CN104974150B

CN104974150B - A kind of carboxamidine derivatives of 3,4 2 chloroisothiazole 5 and its production and use

Info

Publication number: CN104974150B
Application number: CN201510445825.9A
Authority: CN
Inventors: 范志金; 宗广宁; 马刘勇; 李凤云; 朱玉洁; 陈来; 王海霞; 钱晓琳; 郭晓凤; 裴钰; 徐京华
Original assignee: Nankai University
Current assignee: Nankai University
Priority date: 2015-07-24
Filing date: 2015-07-24
Publication date: 2018-03-09
Anticipated expiration: 2035-07-24
Also published as: CN104974150A

Abstract

The invention provides a kind of carboxamidine derivatives of 3,4 two chloroisothiazole 5 and its production and use, and the present invention relates to isothiazole formamidine compound, and they have the chemical structure of general formula as shown in IV.

Description

A kind of chloroisothiazole -5- carboxamidine derivatives of 3,4- bis- and its production and use

Technical field

Technical scheme is related to the heterocyclic compound containing S containing N, and in particular to 3,4- bis- chloroisothiazole class chemical combination Thing, the i.e. chloroisothiazole -5- carboxamidine derivatives of 3,4- bis-.

Background technology

Amidine is also known as imines acid amides, i.e., in amide molecule structure, the oxygen atom on carbonyl is substituted and obtained by nitrogen-atoms The compound arrived.Because the imino group of amidine can mutually be changed with amino, amidine compound is important in organic synthesis Intermediate, many nitrogen-containing heterocycle compounds can be synthesized with this feature of amidine.

Amidine compound has extensive bioactivity, medicine and pesticide field be widely used, be mainly used in antibiotic, The synthesis of the medicines such as antiphlogistic, medical bactericide.Sub- amide group generally existing in medicine and pesticide molecule, such as Greenhill etc. points out that Sodium Iopodate is a kind of oral bile duct, cholecystography medicine, has few side effects, to patient safety, shows The features such as shadow effect is good (Greenhill, et al.Amidines and guanidines in medicinal Chemistry.Prog.Med.Chem., 1993,30,203-326)；Boots companies of Britain have synthesized New-type wide-spectrum acaricide Amitraz, have it is strong tag, fumigate and good penetration, be mainly used in preventing and treating citrus mite class and (Xu Zhenyuan, wait double The study on the synthesis Zhejiang chemical industry of carbonamidine and its intermediate, 1988,19 (6), 1-7).Tso Tat Co., Ltd., Japan's exploitation in 1979 Fluorine bacterium azoles (triflumizole) be exactly the new type bactericide containing sub- amide group, be mainly used in preventing and treating powdery mildew and rice Rice blast, and to Crop securify, (Kozue, et al.Method using agrochemicals for nontoxic to honeybee controlling plant diseases and pests. JP2007246495.2007-09-27.)。

This seminar early-stage Study reports synthesis and bioactivity (the model will of the carboxamidine derivatives of 1,2,3- thiadiazoles Gold, etc., a kind of methyl isophthalic acid containing 4-, the carboxamidine derivatives of 2,3- thiadiazoles and its production and use, the People's Republic of China (PRC) National inventing patent, CN103214476A) and diazosulfide carboxamidine derivatives synthesis and bioactivity (Fan Zhijin, etc., Benzo [1,2,3] thiadiazoles derivative and its preparation method and use, People's Republic of China's national inventing patent, CN1785983A).There is this kind of compound the activity of certain induction resisting tobacco mosaic virus (TMV) and preferably sterilization to live Property.

In order to find and find more efficiently, wide spectrum, low toxicity, low ecological risk and with existing bactericide no interactions resistance The isothiazole derivatives of new type bactericide and more high bioactivity, the present invention design synthesized one kind 3,4- bis- chloroisothiazoles- 5- carboxamidine derivatives, and the biological evaluation of system has been carried out, to provide new candidate chemical combination for New pesticides discovery research Thing.

The content of the invention

The technical problems to be solved by the invention are：A kind of new chloroisothiazole -5- carboxamidine derivatives of 3,4- bis- are provided Synthetic method, there is provided this kind of compound modulates agricultural, gardening and health and the biology of forestry plant insect and the phytopathy original Activity and its assay method, there is provided these compounds should in agriculture field, horticultural field, field of forestry and health field With.

Technical scheme is used by the present invention solves the technical problem：With agriculture field, horticultural field, forestry and Health field insecticidal activity, bactericidal activity, anti-phytoviral activity, induction plant produce the chloroisothiazoles of 3,4- bis- of anti-disease activity The chemical structure of general formula of -5- carboxamidine derivatives is shown in formula IV：

Wherein, X is selected from S or NH；R¹Selected from 5- methylthiazol -2- bases, 2- ethoxyethyl groups, the chloro- 5- trifluoromethyls pyrroles of 3- Pyridine -2- bases；R²Selected from benzyl, 4- methoxyphenyls, 4- aminomethyl phenyls, 3- aminomethyl phenyls, 2- aminomethyl phenyls, 4- bromophenyls, 3- Bromophenyl, 2- bromophenyls, 4- fluorophenyls, 4- nitrobenzophenones, 2- methoxy-benzyls, 2- chloropyridine -5- methylene, 4- methyl are phonetic Pyridine -2- bases, 1,2,4- triazol radicals, cyclohexyl, the fluoro ethyls of 2,2- bis-, cyclopropyl, 2- methylthiomethylenes isopropyl, alkynes third Base, ethoxyethyl group, methyl, ethoxycarbonylmethyl group；

3, the 4- dichloro isothiazole derivatives IV of present invention synthetic method is as follows：

It is specifically divided into following steps：

It should be noted that the expression on unit：Ml is milliliter；Mmol is mM；G is gram；DEG C it is degree Celsius；H is Hour；% is weight/mass percentage composition or concentration or yield；Mm is millimeter；Mg is milligram；μ g/ml are mcg/mls；Cm is li Rice；D is day.

A. the preparation of intermediate II：

7.8g chloroisothiazole -5- formic acid I and the 50ml thionyl chlorides of 3,4- bis- are added in 250ml single necked round bottom flask, The thionyl chloride of access NaOH alkali liquor absorptions volatilization above return duct, 80 DEG C of backflow 5h, solution are changed into light yellow, 74 DEG C of normal pressure Unreacted thionyl chloride is distilled off, be then evaporated under reduced pressure collect 128 DEG C of cut obtain the colourless chloroisothiazoles of 3,4- bis- of 5.9g- 5- formyl chlorides, with gained sterling calculated yield, yield 69.3%；Amount and the volume of reaction vessel prepared by intermediate II is by corresponding Ratio is expanded or shunk.

B. the preparation of intermediate III：

In 100ml single necked round bottom flask, by 9.98mmol substituted aromatic amines or fatty amine R¹NH₂It is dissolved in 30ml anhydrous two In chloromethanes, 9.98mmol 1.01g triethylamines are then added, 10min is stirred under condition of ice bath, 1.80 g, which are gradually added dropwise, is 8.32mmol chloroisothiazole -5- formyl chlorides the II of 3,4- bis- dichloromethane solution, drop finish, 3h are stirred at room temperature, there is Precipitation, Filtering, filter cake are washed twice with ethyl acetate, yellow or white solid are obtained, according to the difference of product, yield 85-95%.In Amount and the volume of reaction vessel prepared by mesosome III is expanded or shunk by corresponding proportion.

C. chloroisothiazole -5- formamidine derivative Is the V of 3,4- bis- preparation：

By the five of 0.68mmol 3,4- bis- chloroisothiazole -5- formamides III and 0.68mmol in 50ml round-bottomed flasks Phosphorus chloride is dissolved in 20ml anhydrous chloroforms, and under nitrogen protection atmosphere, 65 DEG C of backflow 3h, TLC detection reactions are complete, and vacuum distillation removes Go solvent to obtain intermediate 3, the chloroisothiazole -5- chlorimide class compounds of 4- bis-, directly carried out in next step without purifying.

Chlorimide is dissolved in 20ml anhydrous tetrahydro furans, 1.36mmol triethylamine is added, then adds 1.01mmol aminated compounds or phenyl-sulfhydrate compounds R²XH, it is stirred at room temperature, TLC detections are anti-according to the difference of reaction raw materials Stop reaction after answering 2-5 h, be evaporated under reduced pressure concentration and remove THF, residue is dissolved with ethyl acetate, uses saturated sodium bicarbonate successively Solution, saturated nacl aqueous solution wash twice, are stripped twice, merge organic phase, anhydrous sodium sulfate drying, concentration, residue warp 200~300 mesh silica gel column chromatographies purify, according to the petroleum ether that the different eluents of product are 60~90 DEG C: ethyl acetate volume Than for 7: 1~20: 1, rotary evaporation, which goes out to hold agent, obtains yellow solid or oily thick liquid, i.e. the chloroisothiazole formamidines of 3,4- bis- Derivative I V, with gained sterling calculated yield, two-step reaction yield is 30~70%.Amount and reaction vessel prepared by compound IV Volume expanded or shunk by corresponding proportion.Compound IV chemical constitution and physical and chemical parameter is shown in Table 1.

D. chloroisothiazole -5- formamidine compounds the IV of 3,4- bis- of the invention bactericidal activity measure：

Chloroisothiazole -5- formamidine compounds the IV of 3,4- bis- of present invention sterilization or bacteriostatic activity use thalli growth rate Determination method, concretely comprise the following steps：Take 1.8mg samples to be dissolved in appropriate DMF, then told with containing a certain amount of The aqueous solution of warm 20 emulsifying agents is diluted to 500 μ g/ml medicament, and reagent agent is aseptically respectively drawn to 1ml injection trainings Support in ware, then be separately added into 9ml PDA culture mediums, 50 μ g/ml drug containing flat boards are made after shaking up, to add the flat of 1ml aqua sterilisas Plate does blank control, cuts bacterium disk along mycelia outer rim with diameter 4mm card punch, moves on drug containing flat board, in equilateral triangle Put, often processing is repeated 3 times, and culture dish is placed in 24 ± 1 degrees Celsius of constant incubators and cultivated, colony diameter extension to be compareed Each processing bacterium disk extension diameter is investigated after to 2-3 centimetres, averages, relative bacteriostasis rate is calculated compared with blank control, for examination Strain is the kind of most of typical plant pathogen that field actually occurs in China's agricultural production, and its code name and title are such as Under：AS：Tomato early blight bacterium, its Latin are entitled：Alternaria solani、BC：Botrytis cinerea pers, its Latin are entitled： Botrytis cinerea、CA：Peanut Cercospora bacteria, its Latin are entitled：Cercospora arachidicola、GZ：Wheat is red Mildew bacterium, its Latin are entitled：Gibberella zeae、PI：Phytophthora infestans, its Latin are entitled：Phytophthora infestans(Mont.)de Bary、PP：Botryosphaeria berengeriana f. sp, its Latin are entitled： Physalospora piricola、PS： Rhizoctonia solani Kuhn, its Latin are entitled：Pellicularia sasakii、RC：Rhizoctonia cerealis, its Latin are entitled： Rhizoctonia cerealis、SS：Sclerotinia sclerotiorum, its Latin are entitled：Sclerotinia sclerotiorum.

E. chloroisothiazole -5- formamidine compounds the IV of 3,4- bis- of the invention inducing anti-disease activity measure：

The sieve of the chloroisothiazole -5- formamidine compound IV evoking tobacco activity of resisting tobacco mosaic virus of 3,4- bis- of the present invention Choosing method is as follows, and tobacco mosaic virus (TMV) is abbreviated as TMV：

(1) positive controls activating plants agent：It is positive control to select tiadinil of the quality purity purity more than 99.5% Activating plants agent；Tiadinil is abbreviated as TDL；

(2) screening technique of the chloroisothiazole -5- formamidine compounds IV of .3, the 4- bis- anti-TMV activity of evoking tobacco：In vitro The measure of direct antiviral activity is carried out using half leaf method；Live body induction is by the consistent common cigarette of seedling age, and 3 basins are one group, point The tobacco seedlings of 7d pre-treatments, processing mode include not before inoculation：Spray test compounds solution 2 to 3 times, each 10ml, or Soil treatment, each 10ml, measure concentration be 50 μ g/ml, 7d in frictional inoculation TMV on the tobacco leaf newly grown, tobacco seedlings are put After it grows and cultivates 3d under preference temperature and illumination, incidence is checked, comprehensive scab number is calculated as follows out for examinationization Induction antiviral effect of the compound to TMV, each processing set 3 repetitions, and blank control and standard agent control select water respectively And TDL：

Wherein, R be noval chemical compound TMV anti-to tobacco inducing effect, unit：%；CK is that clear water compares being averaged for blade Withered spot number, unit：It is individual；I is that the average withered spot number for handling rear blade is induced through compound, unit：It is individual；

In addition to carrying out the measure of above-mentioned induced activity, while carry out the chloroisothiazole -5- formamidine compounds IV of 3,4- bis- Anti- TMV therapeutic activities, passivation activity and protection activity measure.

The beneficial effects of the invention are as follows：Guide's optimization has been carried out to the chloroisothiazole -5- formamidine compounds IV of 3,4- bis-, and The screening of bacteriostatic activity and antiviral activity has been carried out to the noval chemical compound of synthesis.

The present invention passes through specific preparation and the chloroisothiazole -5- first of 3,4- of the more specific explanation of biological activity determination embodiment bis- Amidine compound IV synthesis and bioactivity and application, the embodiment is only used for illustrating the present invention and unrestricted is sent out Bright, especially bioactivity is merely illustrative of, and unrestricted this patent, embodiment are as follows：

Embodiment 1

The preparation of intermediate II：

Chloroisothiazole -5- formic acid 7.8g and the 50mL thionyl chlorides of 3,4- bis- are added in 250ml single necked round bottom flask, are flowed back The thionyl chloride of access NaOH alkali liquor absorptions volatilization above pipe, 80 DEG C of backflow 5h, solution are changed into light yellow, and 74 DEG C of distillations of normal pressure remove Unreacted thionyl chloride is removed, the cut for being then evaporated under reduced pressure 128 DEG C of collection obtains the colourless chloroisothiazole -5- first of 3,4- bis- of 5.9g Acyl chlorides, with gained sterling calculated yield, yield 69.3%；¹H NMR(CDCl₃)δ：5.92 (s, 1H), 5.68 (s, 1H), 4.24- 4.04 (m, 2H), 2.84-2.68 (m, 2H), 2.34-2.27 (m, 1H), 1.89-1.80 (m, 2H), 1.67-1.57 (m, 2H), 1.46 (s, 9H).

Embodiment 2

The preparation of intermediate III：

It is the substituted aromatic amines such as 1.14g 2- amino -5- methylthiazols by 9.98mmol in 100ml single necked round bottom flask Or fatty amine R¹NH₂The compound solution being dissolved in 30ml anhydrous methylene chlorides, it is 1.01g triethylamines then to add 9.98mmol, 10min is stirred under condition of ice bath, the dichloro that 1.80g is the 8.32mmol chloroisothiazole -5- formyl chlorides II of 3,4- bis- is gradually added dropwise Dichloromethane, drop finish, 3h are stirred at room temperature, there is yellow mercury oxide precipitation, filter, and filter cake is washed twice with ethyl acetate, obtains 2.2g Yellow solid, with gained sterling calculated yield, yield 91.6%；¹H NMR (400MHz, DMSO-d6) δ 7.29 (d, J= 1.3Hz, 1H), 2.32 (d, J=1.1Hz, 3H)

Embodiment 3

3,4- bis- chloroisothiazole -5- formamidine derivative Is V preparation：

By the phosphoric of the 0.68mmol chloroisothiazole -5- formamides of 3,4- bis- and 0.68mmol in 50ml round-bottomed flasks Phosphorus is dissolved in 20ml anhydrous chloroforms, and under nitrogen protection atmosphere, 65 DEG C of backflow 3h, TLC detection reactions are complete, removed under reduced pressure Solvent obtains intermediate 3, the chloroisothiazole -5- chlorimide class compounds of 4- bis-, is directly carried out in next step without purifying.

Chlorimide is dissolved in 20ml anhydrous tetrahydro furans, 1.36mmol triethylamine is added, then adds 1.01mmol primary amine or phenyl-sulfhydrate compounds R²XH, it is stirred at room temperature, TLC detections, according to the differential responses 2-5h of reaction raw materials Afterwards, concentration removes THF, and residue is dissolved with ethyl acetate, washed successively with saturated sodium bicarbonate solution, saturated nacl aqueous solution Twice, it is stripped twice, merges organic phase, anhydrous sodium sulfate drying concentrates, and residue is pure through 200~300 mesh silica gel column chromatographies Change, be 60~90 DEG C of petroleum ether according to the different eluents of product: ethyl acetate volume ratio obtains yellow 7: 1~20: 1 Solid or oily thick liquid, i.e. 3,4- dichloro isothiazole derivatives IV, with gained sterling calculated yield, two step yields 30~ 70%.Compound IV chemical constitution and physical and chemical parameter is shown in Table 1.

Embodiment 4

Chloroisothiazole -5- formamidine derivative Is the V of 3,4- bis- of present invention Antibacterial Activity result：

The code name and title for the frequently seen plants disease fungus that the present invention tests are as follows：AS：Tomato early blight bacterium, its latin name For： Alternaria solani、BC：Botrytis cinerea pers, its Latin are entitled：Botrytis cinerea、CA：Peanut foxiness Germ, its Latin are entitled：Cercospora arachidicola、GZ：Fusarium graminearum, its Latin are entitled：Gibberella zeae、 PI：Phytophthora infestans, its Latin are entitled：Phytophthora infestans(Mont.)de Bary、PP：Apple Fruit Target spot pathogen, its Latin are entitled：Physalospora piricola、PS：Rhizoctonia solani Kuhn, its Latin are entitled： Pellicularia sasakii、RC：Rhizoctonia cerealis, its Latin are entitled：Rhizoctonia cerealis、SS：Sclerotina Sclerotiorum in Winter Rape Core germ, its Latin are entitled：Sclerotinia sclerotiorum, these strains have representativeness well, can represented The kind for most of pathogen that field occurs in agricultural production.It is worth noting that, the compound fz6- enumerated in the present invention 1-2 and fz6-4-4 is that this seminar synthesizes and report the immediate high living with structure of the present invention of (CN103214476A) early stage Property compound, for the bioactivity of the noval chemical compound more of the invention synthesized, the present invention choose the two structures closest to this Subject invention compound and active highest similar compound fz6-1-2 and fz6-4-4, which are used as, to be compareed, in identical condition Under test their bioactivity.Thalli growth rate method measurement result is shown in Table 2, and table 2 shows, in 50 μ g/ml, the present invention closes Into all compounds have different degrees of bactericidal activity：Wherein, compound zgn09-30-1, zgn09-52-1, zgn09- 58-2、 zgn09-63-2、zgn09-68-3、zgn09-77-1、zgn09-78-2、whx01-48、whx02-10、whx02-1、 The inhibiting rate of mly02-25 Phytophthora infestans is higher than 40%, and compound zgn09-52-1 activity is 85% preferably, Compound zgn09-52-1 and whx02-13 is higher by analogue fz6-1-2 and fz66-4-4 to the inhibitory activity of the bacterium and existed More than 10%；Compound zgn09-36, zgn09-37, zgn09-50, zgn09-58-1, zgn09-58-2, zgn09-59-1, zgn09-63-1、 zgn09-63-2、zgn09-73-2、zgn09-74-2、zgn09-76-1、zgn09-77-1、zgn09-78- 2nd, whx01-48, zgn02-7, zgn02-10, zgn02-13, mly02-25 are higher than 50% to the inhibiting rate of peanut Cercospora bacteria, Wherein compound zgn09-59-1, zgn09-73-2, zgn09-76-1, whx01-48, zgn02-13 inhibitory activity higher than pair According to medicament Fluoxastrobin and analogue fz6-1-2, fz66-4-4, compound zgn09-73-2 inhibitory activity highest, it is 92.31%；Compound zgn09-30-1, zgn09-36, zgn09-37, zgn09-50, zgn09-50, zgn09-53-1, zgn09-58-1、zgn09-58-2、 zgn09-59-1、zgn09-63-1、zgn09-68-1、zgn09-73-1、zgn09-76- 1st, zgn09-77-1, whx01-48, whx02-13 are higher than 50% to the inhibitory activity of tomato early blight bacterium, higher than comparison medicament Fluoxastrobin, compound zgn09-59-1, zgn09-73-2 and whx02-13 activity higher than analogue fz6-1-2 and Fz66-4-4, wherein compound zgn09-73-2 inhibitory activity highest, it is 82.35%；Compound zgn09-59-1, zgn09-63-1、zgn09-63-2、zgn09-67、 zgn09-68-1、zgn09-68-2、zgn09-68-3、zgn09-69-2、 zgn09-74-2、zgn09-76-1、zgn09-76-2、 zgn09-77-1、zgn09-78-2、whx01-47、whx01-48、 Whx02-7, whx02-10, whx02-13, mly02-25 are higher than 50%, wherein chemical combination to the inhibitory activity of botrytis cinerea pers Thing zgn09-74-2, whx01-48, whx02-13 inhibitory activity are higher than comparison medicament Fluoxastrobin and analogue fz6-1- 2、fz66-4-4；Compound zgn09-30, zgn09-36, zgn09-53-2, zgn09-56-1, zgn09-58-1, zgn09- 67、zgn09-68-1、zgn09-68-3、zgn09-69-2、 zgn09-74-2、zgn09-76-1、zgn09-78-2、whx01- 47th, whx02-7 is higher than 50% to the inhibiting rate of fusarium graminearum, less than comparison medicament Fluoxastrobin, wherein compound zgn09- 56-1、zgn09-58-1、zgn09-68-1、zgn09-68-3、 zgn09-69-2、zgn09-76-1、zgn09-78-2、 Whx02-7 activity is higher than structure class thing fz6-1-2 and fz66-4-4；Compound zgn09-36, zgn09-53-2, zgn09- 57-1、zgn09-57-2、zgn09-59-1、zgn09-63-2、zgn09-68-3、 zgn09-76-1、zgn09-77-1、 To the inhibiting rate of Botryosphaeria berengeriana f. sp more than 50%, activity is higher than analogue fz6-1-2 by whx01-47, whx02-7, but Less than analogue fz6-4-4, wherein compound zgn09-77-1 inhibitory activity is best, is 91.30%, higher than comparison medicine Agent Fluoxastrobin；Compound zgn09-36, zgn09-37, zgn09-53-2, zgn09-58-1, zgn09-59-1, zgn09-60-1, zgn09-63-2、zgn09-67、zgn09-68-1、zgn09-68-2、zgn09-69-1、 zgn09-69-2、zgn09-74-2、 The suppression of zgn09-76-1, zgn09-77-1, whx01-48, whx02-7, whx02-10, whx02-11 to Sclerotinia sclerotiorum Rate is more than 70%, and activity is higher than analogue fz6-1-2, and compound zgn09-68-3 reaches to the inhibiting rate of the bacterium 100%, it is suitable with comparison medicine Fluoxastrobin, higher than analogue fz6-1-2 and fz6-4-4；Compound zgn09-58-1, zgn09-63-2、zgn09-67、zgn09-68-1、zgn09-68-3、zgn09-77-1、whx01-47、 whx01-48、 Whx02-10 to the inhibitory activity of Rhizoctonia cerealis more than 87%, higher than analogue fz6-1-2 and fz6-4-4, wherein Compound zgn09-68-3 reaches 100% to the inhibitory activity of the bacterium, suitable with Fluoxastrobin；Compound zgn09-30, zgn09- 36、zgn09-57-2、zgn09-58-1、zgn09-63-2、zgn09-67、zgn09-68-1、zgn09-68-3、 zgn09-76- 1st, zgn09-76-2, zgn09-77-1, zgn09-78-2, whx01-48, whx02-7, whx02-13, mly02-25 are to rice The inhibiting rate of sheath blight fungus is higher than 30%, less than comparison medicament Fluoxastrobin and analogue fz6-4-4.It is worth noting that Under 50 μ g/ml concentration, compound zgn09-68-3 reaches to the inhibiting rate of two kinds of bacterium of Sclerotinia sclerotiorum and Rhizoctonia cerealis To 100%, higher than analogue fz6-1-2 and fz6-4-4.Therefore, the noval chemical compound of present invention design synthesis is due to 3,4- The introducing of dichloro isothiazole group, the high-activity compound that the bactericidal activity of target compound is reported early stage with this seminar kill Bacterium activity has obtained significant raising, achieves the effect of unexpected high activity；This is that the invention is different from There is the place of invention.

Embodiment 5

Chloroisothiazole -5- formamidine derivative Is the V of 3,4- bis- of the present invention anti-TMV Activity Results：

The measurement result of TMV activity is shown in Table 3, and table 3 shows, majority of compounds of the invention has preferable anti-TMV's Activity；In 100 mcg/ml, all compounds that the present invention synthesizes have different degrees of anti-TMV activity.

Under passivation pattern, compound zgn09-30, zgn09-31, zgn09-32, zgn09-37, zgn09-53-2, zgn09-56-2、 zgn09-58-2、zgn09-62、zgn09-63-1、zgn09-68-3、zgn09-74-2、zgn09-76-2、 Zgn09-77-1, whx02-13 antiviral activity are higher than 40%, and the structure that activity is higher by this seminar report early stage is similar More than 10%, wherein compound zgn09-63-1's and zgn09-69-1 is anti-by high-activity compound fz6-1-2 and fz6-4-4 Virus activity is respectively 50.83% close to comparison medicine virazole and Ningnanmycin；In the therapeutic mode, compound zgn09-30, zgn09-32、 zgn09-50-1、zgn09-52-2、zgn09-53-2、zgn09-57-1、zgn09-63-1、zgn09-67、 Zgn09-69-2, zgn09-69-3, zgn09-76-2, zgn09-78-2, whx02-10, whx02-13 antiviral activity are high In 40%, activity is higher by similar the high-activity compound fz6-1-2 and fz6-4-4 of structure of this seminar report early stage 10% More than, less than comparison medicament virazole；In protected mode, compound zgn09-52-2, zgn09-58-1, zgn09-69-1, For zgn09-76-2, whx02-13, mly02-25 antiviral activity more than 40%, activity is higher by this seminar report early stage Structure similar to high-activity compound fz6-1-2 and fz6-4-4 more than 20%, wherein compound zgn09-58-1 and mly02- 25 antiviral activity is higher than comparison medicine virazole；Under induction pattern, compound zgn09-30, zgn09-46-1, zgn09- 50-1、zgn09-52-2、 zgn09-56-2、zgn09-63-1、zgn09-63-2、zgn09-67、zgn09-68-1、zgn09- 69-3, zgn09-73-2, whx01-46, whx02-7, whx02-11, mly02-25 antiviral activity more than 40%, wherein Compound zgn09-46-1, zgn09-63-2, whx01-46, whx02-7 antiviral activity are higher than 44%, and activity is higher than this Seminar early stage report structure similar to high-activity compound fz6-1-2 and fz6-4-4, with comparison medicament first thiophene lure amine, BTH and TDL is suitable.Compound zgn09-60-2 is all remarkably higher than this seminar report early stage to the antiviral activity of tetra- patterns of TMV Structure is similar to high-activity compound fz6-1-2 and fz6-4-4.It can be seen that the compound that the present invention synthesizes is due to the different thiophene of 3,4- dichloros The introducing of oxazolyl group, the more preferable anti-TMV for the high-activity compound that target compound is demonstrated by reporting early stage with this seminar live Property, the anti-TMV activity of majority of compounds is above the similar high-activity compound fz6- of structure of this seminar report early stage 1-2 and fz6-4-4, achieve the effect of unexpected high activity；This is that the invention is different from the ground invented Side.

Embodiment 6

Chloroisothiazole -5- carboxamidine derivatives the IV of 3,4- bis- and the insecticide composition of the present invention in preventing and treating agricultural and forestry and Purposes in gardening plant insect pest：

All chloroisothiazole -5- carboxamidine derivatives IV of 3,4- bis- and existing insecticide：Chlopyrifos, sub- Nong, Acetamiprid, Emamectin benzoate, milbemectin, AVM, pleocidin, fenvalerate, esfenvalerate, cypermethrin, efficiently Cypermethrin, Cyhalothrin, decis, Fenpropathrin, Beta- cyfloxylates, Lambda- Cyhalothrins, Permanone, permethrin, allethrin, Biphenthrin, Permethrin, ethofenprox, flumethrin, the chrysanthemum of chlorine fluorine amine cyanogen penta Ester, imidacloprid, Nitenpyram, imidaclothiz, thiacloprid, Diacloden, clothianidin, MTI-446, clothianadin, Da Tenan, diflubenzuron, go out Young urea, Teflubenzuron, deinsectization are grand, HEXAFLUMURON, flufenoxuron, pyridine worm are grand, lufenuron, poisonous insect urea, penfluron, Noviflumuron are more Fluorine urea, its No. CAS be 121451-02-3, flucycloxuron, Novaluron be Rimon, chlorfluazuron, Bay sir 6874 i.e. { 1- [(3.5- bis- chloro- 4) 4-nitrophenoxy phenyl 3-3- (2- chlorobenzenes)-urea }, Bay SIR-8514 are [1- (4- fluoroforms Phenyl) -3- (2- chlorobenzenes)-urea], piperazine worm urea, Bistrifluron be bistrifluron, furan tebufenozide, tebufenozide, chlorine Tebufenozide, methoxyfenozide, ring tebufenozide, Rogor, flolimat, DDVP, orthene, Hostathion, quinalphos, pyridazine Sulphur phosphorus, isazofos, isoprocarb, sevin, Aphox, MTMC, Mobucin, cartap, Bassa, leaf disperse, carbaryl, third Carbosulfan, carbosulfan, cartap, fenisobromolate, Hexythiazox, fenpyroximate, pyridaben, clofentezine, propargite, diafenthiuron, Pymetrozine, Envidor, spiral shell worm ester, spiral shell worm ethyl ester, butene-fipronil, azacyclotin, Buprofezin, phonamiphos, ethiprole, Cupric sulfate, Dimehypo, chlorantraniliprole, Flubendiamide, fluorine cyanogen insect amide, cyanogen insect amide, Tolfenpyrad, chlorfenapyr, pyrazinones, etoxazole, pyrrole Any one or two kinds in mite amine, rattle away young ketone, Nylar, emaricin are applied in combination for preventing and treating agricultural and forestry and garden Skill insect pest of the plant；The weight/mass percentage compositions of 3,4- bis- chloroisothiazole -5- carboxamidine derivatives IV in the composition are 1%-90%, 3,4- bis- chloroisothiazole -5- carboxamidine derivatives IV and the ratio of foregoing pesticidal agent are mass percent 1%: 99% to 99%: 1%；The formulation of composition processing is selected from seed treatment emulsion, aqueous emulsion, microemulsion, suspension emulsion, water-soluble granule, soluble thick Agent, poison grain, aerosol, block poison bait, sustained-release block, dense poison bait, capsule suspension, electrostatic spray agent, oil in water emulsion, smog Tank, granula subtilis, smoke candle, smoke cartridge, smog rod, smog piece, smog ball, granular poison bait, foaming agent, ointment, thermal fog, it is solid/ Gu the agent of liquid mixing dress, the agent of liquid liquid mixing dress, harl agent, solid/mixing dress agent, medicine paint, fine granule, oil suspending agent, oil-dispersing property powder Agent, sheet poison bait, dense jelly, sprinkle pour agent, seed coat agent, liniment, film forming finish, tracking pulvis, ultra low volume liquids, steam are released Put any one in agent；The insect pest of preventing and treating be selected from red spider, Asiatic migrotory locust, reading room management, Chinese rice grasshopper, Patanga japonica (l.Bol.), Single thorn mole cricket, Oriental burmeister, rice thripses, onion thrips, greenhouse thrips, haplothrips aculeatus, Mai Jian pipes thrips, Trialeurodes vaporariorum Westwood, tobacco powder Lice, rice green leafhopper, green leaf hopper, chlorita biguttula, spot clothing plant hopper, brown paddy plant hopper, white backed planthopper, small brown rice planthopper, the flat angle plant hopper of sugarcane, cotton Aphid, green bugs, grain aphid, black peach aphid, kaoliang aphid, radish aphid, icerya purchasi, Pseudaulacaspis pentagona, unaspis shield kuwana, san jose scale, wax insect, Ceroplastes rubens, Didesmococcus koreanus Borchs, pear lace bug, banana lace bug, thin corner piece stinkbug, Orius minutus, slender rice bug, paddy fly, niphe elongata, rice Black stinkbug, green rice bug, green plant bug, alfalfa plant bug, black striped plant bug, chrysopa septempunctata, beautiful Chrysopa, Chinese green lacewing, rain moth, casemaking clothes moth, oriental moth, Brown slug moth, thosea siensis, gelechiid, pink bollworm, brachmia triannuella, diamondback moth, small heart-eating peach worm, eating-core bean worm, small heart-eating peach worm, Apple Spilonota lechriaspis, brown belt length leaf roller, Adoxophyes cyrtosema, striped rice borer, bean-pod borer, corn borer, yellow rice borer, Oeobia undalis, rice It is leaf-roller, bar snout moth's larva, Notarchaderogata, dichocrocis punctiferalis, armyworm, prodenia litura, rice green caterpillar, anomis flava, beet armyworm, big Snout moth's larva, bollworm, ancient cooking vessel point spark, black cutworm, big cutworm, yellow cutworm, robber poison moth, gypsymoth, palaearctic sweet potato, beans day Moth, straight burr rice hesperiidae, pelopidas mathias, Papilio xuthus, Common Mormon, cabbage butterfly, pyrameis indica, a ramie Huang a kind of butterfly harmful to crop plants, beans Yuan Cyanines, Venus ground beetle, wrinkle sheath ground beetle, wheat head ground beetle, pleonomus canaliculatus, Agriotes subrittatus Motschulsky, khapra beetle, attagenus piceus, citrus little Ji fourths Worm, golden edge buprestid beetle, yellow meal worm, dark mealworm, red flour beetle, confused flour beetle, verdigris different beetle, H. parallela, North China are black greatly Gill cockchafer, mulberry borer, longicorn beetle, nadezhdiella cantori, pink neck longicorn, big daikon leaf beetle, daicon leaf beetle, aulacophora femoralis, phyllotreta striolata, Callosobruchus chinensis, pea weevil, broad bean weevil, sitophilus zea-mais, rice weevil, dolerus tritici, pear fruit sawfly, yellowish leukorrhea ichneumon wasp, armyworm white star ichneumon wasp, corn earworm are hanged Cocoon ichneumon wasp, Campoletis chlorideae, snout moth's larva stain wart ichneumon wasp, mosquito, fly, horsefly, wheat midge, contarinia tritici, pachydiplosis oryzae, citrus Big trypetid, melonfly, the latent fly of wheat leaf ash, Americal rice leaf miner, Soybean stem borer, frit fly, Hylemyia Platura Meigen, onion fly, radish fly, full skirt chase after Post that fly, corn borer are strict to post fly, armyworm；The applicable plant of these compositions be selected from paddy, wheat, barley, oat, corn, sorghum, Sweet potato, potato, cassava, soybean, garden pea, broad bean, pea, mung bean, red bean, cotton, silkworm and mulberry, peanut, rape, sesame, to Day certain herbaceous plants with big flowers, beet, sugarcane, coffee, cocoa, ginseng, fritillaria, rubber, coconut, oil palm, sisal hemp, tobacco, tomato, capsicum, radish, Huang Melon, Chinese cabbage, celery, hot pickled mustard tube, beet, rape, green onion, garlic, watermelon, muskmelon, "Hami" melon, pawpaw, apple, citrus, peach, tea, Wild vegetables, bamboo shoots, hops, pepper, banana, papaya, orchid, potted landscape.

Embodiment 7

Chloroisothiazole -5- carboxamidine derivatives the IV of 3,4- bis- and the antimicrobial combination of the present invention in preventing and treating agricultural and forestry and Purposes in gardening plant disease：

All chloroisothiazole -5- carboxamidine derivatives IV of 3,4- bis- and existing bactericide：Diazosulfide, tiadinil, It is abbreviated as TDL, tisocromide, first thiophene and lures amine, 4- methyl isophthalic acids, 2,3- thiadiazoles -5- formic acid, 4- methyl isophthalic acids, 2,3- thiadiazoles -5- first Sour sodium, 4- methyl isophthalic acids, 2,3- thiadiazoles -5- Ethyl formates, DL- beta-aminobutyric acids, isotianil, its English are general entitled： Isotianil, the chloroisothiazole -5- formic acid of 3,4- bis-, the chloroisothiazole -5- sodium formates of 3,4- bis-, the chloroisothiazole -5- formic acid of 3,4- bis- Ethyl ester, virazole, antofine, Ningnanmycin or salicylic acid, cymoxanil, thiram, ziram, Mancozeb, aliette, methyl Thiophanate, Bravo, enemy can pine, procymidone, fenpropidin, thiophanate methyl, thiophanate, Metalaxyl-M, flumorph, alkene acyls Quinoline, mefenoxam, benalaxyl-M, double chlorine zarilamid, flusulfamide, first flusulfamide, thiophene fluorine bacterium amine, flutolanil, tecloftalam, ring Propionyl bacterium amine, cyflufenamid, fenhexamid, zarilamid, Silthiopham, furametpyr, pyrrole metsulfovax, mandipropamid, benzoyl Bacterium amine, fenfuram, carboxin, chlozolinate, iprodione, Fluoxastrobin, dimoxystrobin, fluoxastrobin, kresoxim-methyl, SSF 126, oxime Dimoxystrobin, ZEN 90160, pyraclostrobin, trifloxystrobin, Enestroburin, alkene oxime amine, oxygen ring azoles, bromuconazole, Cyproconazole, phenylate Methyl cyclic-azole, olefin conversion, efficient olefin conversion, epoxiconazole, RH-7592, Fluquinconazole, Flusilazole, Flutriafol, hexaconazole, glyoxalin, kind Bacterium azoles, metconazole, nitrile bacterium azoles, penconazole, propiconazole, prothioconazoles, simeconazoles, Tebuconazole, tetraconazole, Triadimenol, sterilizing Azoles, bitertanol, probenazole, furidazol, imazalil, efficient imazalil, Prochloraz, fluorine bacterium azoles, cyazofamid, Fenamidone, The white spirit of Evil imidazoles, pefurazoate, famoxadones, SYP-Z048, hymexazo, Evil, Guardian, Grandox fumigant, octhilinone, benzene thiophene sulphur Cyanogen, dodemorph, butadiene morpholine, tridemorph, fenpiclonil, fludioxonil, fluazinam, pyrifenox, ring pyridine bacterium amine, pyridine acyl bacterium Amine, fluopicolide, pyridine bacterium amine, cyprodinil, fluorine mepanipyrim, ferimzone, mepanipyrim, pyrimethanil, Fenarimol, fluorobenzene are phonetic Pyridine alcohol, chinomethionat, dithianon, ethoxyquin, oxyquinoline, the third oxygen quinoline, quinoxyfen, diethofencarb, iprovalicarb, benzene thiophene Bacterium amine, Propamocarb, methasulfocarb, edifenphos, different rice blast net, pyrazophos, tolelofos-methyl, blasticidin-S, kasugarnycin, more anti-mildews Element, Polyoxin, valida, jinggangmeisu, streptomysin, metalaxyl, furalaxyl, M 9834, ofurace, mebenil, more bacterium Spirit, benomyl, thiophanate-methyl, triazolone, bupirimate, dimethirimol, ethirimol, difoltan, captan, sterilizing It is pellet, vinclozolin, fluoromide, dimethachlon, Bravo, Isoprothiolane, kitazine, Yekuzuo, pentachloronitrobenzene, third gloomy Zinc, phosethyl-Al, sulphur, Bordeaux mixture, copper sulphate, copper oxychloride, cuprous oxide, Kocide SD, metrafenone, Pencycuron, Diclomezin, Rabcide, pyroquilon, volution bacterium amine, tricyclazole, triforine, more fruit pyridines, the pungent salt of biguanides, iminoctadine, chlorine nitre Amine, benzene flusulfamide, toluene flusulfamide, K-281, fenaminosulf, oxolinic acide, probenazole, bronopol, iodomethane, metham-sodium, Oppose line ester, dazomet, nemamort, lythidathion, cadusafos, fensulfothion, thionazin, fenamiphos, phonamiphos, dichlofenthion, chlorazol Appointing in phosphorus, fosthietan, oxamyl, Aldicarb, carbofuran, vikane, dichloropropylene, dichloro-isonicotinic acid, allyl isothiazole Meaning one or two are applied in combination for preventing and treating agricultural and forestry and gardening plant disease；3,4- bis- chloroisothiazole -5- carbonamidines The total weight/mass percentage compositions of derivative I V in the composition are 1%-90%, 3,4- bis- chloroisothiazole -5- carboxamidine derivatives IV Ratio with foregoing bactericide is mass percent 1%: 99% to 99%: 1%；The object of above-mentioned composition preventing and treating is selected from rice Seedling pythium rot, tomato root rot, the late blight of potato, tobacco black shank, millet powdery mildew, downy mildew of garpe, downy mildew of lettuce, Cucumber downy mildew, cucumber anthracnose；Composition processing formulation be selected from seed treatment emulsion, aqueous emulsion, microemulsion, suspension emulsion, Water-soluble granule, soluble thick agent, poison grain, aerosol, block poison bait, sustained-release block, dense poison bait, capsule suspension, electrostatic spray Agent, oil in water emulsion, smoke candle, granula subtilis, smoke candle, smoke cartridge, smog rod, smog piece, smog ball, granular poison bait, get angry Solid agent, ointment, thermal fog, the agent of solid-liquid mixing dress, the agent of liquid liquid mixing dress, harl agent, solid/mixing fill agent, medicine paint, fine granule, Oil suspending agent, oil-dispersing property pulvis, sheet poison bait, dense jelly, sprinkle and pour agent, seed coat agent, liniment, film forming finish, tracking pulvis, super Any one in low capacity liquor, steam releasing agent；The applicable plant of these compositions is selected from paddy, wheat, barley, swallow Wheat, corn, sorghum, sweet potato, potato, cassava, soybean, garden pea, broad bean, pea, mung bean, red bean, cotton, silkworm and mulberry, peanut, Rape, sesame, sunflower, beet, sugarcane, coffee, cocoa, ginseng, fritillaria, rubber, coconut, oil palm, sisal hemp, tobacco, tomato, Capsicum, radish, cucumber, Chinese cabbage, celery, hot pickled mustard tube, beet, rape, green onion, garlic, watermelon, muskmelon, "Hami" melon, pawpaw, apple, mandarin orange Tangerine and peach, tea, wild vegetables, bamboo shoots, hops, pepper, banana, papaya, orchid, potted landscape.

Embodiment 8

Chloroisothiazole -5- carboxamidine derivatives the IV of 3,4- bis- of the present invention combine with anti-plant virus agent in preventing and treating agricultural respectively With the purposes in forestry and gardening plant virus disease：

3,4- bis- chloroisothiazole -5- carboxamidine derivatives IV and existing antiviral agent diazosulfide, tiadinil, letter TDL, isotianil are written as, its English is general entitled：Isotianil, 4- methyl isophthalic acid, 2,3- thiadiazoles -5- formic acid, 4- methyl - 1,2,3- thiadiazoles -5- sodium formates, 4- methyl isophthalic acids, 2,3- thiadiazoles -5- Ethyl formates, the chloroisothiazole -5- formic acid of 3,4- bis-, 3,4- bis- chloroisothiazole -5- sodium formates, the chloroisothiazole -5- Ethyl formates of 3,4- bis-, DL- beta-aminobutyric acids, virazole, An Tuo Sweet smell, Ningnanmycin, tisocromide, first thiophene lure amine or salicylic acid, cytosintetidemycin, dichloro-isonicotinic acid, allyl isothiazole, well ridge azanol, Any 1 or 2 compound groups are shared in preventing and treating agricultural and forestry and gardening plant virus disease in jinggangmeisu；For preventing The disease for controlling agricultural and forestry and gardening plant virus disease is selected from rice dwarf virus disease, BYDV, stripe virus disease, tomato fern Leaf disease viral disease, pepper mosaic virus disease viral disease and tobacco veinal necrosis virus disease, maize dwarf mosaic, cauliflower mosaic virus, citrus disease Any one of viral disease, cymbidium mosaic virus, cybidium ring spot virus；The applicable plant of these compositions be selected from paddy, wheat, Barley, oat, corn, sorghum, sweet potato, potato, cassava, soybean, garden pea, broad bean, pea, mung bean, red bean, cotton, silkworm Mulberry, peanut, rape, sesame, sunflower, beet, sugarcane, coffee, cocoa, ginseng, fritillaria, rubber, coconut, oil palm, sisal hemp, cigarette Grass, tomato, capsicum, radish, cucumber, Chinese cabbage, celery, hot pickled mustard tube, beet, rape, green onion, garlic, watermelon, muskmelon, "Hami" melon, pawpaw, Apple, citrus and peach, tea, wild vegetables, bamboo shoots, hops, pepper, banana, papaya, orchid, potted landscape；The different thiophene of 3,4- dichloros The total weight/mass percentage compositions of azoles -5- carboxamidine derivatives IV in the composition are 1%-90%, 3,4- bis- chloroisothiazole -5- carbonamidines The ratio of derivative I V and foregoing anti-plant virus agent is mass percent 1%: 99% to 99%: 1%；The agent of composition processing Type is selected from seed treatment emulsion, aqueous emulsion, microemulsion, suspension emulsion, water-soluble granule, soluble thick agent, poison grain, aerosol, block Shape poison bait, sustained-release block, dense poison bait, capsule suspension, electrostatic spray agent, oil in water emulsion, smoke candle, granula subtilis, smoke candle, cigarette Mist cylinder, smog rod, smog piece, smog ball, granular poison bait, foaming agent, ointment, thermal fog, the agent of solid-liquid mixing dress, liquid liquid mixing It is solid dress agent, harl agent, solid/mixing dress agent, medicine paint, fine granule, oil suspending agent, oil-dispersing property pulvis, sheet poison bait, dense jelly, bold and vigorous Pour any one in agent, seed coat agent, liniment, film forming finish, tracking pulvis, ultra low volume liquids, steam releasing agent.

The present invention 3 of table 2, the chloroisothiazole -5- formamidine derivative Is V of the 4- bis- bacteriostatic activity (suppression of 50 mcg/mls Rate/%)

Sequence number	Compound	PI	CA	AS	BC	GZ	PP	SS	RC	PS
											1	zgn09-30-1	50.00	31.25	52.38	25.53	14.29	43.14	64.41	32.69	31.82
2	zgn09-31	15.00	25.00	42.86	34.04	51.43	45.10	57.63	23.08	18.18
											3	zgn09-49	10.00	31.25	23.81	23.40	0.00	21.57	55.93	5.77	22.73
4	zgn09-56-1	20.00	18.75	28.57	40.43	57.14	43.14	33.90	21.15	13.64
											5	zgn09-56-2	10.00	31.25	14.29	31.91	28.57	13.73	33.90	13.46	0.00
6	zgn09-32	10.00	25.00	33.33	23.40	20.00	27.45	11.86	0.00	4.55
											7	zgn09-57-2	20.00	12.50	23.81	17.02	14.29	54.90	13.56	1.92	31.82
8	zgn09-57-1	10.00	12.50	28.57	27.66	40.00	52.94	28.81	5.77	27.27
											9	zgn09-36	35.00	62.50	52.38	44.68	51.43	72.55	74.58	53.85	36.36
10	zgn09-58-2	20.00	56.25	52.38	44.68	25.71	39.22	49.15	30.77	18.18
											11	zgn09-58-1	25.00	62.50	52.38	46.81	54.29	41.18	72.88	96.15	45.45
12	zgn09-37	30.00	50.00	57.14	23.40	22.86	27.45	84.75	40.38	13.64
											13	zgn09-59-1	40.00	75.00	61.90	53.19	45.71	60.78	81.36	30.77	22.73
14	zgn09-63-2	55.56	53.85	29.41	68.00	44.83	53.85	72.50	93.55	75.00
											15	zgn09-52-1	85.00	12.50	42.86	48.94	17.14	39.22	61.02	1.92	18.18
16	zgn09-76-2	33.33	38.46	23.53	68.00	44.83	7.69	40.00	80.65	45.00
											17	zgn09-60-2	11.11	30.77	17.65	36.00	27.59	30.77	55.00	45.16	25.00
18	zgn09-73-2	27.78	92.31	82.35	24.00	27.59	38.46	40.00	29.03	25.00
											19	zgn09-63-1	16.67	53.85	52.94	52.00	34.48	46.15	60.00	61.29	25.00
20	zgn09-53-2	10.00	31.25	38.10	34.04	51.43	64.71	71.19	34.62	18.18
											21	zgn09-50-1	20.00	56.25	52.38	23.40	28.57	33.33	54.24	69.23	27.27
22	zgn09-60-1	11.11	30.77	5.88	24.00	31.03	23.08	75.00	41.94	5.00
											23	zgn09-53-1	20.00	31.25	52.38	17.02	17.14	23.53	13.56	0.00	13.64
24	zgn09-52-2	15.00	25.00	42.86	25.53	17.14	45.10	59.32	11.54	4.55
											25	zgn09-51	38.89	69.23	58.82	64.00	55.17	84.62	77.50	80.65	45.00
26	zgn09-77-1	47.37	66.67	57.14	58.33	34.78	91.30	93.33	92.59	52.94
											27	zgn09-62	11.11	30.77	23.53	16.00	27.59	30.77	15.00	41.94	20.00
28	zgn09-78-2	52.63	58.33	21.43	50.00	69.57	52.17	66.67	77.78	35.29
											29	zgn09-67	16.67	46.15	41.18	68.00	51.72	38.46	77.50	87.10	30.00
30	zgn09-69-1	11.11	38.46	35.29	48.00	41.38	19.23	75.00	48.39	15.00
											31	zgn09-69-2	11.11	46.15	41.18	60.00	58.62	46.15	70.00	80.65	25.00
32	zgn09-69-3	0.00	23.08	23.53	44.00	20.69	42.31	35.00	45.16	20.00
											33	zgn09-68-1	16.67	46.15	23.53	64.00	62.07	38.46	77.50	87.10	40.00
34	zgn09-68-2	11.11	30.77	41.18	56.00	44.83	23.08	72.50	74.19	15.00
											35	zgn09-68-3	55.56	46.15	52.94	80.00	68.97	61.54	100.00	100.00	50.00
36	whx02-11	10.00	37.93	17.65	47.62	25.00	33.90	75.51	75.00	14.75
											37	whx02-7	36.84	50.00	28.57	70.83	56.52	73.91	70.00	81.48	47.06
38	whx 02-13	75.00	72.41	67.65	90.48	0.00	38.98	55.10	80.00	73.77
											39	whx01-47	5.56	46.15	29.41	72.00	75.86	57.69	65.00	87.10	20.00
40	whx02-10	52.63	50.00	42.86	54.17	30.43	43.48	73.33	92.59	11.76
											41	zgn09-74-2	22.22	53.85	41.18	84.00	51.72	26.92	77.50	77.42	15.00
42	mly02-25	50.00	51.72	52.94	80.95	15.00	44.07	51.02	75.00	54.10
											43	fz6-1-2	14.29	20.00	23.33	50.00	12.82	40.00	35.00	61.11	54.22
44	fz6-4-4	60.00	64.00	60.00	82.69	53.85	96.67	95.00	81.94	92.77
											45	Fluoxastrobin	100.00	68.00	44.26	78.95	100.00	64.91	100.00	100.00	83.78

The present invention 3 of table 3, (100 is micro- for the activity of the chloroisothiazole -5- formamidine derivative Is V of 4- bis- resisting tobacco mosaic virus Inhibiting rate/% of grams per milliliter)

Sequence number	Compound number	Passivation ± SD	Treatment ± SD	Protection ± SD	Induction ± SD
						1	zgn09-30	47.92±3.14	42.50±4.33	33.33±5.20	42.50±5.73
2	zgn09-31	43.75±3.75	7.08±7.53	31.25±6.61	14.17±5.20
						3	zgn09-49	20.42±5.05	0.83±1.44	5.42±4.73	20.42±5.05
4	zgn09-56-1	35.42±5.05	34.58±5.05	16.25±3.75	38.33±5.91
						5	zgn09-56-2	43.33±3.81	39.58±6.41	25.83±6.17	41.25±4.51
6	zgn09-32	40.42±2.60	41.67±4.02	7.50±6.96	36.67±6.41
						7	zgn09-57-2	38.75±4.51	33.75±3.75	38.33±5.64	13.33±7.64
8	zgn09-57-1	38.33±8.32	41.25±6.96	22.92±5.05	14.58±5.20
						9	zgn09-36	35.42±5.05	36.67±7.11	30.00±5.73	18.33±4.02
10	zgn09-58-2	43.33±5.05	39.58±5.91	6.67±1.44	22.92±4.73
						11	zgn09-58-1	33.75±2.50	28.33±6.29	47.92±5.20	39.58±5.20
12	zgn09-37	42.92±5.05	30.42±6.17	36.67±5.05	32.50±5.73
						13	zgn09-59-1	35.42±5.05	18.33±6.29	5.42±2.60	30.00±5.00
14	zgn09-63-2	30.83±3.82	35.83±6.88	35.42±2.60	44.17±4.39
						15	zgn09-52-1	13.75±9.92	30.42±7.53	10.00±4.51	6.25±6.61
16	zgn09-76-2	41.67±5.05	44.58±1.91	41.67±6.17	35.83±3.82
						17	zgn09-60-2	44.33±4.05	46.50±3.70	45.18±2.40	52.09±4.85
18	zgn09-73-2	33.75±4.51	28.33±5.91	25.42±6.41	40.42±6.17
						19	zgn09-63-1	50.83±3.82	45.00±8.20	38.75±6.25	43.75±1.25
20	zgn09-53-2	44.17±2.60	41.67±5.64	25.83±4.39	20.42±4.39
						21	zgn09-50-1	31.67±6.29	53.75±3.31	4.58±1.91	41.67±4.39
22	zgn09-60-1	34.17±5.63	9.58±4.73	38.75±5.73	23.33±7.53
						23	zgn09-53-1	31.25±4.51	33.33±8.78	28.75±5.73	38.33±5.05
24	zgn09-52-2	34.17±5.05	46.67±6.17	46.67±6.29	42.08±3.82
						25	zgn09-51	5.83±5.63	24.58±5.20	37.92±5.91	2.92±3.15
26	zgn09-77-1	48.33±5.05	25.42±6.29	12.92±5.05	30.00±7.81
						27	zgn09-62	40.00±3.31	24.17±2.60	36.67±3.82	37.08±4.02
28	zgn09-78-2	37.50±1.25	42.92±4.02	37.50±2.50	38.75±3.31
						29	zgn09-67	37.08±3.82	51.67±3.15	26.67±6.29	40.83±6.41
30	zgn09-69-1	51.67±2.60	4.58±4.02	40.83±3.15	38.75±5.00
						31	zgn09-69-2	33.75±5.73	46.67±5.05	24.17±5.91	37.50±6.96
32	zgn09-69-3	35.00±3.75	47.50±3.31	22.50±5.73	40.42±5.20
						33	zgn09-68-1	23.75±4.51	37.50±3.31	22.08±7.32	40.42±5.91
34	zgn09-68-2	38.75±4.51	37.50±9.44	33.33±4.02	39.17±4.39
						35	zgn09-68-3	44.17±5.05	37.92±2.60	26.67±5.91	29.58±4.02
36	whx02-11	36.67±3.14	35.00±2.50	24.58±5.91	40.42±4.02
						37	whx02-7	35.00±5.73	5.42±3.82	21.67±6.29	45.42±4.02
38	whx02-13	43.33±3.82	40.83±5.20	45.83±4.39	34.17±3.82
						39	whx01-47	39.17±5.64	45.83±4.73	20.00±5.00	39.58±5.64
40	whx02-10	39.17±3.14	45.00±3.31	17.50±6.96	39.17±6.29
						41	zgn09-74-2	47.50±3.75	37.08±6.29	15.00±4.51	39.58±5.05
42	mly02-25	35.00±4.51	34.17±7.53	48.33±4.73	41.67±4.73
						43	fz6-1-2	31.58±4.74	31.90±5.02	8.44±5.39	42.92±3.82
44	fz6-4-4	12.72±2.74	27.14±5.15	22.22±4.69	34.58±5.05
						46	First thiophene lures amine	27.50±3.75	33.33±3.33	50.83±5.20	49.17±2.60
47	BTH	5.42±5.64	46.25±8.20	49.58±3.82	48.75±4.51
						48	Virazole	47.92±5.64	47.50±3.31	45.42±6.88	40.00±5.00
49	TDL	23.33±4.39	26.25±5.73	39.58±4.73	49.58±5.64
						50	Ningnanmycin	50.00±4.51	26.67±5.20	40.42±5.64	39.17±6.88

Claims

1. one kind 3, the chloroisothiazole -5- carboxamidine derivatives of 4- bis-, it is characterised in that there is the chemical structure of general formula as shown in formula IV：

Wherein, X is selected from S or NH；Work as R¹For 2- ethoxyethyl groups when；R²Select 4- methoxyphenyls, 4- bromophenyls；Work as R¹It is chloro- for 3- During 5- trifluoromethyl pyridine -2- bases；R²Selected from benzyl, 4- methoxyphenyls, 4- aminomethyl phenyls, 3- aminomethyl phenyls, 4- bromophenyls, 2- bromophenyls, 2- chloropyridine -5- methylene, 4- methylpyrimidine -2- bases, cyclohexyl, ethoxyethyl group.

2. chloroisothiazole -5- carboxamidine derivatives the IV of 3,4- bis- described in claim 1 are being prepared with agriculturally acceptable auxiliary agent Purposes in killing plant pathogenic fungi agent.

3. chloroisothiazole -5- carboxamidine derivatives the IV of 3,4- bis- described in claim 1 are being prepared with agriculturally acceptable auxiliary agent Purposes in induced resistance of plant activiator.

4. chloroisothiazole -5- carboxamidine derivatives the IV of 3,4- bis- described in claim 1 are being prepared with agriculturally acceptable auxiliary agent Purposes in resisting tobacco mosaic virus agent.