CN102367240A - 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
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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 contain 1; 2; Acceptable salt on the imide thiazolone compounds (alkane ketone or thioketones) of the female ring of 3-thiadiazoles, its acylthioureas type midbody and possible optical isomer, cis-trans-isomer or the Pesticide Science; Their preparation method, and they are as the application of plant disease controlling agent.
Background technology
The tradition agricultural chemicals is to be target directly to kill harmful organism mostly; Unavoidably can bring the problem of pesticide hazards, so the research and development of Green Chemistry agricultural chemicals, 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 having the novel green chemical pesticide of brand-new mechanism of action, utilizing system of defense and the useful secondary metabolite of plant self to come preventing disease pest control is one of main direction of novel pesticide exploitation from now on.
Plant receives pathogen to induce the disease-resistant performance of the system that can produce, and also claims systemic acquired resistance, and inducing also of chemical substance (plant disease-resistant activator) can produce systemic acquired resistance.Compare the plant disease-resistant activator with traditional agricultural chemicals following characteristics are arranged: (1) no obvious sterilization itself or bacteriostatic action just can excite the autoimmunization of plant in condition of living body; (2) induce the disease resistance of generation to have effect of holding and wide spectrum characteristic; (3) induce the plant of processing after after a while, could show resistance to pathogenic bacteria; (4) be difficult for developing immunity to drugs; (5) there is not influence to not having pathogenic bacterium, free from environmental pollution, help keeping complicated and delicate balance and the environment protection of the ecosystem, be typical environmental agricultural chemicals.Therefore, the plant disease-resistant activator becomes the new focus of current novel pesticide initiative research.
The abiotic source plant disease-resistant activator of having reported has endogenous ethene (Et), Whitfield's ointment (SA), jasmonic (JA), external source 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 arranged; 2-two chloro-3; The 3-diformazan basic ring third carboxylic ester (DDCC), wintergreen oil (MeSA) verivate, methyl jasmonate [J.Pesticide Sci, 1992,6 such as (MJ); 107.Plant Pathology; 1992,41,444.].At present; Commercial plant disease-resistant activator has: the plant activator Acibenzolar BTH (benzo [1 of Syngenta exploitation; 2,3]-thiadiazoles-7-thiocarboxylic acid methyl esters) and plant activator tiadinil TDL (3 '-chloro-4, the 4 '-dimethyl--1 of Japanese agricultural chemicals Zhu Shi commercial firm research and development; 2,3-thiadiazoles-5-formylaniline).Research confirms, in lead compound, introduces 1,2, and 3-thiadiazoles group can improve biological activity usually or enlarge its biological activity spectrum.
The object of the invention is; Serve and preserve the ecological environment, create the general orientation of modern green agriculture, to the disease control of cash crop; On the basis of appropriate design, formulate novel structure, be convenient to the disease-resistant activator that suitability for industrialized production, quality and cost can obtain fine control.
Summary of the invention
The object of the invention is, provides one type to contain 1,2, the synthetic and purposes aspect plant protection of imide thiazolidine (sulphur) ketone compounds of the female ring of 3-thiadiazoles and acylthioureas type midbody thereof.
A kind ofly contain 1,2, the acylthioureas type midbody of the female ring of 3-thiadiazoles is characterized in that, contains following structural formula:
Wherein, R
1, R
2Be selected from following group: H, C independently of one another
1～C
9Saturated or the unsaturated alkyl of straight or branched or cyclic, be with substituent C
1～C
9Straight or branched or cyclic saturated or unsaturated alkyl, phenyl, substituted-phenyl, benzyl, substituted benzyl and five yuan or hexa-member heterocycle;
Said substituting group is halogeno-group, hydroxyl, alkoxyl group, amino, substituted-amino, carboxyl, cyanic acid, ester group, carboxamido-group or nitro;
Said five yuan or hexa-member heterocycle is nitrogenous, in the oxygen, three kinds of elements of sulphur one or more;
X
1Be O or S.
Said R
1Can also be selected from the group of following structure:
Wherein A, B are H or C
1～C
9Alkyl.Preferably, said R
1A kind of in methyl, ethyl, propyl group, chloromethyl, brooethyl, phenyl, the substituted-phenyl; More preferably, be methyl, ethyl, chloromethyl.
Said R
2Be selected from H, C
1～C
5The C in saturated or unsaturated alkyl, fluorine or chlorine generation
1～C
5Saturated or unsaturated alkyl, phenyl or substituted-phenyl and five yuan or hexa-member heterocycle.
Above-mentionedly arbitraryly describedly contain 1; 2; The imide thiazolone compound that the acylthioureas type midbody of the female ring of 3-thiadiazoles obtains has following structural formula:
Wherein, R
1, R
2Be selected from following group: H, C independently of one another
1～C
9Saturated or the unsaturated alkyl of straight or branched or cyclic, be with substituent C
1～C
9Straight or branched or cyclic saturated or unsaturated alkyl, phenyl, substituted-phenyl, benzyl, substituted benzyl and five yuan or hexa-member heterocycle;
R
3, R
4Independently be selected from following group: H, C separately
1～C
9Saturated or the unsaturated alkyl of straight or branched, be with substituent C
1～C
9Saturated or the unsaturated alkyl and the halogeno-group of straight or branched; Perhaps 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; Perhaps R
3And R
4The singly-bound merging is constructed as follows double bond structure.
Wherein, R
5, R
6Be selected from following group: H, C independently of one another
1～C
9Saturated or the unsaturated alkyl of straight or branched or cyclic, be with substituent C
1～C
9Straight or branched or cyclic saturated or unsaturated alkyl, phenyl, substituted-phenyl, benzyl, substituted benzyl and five yuan or hexa-member heterocycle;
Said substituting group is halogeno-group, hydroxyl, alkoxyl group, amino, substituted-amino, carboxyl, cyanic acid, ester group, carboxamido-group or nitro;
Said five yuan or hexa-member heterocycle is nitrogenous, in the oxygen, three kinds of elements of sulphur one or more;
X
1Be O or S, X
2Be O or S; X
1, X
2For being preferably O;
Said R
1Can also be:
Wherein A, B are H or C
1～C
9Alkyl.
Said imide thiazolone compound comprises acceptable salt on optical isomer, cis-trans-isomer or the Pesticide Science.
The preparation method of above-mentioned imide thiazolone compound comprises following steps:
A) acylhydrazone of 'beta '-ketoester and acethydrazide formation is carrying out ring-closure reaction in the presence of certain temperature of reaction and THIONYL CHLORIDE 97;
B) product of above-mentioned ring-closure reaction is hydrolyzed and chloride;
C) the synthetic preparation with the acylthioureas verivate of the original position of acyl group lsothiocyanates;
D) ring-closure reaction through substituted halogenated acetic acids ester and above-mentioned product makes up imide thiazolone heterocycle, obtains said imide thiazolone compound;
E) at R
3=R
4Under the situation of=H, can have the product of following area structure character through Knoevenagel type prepared in reaction:
Acylthioureas type midbody and imide thiazolone application of compound are used to prepare plant disease controlling agent as stated.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.
Said R
2Preferred C
1～C
3Saturated alkyl, phenyl or substituted-phenyl.
General formula is that the compound method of (A) and compound (B) is following:
Wherein, general structure is that 5 compound also can (general structure be R in 5 the compound through compound 4
3=R
4=H) Knoevenagel type prepared in reaction.In the reaction of Knoevenagel type, the mol ratio of thiazolidine (sulphur) ketone and aldehyde is 1: 1～1.5.
Embodiment
Through embodiment the present invention is specifically described below.Be necessary to be pointed out that at this; Following examples only are used for the present invention is described further; Can not be interpreted as the restriction to protection domain of the present 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) ETHYLE ACETATE; Slowly splash into 14.72g (0.25mol) Hydrazine Hydrate 80 under the stirring at room, room temperature reaction 3h is after reaction finishes; Ethanol, water and remaining ETHYLE ACETATE are removed in underpressure distillation, get bullion acethydrazide 18.15g (productive rate 98%).
Embodiment 2
In a 50mL round-bottomed flask, add 14.82g (0.22mol) acethydrazide, 10mL absolute ethyl alcohol; Stir and slowly splash into 26.03g (0.2mol) methyl aceto acetate down; Dropwise back backflow 2h, reaction finishes back (TLC follows the tracks of reaction), and ethanol is removed in underpressure distillation; Residual solids is poured in the 50mL frozen water, filtered after drying and get thick product 35.75g (productive rate 96%).
Embodiment 3
In a 100mL round-bottomed flask, add 17mL (0.24mol) sulfur oxychloride, 20mL chloroform, ice bath cooling gradation down adds 37.25g (0.2mol) 3-acetyl hydrazone-ethyl n-butyrate, keeps temperature to add.Remove ice bath, continue to stir 6h under the room temperature, reaction finishes back (TLC tracking), and 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 absolute ethyl alcohol; Splash into the saturated aqueous solution that 4.83g (0.12mol) sodium hydroxide is made under the stirring at room; React 30min under the room temperature, reaction finishes back (TLC tracking), and 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, filter back recrystallization (absolute ethyl alcohol) 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 the back underpressure distillation and removes the excess chlorination sulfoxide; Underpressure distillation gets 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 thiocyanide and 5mL acetonitrile, ice bath stirs down, slowly drips 1.62g (0.01mol) 4-methyl 1; 2; 3-thiadiazoles-5-formyl chloride dropwises continued and stirs 30min, and reaction finishes back (TLC follows the tracks of reaction).Drip the solution that 0.93g (0.01mol) aniline and 3mL acetonitrile are made into again, dropwise continued and stir 30min.Reaction finishes back (TLC follows the tracks of reaction), and mixture is poured in the 30mL water, leaches 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 thiocyanide and 5mL acetonitrile, ice bath stirs down, slowly drips 1.62g (0.01mol) 4-methyl 1; 2; 3-thiadiazoles-5-formyl chloride dropwises continued and stirs 30min, and reaction finishes back (TLC follows the tracks of reaction).Drip the solution that 1.07g (0.01mol) para-totuidine and 3mL acetonitrile are made into again; Dropwise continued and stir 30min; Reaction finishes back (TLC follows the tracks of reaction), and mixture is poured in the 30mL water, leaches 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 thiocyanide and 5mL acetonitrile, ice bath stirs down, slowly drips 1.62g (0.01mol) 4-methyl 1,2,3-thiadiazoles-5-formyl chloride.Dropwise continued and stir 30min, reaction finishes back (TLC follows the tracks of reaction), drips the solution that 1.07g (0.01mol) Ortho Toluidine and 3mL acetonitrile are made into again.Dropwise continued and stir 30min, reaction finishes back (TLC follows the tracks of reaction), and mixture is poured in the 30mL water, leaches 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)-and N '-(4-aminomethyl phenyl) thiocarbamide, 1.01g (6mmol) METHYL BROMOACETATE, 0.49g (6mmol) anhydrous sodium acetate and 5mL absolute ethyl alcohol, reflux; System becomes purple by yellow gradually; Continue reaction 1h, reaction finishes back (TLC follows the tracks of reaction), and ethanol is removed in underpressure distillation.Gained solid recrystallization (95% ethanol) gets 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)-and N '-(3-fluorophenyl) thiocarbamide, 1.00g (6mmol) METHYL BROMOACETATE, 0.49g (6mmol) anhydrous sodium acetate and 5mL absolute ethyl alcohol, reflux; System becomes purple by yellow gradually; Continue reaction 1h, reaction finishes back (TLC follows the tracks of reaction), and ethanol is removed in underpressure distillation.Gained solid recrystallization (95% ethanol) gets 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 absolute ethyl alcohol; Back flow reaction 30min separates out yellow solid, and reaction finishes back (TLC follows the tracks of reaction) filtration, recrystallization (chloroform: absolute ethyl alcohol) get 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 absolute ethyl alcohol; Back flow reaction 30min separates out yellow solid, and reaction finishes back (TLC follows the tracks of reaction) filtration, recrystallization (chloroform: absolute ethyl alcohol) get 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 according to the effective content that supplies the reagent agent with preparation; Prepare medicament by experimental concentration, after cucumber seedling is unearthed, carry out the spraying first time immediately and induce (supplying reagent agent and contrast medicament all to spray induces), supplying the reagent agent evenly to spray application to the positive back side of blade; Be advisable with blade face droplet uniformity; Whenever induced 1 time at a distance from 3 days, continuous induction 3 times is induced inoculation in back 3 days the 3rd time.Each pathogenic bacteria is all adopted the spray pattern inoculation.
Calculate preventive effect according to the following grade scale investigation state of an illness.
Sick leaf grade scale:
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.
Drug effect method of calculation: press the column index formula according to disease index and calculate control effect, press the significance of difference that the DMRT method is measured preventive effect between processing again.
The inducing anti-disease activity example of part of compounds of the present invention
The structure of example compound is as follows with numbering:
Table 1 is the inducing anti-disease activity example [supplying the reagent agent all to establish 50ppm (50mg/L)] to bacterial spot of tomato
Table 1
Table 2 is target compound inducing anti-disease results [supplying the reagent agent all to establish 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 |
[0102]?
| 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 |
[0103]?
| 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 (8)
1. one kind contains 2, and the acylthioureas type midbody of the female ring of 3-thiadiazoles is characterized in that, contains following structural formula:
Wherein, R
1, R
2Be selected from following group: H, C independently of one another
1～C
9Saturated or the unsaturated alkyl of straight or branched or cyclic, be with substituent C
1～C
9Straight or branched or cyclic saturated or unsaturated alkyl, phenyl, substituted-phenyl, benzyl, substituted benzyl and five yuan or hexa-member heterocycle;
Said substituting group is halogeno-group, hydroxyl, alkoxyl group, amino, substituted-amino, carboxyl, cyanic acid, ester group, carboxamido-group or nitro;
Said five yuan or hexa-member heterocycle is nitrogenous, in the oxygen, three kinds of elements of sulphur one or more;
X
1Be O or S.
2. according to claim 1ly a kind ofly contain 1,2, the acylthioureas type midbody of the female ring of 3-thiadiazoles is characterized in that said R
1Can also be selected from the group of following structure:
Wherein A, B are H or C
1～C
9Alkyl.
3. according to claim 1ly a kind ofly contain 1,2, the acylthioureas type midbody of the female ring of 3-thiadiazoles is characterized in that said R
1A kind of in methyl, ethyl, propyl group, chloromethyl, brooethyl, phenyl, the substituted-phenyl.
4. according to claim 1ly a kind ofly contain 1,2, the acylthioureas type midbody of the female ring of 3-thiadiazoles is characterized in that said R
2Be selected from H, C
1～C
5The C in saturated or unsaturated alkyl, fluorine or chlorine generation
1～C
5Saturated or unsaturated alkyl, phenyl or substituted-phenyl and five yuan or hexa-member heterocycle.
5. claim 1 to 4 is arbitrary describedly contains 1,2, and the imide thiazolone compound that the acylthioureas type midbody of the female ring of 3-thiadiazoles obtains is characterized in that said imide thiazolone compound has following structural formula:
Wherein, R
1, R
2Be selected from following group: H, C independently of one another
1～C
9Saturated or the unsaturated alkyl of straight or branched or cyclic, be with substituent C
1～C
9Straight or branched or cyclic saturated or unsaturated alkyl, phenyl, substituted-phenyl, benzyl, substituted benzyl and five yuan or hexa-member heterocycle;
R
3, R
4Independently be selected from following group: H, C separately
1～C
9Saturated or the unsaturated alkyl of straight or branched, be with substituent C
1～C
9Saturated or the unsaturated alkyl and the halogeno-group of straight or branched; Perhaps 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; Perhaps R
3And R
4The singly-bound merging is constructed as follows double bond structure.
Wherein, R
5, R
6Be selected from following group: H, C independently of one another
1～C
9Saturated or the unsaturated alkyl of straight or branched or cyclic, be with substituent C
1～C
9Straight or branched or cyclic saturated or unsaturated alkyl, phenyl, substituted-phenyl, benzyl, substituted benzyl and five yuan or hexa-member heterocycle;
Said substituting group is halogeno-group, hydroxyl, alkoxyl group, amino, substituted-amino, carboxyl, cyanic acid, ester group, carboxamido-group or nitro;
Said five yuan or hexa-member heterocycle is nitrogenous, in the oxygen, three kinds of elements of sulphur one or more;
X
1Be O or S, X
2Be O or S;
Said R
1Can also be:
Wherein A, B are H or C
1～C
9Alkyl.
6. contain 1 according to claim 6; 2; The imide thiazolone compound that the acylthioureas type midbody of the female ring of 3-thiadiazoles obtains is characterized in that said imide thiazolone compound comprises acceptable salt on optical isomer, cis-trans-isomer or the Pesticide Science.
7. the preparation method of claim 5 or 6 imide thiazolone compound is characterized in that, comprises following steps:
A) acylhydrazone of 'beta '-ketoester and acethydrazide formation is carrying out ring-closure reaction in the presence of certain temperature of reaction and THIONYL CHLORIDE 97;
B) product of above-mentioned ring-closure reaction is hydrolyzed and chloride;
C) the synthetic preparation with the acylthioureas verivate of the original position of acyl group lsothiocyanates;
D) ring-closure reaction through substituted halogenated acetic acids ester and above-mentioned product makes up imide thiazolone heterocycle, obtains said imide thiazolone compound;
E) at R
3=R
4Under the situation of=H, can have the product of following area structure character through Knoevenagel type prepared in reaction:
In the reaction of Knoevenagel type, the mol ratio of thiazolidine (sulphur) ketone and aldehyde is 1: 1～1.5.
8. claim 1,2,3,4,5 or 6 described acylthioureas type midbodys or imide thiazolone application of compound; It is characterized in that; Be used to prepare plant disease controlling agent, said Plant diseases comprises rice sheath blight disease, bacterial blight of rice, rice blast, tomato spot disease, melon anthrax or cucurbits powdery mildew.
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| CN103012316A (en) * | 2012-11-29 | 2013-04-03 | 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 |
| CN103044413A (en) * | 2012-11-29 | 2013-04-17 | 浙江工业大学 | Thiadiazolyl thiourea derivative, as well as preparation and application thereof as plant growth regulator |
| CN103058955A (en) * | 2012-11-29 | 2013-04-24 | 浙江工业大学 | Thiadiazole thiourea derivative as well as preparation and application thereof as plant growth regulator |
| CN103102330A (en) * | 2012-11-29 | 2013-05-15 | 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 |
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| 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 |
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| CN103058955A (en) * | 2012-11-29 | 2013-04-24 | 浙江工业大学 | Thiadiazole thiourea derivative as well as preparation and application thereof as plant growth regulator |
| CN103102330A (en) * | 2012-11-29 | 2013-05-15 | 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 |
| CN103012316A (en) * | 2012-11-29 | 2013-04-03 | 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 |
| 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 |
| 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 |
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| CN106458909A (en) * | 2014-05-19 | 2017-02-22 | 先正达参股股份有限公司 | Insecticidally active amide derivatives with sulfur-substituted phenyl or pyridine groups |
| US9701659B2 (en) | 2014-05-19 | 2017-07-11 | Syngenta Participations Ag | Insecticidally active amide derivatives with sulfur-substituted phenyl or pyridine groups |
| CN106458909B (en) * | 2014-05-19 | 2020-03-17 | 先正达参股股份有限公司 | Insecticidal amide derivatives with sulfur-substituted phenyl or pyridine groups |
| US10494366B2 (en) | 2014-12-01 | 2019-12-03 | Syngenta Participations Ag | Pesticidally active amide heterocyclic derivatives with sulphur containing substituents |
| CN106665607A (en) * | 2016-12-26 | 2017-05-17 | 蔡志浩 | Compound plant fungicide |
| CN106665605A (en) * | 2016-12-26 | 2017-05-17 | 蔡志浩 | Compound botanical fungicide |
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| 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 |
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