CN103102330A - N-4-methyl-1,2,3-thiadiazole-4-acyl-N-substituted phenylthiourea derivative as well as preparation and application thereof - Google Patents
N-4-methyl-1,2,3-thiadiazole-4-acyl-N-substituted phenylthiourea derivative as well as preparation and application thereof Download PDFInfo
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- CN103102330A CN103102330A CN2012104979318A CN201210497931A CN103102330A CN 103102330 A CN103102330 A CN 103102330A CN 2012104979318 A CN2012104979318 A CN 2012104979318A CN 201210497931 A CN201210497931 A CN 201210497931A CN 103102330 A CN103102330 A CN 103102330A
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- 0 *C(c1cccc2c1S[N+]N2)=O Chemical compound *C(c1cccc2c1S[N+]N2)=O 0.000 description 2
- VJQYLJSMBWXGDV-UHFFFAOYSA-N Cc1c(C(Nc2cc(Cl)c(C)cc2)=O)[s]nn1 Chemical compound Cc1c(C(Nc2cc(Cl)c(C)cc2)=O)[s]nn1 VJQYLJSMBWXGDV-UHFFFAOYSA-N 0.000 description 1
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Abstract
The invention discloses an N-4-methyl-1,2,3-thiadiazole-4-acyl-N-substituted phenylthiourea derivative (I), and discloses a preparation method thereof, and an application of N-4-methyl-1,2,3-thiadiazole-4-acyl-N-substituted phenylthiourea derivative as a sterilizing agent. The invention provides a new N-4-methyl-1,2,3-thiadiazole-4-acyl-N-substituted phenylthiourea derivative, and provides a preparation and an application thereof. The N-4-methyl-1,2,3-thiadiazole-4-acyl-N-substituted phenylthiourea derivative provided by the invention has excellent sterilization activity.
Description
(1) technical field
The present invention relates to a kind of N-4-methyl isophthalic acid, 2,3-thiadiazoles-4-acyl group-N-substituted-phenyl thiourea derivative and its preparation method and application.
(2) background technology
Heterogeneous ring compound has been the main flow of novel pesticide development, and, in agricultural chemicals newly developed, more than 90%, is all heterocyclic pesticide.In heterogeneous ring compound, take again nitrogen heterocyclic ring as main.In recent years, plant induced resistance agent thiadinal, the research and development of BTH success listing, caused everybody research to thiadiazole compound.
Thiourea has diversified biological activity.A lot of bibliographical information thiourea derivatives have extensive biological activity, are applied to medicine, pesticide field.Some thioureas have developed into commercial agricultural chemicals, and as sterilant thiophanate class (1), in soil, the thiophanate methyl metabolism is derosal, and its possible bactericidal potency is that the derosal formed in fungus body works.Commercialization Thiourea sterilant, Chlormethiuron (2), chemistry N by name, N-dimethyl-N-(2-methyl-4-chlorine substituted benzene) thiocarbamide, take off on nitrogen its activity after methyl and can not reduce.But be prohibited from using because toxicity is too strong.
(3) summary of the invention
The object of the present invention is to provide a kind of new N-4-methyl isophthalic acid; 2; 3-thiadiazoles-4-acyl group-N-substituted-phenyl thiourea derivative; and provide its preparation method and application; N-4-methyl isophthalic acid provided by the invention; 2,3-thiadiazoles-4-acyl group-N-substituted-phenyl thiourea derivative has excellent fungicidal activity.
The technical solution used in the present invention is as follows:
A kind of suc as formula the N-4-methyl isophthalic acid shown in I, 2,3-thiadiazoles-4-acyl group-N-substituted-phenyl thiourea derivative:
I
In formula I, R is chlorine, fluorine, nitro, methyl.
The present invention also provides the methyl isophthalic acid of the N-4-shown in formula I, the preparation method of 2,3-thiadiazoles-4-acyl group-N-substituted-phenyl thiourea derivative:
Chloride compounds shown in formula II is dissolved in organic solvent A and obtains solution A, NH
4nCS is dissolved in methylene dichloride and polyoxyethylene glycol PEG600 and obtains solution B, wherein the consumption of polyoxyethylene glycol PEG600 is 3 ~ 5% of methylene dichloride quality, solution B adds in solution A, heated and stirred back flow reaction 15 ~ 100min(is 12 ~ 40min preferably), then standing cooling, suction filtration, add solution C in filtrate, described solution C is that the substituted aniline compounds shown in formula IV is dissolved in organic solvent C and obtains, stirring at room reaction 7 ~ 10 hours, after reaction finishes, the reaction solution separating treatment obtains the N-4-methyl isophthalic acid, 2, 3-thiadiazoles-4-acyl group-N-substituted-phenyl thiourea derivative product, described organic solvent A is acetonitrile, tetrahydrofuran (THF) or methylene dichloride, described organic solvent C is acetonitrile, tetrahydrofuran (THF) or methylene dichloride, preferably acetonitrile, chloride compounds shown in described formula II, NH
4the ratio of the amount of substance of the amino benzenes compounds shown in NCS, formula IV is 1:1:1,
In formula IV, R is chlorine, fluorine, nitro, methyl.
The reaction equation of described reaction is as follows:
In described method; described reaction solution method for separating and processing is: after reaction finishes; standing 5 ~ 20 hours of reaction solution; get filter cake after suction filtration; obtain N-4-methyl isophthalic acid with arbitrary volume than the mixed solvent recrystallization mixed with DMF and water; 2,3-thiadiazoles-4-acyl group-N-substituted-phenyl thiourea derivative product.
The consumption of described organic solvent A is counted 1 ~ 3mL/mmol with the amount of substance of the acyl chlorides shown in formula II, preferably 1.5 mL/mmol.
Total consumption of described methylene dichloride and polyoxyethylene glycol PEG600 is with NH
4the amount of substance of NCS is counted 1 ~ 3mL/mmol, preferably 1.6 mL/mmol.
The consumption of described organic solvent C is counted 0.5 ~ 1mL/mmol with the amount of substance of the substituted aniline compounds shown in formula IV, preferably 1.0 mL/mmol.
Comparatively concrete, the N-4-methyl isophthalic acid shown in described formula I, the preparation method of 2,3-thiadiazoles-4-acyl group-N-substituted-phenyl thiourea derivative carries out according to the following steps:
Chloride compounds shown in formula II is dissolved in organic solvent A and obtains solution A, NH
4nCS is dissolved in methylene dichloride and polyoxyethylene glycol PEG600 and obtains solution B, wherein the consumption of polyoxyethylene glycol PEG600 is 3 ~ 5% of methylene dichloride quality, solution B adds in solution A, heated and stirred back flow reaction 15 ~ 100min, then standing cooling, suction filtration, in filtrate, add the substituted aniline compounds shown in formula IV to be dissolved in the solution C obtained in organic solvent C, stirring at room reaction 7 ~ 10 hours, after reaction finishes, standing 5 ~ 15 hours of reaction solution, get filter cake after suction filtration, obtain N-4-methyl isophthalic acid with arbitrary volume than the mixed solvent recrystallization mixed with DMF and water, 2, 3-thiadiazoles-4-acyl group-N-substituted-phenyl thiourea derivative product, described organic solvent A is acetonitrile, tetrahydrofuran (THF) or methylene dichloride, described organic solvent C is acetonitrile, tetrahydrofuran (THF) or methylene dichloride, replacement chloride compounds shown in described formula II, NH
4the ratio of the amount of substance of the substituted aniline compounds shown in NCS, formula IV is 1:1:1.
In the inventive method, the chloride compounds shown in formula II can prepare by the following method: the compound shown in formula V and SOCl
2carry out chlorination reaction and obtain the chloride compounds shown in formula II, this is to well known to a person skilled in the art the preparation method.
N-4-methyl isophthalic acid shown in formula I of the present invention; 2; 3-thiadiazoles-4-acyl group-N-substituted-phenyl thiourea derivative can be applied as sterilant; concrete; described N-4-methyl isophthalic acid; 2,3-thiadiazoles-4-acyl group-N-substituted-phenyl thiourea derivative can be used as the sterilant of wheat scab, the late blight of potato, ring rot of apple, cucumber Fusarium oxysporum or the cercospora brown spot of peanut.
More specifically, (5-(2 for N-, the 5-dichlorophenyl)-N '-(4-methyl isophthalic acid, 2,3-thiadiazoles-5-yl)-thiocarbamide, N-(5-(3-nitrophenyl))-N '-(4-methyl isophthalic acid, 2,3-thiadiazoles-5-yl)-thiocarbamide, N-(5-(4-aminomethyl phenyl))-N '-(4-methyl isophthalic acid, 2,3-thiadiazoles-5-yl)-thiocarbamide, N-(5-(4-nitrophenyl))-N '-(4-methyl isophthalic acid, 2,3-thiadiazoles-5-yl)-thiocarbamide is as the application of the sterilant of wheat scab.
(5-(2 for N-, the 5-dichlorophenyl)-N '-(4-methyl isophthalic acid, 2,3-thiadiazoles-5-yl)-thiocarbamide, N-(5-(4-aminomethyl phenyl))-N '-(4-methyl isophthalic acid, 2,3-thiadiazoles-5-yl)-thiocarbamide, N-(5-(4-nitrophenyl))-N '-(4-methyl isophthalic acid, 2,3-thiadiazoles-5-yl)-thiocarbamide are as the application of the sterilant of the late blight of potato.
(5-(2 for N-, the 5-dichlorophenyl)-N '-(4-methyl isophthalic acid, 2,3-thiadiazoles-5-yl)-thiocarbamide, N-(5-(4-fluorophenyl)-N '-(4-methyl isophthalic acid, 2,3-thiadiazoles-5-yl)-thiocarbamide, N-(5-(3-nitrophenyl))-N '-(4-methyl isophthalic acid, 2,3-thiadiazoles-5-yl)-thiocarbamide, N-(5-(4-aminomethyl phenyl))-N '-(4-methyl isophthalic acid, 2,3-thiadiazoles-5-yl)-thiocarbamide, N-(5-(4-nitrophenyl))-N '-(4-methyl isophthalic acid, 2,3-thiadiazoles-5-yl)-thiocarbamide are as the application of the sterilant of ring rot of apple.
(5-(2 for N-, the 5-dichlorophenyl)-N '-(4-methyl isophthalic acid, 2,3-thiadiazoles-5-yl)-thiocarbamide, N-(5-(4-fluorophenyl)-N '-(4-methyl isophthalic acid, 2,3-thiadiazoles-5-yl)-thiocarbamide, N-(5-(3-nitrophenyl))-N '-(4-methyl isophthalic acid, 2,3-thiadiazoles-5-yl)-thiocarbamide, N-(5-(4-aminomethyl phenyl))-N '-(4-methyl isophthalic acid, 2,3-thiadiazoles-5-yl)-thiocarbamide, N-(5-(4-nitrophenyl))-N '-(4-methyl isophthalic acid, 2,3-thiadiazoles-5-yl)-thiocarbamide are as the application of the sterilant of cucumber Fusarium oxysporum.
(5-(2 for N-, the 5-dichlorophenyl)-N '-(4-methyl isophthalic acid, 2,3-thiadiazoles-5-yl)-thiocarbamide, N-(5-(4-fluorophenyl)-N '-(4-methyl isophthalic acid, 2,3-thiadiazoles-5-yl)-thiocarbamide, N-(5-(3-nitrophenyl))-N '-(4-methyl isophthalic acid, 2,3-thiadiazoles-5-yl)-thiocarbamide, N-(5-(4-nitrophenyl))-N '-(4-methyl isophthalic acid, 2,3-thiadiazoles-5-yl)-thiocarbamide is as the application of the sterilant of the cercospora brown spot of peanut.
(4) embodiment
Below in conjunction with embodiment, the invention will be further described, but protection scope of the present invention is not limited to this.
Be prepared as follows raw material:
Described 4-methyl isophthalic acid, 2,3-thiadiazoles-5-formic acid makes by the following method:
Diethyl carbonate mixes than 1:0.95 by amount of substance with 85% hydrazine hydrate, reflux under 50 ℃ 20 minutes, then stir 30 hours under 25 ℃, remove methyl alcohol, water and a small amount of complete diethyl carbonate of unreacted under reduced pressure, obtain colourless transparent liquid, obtain the carbazic acid ethyl ester in formula 1;
Carbazic acid ethyl ester shown in formula 1 mixes with amount of substance 1:1 with methyl aceto acetate, and in alcohol solvent, stirring at normal temperature is 6 hours, removes ethanol under reduced pressure, obtains white solid, is the 3-methoxycarbonyl hydrazone ethyl butyrate shown in formula 2;
3-methoxycarbonyl hydrazone ethyl butyrate shown in formula 2 and excessive thionyl chloride, take methylene dichloride as solvent, stirring at room 20 hours, boil off excessive thionyl chloride under normal pressure, then underpressure distillation, collect 400Pa, the faint yellow cut of 76-78 ℃, make the 4-methyl isophthalic acid shown in formula 3,2,3-thiadiazoles-5-ethyl formate.
4-methyl isophthalic acid shown in formula 3,2,3-thiadiazoles-5-ethyl formate and excessive sodium hydroxide, take anhydrous methanol as solvent, stirring at room 24 hours, boil off anhydrous methanol under normal pressure, then by dissolution of solid in water, drip concentrated hydrochloric acid, faint yellow solid appears, make the 4-methyl isophthalic acid shown in formula 4,2,3-thiadiazoles-5-formic acid.
1.0 the g4-methyl isophthalic acid, 2,3-thiadiazoles-5-formic acid and 10 mL SOCl
2under the condition of reflux, carry out chlorination reaction, reaction steams excessive thionyl chloride after finishing under the water pump reduced pressure, obtains the 4-methyl isophthalic acid, 2,3-thiadiazoles-5-formyl chloride.
Above-mentioned preparation can be done several pots more, makes raw material for the following example.
Example 1:N-(the preparation of 5-(2,5-dichlorophenyl)-N '-(4-methyl isophthalic acid, 2,3-thiadiazoles-5-yl)-thiocarbamide
In the round-bottomed flask of 100mL, in acyl chlorides 10mmol is dissolved in the solution of 20 mL methylene dichloride, adds and be dissolved with 0.97g(10mmol) NH
4the PEG-600 solution of the methylene dichloride of NCS (10mL, methylene dichloride 9.5 mL wherein, PEG-600 0.5 mL), stirring and refluxing 15min, standing cooling, suction filtration, obtain orange solution, add the 10mmol 2 made according to the method described above, the 5-dichlorphenamide bulk powder is dissolved in the solution of 5 mL anhydrous acetonitriles, stirring at room 10h, standing over night, suction filtration, the mixed solvent recrystallization that filter cake mixes with volume ratio 1:1 with DMF and water obtains product.
Yellow solid, productive rate 85.9 %, fusing point %:181-183 ℃;
1h NMR:8.35 (s, 1H, NH), 8.14 (s, 1H, NH), 7.39-7.44 (m, 1H, Ph), 7.18-7.30 (m, 1H, Ph), 7.13-7.17 (m, 1H, Ph), 2.81 (s, 3H, CH
3); ESI-MS:346 (M-1); Anal. calcd. For C
11h
8cl
2n
4oS
2: C 38.05, and H 2.32, and N 16.13; Found:C 37.88, and H 2.21, N 16.32.
Example 2:N-(the preparation of 5-(4-fluorophenyl)-N '-(4-methyl isophthalic acid, 2,3-thiadiazoles-5-yl)-thiocarbamide
In the round-bottomed flask of 100mL, in acyl chlorides 10mmol is dissolved in the solution of 20 mL methylene dichloride, adds and be dissolved with 0.97g(10mmol) NH
4pEG-600 solution (the 10mL of the methylene dichloride of NCS, methylene dichloride 9.5 mL wherein, PEG-600 0.5 mL), stirring and refluxing 15min, standing cooling, suction filtration, obtain orange solution, adds prepared 10mmol 4-fluoroaniline to be dissolved in the solution of 5 mL anhydrous acetonitriles, stirring at room 10h, standing over night, suction filtration, get the mixed solvent recrystallization that filter cake mixes with volume ratio 1:2 with DMF and water and obtain product.
Yellow solid, productive rate 83.8 %, fusing point: 166-168 ℃;
1h NMR:11.96 (s, 1H, NH), 10.00 (s, 1H, NH), 7.63-7.66 (m, 1H, Ph), 7.26-7.29 (m, 2H, Ph), 2.80 (s, 3H, CH
3); ESI-MS:295 (M-1); Anal. calcd. For C
11h
9fN
4oS
2: C 44.58, and H 3.06, and N 18.91; Found:C 44.46, and H 3.13, N 18.76.
The preparation of example 3:N-(5-(3-nitrophenyl))-N '-(4-methyl isophthalic acid, 2,3-thiadiazoles-5-yl)-thiocarbamide
In the round-bottomed flask of 100mL, in acyl chlorides 10mmol is dissolved in the solution of 20 mL acetonitriles, adds and be dissolved with 0.97g(10mmol) NH
4pEG-600 solution (the 10mL of the methylene dichloride of NCS, methylene dichloride 9.5 mL wherein, PEG-600 0.5 mL), stirring and refluxing 15min, standing cooling, suction filtration, obtain orange solution, adds prepared 10mmol 3-N-methyl-p-nitroaniline to be dissolved in the solution of 10 mL anhydrous acetonitriles, stirring at room 10h, standing over night, suction filtration, get the mixed solvent recrystallization that filter cake mixes with volume ratio 2:1 with DMF and water and obtain product.
Yellow solid, productive rate 85.8 %, fusing point: 115-117 ℃;
1h NMR:12.20 (s, 1H, NH), 8.71 (s, 1H, NH), 8.13 (m,
j=8.48Hz, 1H, Ph), 8.02 (d,
j=7.72Hz, 1H, Ph), 7.71 (t,
j=8.09Hz, 1H, Ph), 2.82 (s, 3H, CH
3); ESI-MS:322 (M-1); Anal. calcd. For C
11h
9n
5o
3s
2: C 40.86, and H 2.81, and N 21.66; Found:C 40.89, and H 3.01, N 21.66.
The preparation of example 4:N-(5-(4-aminomethyl phenyl))-N '-(4-methyl isophthalic acid, 2,3-thiadiazoles-5-yl)-thiocarbamide
In the round-bottomed flask of 100mL, in acyl chlorides 10mmol is dissolved in the solution of 20 mL tetrahydrofuran (THF)s, adds and be dissolved with 0.97g(10mmol) NH
4pEG-600 solution (the 10mL of the methylene dichloride of NCS, methylene dichloride 9.5 mL wherein, PEG-600 0.5 mL), stirring and refluxing 15min, standing cooling, suction filtration, obtain orange solution, adds prepared 10mmol 4-monomethylaniline to be dissolved in the solution of 5 mL tetrahydrofuran (THF)s, stirring at room 10h, standing over night, suction filtration, get the mixed solvent recrystallization that filter cake mixes with volume ratio 3:1 with DMF and water and obtain product.
Yellow solid, productive rate 88.9 %, fusing point: 137-138 ℃;
1h NMR:12.10 (s, 1H, NH), 11.96 (s, 1H, NH), 7.53 (d,
j=8.30Hz, 2H, Ph), 7.22 (d,
j=8.30Hz, 2H, Ph), 2.80 (s, 3H, CH
3), 2.31 (s, 3H, CH
3); ESI-MS:291 (M-1); Anal. calcd. For C
12h
12n
4oS
2: C 49.29, and H 4.14, and N 19.16; Found:C 49.10, and H 4.56, N 19.44.
The preparation of example 5:N-(5-(4-nitrophenyl))-N '-(4-methyl isophthalic acid, 2,3-thiadiazoles-5-yl)-thiocarbamide
In the round-bottomed flask of 100mL, in acyl chlorides 10mmol is dissolved in the solution of 10 mL methylene dichloride, adds and be dissolved with 0.97g(10mmol) NH
4pEG-600 solution (the 10mL of the methylene dichloride of NCS, methylene dichloride 9.5 mL wherein, PEG-600 0.5 mL), stirring and refluxing 15min, standing cooling, suction filtration, obtain orange solution, adds prepared 10mmol 4-N-methyl-p-nitroaniline to be dissolved in the solution of 5 mL methylene dichloride, stirring at room 10h, standing over night, suction filtration, get the mixed solvent recrystallization that filter cake mixes with volume ratio 1:1 with DMF and water and obtain product.
Yellow solid, productive rate 87.6 %, fusing point: 175-177 ℃;
1h NMR:12.31 (bs, 2H, NH), 8.28 (d,
j=9.10Hz, 2H, Ph), 8.04 (d,
j=9.10Hz, 2H, Ph), 2.81 (s, 3H, CH
3); ESI-MS:322 (M-1); Anal. calcd. For C
11h
9n
5o
3s
2: C 40.86, and H 2.81, and N 21.66; Found:C 40.77, and H 2.78, N 21.54.
The fungicidal activity test of compound
Adopt biomass growth rate assay method (mycelium growth rate test), reagent agent is diluted to certain multiple under aseptic condition, then respectively drawing the 1mL liquid injects in culture dish, the LB substratum that adds respectively again 9mL, make 50 ug/mL pastille flat boards after shaking up, with the flat board that adds the 1mL aqua sterilisa, do blank.Cut the bacterium dish with the punch tool of diameter 4mm along the mycelia outer rim, move on the pastille flat board.Every processing triplicate.Culture dish is placed in 24 ± 1 ℃ of constant incubators and cultivates.Within 72 hours, " Invest, Then Investigate " is respectively processed bacterium dish expansion diameter, averages, and with blank, relatively calculates relative bacteriostasis rate, sees the following form 1.
Table 1. is implemented the fungicidal activity (50 ppm, % inhibiting rate) of compound
Claims (10)
1. one kind suc as formula the N-4-methyl isophthalic acid shown in I, 2,3-thiadiazoles-4-acyl group-N-substituted-phenyl base thiourea derivative:
I
In formula I, R is chlorine, fluorine, nitro, methyl etc.
2. as claimed in claim 1 suc as formula the N-4-methyl isophthalic acid shown in I, the preparation method of 2,3-thiadiazoles-4-acyl group-N-substituted-phenyl thiourea derivative is characterized in that described method is:
Chloride compounds shown in formula II is dissolved in organic solvent A and obtains solution A, NH
4nCS is dissolved in methylene dichloride and polyoxyethylene glycol PEG600 and obtains solution B, wherein the consumption of polyoxyethylene glycol PEG600 is 3 ~ 5% of methylene dichloride quality, solution B adds in solution A, heated and stirred back flow reaction 15 ~ 100min, then standing cooling, suction filtration, add solution C in filtrate, described solution C is that the 5-shown in formula IV replaces-1, 3, 4-thiadiazoles-2-aminated compounds is dissolved in organic solvent C and obtains, stirring at room reaction 7 ~ 10 hours, after reaction finishes, the reaction solution separating treatment obtains the N-4-methyl isophthalic acid, 2, 3-thiadiazoles-4-acyl group-N-substituted-phenyl thiourea derivative product, described organic solvent A is acetonitrile, tetrahydrofuran (THF) or methylene dichloride, described organic solvent C is acetonitrile, tetrahydrofuran (THF) or methylene dichloride, chloride compounds shown in described formula II, NH
4the ratio of the amount of substance of the substituted aniline compounds shown in NCS, formula IV is 1:1:1,
In formula IV, R is chlorine, fluorine, nitro, methyl.
3. method as claimed in claim 2; it is characterized in that described reaction solution method for separating and processing is: after reaction finishes; standing 5 ~ 15 hours of reaction solution; get filter cake after suction filtration; obtain N-4-methyl isophthalic acid with arbitrary volume than the mixed solvent recrystallization mixed with DMF and water; 2,3-thiadiazoles-4-acyl group-N-substituted anilinic thiourea derivative product.
4. method as claimed in claim 2 is characterized in that described method is:
Chloride compounds shown in formula II is dissolved in organic solvent A and obtains solution A, NH
4nCS is dissolved in methylene dichloride and polyoxyethylene glycol PEG600 and obtains solution B, wherein the consumption of polyoxyethylene glycol PEG600 is 3 ~ 5% of methylene dichloride quality, solution B adds in solution A, heated and stirred back flow reaction 15 ~ 100min, then standing cooling, suction filtration, in filtrate, add the substituted aniline compounds shown in formula IV to be dissolved in the solution C obtained in organic solvent C, stirring at room reaction 7 ~ 10 hours, after reaction finishes, standing 5 ~ 15 hours of reaction solution, get filter cake after suction filtration, obtain N-4-methyl isophthalic acid with arbitrary volume than the mixed solvent recrystallization mixed with DMF and water, 2, 3-thiadiazoles-4-acyl group-N-substituted-phenyl thiourea derivative product, described organic solvent A is acetonitrile, tetrahydrofuran (THF) or methylene dichloride, described organic solvent C is acetonitrile, tetrahydrofuran (THF) or methylene dichloride, replacement chloride compounds shown in described formula II, NH
4the ratio of the amount of substance of the substituted aniline compounds shown in NCS, formula IV is 1:1:1.
5. as claimed in claim 1 suc as formula the N-4-methyl isophthalic acid shown in I, 2,3-thiadiazoles-4-acyl group-N-substituted anilinic thiourea derivative is as the application of sterilant.
6. application as claimed in claim 5, (5-(2 to it is characterized in that N-, the 5-dichlorophenyl)-N '-(4-methyl isophthalic acid, 2,3-thiadiazoles-5-yl)-thiocarbamide, N-(5-(3-nitrophenyl))-N '-(4-methyl isophthalic acid, 2,3-thiadiazoles-5-yl)-thiocarbamide, N-(5-(4-aminomethyl phenyl))-N '-(4-methyl isophthalic acid, 2,3-thiadiazoles-5-yl)-thiocarbamide, N-(5-(4-nitrophenyl))-N '-(4-methyl isophthalic acid, 2,3-thiadiazoles-5-yl)-thiocarbamide is as the application of the sterilant of wheat scab.
7. application as claimed in claim 5, (5-(2 to it is characterized in that N-, the 5-dichlorophenyl)-N '-(4-methyl isophthalic acid, 2,3-thiadiazoles-5-yl)-thiocarbamide, N-(5-(4-aminomethyl phenyl))-N '-(4-methyl isophthalic acid, 2,3-thiadiazoles-5-yl)-thiocarbamide, N-(5-(4-nitrophenyl))-N '-(4-methyl isophthalic acid, 2,3-thiadiazoles-5-yl)-thiocarbamide is as the application of the sterilant of the late blight of potato.
8. application as claimed in claim 5, (5-(2 to it is characterized in that N-, the 5-dichlorophenyl)-N '-(4-methyl isophthalic acid, 2,3-thiadiazoles-5-yl)-thiocarbamide, N-(5-(4-fluorophenyl)-N '-(4-methyl isophthalic acid, 2,3-thiadiazoles-5-yl)-thiocarbamide, N-(5-(3-nitrophenyl))-N '-(4-methyl isophthalic acid, 2,3-thiadiazoles-5-yl)-thiocarbamide, N-(5-(4-aminomethyl phenyl))-N '-(4-methyl isophthalic acid, 2,3-thiadiazoles-5-yl)-thiocarbamide, N-(5-(4-nitrophenyl))-N '-(4-methyl isophthalic acid, 2,3-thiadiazoles-5-yl)-thiocarbamide is as the application of the sterilant of ring rot of apple.
9. application as claimed in claim 5, (5-(2 to it is characterized in that N-, the 5-dichlorophenyl)-N '-(4-methyl isophthalic acid, 2,3-thiadiazoles-5-yl)-thiocarbamide, N-(5-(4-fluorophenyl)-N '-(4-methyl isophthalic acid, 2,3-thiadiazoles-5-yl)-thiocarbamide, N-(5-(3-nitrophenyl))-N '-(4-methyl isophthalic acid, 2,3-thiadiazoles-5-yl)-thiocarbamide, N-(5-(4-aminomethyl phenyl))-N '-(4-methyl isophthalic acid, 2,3-thiadiazoles-5-yl)-thiocarbamide, N-(5-(4-nitrophenyl))-N '-(4-methyl isophthalic acid, 2,3-thiadiazoles-5-yl)-thiocarbamide is as the application of the sterilant of cucumber Fusarium oxysporum.
10. application as claimed in claim 5, (5-(2 to it is characterized in that N-, the 5-dichlorophenyl)-N '-(4-methyl isophthalic acid, 2,3-thiadiazoles-5-yl)-thiocarbamide, N-(5-(4-fluorophenyl)-N '-(4-methyl isophthalic acid, 2,3-thiadiazoles-5-yl)-thiocarbamide, N-(5-(3-nitrophenyl))-N '-(4-methyl isophthalic acid, 2,3-thiadiazoles-5-yl)-thiocarbamide, N-(5-(4-nitrophenyl))-N '-(4-methyl isophthalic acid, 2,3-thiadiazoles-5-yl)-thiocarbamide is as the application of the sterilant of the cercospora brown spot of peanut.
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| CN106699776A (en) * | 2016-07-28 | 2017-05-24 | 浙江工业大学 | 1,2,4-triazolothiadiazole thioether derivative and preparation method and application thereof |
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| CN101973959A (en) * | 2010-06-12 | 2011-02-16 | 利尔化学股份有限公司 | 4-methyl-1,2,3-thiadiazole-5-formyl urea compounds and preparation method and application thereof |
| CN102367240A (en) * | 2011-01-25 | 2012-03-07 | 华东理工大学 | 1,2,3-thiadiazole mother ring-contained iminothiazolone compounds, intermediate thereof, and preparation methods and applications of compound and intermediate |
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| CN101973959A (en) * | 2010-06-12 | 2011-02-16 | 利尔化学股份有限公司 | 4-methyl-1,2,3-thiadiazole-5-formyl urea compounds and preparation method and application thereof |
| CN102367240A (en) * | 2011-01-25 | 2012-03-07 | 华东理工大学 | 1,2,3-thiadiazole mother ring-contained iminothiazolone compounds, intermediate thereof, and preparation methods and applications of compound and intermediate |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106699776A (en) * | 2016-07-28 | 2017-05-24 | 浙江工业大学 | 1,2,4-triazolothiadiazole thioether derivative and preparation method and application thereof |
| CN106699776B (en) * | 2016-07-28 | 2019-04-26 | 浙江工业大学 | A kind of 1,2,4- Triterpenic acid sulfide derivative and its preparation method and application |
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