CN102367240B - 1,2,3-thiadiazole mother ring-contained iminothiazolone compounds, intermediate thereof, and preparation methods and applications of compound and intermediate - Google Patents
1,2,3-thiadiazole mother ring-contained iminothiazolone compounds, intermediate thereof, and preparation methods and applications of compound and intermediate Download PDFInfo
- Publication number
- CN102367240B CN102367240B CN201110027500.0A CN201110027500A CN102367240B CN 102367240 B CN102367240 B CN 102367240B CN 201110027500 A CN201110027500 A CN 201110027500A CN 102367240 B CN102367240 B CN 102367240B
- Authority
- CN
- China
- Prior art keywords
- group
- phenyl
- thiadiazole
- compound
- compounds
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 0 C**C(C)N=*=* Chemical compound C**C(C)N=*=* 0.000 description 1
Landscapes
- Nitrogen- Or Sulfur-Containing Heterocyclic Ring Compounds With Rings Of Six Or More Members (AREA)
- Plural Heterocyclic Compounds (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
The invention relates to 1,2,3-thiadiazole mother ring-contained iminothiazolone (iminothiazolidinethione) compounds (A), an acylthiourea intermediate (B) thereof, preparations of possible optical isomers, cis-isomers, trans-isomers, or pharmaceutically acceptable salts thereof, and an application of the compounds (A) as a plant disease control agent. The compounds have a high disease resistance induction activity on plant diseases (such as paddy rice sheath blight, paddy rice bacterial leaf blight, paddy rice blast, tomato spot diseases, cucurbit anthracnose, cucurbit powdery mildew and the like).
Description
Technical field
The present invention relates to containing 1; 2; acceptable salt in the imide thiazolone compounds (alkane ketone or thioketones) of 3-thiadiazole mother ring, its acylthioureas type intermediate and possible optical isomer, cis-trans-isomer or Pesticide Science; their preparation method, and they are as the application of plant disease controlling agent.
Background technology
Tradition agricultural chemicals is that directly to kill harmful organism be target mostly, unavoidably can bring the problem of pesticide hazards, therefore the research and development of green chemical pesticide, production and application become the great matter of science and technology concerning industrial or agricultural progress, environmental ecology Sustainable development, food safety and health and even social stability.In the novel green chemical pesticide with brand-new mechanism of action, utilizing the system of defense of plant self and useful secondary metabolite to carry out preventing disease pest control is one of main direction of novel pesticide exploitation from now on.
Plant is subject to pathogen induction can produce the disease-resistant performance of system, also claims systemic acquired resistance, and the induction of chemical substance (Plant activator) also can produce systemic acquired resistance.Plant activator has following features compared with traditional agricultural chemicals: (1) is own without obvious sterilization or bacteriostatic action, just can excite the autoimmunization of plant in condition of living body; (2) disease resistance that induction produces has holding effect and wide spectrum characteristic; (3) plant that induction is processed is through showing resistance to pathogenic bacteria after a period of time; (4) be difficult for developing immunity to drugs; (5) on not thering is pathogenic bacterium without impact, free from environmental pollution, be conducive to maintain ecosystem complexity and delicate balance and environment protection, be typical environmental agricultural chemicals.Therefore, Plant activator becomes the new focus of current novel pesticide initiative research.
The abiotic source Plant activator of having reported has endogenous ethene (Et), Whitfield's ointment (SA), jasmonic (JA), external source have a diazosulfide (BTH), beta-aminobutyric acid (BABA), 2, 6-dichloro-isonicotinic acid (INA) and formicester thereof, N-cyanogen methyl-2-chlorine Isonicotinamide (NCI), allyl isothiazole (Probenazole), 2, 2-bis-chloro-3, 3-diformazan basic ring the third carboxylic ester (DDCC), wintergreen oil (MeSA) derivative, [the J.Pesticide Sci such as methyl jasmonate (MJ), 1992, 6, 107.Plant Pathology, 1992, 41, 444.].At present, commercial Plant activator has: the activating plants agent Acibenzolar BTH (benzo [1 of Syngenta exploitation, 2,3]-thiadiazoles-7-thiocarboxylic acid methyl esters) and the activating plants agent tiadinil TDL (3 '-chloro-4 of Japanese agricultural chemicals Zhu Shi commercial firm research and development, 4 '-dimethyl-1,2,3-thiadiazoles-5-formylaniline).Studies confirm that, in lead compound, introduce 1,2,3-thiadiazoles group, conventionally can improve biological activity or expand its biological activity spectrum.
The object of the invention is; serve and preserve the ecological environment, create the general orientation of Modern Green agricultural, for the disease control of cash crop; on the basis of appropriate design, initiative novel structure, be convenient to suitability for industrialized production, quality and cost and can obtain the disease-resistant activator of fine control.
Summary of the invention
The object of the invention is, the synthetic of imide thiazolidine (sulphur) ketone compounds of a class containing 1,2,3-thiadiazole mother ring and acylthioureas type intermediate thereof and the purposes aspect plant protection thereof are provided.
A kind of acylthioureas type intermediate containing 1,2,3-thiadiazole mother ring, is characterized in that, contains following structural formula:
Wherein, R
1, R
2be selected from independently of one another following group: H, C
1～C
9saturated or the unsaturated alkyl of straight or branched or ring-type, be with substituent C
1～C
9saturated or unsaturated alkyl, phenyl, substituted-phenyl, benzyl, substituted benzyl and five yuan or the hexa-member heterocycle of straight or branched or ring-type;
Described substituting group is halogeno-group, hydroxyl, alkoxyl group, amino, substituted-amino, carboxyl, cyano group, ester group, amide group or nitro;
Described five yuan or hexa-member heterocycle is nitrogenous, one or more in oxygen, three kinds of elements of sulphur;
X
1for O or S.
Described R
1can also be selected from the group of following structure:
wherein A, B are H or C
1～C
9alkyl.Preferably, described R
1for the one in methyl, ethyl, propyl group, chloromethyl, brooethyl, phenyl, substituted-phenyl; More preferably, be methyl, ethyl, chloromethyl.
Described R
2be selected from H, C
1～C
5saturated or unsaturated alkyl, the C in fluorine or chlorine generation
1～C
5saturated or unsaturated alkyl, phenyl or substituted-phenyl and five yuan or hexa-member heterocycle.
The imide thiazolone compound that above-mentioned arbitrary described acylthioureas type intermediate containing 1,2,3-thiadiazole mother ring obtains, has following structural formula:
Wherein, R
1, R
2be selected from independently of one another following group: H, C
1～C
9saturated or the unsaturated alkyl of straight or branched or ring-type, be with substituent C
1～C
9saturated or unsaturated alkyl, phenyl, substituted-phenyl, benzyl, substituted benzyl and five yuan or the hexa-member heterocycle of straight or branched or ring-type;
R
3, R
4independently be selected from separately following group: H, C
1～C
9saturated or the unsaturated alkyl of straight or branched, be with substituent C
1～C
9saturated or unsaturated alkyl and the halogeno-group of straight or branched; Or R
3and R
4common formation-CH
2-X
m-(CH
2)
n-CH
2-, wherein X=O, NH, NR, S, m=0,1 or 2, n=0,1,2,3 or 4; Or R
3and R
4singly-bound merging is constructed as follows double bond structure.
Wherein, R
5, R
6be selected from independently of one another following group: H, C
1～C
9saturated or the unsaturated alkyl of straight or branched or ring-type, be with substituent C
1～C
9saturated or unsaturated alkyl, phenyl, substituted-phenyl, benzyl, substituted benzyl and five yuan or the hexa-member heterocycle of straight or branched or ring-type;
Described substituting group is halogeno-group, hydroxyl, alkoxyl group, amino, substituted-amino, carboxyl, cyano group, ester group, amide group or nitro;
Described five yuan or hexa-member heterocycle is nitrogenous, one or more in oxygen, three kinds of elements of sulphur;
X
1for O or S, X
2for O or S; X
1, X
2for being preferably O;
Described R
1can also be:
wherein A, B are H or C
1～C
9alkyl.
Described imide thiazolone compound comprises acceptable salt in optical isomer, cis-trans-isomer or Pesticide Science.
The preparation method of above-mentioned imide thiazolone compound, comprises following steps:
A) acylhydrazone that 'beta '-ketoester and acethydrazide form carries out ring-closure reaction under certain temperature of reaction and thionyl chloride existence;
B) product of above-mentioned ring-closure reaction is hydrolyzed and chloride;
C) the synthetic preparation with acylthioureas derivative of the original position of acyl group lsothiocyanates;
D) build imide thiazolone heterocycle by the halogenated acetic acids ester of replacement and the ring-closure reaction of above-mentioned product, obtain described imide thiazolone compound;
E) at R
3=R
4in the situation of=H, can there is by Knoevenagel type reaction preparation the product of lower area structure character:
The application of acylthioureas type intermediate and imide thiazolone compound as mentioned above, for the preparation of plant disease controlling agent.The example of Plant diseases includes but not limited to: rice sheath blight disease, bacterial blight of rice, rice blast, tomato spot disease, melon anthrax, cucurbits powdery mildew etc.
Described R
2preferably C
1～C
3saturated alkyl, phenyl or substituted-phenyl.
General formula is that the synthetic method of (A) and compound (B) is as follows:
Wherein, the compound that general structure is 5 also can be by compound 4 (R in the compound that general structure is 5
3=R
4=H) the reaction preparation of Knoevenagel type.In the reaction of Knoevenagel type, the mol ratio of thiazolidine (sulphur) ketone and aldehyde is 1: 1～1.5.
Embodiment
Below by embodiment, the present invention is specifically described.Be necessary to be pointed out that at this; following examples are only for the invention will be further described; can not be interpreted as limiting the scope of the invention, some nonessential improvement and adjustment that the professional and technical personnel in this field content according to the present invention is made, still belong to protection scope of the present invention.
Embodiment 1
In a 100mL round-bottomed flask, add 26.41g (0.3mol) ethyl acetate, under stirring at room temperature, slowly splash into 14.72g (0.25mol) hydrazine hydrate, room temperature reaction 3h, after reaction finishes, ethanol, water and remaining ethyl acetate are removed in underpressure distillation, obtain crude product acethydrazide 18.15g (productive rate 98%).
Embodiment 2
In a 50mL round-bottomed flask, add 14.82g (0.22mol) acethydrazide, 10mL dehydrated alcohol, under stirring, slowly splash into 26.03g (0.2mol) methyl aceto acetate, dropwise rear backflow 2h, after reaction finishes (TLC follows the tracks of reaction), ethanol is removed in underpressure distillation, residual solids is poured in 50mL frozen water, after filtering, be dried to obtain thick product 35.75g (productive rate 96%).
Embodiment 3
In a 100mL round-bottomed flask, add 17mL (0.24mol) sulfur oxychloride, 20mL chloroform, the cooling lower gradation of ice bath adds 37.25g (0.2mol) 3-acetyl hydrazone-ethyl butyrate, keeps temperature to add.Remove ice bath, continue to stir 6h under room temperature, after reaction finishes (TLC tracking), chloroform and excess chlorination sulfoxide are removed in underpressure distillation, and underpressure distillation obtains colourless transparent liquid 27.87g (productive rate 81%).
Embodiment 4
In a 100mL round-bottomed flask, add 17.21g (0.1mol) 4-methyl isophthalic acid, 2,3-thiadiazoles-5-ethyl formate, 20mL dehydrated alcohol, under stirring at room temperature, splash into the saturated aqueous solution that 4.83g (0.12mol) sodium hydroxide is made into, under room temperature, react 30min, after reaction finishes (TLC tracking), ethanol is removed in underpressure distillation, in remaining aqueous solution, slowly drip concentrated hydrochloric acid, to system be slightly acidic, separate out a large amount of white solids, after filtering, recrystallization (dehydrated alcohol) obtains white solid 15.76g (productive rate 92%).
Embodiment 5
In a 50mL round-bottomed flask, add 7.24g (50mmol) 4-methyl isophthalic acid, 2,3-thiadiazoles-5-formic acid, 5mL (60mmol) sulfur oxychloride, two DMF, reflux 2h, reaction finishes rear underpressure distillation and removes excess chlorination sulfoxide, underpressure distillation obtains colourless liquid 7.77g (productive rate 96%), and sealing is preserved.
Embodiment 6
In a 50mL round-bottomed flask, add 0.84g (0.011mol) ammonium thiocyanate and 5mL acetonitrile, under ice bath stirs, slowly drip 1.62g (0.01mol) 4-methyl 1,2,3-thiadiazoles-5-formyl chloride, dropwise rear continuation and stir 30min, after reaction finishes (TLC follows the tracks of reaction).Drip again the solution that 0.93g (0.01mol) aniline and 3mL acetonitrile are made into, dropwise rear continuation and stir 30min.After reaction finishes (TLC follows the tracks of reaction), mixture is poured in 30mL water, leached yellow mercury oxide, recrystallization (95% ethanol) obtains 2.39g yellow solid (productive rate 86%).
1H NMR(400MHz，DMSO-d
6)δ(ppm)：12.17(s，1H，O＝C-NH)，12.07(s，1H，Ph-NH)，7.69(d，J＝7.8Hz，2H，Ph-H)，7.44(t，J＝7.8Hz， 2H，Ph-H)，7.29(t，J＝7.3Hz，1H，Ph-H)，2.82(s，3H，N-C-CH
3)。
Embodiment 7
In a 50mL round-bottomed flask, add 0.84g (0.011mol) ammonium thiocyanate and 5mL acetonitrile, under ice bath stirs, slowly drip 1.62g (0.01mol) 4-methyl 1,2,3-thiadiazoles-5-formyl chloride, dropwise rear continuation and stir 30min, after reaction finishes (TLC follows the tracks of reaction).Drip again the solution that 1.07g (0.01mol) para-totuidine and 3mL acetonitrile are made into, dropwise rear continuation and stir 30min, after reaction finishes (TLC follows the tracks of reaction), mixture is poured in 30mL water, leached yellow mercury oxide, recrystallization (95% ethanol) obtains 2.51g yellow solid (productive rate 86%).
1H NMR(400MHz，DMSO-d
6)δ(ppm)：12.10(s，1H，O＝C-NH)，11.99(s，1H，Ph-NH)，7.54(d，J＝8.1Hz，2H，Ph-H)，7.22(d，J＝8.1Hz，2H，Ph-H)，2.80(s，3H，N-C-CH
3)，2.31(s，3H，Ph-CH
3)。
Embodiment 8
In a 50mL round-bottomed flask, add 0.85g (0.011mol) ammonium thiocyanate and 5mL acetonitrile, ice bath slowly drips 1.62g (0.01mol) 4-methyl 1,2,3-thiadiazoles-5-formyl chloride under stirring.Dropwise rear continuation and stir 30min, after reaction finishes (TLC follows the tracks of reaction), then drip the solution that 1.07g (0.01mol) Ortho Toluidine and 3mL acetonitrile are made into.Dropwise rear continuation and stir 30min, after reaction finishes (TLC follows the tracks of reaction), mixture is poured in 30mL water, leach yellow mercury oxide, recrystallization (95% ethanol) obtains 2.38g yellow solid (productive rate 82%).
1H NMR(400MHz，DMSO-d
6)δ(ppm)：12.22(s，1H，O＝C-NH)，11.81(s，1H，Ph-NH)，7.56(d，J＝6.8Hz，1H，Ph-H)，7.29(m，3H，Ph-H)，2.83(s，3H，N-C-CH
3)，2.28(s，3H，Ph-CH
3)。
Embodiment 9
In a 50mL round-bottomed flask, add 1.46g (5mmol) N-(4-methyl 1,2,3-thiadiazoles-5-formyl)-N '-(4-aminomethyl phenyl) thiocarbamide, 1.01g (6mmol) ethyl bromoacetate, 0.49g (6mmol) anhydrous sodium acetate and 5mL dehydrated alcohol, reflux, system becomes purple by yellow gradually, continue reaction 1h, after reaction finishes (TLC follows the tracks of reaction), ethanol is removed in underpressure distillation.Gained solid recrystallization (95% ethanol) obtains 1.44g purple solid (productive rate 87%).
1H NMR(400MHz，DMSO-d
6)δ(ppm)：7.36(d，J＝7.8Hz，2H，Ph-H)，7.25(d，J＝7.8Hz，2H，Ph-H)，4.21(s，2H，CH
2)，2.70(s，3H，N-C-CH
3)，2.40(s，3H，Ph-CH
3)。
Embodiment 10
In a 50mL round-bottomed flask, add 1.48g (0.01mol) N-(4-methyl 1,2,3-thiadiazoles-5-formyl)-N '-(3-fluorophenyl) thiocarbamide, 1.00g (6mmol) ethyl bromoacetate, 0.49g (6mmol) anhydrous sodium acetate and 5mL dehydrated alcohol, reflux, system becomes purple by yellow gradually, continue reaction 1h, after reaction finishes (TLC follows the tracks of reaction), ethanol is removed in underpressure distillation.Gained solid recrystallization (95% ethanol) obtains 1.43g purple solid (productive rate is 88%).
1H NMR(400MHz，DMSO-d
6)δ(ppm)：7.64(m，1H，Ph-H)，7.39(m，2H，Ph-H)，7.30(d，J＝8.0Hz，1H，Ph-H)，4.25(s，2H，CH
2)，2.73(s，3H，N-C-CH
3)。
Embodiment 11
In a 25mL round-bottomed flask, add 0.15g (0.5mmol) 3-(phenyl)-2-(4-methyl 1,2,3-thiadiazoles-5-formyl) imines-4-thiazolidone, 0.07g (0.6mmol) p-tolyl aldehyde, two piperidines and 5mL dehydrated alcohol, back flow reaction 30min, separate out yellow solid, after reaction finishes, (TLC follows the tracks of reaction) filtration, recrystallization (chloroform: dehydrated alcohol) obtain 0.20g yellow solid (productive rate 95%).
1H NMR(400MHz，CDCl
3)δ(ppm)：8.03(s，1H，CH)，7.60(d，J＝7.45Hz，5H，Ph-H)，7.36(t，J＝8.63Hz，4H，Ph-H)，2.89(s，3H，N-C-CH
3)，2.46(s，3H，Ph-CH
3)。
Embodiment 12
In a 25mL round-bottomed flask, add 0.16g (0.5mmol) 3-(4-aminomethyl phenyl)-2-(4-methyl 1,2,3-thiadiazoles-5-formyl) imines-4-thiazolidone, 0.06g (0.6mmol) phenyl aldehyde, two piperidines and 5mL dehydrated alcohol, back flow reaction 30min, separate out yellow solid, after reaction finishes, (TLC follows the tracks of reaction) filtration, recrystallization (chloroform: dehydrated alcohol) obtain 0.20g yellow solid (productive rate 99%).
1H NMR(400MHz，CDCl
3)δ(ppm)：8.03(s，1H，CH)，7.67(s，2H，Ph-H)，7.51(s，3H，Ph-H)，7.37(s，2H，Ph-H)，2.89(s，3H，N-C-CH
3)，2.48(s，3H，Ph-CH
3)。
The biological activity test method of related compound
Calculate the extension rate of test preparation according to the effective content of reagent agent, prepare medicament by experimental concentration, the induction (reagent agent and contrast the medicament induction of all spraying) of spraying for the first time immediately after cucumber seedling is unearthed, reagent agent is evenly sprayed application to the positive back side of blade, be advisable with blade face droplet uniformity, every induction in 3 days 1 time, continuous induction 3 times, the 3rd induction inoculation in latter 3 days.Each pathogenic bacteria all adopts spray pattern inoculation.
Calculate preventive effect according to the state of an illness of grade scale investigation below.
Sick leaf grade scale:
0 grade: without 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 the more than 50 of whole leaf area.
Drug effect method of calculation: press column index formula according to disease index and calculate prevention effect, then press the significance of difference of preventive effect between the processing of DMRT method mensuration.
The inducing anti-disease activity example of part of compounds of the present invention
The structure of example compound and numbering are as follows:
Table 1 is the inducing anti-disease activity example [reagent agent is all established 50ppm (50mg/L)] to bacterial spot of tomato
Table 1
Table 2 is target compound inducing anti-disease results [reagent agent is all established 50ppm (50mg/L)] to rice sheath blight disease
Table 2
| Compound structure | Average disease refers to | Preventive effect (%) |
| P-A-01 | 42.22 | 52.03 |
| P-A-02 | 27.78 | 68.44 |
| P-A-03 | 41.48 | 52.88 |
| P-A-04 | 26.79 | 69.57 |
| P-A-05 | 44.44 | 49.51 |
| P-A-06 | 37.28 | 57.64 |
| P-B-01 | 33.09 | 62.41 |
| P-B-02 | 35.93 | 59.19 |
| P-B-03 | 49.88 | 43.34 |
| P-B-04 | 32.84 | 62.69 |
| P-B-05 | 37.90 | 56.94 |
| P-B-06 | 33.46 | 61.99 |
| P-C-01 | 25.80 | 70.69 |
| P-C-02 | 27.53 | 68.72 |
| P-C-03 | 13.33 | 84.85 |
| P-C-04 | 21.48 | 75.60 |
| P-C-05 | 20.00 | 77.28 |
| P-C-06 | 32.22 | 63.39 |
| P-C-07 | 31.98 | 63.67 |
| P-C-08 | 37.78 | 57.08 |
| P-C-09 | 29.14 | 66.90 |
| P-C-10 | 46.42 | 47.27 |
| P-C-11 | 45.93 | 47.83 |
| P-C-12 | 42.59 | 51.61 |
| P-C-13 | 56.54 | 35.76 |
| P-C-14 | 43.70 | 50.35 |
| P-C-15 | 64.20 | 27.07 |
| P-C-16 | 43.58 | 50.49 |
| P-C-17 | 9.88 | 88.78 |
| P-C-18 | 18.27 | 79.24 |
| P-C-19 | 40.12 | 54.42 |
| P-C-20 | 32.35 | 63.25 |
| P-C-21 | 21.36 | 75.74 |
| P-C-22 | 42.59 | 51.61 |
| P-C-23 | 34.69 | 60.59 |
| P-C-24 | 27.53 | 68.72 |
| P-C-25 | 31.28 | 64.47 |
| P-C-26 | 29.38 | 66.62 |
| P-C-27 | 28.15 | 68.02 |
| P-C-28 | 46.79 | 46.84 |
| P-C-29 | 38.89 | 55.82 |
| P-C-30 | 27.16 | 69.14 |
| P-C-31 | 12.10 | 86.26 |
| P-C-32 | 35.68 | 59.47 |
| P-C-33 | 29.51 | 66.48 |
| P-C-34 | 27.04 | 69.28 |
| P-C-35 | 37.78 | 57.08 |
| P-C-36 | 29.51 | 66.48 |
| P-C-37 | 52.10 | 40.81 |
Claims (4)
1. the acylthioureas type intermediate containing 1,2,3-thiadiazole mother ring, is characterized in that, contains following structural formula:
Wherein, R
1be selected from H, C
1～C
9the saturated hydrocarbyl of straight or branched, be with substituent C
1～C
9the saturated hydrocarbyl of straight or branched;
R
2be selected from phenyl, substituted-phenyl;
Described substituting group is halogeno-group, hydroxyl, alkoxyl group, amino, cyano group or nitro;
X
1for O.
2. one according to claim 1, containing the acylthioureas type intermediate of 1,2,3-thiadiazole mother ring, is characterized in that described R
1for the one in methyl, ethyl, propyl group, chloromethyl, brooethyl.
3. the imide thiazolone compound that the acylthioureas type intermediate containing 1,2,3-thiadiazole mother ring described in claim 1 or 2 obtains, is characterized in that, described imide thiazolone compound has following structural formula:
Wherein, R
1be selected from H, C
1～C
9the saturated hydrocarbyl of straight or branched, be with substituent C
1～C
9the saturated hydrocarbyl of straight or branched, R
2be selected from phenyl, substituted-phenyl;
R
3, R
4be selected from H; Or R
3and R
4singly-bound merging is constructed as follows double bond structure:
Wherein, R
5, R
6be selected from independently of one another following group: H, phenyl, substituted-phenyl;
Described substituting group is halogeno-group, hydroxyl, alkoxyl group, amino, cyano group or nitro;
X
1for O, X
2for O.
4. the application of the acylthioureas type intermediate described in claim 1 or 2 or imide thiazolone compound claimed in claim 3, is characterized in that, for the preparation of plant disease controlling agent, described Plant diseases is selected from rice sheath blight disease, tomato spot disease.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110027500.0A CN102367240B (en) | 2011-01-25 | 2011-01-25 | 1,2,3-thiadiazole mother ring-contained iminothiazolone compounds, intermediate thereof, and preparation methods and applications of compound and intermediate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110027500.0A CN102367240B (en) | 2011-01-25 | 2011-01-25 | 1,2,3-thiadiazole mother ring-contained iminothiazolone compounds, intermediate thereof, and preparation methods and applications of compound and intermediate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102367240A CN102367240A (en) | 2012-03-07 |
| CN102367240B true CN102367240B (en) | 2014-06-18 |
Family
ID=45759836
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201110027500.0A Expired - Fee Related CN102367240B (en) | 2011-01-25 | 2011-01-25 | 1,2,3-thiadiazole mother ring-contained iminothiazolone compounds, intermediate thereof, and preparation methods and applications of compound and intermediate |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102367240B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2016087257A1 (en) * | 2014-12-01 | 2016-06-09 | Syngenta Participations Ag | Pesticidally active amide heterocyclic derivatives with sulphur containing substituents |
Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103102330B (en) * | 2012-11-29 | 2015-02-25 | 浙江工业大学 | N-4-methyl-1,2,3-thiadiazole-4-acyl-N-substituted phenylthiourea derivative as well as preparation and application thereof |
| CN103058955B (en) * | 2012-11-29 | 2015-02-25 | 浙江工业大学 | Thiadiazole thiourea derivative as well as preparation and application thereof as plant growth regulator |
| CN103012316B (en) * | 2012-11-29 | 2015-03-25 | 浙江工业大学 | N-4-methyl-1,2,3-thiadiazole-4-acyl-N-substituted 1,3,4-thiadiazole thiourea derivative and preparation method and application thereof |
| CN103044413B (en) * | 2012-11-29 | 2015-05-06 | 浙江工业大学 | Thiadiazolyl thiourea derivative, as well as preparation and application thereof as plant growth regulator |
| CN103613564B (en) * | 2013-12-12 | 2015-05-06 | 浙江工业大学 | Preparation method of amido urea derivative containing 1, 2, 3-thiadiazole |
| WO2015177063A1 (en) * | 2014-05-19 | 2015-11-26 | Syngenta Participations Ag | Insecticidally active amide derivatives with sulfur-substituted phenyl or pyridine groups |
| CN106665605A (en) * | 2016-12-26 | 2017-05-17 | 蔡志浩 | Compound botanical fungicide |
| CN106665607A (en) * | 2016-12-26 | 2017-05-17 | 蔡志浩 | Compound plant fungicide |
| CN107935961B (en) * | 2017-12-01 | 2019-10-29 | 赣南师范大学 | A kind of preparation method of 2- imino thiazole alkane -4- ketone compounds |
| MX2022000421A (en) * | 2019-07-10 | 2022-02-10 | Bayer Ag | Process of preparing 2-(phenylimino)-1,3-thiazolidin-4-ones. |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1180297A (en) * | 1995-03-31 | 1998-04-29 | 日本农药株式会社 | Agricultural and horticultural disease controller and method for controlling diseases |
| CN1207739A (en) * | 1995-12-07 | 1999-02-10 | 拜尔公司 | 1,2, 3-thiadiazole carboxylic acid (thio) esters and their use as pest control agents and microbicides |
| CN101020667A (en) * | 2007-03-12 | 2007-08-22 | 南开大学 | New compound with activity of inducing secondary metabolism of Hypericum plant |
-
2011
- 2011-01-25 CN CN201110027500.0A patent/CN102367240B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1180297A (en) * | 1995-03-31 | 1998-04-29 | 日本农药株式会社 | Agricultural and horticultural disease controller and method for controlling diseases |
| CN1207739A (en) * | 1995-12-07 | 1999-02-10 | 拜尔公司 | 1,2, 3-thiadiazole carboxylic acid (thio) esters and their use as pest control agents and microbicides |
| CN101020667A (en) * | 2007-03-12 | 2007-08-22 | 南开大学 | New compound with activity of inducing secondary metabolism of Hypericum plant |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2016087257A1 (en) * | 2014-12-01 | 2016-06-09 | Syngenta Participations Ag | Pesticidally active amide heterocyclic derivatives with sulphur containing substituents |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102367240A (en) | 2012-03-07 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102367240B (en) | 1,2,3-thiadiazole mother ring-contained iminothiazolone compounds, intermediate thereof, and preparation methods and applications of compound and intermediate | |
| EP0639574B1 (en) | 2-aminothiazolecarboxamide derivatives, processes for their preparation and their use for controlling phytopathogenic organisms | |
| CA2195064C (en) | Amino-acid amide derivatives, processes for preparing the same, agricultural or horticultural fungicides, and method for killing fungi | |
| AU671682B2 (en) | N-acetonylbenzamides and their use as fungicides | |
| EP2017268B1 (en) | 1,2-benzisothiazole derivative, and agricultural or horticultural plant disease-controlling agent | |
| EA038960B1 (en) | Herbicidal phenylpyrimidines | |
| JP5500582B2 (en) | Pyrazole-4-carboxamide derivatives, methods for producing them, and fungicides containing them as active ingredients | |
| JPS6147403A (en) | Method of repelling plant pathoginic fungi by use of fungicidal composition containing n-acetonylbenzamide | |
| US20220348550A1 (en) | 2-(1,2,4-triazolyl) benzoyl arylamine active compound for inhibiting wheat take-all pathogen | |
| CN110183386B (en) | Diclazuril derivative, application thereof and bactericide containing diclazuril derivative | |
| JPH0812510A (en) | Pyrazolecarboxylic acid derivative and plant blight controlling agent | |
| RU2036195C1 (en) | Benzimidazole derivatives and intermediate compounds for their synthesis | |
| RU2475490C1 (en) | N-ACYLATED 3-AMINO-4,6-DIMETHYLTHIENO[2,3-b]PYRIDINE-2-CARBOXAMIDES AS ANTIDOTES OF 2,4-D ON SUNFLOWER | |
| JP4478854B2 (en) | 2-anilinopyrimidinone derivatives and production intermediates, production methods thereof, and agricultural chemicals containing them as active ingredients | |
| CN102977088B (en) | 4-tertiary butyl-5-(1, 2, 4-triazole-1-base)-2-acylaminothiazole with bactericidal activity and method for preparing 4-tertiary butyl-5-(1, 2, 4-triazole-1-base)-2-acylaminothiazole with bactericidal activity | |
| CN108440412B (en) | 2-pyrazole amide cyclohexyl sulfonamide compound, preparation method and application thereof | |
| CN106543139A (en) | A kind of triadimefon compound and application thereof | |
| JP4270594B2 (en) | N-acetonylbenzamide compound having bactericidal activity | |
| CN114539180A (en) | Isoxazoline-containing bisamide compound and preparation method and application thereof | |
| CN110734403B (en) | (S) -2- (1H-pyrazole-4-formamido) propyl benzoate compound and preparation method and application thereof | |
| JP3310637B2 (en) | Amino acid amide derivatives | |
| CN106220559B (en) | N-3- pyridine acyl-dehydroabietylamine derivatives and its preparation method and application | |
| CN110963963A (en) | Pyridine amide compound and sterilization application thereof | |
| JP2834482B2 (en) | Herbicide composition | |
| US20100261920A1 (en) | Amide compound and bacterial disease control agent for agricultural and horticultural use |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20140618 Termination date: 20150125 |
|
| EXPY | Termination of patent right or utility model |