom; N=0,1,2,3,4,5 ... Or (CH
2)
nRepresentative has the alkyl of side chain; Y represents Cl
-, Br
-, F
-, I
-, AcO
-, acetylsalicylate, citrate, salicylate, tosic acid root, bisulfate ion, or other negative ions.R
1Represent the alkyl of 1-6 carbon atom, the alkoxyl group of a 1-6 carbon atom, the thiazolinyl or the aryl of a 1-6 carbon atom; R
2Represent the alkyl of 1-6 carbon atom, the alkoxyl group of a 1-6 carbon atom, the thiazolinyl or the aryl of a 1-6 carbon atom; Or R
1, R
2Be selected from following structure:
2. compound as claimed in claim 1 is characterized in that, general formula (I, II) in:
N=1～4; X represents N, O, S; Y represents Cl
-, Br
-, F
-, I
-, AcO
-, acetylsalicylate, citrate, salicylate, tosic acid root, bisulfate ion, or other negative ions; R
1, R
2Be selected from H, C
1-C
4Alkyl or R
1=R
2Be selected from following structure:
3. the described compound of claim 1 or its compsn are used for the purposes of activated plant self disease-resistant performance and prevention and controlling plant disease.
4. a fungicide mixture contains compound as claimed in claim 1 and goes up acceptable carrier with agricultural, and the weight percentage of active ingredient is 1-99% in the compsn.
5. the method for a controlling plant disease is characterized in that: to the fungicide mixture as claimed in claim 4 of plant seed and foliage applying significant quantity.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
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| CN103333112A (en) * | 2013-06-14 | 2013-10-02 | 南开大学 | Preparation and application of bixafen type derivatives |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103333113A (en) * | 2013-06-14 | 2013-10-02 | 南开大学 | Preparation and application research of fluxapyroxad analogue derivative |
| CN103333112A (en) * | 2013-06-14 | 2013-10-02 | 南开大学 | Preparation and application of bixafen type derivatives |
| CN103333112B (en) * | 2013-06-14 | 2018-09-28 | 南开大学 | The preparation and application of biphenyl pyrrole bacterium amine derivant |
| CN103333113B (en) * | 2013-06-14 | 2018-09-28 | 南开大学 | The preparation and application study of fluxapyroxad like derivatives |
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