CN109053801B - Triphenyl phosphonium salt compound and its preparation method and use - Google Patents

Triphenyl phosphonium salt compound and its preparation method and use Download PDF

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CN109053801B
CN109053801B CN201810938900.9A CN201810938900A CN109053801B CN 109053801 B CN109053801 B CN 109053801B CN 201810938900 A CN201810938900 A CN 201810938900A CN 109053801 B CN109053801 B CN 109053801B
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覃兆海
王家尧
刘雪莲
唐大超
肖玉梅
李佳奇
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Beijing Hairuo Pharmaceutical Co.,Ltd.
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China Agricultural University
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/28—Phosphorus compounds with one or more P—C bonds
    • C07F9/54—Quaternary phosphonium compounds
    • C07F9/5442—Aromatic phosphonium compounds (P-C aromatic linkage)
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N57/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds
    • A01N57/18—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds having phosphorus-to-carbon bonds
    • A01N57/22—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds having phosphorus-to-carbon bonds containing aromatic radicals
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N57/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds
    • A01N57/18—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds having phosphorus-to-carbon bonds
    • A01N57/24—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds having phosphorus-to-carbon bonds containing heterocyclic radicals

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Abstract

The invention discloses a phosphonium salt compound and a preparation method and application thereof. The structural formula of the phosphonium salt compound is shown as a formula I, and the definition of each substituent group is shown in the specification. The preparation method comprises the following steps: the compound shown in the formula VII and triphenylphosphine are subjected to nucleophilic reaction in an organic solvent under the condition of a catalyst or no catalyst to obtain the compound shown in the formula I, the preparation method is simple, the obtained compound shown in the formula I can be used for preventing and treating diseases caused by various germs such as oomycetes, basidiomycetes, ascomycetes, imperfect fungi and the like on various plants, the effect on wheat powdery mildew, corn rust, watermelon anthracnose and the like is particularly good, and a good prevention and treatment effect can be obtained under low concentration.

Description

Triphenyl phosphonium salt compound and its preparation method and use
Technical Field
The invention relates to a triphenyl phosphonium salt compound and a preparation method and application thereof.
Background
Since the synthesis of tetrakis (hydroxymethyl) phosphonium salts by Messinger et al in 1888, quaternary phosphonium salts and their derivatives have developed rapidly. Alkyl quaternary phosphonium salt compounds that began to be produced and used in about 1990 are a new generation of highly effective, broad spectrum fungicides. The bactericide has the advantages of high efficiency, broad spectrum, strong surface activity, strong slime stripping and cleaning effect, low foamability, low dosage, low toxicity, no environmental pollution, good compatibility, wide pH value application range (pH 2-12), good chemical stability and the like, is a representative of a new generation of cationic surfactant bactericide, and is widely applied to the fields of medical sanitation, oil field exploitation, water treatment, food industry, agriculture, daily life and the like.
Meanwhile, the quaternary phosphonium salt has high affinity to mitochondria, so that the quaternary phosphonium salt is widely used for mitochondria targeted delivery of medicaments in the field of medicines, and the targeted aggregation capability inside mitochondria can be improved by 1000 times compared with that of non-targeted medicaments, thereby being beneficial to reducing the use amount of the medicaments and reducing toxic and side effects.
Disclosure of Invention
The invention aims to provide a triphenyl phosphonium salt compound and a preparation method thereof.
The structural general formula of the phosphonium salt compound provided by the invention is shown as formula I:
Figure BDA0001768554610000011
in the formula I, X is selected from CH2N, S or O; y is selected from halogen (Cl, Br or I), CH3SO3、CF3CO2、CH3CO2、CF3SO3、PhCO2、HOC6H4CO2、(CH2CO2)2、(CHCO2)2And any of formula W; n is an integer of 0 to 16; q is selected from formula Ia or formula Ib;
Figure BDA0001768554610000012
in the formula W, R1Represents H or C1～C12Alkyl groups of (a);
in the formula Ia, Ar is selected from the following A1～A8Any one of, Q1Selected from H or B1～B11Any one of the above;
Figure BDA0001768554610000021
in the formula Ib, U is selected from any one of O, NH, S, OCO, SC O, NHC O, NHC S, and Q2Is selected from C1～C4Any one of (a);
Figure BDA0001768554610000022
wherein A is1-A8The formula A1、A2And A5In, R2、R3、R4、R5And R6Are all selected from hydrogen and C1-C8Alkyl of (C)1-C8Alkoxy group of (C)1-C8Alkylthio of, C1-C8Fluoroalkyl of, C1-C8At least one of fluoroalkoxy group of (a), halogen selected from any one of fluorine, chlorine, bromine and iodine, nitro group, cyano group, phenoxy group, pyridyloxy group, methanesulfonyl group and trifluoromethanesulfonyl group; m is an integer of 0 to 4; o, q and r are each an integer of 0 to 5; p is an integer of 0 to 3; r2、R3、R5And R6Is at least one of the remaining 5 binding sites, wherein when m, o, q and r are>1 is, R2、R3、R5And R6May be the same or different; r4Is at least one of the remaining 3 binding sites, wherein, when p is>1 is, R4May be the same or different; formula A2N may be located at any of positions 3, 4, 5 and 6.
Wherein B is1-B10The formula B1In, R7Selected from hydrogen, C1-C5Alkyl of (C)1-C5Alkoxy group of (C)1-C5Fluoroalkyl of, C1-C5At least one of fluoroalkoxy group, halogen, nitro group, cyano group, phenoxy group, pyridyloxy group, carboxyl group, methanesulfonyl group and trifluoromethanesulfonyl group of (a), the halogen is selected from any one of fluorine, chlorine, bromine and iodine, and s is an integer of 0 to 5; r7Is at least one of the remaining 5 binding sites, wherein when s is>1 is, R7May be the same or different; the formula B6In, R8And R9Are all selected from hydrogen and C1-C5Alkyl of (C)1-C5Alkoxy group of (C)1-C5By the fluorination ofAlkyl radical, C1-C5And (3) any one of the fluoroalkoxy group and the halogen.
Wherein C is1-C4The formula C1And C3Wherein Z is selected from N or CH, and M is selected from NH or O.
The structural general formula of the phosphonium salt compound provided by the invention is shown as a formula I, and the phosphonium salt compound is preferably as follows: in the formula I, X is selected from CH2Or O; y is selected from halogen, AcO (CH)3CO2) P-toluenesulfonyl (TsO), PhCO2And HOC6H4CO2Any one of (a); n is an integer of 4 to 11; q is selected from Ia or Ib.
More preferred structures are: in the formula Ia, Ar is selected from A1、A3、A4Or A6，Q1Is selected from H; in the formula Ib, U is selected from any one of O, OCO and SC ═ O, and Q2Is selected from C1～C4Any one of the above.
The terms referred to in the definition of said compounds of formula I according to the invention represent the following substituents:
halogen: refers to fluorine, chlorine, bromine, iodine.
Alkyl groups: represents a linear or branched alkyl group, such as: methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, tert-pentyl and the like.
Aryl groups and the aryl moiety of aryloxy groups include phenyl, pyridyl, furyl, and the like.
In addition, in the compound of formula I, different substituents are connected to a carbon-carbon double bond or a carbon-nitrogen double bond to form geometric isomers (Z and E represent different configurations respectively). The compound of the formula I can be Z-type isomer, E-type isomer or a mixture of the two in any proportion.
The compound of formula I of the invention can be specifically selected from the following numbered compounds
Figure BDA0001768554610000031
Figure BDA0001768554610000032
Figure BDA0001768554610000041
Figure BDA0001768554610000051
Figure BDA0001768554610000061
Figure BDA0001768554610000071
Figure BDA0001768554610000081
Figure BDA0001768554610000091
Figure BDA0001768554610000101
Figure BDA0001768554610000111
Figure BDA0001768554610000121
Figure BDA0001768554610000131
Figure BDA0001768554610000141
Figure BDA0001768554610000151
Figure BDA0001768554610000161
Figure BDA0001768554610000171
Figure BDA0001768554610000181
Figure BDA0001768554610000191
Figure BDA0001768554610000201
Figure BDA0001768554610000211
Figure BDA0001768554610000221
Figure BDA0001768554610000231
Figure BDA0001768554610000241
Figure BDA0001768554610000251
Figure BDA0001768554610000261
Figure BDA0001768554610000271
Figure BDA0001768554610000281
The compound of formula I of the invention can be specifically selected from the following numbered compounds
Figure BDA0001768554610000282
Figure BDA0001768554610000283
Figure BDA0001768554610000291
Figure BDA0001768554610000301
Another object of the present invention is to provide a method for preparing the above phosphonium salt compound (compound represented by formula I).
The preparation method of the phosphonium salt compound (the compound shown in the formula I) provided by the invention comprises the following steps: and (2) carrying out nucleophilic reaction on the compound shown in the formula VII and triphenylphosphine in an organic solvent under the condition of a catalyst or no catalyst to obtain the compound shown in the formula I.
Figure BDA0001768554610000302
In formula VII, Y, Q, X and n are defined as formula I; in the preparation method, the catalyst is sodium iodide or potassium iodide.
The molar ratio of the catalyst to the compound shown in the formula VII is (0.01-0.1): 1.
The reaction temperature of the nucleophilic reaction is 25-180 ℃, preferably 80-115 ℃, specifically 82 ℃, and the reaction time is 4-24 hours, specifically 8-12 hours.
The molar ratio of the compound shown in the formula VII to the triphenylphosphine is 1: (1-2), specifically, 1: (1-1.3).
The organic solvent is at least one selected from acetonitrile, ethylene glycol dimethyl ether, benzene, toluene and 1, 2-dichloroethane.
The nucleophilic reaction can be specifically carried out according to the following steps: vacuumizing the catalyst, triphenylphosphine, a compound shown in a formula VII and magnetons, and filling nitrogen; adding an organic solvent under the protection of nitrogen, stirring at room temperature for 5-10min, and reacting at 80-115 ℃ for 8-12h to obtain the compound shown in the formula I.
In the above preparation method, the compound represented by the formula VII is prepared as follows: reacting a compound shown in a formula IV (or a compound shown in a formula V) with a compound shown in a formula VI in an organic solvent in the presence of a catalyst (or in the presence of an acid binding agent) to obtain a compound shown in a formula VII.
Figure BDA0001768554610000311
In the formula IV, Q1And Ar is as defined for formula Ia; in the formula V, Q2Is as defined in formula Ib; in formula VI, X, Y and n are defined as formula I, and U is defined as formula Ib. When formula IV is reacted with formula VI, U is a COO group. In the preparation method, the acid-binding agent is pyridine, triethylamine, ethylenediamine, potassium carbonate, cesium carbonate, NMM (N-methylmorpholine) and NaH; the catalyst is EDCI/HOBT, CDI, DMAP/DCC, HATU/DIPEA, DIC and the like.
The molar ratio of the acid-binding agent to the compound shown in the formula IV is (2-5) to 1, and specifically, the acid-binding agent can be: (2-3):1. The molar ratio of the catalyst to the compound shown in the formula IV is (1-2.5) to 1, and specifically, the molar ratio can be: (1.2-2):1. Wherein the molar ratio of the compound shown as IV to the compound shown as formula VI is 1: (1-2), specifically 1: 1.05.
The molar ratio of the acid-binding agent to the compound shown in the formula V is (2-5) to 1, and specifically, the acid-binding agent can be: (2-3):1. The molar ratio of the catalyst to the compound shown in the formula V is (1-2.5):1, and specifically, the molar ratio can be: (1.2-2):1. Wherein the molar ratio of the compound shown as V to the compound shown as the formula VI is 1: (1-2), specifically 1: 1.05.
The reaction temperature is-20-35 ℃, and the reaction time is 1-6 h.
The organic solvent is dichloromethane, tetrahydrofuran, acetonitrile, N-Dimethylformamide (DMF), 1, 4-dioxane and toluene.
The reaction is selected to be carried out according to the following steps (taking the reaction of the compound shown as the formula IV and the compound shown as the formula VI as an example): vacuumizing the compound shown in the formula IV, a catalyst DMAP/DCC and a magneton, and filling nitrogen; adding an organic solvent under the protection of nitrogen, cooling to-10 ℃ in an ice salt bath, stirring for 5-10min, diluting the compound shown in the formula V in the solvent, slowly dropping the diluted compound into a reaction bottle, and reacting for 0.5-4h to obtain the compound shown in the formula VII.
Figure BDA0001768554610000312
In the preparation method, the compound shown in the formula IV is prepared by the following method: and (3) reacting the compound shown in the formula II and an acid-binding agent in an organic solvent with the compound shown in the formula III to obtain the compound shown in the formula IV.
In the formula II, Ar is defined as the formula I; in the formula III, R1The definitions of (A) and (B) are the same as those of formula I. In the preparation method, the acid-binding agent is pyridine, triethylamine, ethylenediamine, potassium carbonate, cesium carbonate and NaH.
The molar ratio of the catalyst to the compound shown in the formula II is (2-5) to 1, and specifically, the molar ratio can be: (2-3):1. Wherein the molar ratio of the compound shown in II to the compound shown in the formula III is 1: (1-1.2), specifically 1: 1.05.
The reaction temperature is-20-35 ℃, and the reaction time is 1-6 h.
The organic solvent is dichloromethane, tetrahydrofuran, acetonitrile, N-Dimethylformamide (DMF), 1, 4-dioxane and toluene.
The reaction can be specifically carried out according to the following steps: vacuumizing an acid binding agent, a compound shown as a formula II and magnetons, and filling nitrogen; adding organic solvent under nitrogen protection, cooling to-10 deg.C in ice salt bath, stirring for 5-10min, diluting with the solvent of formula III, and slowly dropping into the reaction bottle for reaction for 0.5-4h to obtain the compound of formula IV.
The compounds of formula II, formula III, formula V and formula VI of the present invention can be obtained commercially or by a one-step reaction of starting materials, such as: the compound shown in the formula II can be biphenyl-2-amine containing various substituents, aryl pyridine amine, aniline, benzylamine and various heterocyclic amines. The compound shown in the formula III can be obtained by one-step reaction of various substituted benzoic acids, phenylacetic acids, various substituted heterocyclic formic acids and the like.
The invention also provides a bactericide composition and a preparation method thereof.
The composition comprises a phosphonium salt compound (a compound shown as a formula I) and an agriculturally acceptable carrier, wherein the mass percentage of the phosphonium salt compound (an active ingredient) in a single agent is 0.1-99%, and specifically 30-60%.
The phosphonium salt compound can be a single compound or a mixture of several compounds.
The preparation method of the bactericide composition provided by the invention comprises the following steps: the compound is prepared by uniformly mixing a phosphonium salt compound (a compound shown in a formula I) and an agriculturally acceptable carrier.
The agriculturally acceptable carrier has the following characteristics: 1) formulated with the active ingredient to facilitate application to the site to be treated, for example: plants, seeds or soil; 2) is favorable for storage, transportation or operation; 3) and may be a solid or liquid, including a substance that is normally a gas but has been compressed into a liquid. In any case, carriers commonly used in formulating agricultural germicidal preparations may be used.
The agriculturally acceptable carrier may in particular be selected from a solid carrier and/or a liquid carrier.
The solid carrier is selected from at least one of natural or synthetic silicate, ammonium sulfate, calcium sulfate, aluminum oxide silicate, natural or synthetic resin, polychloroprene, starch, bentonite and wax, wherein the natural or synthetic silicate can be selected from at least one of attapulgite, talc, aluminum silicate, diatomite, mica, montmorillonite and calcium silicate, and the natural or synthetic resin can be selected from at least one of benzofuran resin, styrene polymer (molecular weight is 5-20 ten thousand) and styrene copolymer (such as styrene-butadiene copolymer); the wax may be chosen in particular from beeswax and/or paraffin wax.
The liquid carrier is at least one selected from water, C1-C4 alcohol, C3-C8 ketone, specifically ethanol and/or ethylene glycol, aromatic hydrocarbon, specifically acetone, methyl ethyl ketone and cyclohexanone, petroleum fraction, specifically kerosene and/or mineral oil, and C6-C12 chlorinated hydrocarbon, specifically carbon tetrachloride, dichloromethane and trichloroethane.
Typically, the biocide compositions will be processed to a concentrate form for shipment and diluted by the user prior to application.
To facilitate dilution, the disinfectant compositions provided herein may also include a surfactant.
The surfactant may be added in an amount acceptable for agricultural fungicides.
The surfactant may be selected from at least one of an emulsifier, a dispersant, a wetting agent, and a penetrant.
The emulsifier can be at least one selected from agricultural milk 500# (calcium alkylbenzene sulfonate), agricultural milk 600# phosphate (phenyl phenol polyoxyethylene ether), agricultural milk 700# (alkylphenol formaldehyde resin polyoxyethylene ether), agricultural milk 1600# (phenyl phenol polyoxyethylene polypropylene ether), polyoxyalkylene alkyl aryl ether and ethylene oxide-propylene oxide block copolymer.
The dispersant may be at least one selected from the group consisting of polycarboxylate, lignosulfonate, alkylphenol polyoxyethylene formaldehyde condensate sulfate, calcium alkylbenzene sulfonate, sodium benzene sulfonate formaldehyde condensate, sodium lauryl sulfate, sulfonated castor oil sodium salt, sodium alkylaryl sulfonate, alkylphenol polyoxyethylene pyrimidine, fatty acid polyoxyethylene ester and ester polyoxyethylene pyrimidine.
The wetting agent is selected from at least one of sodium dodecyl sulfate, sodium dodecyl benzene sulfonate, nekal BX, fructus Gleditsiae Abnormalis powder, faeces Bombycis and fructus Sapindi Mukouossi powder.
The penetrating agent can be selected from at least one of siloxane polyoxyethylene ether, alkyl aryl sulfonate, alcohol ether succinate and phenol ether succinate.
Of course, other additives may be added to the fungicide composition of the present invention as appropriate.
The addition amount of the other auxiliary agents is the amount acceptable in the agricultural bactericide.
The other auxiliary agent may be at least one selected from a disintegrant, a defoamer, an antifreeze and a thickener.
The disintegrant is at least one selected from bentonite, urea, ammonium sulfate, aluminum chloride and glucose.
The defoaming agent is at least one selected from silicone oil, silicone compounds, C10-C20 saturated fatty acid compounds and C8-C10 fatty alcohol compounds.
The antifreeze is at least one selected from ethylene glycol, propylene glycol, glycerol and polyethylene glycol.
The thickening agent is selected from at least one of xanthan gum, polyvinyl alcohol and polyethylene glycol.
The bactericide composition prepared by the invention can be prepared into various dosage forms such as wettable powder, granules, concentrated emulsion, missible oil, suspending agent, aerosol or aerosol by adding corresponding components according to the method known by the technicians in the field. Meanwhile, the bactericide composition of the invention can be applied in effective amount according to different crops and diseases, and can be applied by a method of foliar spray, seed treatment or soil treatment.
The invention also provides a composition containing at least two active components.
The active composition of the composition comprises a phosphonium salt compound (a compound shown as a formula I) and at least one other active compound. The other active compound may be at least one of known bactericides, acaricides, nematicides, insecticides, herbicides, fertilizers, growth regulators, safeners and semiochemicals, and further preferably bactericides and insecticides.
The composition is a bactericidal composition, is a composition prepared from a compound shown in a formula I and one or more other bactericides and a preparation thereof, and is used for enlarging the prevention and treatment range of products. Such other biocides include: 2- (thiocyanomethylthio) benzothiazole, 2-phenylphenol, 8-hydroxyquinoline sulfate, ametoctradin, amisol, antimycin, erysiphe necator, azaconazole, azoxystrobin, bacillus subtilis, benalaxyl, benomyl, benthiavalicarb-isopropyl, benzovindiflupyr, biphenyl, thifluzole, bitertanol, bixafen, blasticidin-S, borax, bordeaux mixture, boscalid, bromuconazole, butralin, captafol, carbendazim, carboxin, cyprodinil, carvone, dicyclopentadine, chlorothalonil, ethiprole, coniothyrium minium, copper oxychloride, cuprous oxide, cyazofamid, cyflufenamid, cymoxanil, cyproconazole, cyprodinil, dazomethion, dazomet, diethylbiguanide, dichlorfenac, diclorfenpropamocarb, pyridaben, niclosamide, diethofencarb, difenoconazole, fluoxamid, dimethomorph, dimoxystrobin, diniconazole-M, dinotefuran, dinocap, diphenylamine, dithianon, moroxydine, dodine, edifenphos, enestroburin, epoxiconazole, ethaboxam, ethoxyquin, chloroquine, famoxadone, fenamidone, fenarimol, fenbuconazole, methylfuroamide, fenhexamid, fenpropathrin, fenpiclonil, fenpropimorph, fentin, fermetraz, ferimzone, fluazinam, fludioxonil, flumorph, fluopyram, fluoxastrobin, fluquinconazole, flusilazole, fluvalicarb, flutolanilide, flutriafol, flutriafolpet, fosetyl, furametpyr, furamex, furametpyr, hexaconazole, hymexazol, imazalil, imibenconazole, ipconazole, iprobenfos, iprodione, iprovalicarb, isoprothiolane, isopyramid, kasugamycin, kresoxim-methyl, laminarin, mancopper, mancozeb, mandipropamid, maneb, metalaxyl, mefenoxam, mepanipyrim, imazamide, metam, metconazole, sulfydryl, methyl isothiocyanate, metiram, metominostrobin, metrafenone, milbemycin, myclobutanil, metconazole, sodium metiram, phthalazinate, fluoropyrimidinol, cinisothiazolone, meturamide, oleic acid, orysastrobin, oxaziclorinin, oxindol fumarate, carboxin, isoprothiolate, penconazole, pencycuron, penflufen, pentachlorophenol, penoxphenol laurate, penthiopyrad, phthalein, picoxystrobin, polyoxin, thiabendazole, prochloraz, propamocarb, propiconazole, propineb, iodoquinconazole, prothioconazole, pyraclostrobin, pyraoxystrobin, pyribencarb, pyriproxyfen, pyrimethanil, pyrimorph, pyriofenone, chloroquinone, imazaquin, quinoxyfen, quinclorac, quintozene, sedaxane, sulfenamide, simeconazole, sodium pentachlorophenate, spiroxamine, sulfur, tebuconazole, isobutoxyquinoline, tetrachloronitrobenzene, flutolazol, thiabendazole, thifluzamide, thiophanate-methyl, thiram, tolanil, tolylfluanid, triadimenol, imidazoxazine, tricyclazole, tridemorph, trifloxystrobin, triflumizole, triforine, triticonazole, validamycin, valcyazone, dimeticone, zinone, ziram, fenpropineb, fenpropiconazole, fenpicloram, fentrazone, fenpicloram, cyhalothrin, trifloxystrobin, trifl, chlobenthiazone, fluazinam, benzimidazole, tetrachloroquinoxaline, cyhalonil, ethaboxam, fenphostin, dichloronaphthoquinone, sclerotium, benzytriazole, metidine, dichlormate, nitrooctyl ester, nitrobutyl ester, pyrithiobac, fenamiphos, doxycycline, diketene, epoxiconazole, fenaminosulf, propionitrile, coatin, flufenazole, furametpyr, fenpyrazamide, furametpyr, griseofulvin, quinolinylacrylate, cyclohexaphos, isophosphorus, fenamidone, fenazamide, benzocyclovir, metocloprid, metoclopramide, trifolium, thiflufenamid, metiram, natamycin, clofenphos, propamocarb, pyraclostrobin, picoline, clopyralid, hydroxyquinolyl, quinolyl, quinazol, fluquinconazole, pyrazofen, salicylanilide, penflufenacetone, penethiprole, thiabendazole, dicofol, thiocyanobenzamide, fenbuconazole, cyprodinil, ethaboxam, asomate, cyhalodiamide and the like.
The composition is a composition prepared from a compound shown as a formula I and one or more other insecticides and preparations for expanding the control range of products, the other insecticides comprise avermectin, acephate, acetamiprid, fenpropathrin, fenpropaphos, fenthion, fenpropaphos, fenthion, fenpropaphos, fenthion, fenpropathrin, fenpropaphos, fenpropathrin, fenthion, fenpropathrin, fenpropaphos, fenpropathrin, fenthion, fenpropathrin, fenpropaphos, fenthion, fenpropaphos, fenthion, fenpropaphos, fenpropathrin, fenpropaphos, fenthion, fenpropaphos, fenthion, fenpropathrin, fenthion, fenpropathrin, fenthion, fenpropaphos, fenpropathrin, fenpropaphos, fenpropathrin, fenprophos, fenpropathrin, fenpropaphos, fenprophos, fenpropathrin, fenthion, fenpropaphos, fenpropathrin, fenthion, fenpropaphos, fenthion, fenpropathrin, fenprophos, fenpropathrin, fenprophos, fenpropathrin, fenthion, fenpropathrin, fenthion, fenprophos, fenpropathrin, fenprophos, fenpropathrin, fenthion, fenprophos, fenthion, fenprophos, fenpropathrin, fenpropaphos, fenprophos, fenthion, fenprophos, fenprophen, fenprophos, fenprophen, fenprophos, fenprophen, fenprop.
In addition, the compound shown in the formula I and the application of the composition containing the compound shown in the formula I in the preparation of bactericides also belong to the protection scope of the invention.
The compound shown in the formula I has broad-spectrum and excellent bactericidal activity, and can be used for preventing and controlling four fungi on various crops: diseases caused by fungi of the ascomycetes, basidiomycetes, deuteromycetes and oomycetes classes. Can obtain good control effect at very low dosage. Meanwhile, the compounds shown in the formula I have certain systemic property and can be used as foliar and soil bactericides for preventing and treating diseases on various crops. The following diseases can be specifically controlled: pepper blight, tomato early blight, tomato late blight, tomato gray mold, rice blast, wheat leaf spot, apple ring spot, rice sheath blight, rice blast, rice false smut, rice bakanae disease, wheat powdery mildew, wheat scab, rape sclerotinia rot, cucumber downy mildew, cucumber fusarium wilt, cucumber gray mold, cucumber powdery mildew, apple powdery mildew, watermelon anthracnose, peanut brown spot, melon and fruit rot, cotton fusarium wilt, cotton verticillium wilt and cotton blight.
Drawings
FIG. 1 is a scheme for the preparation of compounds of formula I.
Detailed Description
The present invention is described below with reference to specific embodiments, but the present invention is not limited thereto, and any modification, equivalent replacement, and improvement made within the spirit and principle of the present invention should be included in the scope of the present invention.
The experimental procedures used in the following examples are all conventional procedures unless otherwise specified.
Materials, reagents and the like used in the following examples are commercially available unless otherwise specified.
Firstly, the preparation example of the compound shown in the formula I is as follows: the corresponding preparation flow chart is shown in figure 1:
example 1 preparation of Compound Ia8a-1 (i.e., formula Ia)nN is 8, Y is Br, Q1＝H，Ar＝A1/[(R2)m＝H,(R3)o＝H]A compound of (1)
1. Preparation of N- [ (1,1' -biphenyl) -2-yl ] -11-bromoundecanamide
A250 mL three-necked flask was charged with 2g (9.13mmol) of 2-iodoaniline, 1.3g (10.96mmol) of phenylboronic acid and 2.5g (18.26mmol) of potassium carbonate. Adding toluene: ethanol: 120ml of a mixed solution of 10:1:1 water was stirred, and 300mg (0.26mmol) of tetrakis (triphenylphosphine) palladium was added. Heating and refluxing for 8 hours to completely react to obtain 1.4g of ortho-aminobiphenyl with the yield of 91 percent.
A100 mL round bottom flask was charged with 1g (3.77mmol) of 11-bromoundecanoic acid, EDCI (0.72g, 3.77mmol) and HoBT (0.5g, 3.77mmol), and reacted with 40mL of dichloromethane for 15 min. Ortho-aminobiphenyl (0.61g,3.6mmol) and NMM (0.77g,7.55mmol) were then added. After 4 hours of reaction, 1.35g N- [ (1,1'-biphenyl) -2-yl ] -11-bromoundecanamide { N- [ (1,1' -biphenyl) -2-yl ] -11-bromoundecanamide } was obtained with a yield of 86%.
1H NMR(300MHz,CDCl3)δ8.21(d,J＝8.2Hz,1H),7.45–7.24(m,6H),7.17–7.13(m,1H),7.12–7.04(m,2H),3.32(t,J＝6.8Hz,2H),2.10(t,J＝7.5Hz,2H),1.84–1.68(m,2H),1.54–1.42(m,2H),1.38–1.28(m,2H),1.18(s,10H).
13C NMR(75MHz,CDCl3)δ170.86,137.88,134.45,131.82,129.65,128.95,128.72,128.08,127.63,123.86,121.24,37.48,33.66,32.48,29.01,28.95,28.91,28.74,28.39,27.81,25.10.
2. Preparation of Compound Ia8a-1
A100 mL three-necked flask was charged with 0.6g (1.45mmol) of N- [ (1,1'-biphenyl) -2-yl ] -11-bromoundecanamide { N- [ (1,1' -biphenyl) -2-yl ] -11-bromoundecamide }, 0.5g (1.9mmol) of triphenylphosphine, 12mg (0.72ummol) of potassium iodide and magnetite, evacuated and charged with nitrogen. Adding 30ml acetonitrile under nitrogen protection, stirring at room temperature for 5-10min, heating and refluxing at 90 deg.C for 12h, and separating by column chromatography to obtain 0.87g white solid powder with yield of 90%.
Structural formula corroboration data:
1H NMR(300MHz,CDCl3)δ8.11(d,J＝8.2Hz,1H),7.78–7.59(m,15H),7.43–7.30(m,3H),7.27–7.18(m,4H),7.14(dd,J＝7.6,1.6Hz,1H),7.06(t,J＝7.4Hz,1H),3.47(s,2H),2.08(t,J＝7.5Hz,2H),1.61–1.37(m,6H),1.21–1.04(m,10H).
13C NMR(75MHz,CDCl3)δ170.94,137.32,134.74,134.69,134.48,133.28,133.14,132.19,130.25,130.08,129.63,129.33,128.62,127.62,123.81,121.38,118.42,117.28,37.25,30.09,29.89,28.77,28.74,28.65,28.57,24.98,22.74,22.23,22.18,22.08.
number Ia4-11a-1～Ia4-11b-1 to Ia4-11a-80～Ia4-11The compounds of b-80 were prepared according to the method of example 1. Wherein the partial compound nuclear magnetism is as follows:
compound Ia8a-31H NMR and13c NMR was as follows:
1H NMR(300MHz,CDCl3)δ7.93(d,J＝8.0Hz,1H),7.76–7.56(m,15H),7.40–7.27(m,2H),7.25–7.13(m,4H),7.13–7.02(m,2H),3.54–3.35(m,2H),2.10(t,J＝7.5Hz,2H),1.63–1.33(m,6H),1.21–0.99(m,10H).
13C NMR(75MHz,CDCl3)δ171.22,139.94,134.85,134.82,134.23,134.15,133.27,133.14,130.33,130.16,129.89,129.51,128.77,128.27,127.49,127.01,124.47,122.94,118.19,117.06,37.12,30.11,29.90,28.71,28.61,28.58,25.04,23.02,22.35,22.17,22.11.
compound Ia8a-51H NMR and13c NMR was as follows:
1H NMR(300MHz,CDCl3)δ7.79–7.57(m,15H),7.37(dd,J＝8.3,5.1Hz,2H),7.24–7.15(m,2H),7.13–7.06(m,2H),3.51–3.30(m,2H),2.15(t,J＝7.5Hz,2H),1.62–1.33(m,6H),1.24–0.97(m,10H).
13C NMR(75MHz,CDCl3)δ171.55,138.69,134.89,134.85,134.20,133.26,133.13,132.35,132.10,131.17,130.50,130.34,130.27,130.18,129.48,128.46,128.33,125.03,124.40,118.18,117.04,36.87,30.09,29.88,28.67,28.59,28.48,25.08,23.03,22.36,22.16,22.10.
compound Ia8a-211H NMR and13c NMR was as follows:
1H NMR(300MHz,CDCl3)δ8.12(s,1H),7.79–7.59(m,16H),7.51(dd,J＝30.9,8.3Hz,4H),7.22(dd,J＝7.7,4.0Hz,1H),7.14(d,J＝4.2Hz,2H),3.47–3.31(m,2H),2.16(t,J＝7.4Hz,2H),1.67–1.45(m,4H),1.45–1.31(m,2H),1.28–1.01(m,10H).
13C NMR(75MHz,CDCl3)δ171.75,144.03,134.92,134.88,134.16,133.26,133.13,131.84,130.35,130.18,129.62,129.44,128.66,125.41,118.56,118.18,117.04,110.37,36.60,30.09,29.89,28.67,28.64,28.54,28.41,25.01,22.98,22.32,22.15,22.09.
compound Ia8a-261H NMR and13c NMR was as follows:
1H NMR(300MHz,DMSO)δ8.80(s,1H),7.78–7.57(m,15H),7.47(dd,J＝8.7,5.4Hz,1H),7.37(d,J＝2.0Hz,1H),7.35–7.28(m,1H),7.25(dd,J＝8.3,2.0Hz,1H),6.84(ddd,J＝11.8,8.4,2.9Hz,2H),3.54–3.25(m,2H),2.18(t,J＝7.5Hz,2H),1.65–1.45(m,4H),1.45–1.29(m,2H),1.26–1.00(m,10H).
13C NMR(75MHz,CDCl3)δ172.22,161.45,158.20,138.26,136.25,134.85,134.82,133.18,133.05,131.81,131.18,130.61,130.28,130.11,130.02,128.15,118.26,117.12,116.05,115.75,114.88,114.59,36.25,30.00,29.80,28.57,28.51,28.33,25.04,22.78,22.12.
example 2 preparation of Compound Ia8a-115 (i.e., formula Ia)nN is 8, Y is Br, Q1＝B5，Ar＝A1/[(R2)m＝H,(R3)o＝4-Cl]A compound of (1)
1. Preparation of 2-chloro-N- (4-chlorobiphenyl-2-yl) -N- (11-bromoundecanoyl) nicotinamide
A100 mL round bottom flask was charged with 1g (3.77mmol) of 11-bromoundecanoic acid, EDCI (0.72g, 3.77mmol) and HoBT (0.5g, 3.77mmol), and reacted with 40mL of dichloromethane for 15 min. Then, 1.24g (3.6mmol) of Boscalid {2-Chloro-N- (4'-Chloro- [1,1' -biphenyl ] -2-yl) nicotinamide } was added. After 4h of reaction, 1.5g of 2-chloro-N- (4-chlorobiphenyl-2-yl) -N- (11-bromoundecanoyl) nicotinamide was obtained, with a yield of 93%.
Structural formula corroboration data:
1H NMR(300MHz,CDCl3)δ8.40(dd,J＝4.8,1.9Hz,1H),7.59–7.39(m,7H),7.33–7.24(m,3H),3.42(t,J＝6.8Hz,2H),2.39–2.23(m,1H),2.05(dt,J＝17.3,7.2Hz,1H),1.94–1.80(m,2H),1.50–1.04(m,15H).
13C NMR(75MHz,CDCl3)δ174.45,168.36,149.49,145.31,139.63,136.13,136.05,135.08,134.20,133.52,130.97,129.69,129.64,129.21,129.13,128.60,121.91,36.58,33.71,32.46,28.94,28.84,28.82,28.46,28.34,27.78,23.64.
2. preparation of Compound Ia8a-115
A100 mL three-necked flask was charged with 0.78g (1.32mmol) of 2-Chloro-N- (4-chlorobiphenyl-2-yl) -N- (11-bromoundecanoyl) nicotinamide {2-Chloro-N- (4'-Chloro- [1,1' -biphenol ] -2-yl) -N- (11-bromoundecanoyl) -nicotinamide }, 0.53g (2mmol) of triphenylphosphine, 12mg (72ummol) of potassium iodide and magnetite, evacuated and charged with nitrogen. Adding 30ml acetonitrile under nitrogen protection, stirring at room temperature for 5-10min, heating and refluxing at 90 deg.C for 10h, and separating by column chromatography to obtain 1g white solid powder with yield of 88%.
Structure confirmation data:
1H NMR(300MHz,CDCl3)δ8.23(dd,J＝4.8,1.9Hz,1H),7.74–7.57(m,15H),7.47–7.14(m,10H),3.60–3.42(m,2H),2.28–1.79(m,2H),1.48(4,6H),1.25–0.87(m,12H).
13C NMR(75MHz,CDCl3)δ174.42,168.27,149.35,145.29,139.46,136.01,135.96,134.90,134.73,134.69,134.02,133.47,133.27,133.13,130.94,130.24,130.07,129.66,129.23,129.05,128.49,121.96,118.42,117.29,36.48,30.06,29.86,28.65,28.59,28.29,23.52,22.75,22.25,22.19,22.08.
number Ia4-11a-81～Ia4-11b-81 to Ia4-11a-184～Ia4-11The compounds of b-184 were prepared as in example 1; number Ia4-11a-185～Ia4-11b-185 to Ia4-11a-553～Ia4-11The compounds of b-553 were prepared according to the methods of examples 1 and 2.
Example 3 preparation of Compound Ib6a-2 (i.e., formula Ib)nN is 6, Y is Br, Q2＝C1bA compound of (1)
A100 mL three-necked flask was charged with 2.35g (8.2mmol) of methyl (E) -2- (2-bromomethyl) phenyl-2-methoxyiminoacetate, 8-bromo-n-octanol (1.8g,8.61mmol) and 30mL of THF solution, cooled to 5 ℃ or below, and then 3.91g (12mmol) of Cs was added2CO3After stirring for 1 hour, the reaction mixture was warmed to room temperature (25 ℃ C.) and allowed to continue for 8 hours. Vacuum spin-drying, and performing column chromatography to obtain product (E) -2- [2- (8-bromooctyloxy) methylene) phenyl-2-methoxyimino acetic acid methyl ester 2.7g with yield of 80%
1H NMR(300MHz,CDCl3)δ7.49–7.32(m,3H),7.21–7.14(m,1H),4.38(s,2H),4.04(s,3H),3.87(s,3H),3.39(dt,J＝13.6,6.8Hz,4H),1.93–1.79(m,2H),1.49–1.38(m,2H),1.32(s,6H).
A100 mL three-necked flask was charged with 1.07g (2.59mmol) of methyl (E) -2- [2- (8-bromooctyloxy) methylene) phenyl-2-methoxyiminoacetate, 0.82g (3.1mmol) of triphenylphosphine, 18mg (108ummol) of potassium iodide and magneton, evacuated, and charged with nitrogen. Adding 30ml acetonitrile under nitrogen protection, stirring at room temperature for 5-10min, heating and refluxing at 90 deg.C for 10h, and separating by column chromatography to obtain 0.74g white solid powder with yield of 42%.
1H NMR(300MHz,CDCl3)δ7.81–7.59(m,15H),7.36–7.20(m,3H),7.09–7.02(m,1H),4.26(s,2H),3.92(s,3H),3.73(s,3H),3.57(s,2H),3.24(t,J＝6.6Hz,2H),1.58–1.47(m,2H),1.45–1.34(m,2H),1.24–1.10(m,6H).
Number Ib4-11The compounds of the a series were prepared as in example 3.
Example 4 preparation of Compound Ib8b-2 (i.e., formula Ib)nN is 8, Y is Br, Q2＝C1bThe compound of (1):
a30 mL THF solution containing 2.4g (9mmol) of 11-bromoundecanoic acid was charged into a 100mL three-necked flask, the temperature was reduced to 5 ℃ or below, 3.91g (12mmol) Cs2CO3 was added, and after stirring for 1 hour, 2.35g (8.2mmol) of methyl (E) -2- (2-bromomethyl) phenyl-2-methoxyiminoacetate was added, and the reaction was continued for 8 hours while warming to room temperature (25 ℃). Vacuum spin-drying to obtain yellow viscous liquid, and performing column chromatography to obtain pink viscous liquid 3.2g with yield of 83%.
1H NMR(300MHz,CDCl3)δ7.47–7.34(m,3H),7.20–7.13(m,1H),4.97(s,2H),4.03(s,3H),3.86(s,3H),3.62(t,J＝6.5Hz,2H),2.28(td,J＝7.6,2.1Hz,2H),1.69–1.50(m,6H),1.27(s,10H).
A100 mL three-necked flask was charged with 1.2g (2.59mmol) of methyl (E) -2- [2- (11-bromoundecanoyl) methylene) phenyl-2-methoxyiminoacetate, 0.82g (3.1mmol) of triphenylphosphine, 18mg (108ummol) of potassium iodide and magneton, evacuated, and charged with nitrogen. Adding 30ml acetonitrile under nitrogen protection, stirring at room temperature for 5-10min, heating and refluxing at 90 deg.C for 10 hr, and separating by column chromatography to obtain 0.99g white solid powder with yield of 52%.
1H NMR(300MHz,DMSO-d6)δ7.96–7.85(m,3H),7.86–7.71(m,12H),7.48–7.35(m,3H),7.25–7.18(m,1H),4.87(s,2H),3.92(s,3H),3.74(s,3H),3.56(s,2H),2.22(t,J＝7.4Hz,2H),1.46(s,6H),1.33–1.12(m,10H).
13C NMR(75MHz,DMSO-d6)δ172.52,162.77,148.93,134.98(d,J＝3.1Hz),133.69(d,J＝9.8Hz),130.34(d,J＝12.4Hz),129.33,128.90,128.65,128.15,119.28,118.15,63.92,63.45,52.69,33.34,30.00,28.98–28.58(m),28.50,28.16,24.33.
Number Ib4-11b and Ib4-11The compounds of c were prepared as in example 4.
Wherein, compound Ib2b-2: a pink viscous liquid with a yield of 53%, 1H NMR as follows:
1H NMR(300MHz,Chloroform-d)δ7.69–7.55(m,9H),7.51(td,J＝7.6,3.7Hz,6H),7.23–7.13(m,3H),6.97(dq,J＝5.3,2.5Hz,1H),4.71(s,2H),3.79(s,3H),3.61(s,3H),3.59–3.41(m,2H),2.19(t,J＝6.7Hz,2H),1.80(p,J＝7.1Hz,2H),1.54(p,J＝7.8,7.3Hz,2H).
second, examples of compositions comprising compounds of formula I are as follows: (the following components are calculated according to the mass percentage, and the active components are added after being folded in hundred)
Example 5 a wettable powder containing 50% of a compound of formula I was prepared:
the wettable powder comprises the following components: 50% of a compound shown as a formula I, 5% of a dispersant polycarboxylate, 3% of wetting agent sodium dodecyl sulfate and 42% of a solid carrier or disintegrant bentonite; the components are mixed according to the proportion to obtain a mixture, and the mixture is subjected to airflow crushing to obtain the 50% wettable powder.
Example 6 an emulsifiable concentrate containing 30% of a compound of formula I was prepared:
the missible oil comprises the following components: 30% of a compound shown in formula I, 12% of an emulsifier polyoxyalkylene alkyl aryl ether, 10% of a penetrant alkyl aryl sulfonate and 48% of liquid carrier cyclohexanone; the components were mixed in the proportions described to give a clear solution of 30% compound.
Example 7 preparation of water dispersible granules containing 60% of a compound of formula I:
the composition of the water dispersible granule is as follows: 70% of a compound shown as a formula I, 3% of a dispersant calcium alkylbenzene sulfonate salt, 3% of a dispersant lignosulfonate, 4% of wetting agent sodium dodecyl sulfate and 20% of solid carrier or filler starch; the components are mixed according to the proportion to prepare the water dispersible granule of 70 percent of the compound shown in the formula I.
Thirdly, measuring the biological activity:
example 8, bactericidal activity assay:
the compounds of formula I of the present invention are used to test various fungal diseases of plants by the following methods:
a hypha growth rate measuring method is adopted: the test is carried out according to the agricultural industry standard (NY/T1156.2-2006) of the people's republic of China by adopting a hypha growth rate method. Punching the activated various pathogenic bacteria on an ultra-clean laboratory bench by using a puncher with the diameter of 5mm under the aseptic condition, cutting off the bacterial cakes, inoculating the bacterial cakes to the center of the cooled medicine-containing culture medium by using a No. 11 scalpel, covering a dish cover, inversely placing the bacterial cakes in an incubator at 25 ℃ for culture, and taking an average value when counting results.
And (3) after the CK diameter reaches 6-8cm, measuring the diameter of each processed colony by a cross method, calculating the colony growth diameter by adopting a formula (1), and taking the average value.
Colony growth diameter-colony diameter-fungus cake diameter (1)
The growth diameter of the blank colonies and the growth diameter of the drug-treated colonies were used to calculate the rate of inhibition of the growth of the pathogenic bacteria by the respective compounds, as shown in the following equation (2).
Hypha growth inhibition (%) (control colony growth diameter-agent-treated colony growth diameter)/control colony growth diameter × 100 (2)
Table 1, results of comparative tests on bactericidal activity of Ia series of partial compounds
0.07μM Sclerotium of colza Botrytis cinerea (Fr.) Kuntze Phytophthora capsici Rice grain withered Watermelon anthrax Brown spot of peanut Rice blast Pythium aphanidermatum TomatoLate blight Gibberella cerealis
Boscalid 99.52 72.44 19.42 76.74 50.98 95.41 95.71 85.47 41.73 22.4
Ia8a-3 92.35 57.24 87.23 69.78 92.92 72.43 72.4 60.8 78.48 18.75
Ia8a-4 93.78 56.72 86.57 69.54 91.83 76.52 76.69 71.49 72.97 27.6
Ia8a-5 54.33 63.42 81.29 68.82 84.48 67.84 71.06 55.87 51.71 19.53
Ia8a-8 95.93 65.22 88.55 73.62 96.73 78.56 76.15 74.23 82.15 28.39
Ia8a-10 94.02 61.62 80.41 67.87 76.31 67.84 63.02 55.32 73.49 25.26
Ia8a-11 92.11 63.94 85.25 66.91 80.66 75.5 74.01 70.12 76.9 22.92
Ia8a-13 91.39 86.09 92.07 69.3 98.91 75.5 73.74 71.22 94.49 27.08
Ia8a-14 93.07 79.39 90.31 69.78 99.46 73.2 73.47 66.83 83.2 24.22
Ia8a-15 87.57 90.21 95.38 58.99 72.22 65.54 71.6 50.66 64.04 33.33
Ia8a-21 90.44 61.75 91.41 68.59 100 72.69 73.2 68.75 75.07 23.44
Ia8a-26 87.57 60.84 81.07 58.75 84.48 66.31 71.6 51.75 62.99 22.92
The results of bactericidal experiments show that 11 compounds of the formula I series all show excellent broad-spectrum bactericidal activity at the concentration of 0.07 mu M. Compared with the control medicament, namely boscalid, each medicament has similar or even better bactericidal activity than boscalid, particularly Ia8a-3、Ia8a-13、Ia8a-14、Ia8a-15 and Ia8a-21 shows good bactericidal effect on botrytis cinerea, phytophthora capsici leonian, watermelon anthrax and tomato late blight.
Table 2, Ib series partial compound bactericidal activity comparative test results
Figure BDA0001768554610000401
Figure BDA0001768554610000411
The results of bactericidal experiments found that at a concentration of 0.07. mu.M, 3 compounds I of the formula Ib seriesb8b-2 and Ib5b-2 exhibits excellent broad-spectrum bactericidal activity. Comparison with the control drug kresoxim-methyl, Ib8b-2 and Ib5b-2 has similar and even superior bactericidal activity to kresoxim-methyl, especially on pythium aphanidermatum, botrytis cinerea, phytophthora capsici, apple ring rot and tomato late blight Ib8b-2 shows good bactericidal effect.

Claims (15)

1. A compound having the general structural formula shown in formula I:
Figure FDA0002404234600000011
in the formula I, X is selected from CH2(ii) a Y is selected from halogen; the halogen is selected from any one of chlorine, bromine and iodine; n is an integer of 4 to 11; q is selected from the following formula Ia or Ib;
Figure FDA0002404234600000012
in the formula Ia, Ar is selected from the following A1，Q1Is selected from H;
Figure FDA0002404234600000013
in the formula Ib, U is selected from COO and Q2Is selected from C1；
Figure FDA0002404234600000014
Wherein, the formula A1In, R2Is at least one of hydrogen and halogen; r3Is selected from C1-C8Alkyl of (C)1-C8At least one of alkylthio, halogen and cyano of (a);
the halogen is selected from any one of fluorine, chlorine, bromine and iodine; o is an integer of 0 to 4; m is an integer of 0 to 4;
the formula C1Wherein Z is selected from N and M is selected from O.
2. A process for the preparation of a compound of formula I as claimed in claim 1, comprising the steps of: carrying out nucleophilic reaction on a compound shown in a formula VII and triphenylphosphine in the presence of a catalyst to obtain a compound shown in a formula I;
Figure FDA0002404234600000015
in formula VII, Y, Q, X and n are defined as in formula I.
3. The method of claim 2, wherein: the catalyst is sodium iodide or potassium iodide;
the molar ratio of the catalyst to the compound shown in the formula VII is (0.01-0.1): 1;
the reaction temperature of the nucleophilic reaction is 25-180 ℃, and the reaction time is 4-24 h;
the molar ratio of the compound shown in the formula VII to the triphenylphosphine is 1: (1-2);
the nucleophilic reaction is carried out in an organic solvent selected from at least one of acetonitrile, ethylene glycol dimethyl ether, benzene, toluene and 1, 2-dichloroethane.
4. The production method according to claim 3, characterized in that: the reaction temperature of the nucleophilic reaction is 80-115 ℃, and the reaction time is 8-12 h.
5. The production method according to any one of claims 2 to 4, characterized in that: the nucleophilic reaction is specifically carried out according to the following steps: vacuumizing the catalyst, triphenylphosphine, a compound shown in a formula VII and magnetons, and filling nitrogen; adding an organic solvent under the protection of nitrogen, stirring at room temperature for 5-10min, and reacting at 80-115 ℃ for 8-12h to obtain the compound shown in the formula I.
6. A compound having the general structural formula as shown in formula VII:
Figure FDA0002404234600000021
in formula VII, Y, Q, X and n are each as defined for formula I corresponding to Y, Q, X and n;
however, when Q is the formula Ia as described in claim 1, in which formula Ia Ar is selected from the group consisting of A1，Q1Is selected from H, A1Wherein o is 4; m is 4.
7. A process for the preparation of a compound of formula VII as claimed in claim 6, comprising the steps of:
reacting a compound shown in a formula IV with a compound shown in a formula VI in the presence of a catalyst, or reacting a compound shown in a formula V with a compound shown in a formula VI in the presence of an acid-binding agent to obtain a compound shown in a formula VII;
Figure FDA0002404234600000022
in the formula IV, Q1And Ar are as defined in claim 1 for formula Ia; however, in said formula Ia, Ar is selected from said A1，Q1Is selected from H, A1Wherein o is 4; m is 4;
in the formula V, Q2Is as defined in claim 1, of formula Ib;
in formula VI, X, Y and n are each as defined for formula I, and U is each as defined for formula Ib as defined in claim 1.
8. The method of claim 7, wherein:
the acid scavenger is selected from at least one of the following: pyridine, triethylamine, ethylenediamine, potassium carbonate, cesium carbonate, N-methylmorpholine and NaH; the catalyst is selected from at least one of the following: EDCI/HOBT, CDI, DMAP/DCC, HATU/DIPEA and DIC;
the molar ratio of the acid-binding agent to the compound shown in the formula IV is (2-5) to 1;
the molar ratio of the catalyst to the compound shown as the formula IV is (1-2.5) to 1, wherein the molar ratio of the compound shown as the formula IV to the compound shown as the formula VI is 1: (1-2);
the molar ratio of the acid-binding agent to the compound shown in the formula V is (2-5) to 1; the molar ratio of the catalyst to the compound shown in the formula V is (1-2.5) to 1; wherein the molar ratio of the compound shown as V to the compound shown as the formula VI is 1: (1-2);
the reaction temperature is-20-35 ℃, and the reaction time is 1-6 h;
the reaction is carried out in an organic solvent selected from at least one of: dichloromethane, tetrahydrofuran, acetonitrile, N-dimethylformamide, 1, 4-dioxane, and toluene.
9. A composition comprising a compound of formula I as described in claim 1 and an agriculturally acceptable carrier.
10. The composition of claim 9, wherein: the mass percentage of the compound shown in the formula I in the composition is 0.1-99%.
11. The composition of claim 10, wherein: the mass percentage content of the compound shown in the formula I in the composition is 30-60%.
12. The composition according to any one of claims 9-11, characterized in that: the composition also comprises at least one other active compound; the other active compounds are at least one of the known classes of fungicides, acaricides, nematicides, insecticides, herbicides, fertilizers, growth regulators, safeners and semiochemicals.
13. The composition according to any one of claims 9-11, characterized in that: the agriculturally acceptable carrier is selected from a solid carrier and/or a liquid carrier;
the solid carrier is selected from at least one of natural or synthetic silicate, ammonium sulfate, calcium sulfate, aluminum oxide silicate, natural or synthetic resin, polychloroprene, starch, bentonite and wax, wherein the natural or synthetic silicate is selected from at least one of attapulgite, talc, aluminum silicate, diatomite, mica, montmorillonite and calcium silicate, and the natural or synthetic resin is selected from at least one of benzofuran resin, styrene polymer and styrene copolymer; the wax is selected from beeswax and/or paraffin wax;
the liquid carrier is selected from water and C1-C4Alcohol of (1), C3-C8Ketones, aromatic hydrocarbons, petroleum fractions and C6-C12Wherein the alcohol is ethanol and/or ethylene glycol; the ketone is at least one of acetophenone, acetone, methyl ethyl ketone and cyclohexanone; the aromatic hydrocarbon is at least one of benzene, toluene and xylene; the petroleum fraction is keroseneAnd/or mineral oil; the chlorinated hydrocarbon is at least one of carbon tetrachloride, dichloromethane and trichloroethane;
the composition also comprises a surfactant;
the surfactant is selected from at least one of an emulsifier, a dispersant, a wetting agent and a penetrating agent;
the emulsifier is at least one selected from calcium alkyl benzene sulfonate, phenyl phenol polyoxyethylene ether, alkylphenol formaldehyde resin polyoxyethylene ether, phenethyl phenol polyoxyethylene polypropylene ether, polyoxyalkylene alkyl aryl ether and ethylene oxide-propylene oxide block copolymer;
the dispersant is selected from at least one of polycarboxylate, lignosulfonate, alkylphenol polyoxyethylene formaldehyde condensate sulfate, calcium alkylbenzene sulfonate, sodium benzene sulfonate formaldehyde condensate, sodium lauryl sulfate, sulfonated castor oil sodium salt, sodium alkyl aryl sulfonate, alkylphenol polyoxyethylene pyrimidine, fatty acid polyoxyethylene ester and ester polyoxyethylene pyrimidine;
the wetting agent is selected from at least one of sodium dodecyl sulfate, sodium dodecyl benzene sulfonate, nekal BX, Chinese honeylocust powder, silkworm excrement and soapberry powder;
the composition also comprises other auxiliary agents;
the other auxiliary agent is selected from at least one of a disintegrating agent, a defoaming agent, an antifreezing agent and a thickening agent;
the disintegrant is selected from at least one of bentonite, urea, ammonium sulfate, aluminum chloride and glucose;
the defoaming agent is at least one selected from silicone oil, silicone compounds, C10-C20 saturated fatty acid compounds and C8-C10 fatty alcohol compounds;
the antifreeze is selected from at least one of ethylene glycol, propylene glycol, glycerol and polyethylene glycol;
the thickening agent is at least one of xanthan gum, polyvinyl alcohol and polyethylene glycol.
14. Use of a compound of formula I according to claim 1 or a composition according to any one of claims 9 to 13 for the preparation of a plant fungicide or a soil fungicide.
15. Use according to claim 14, characterized in that: the plant fungicide or the soil fungicide is used for controlling diseases caused by fungi of at least one of the following fungal classes: ascomycetes, basidiomycetes, deuteromycetes and oomycetes.
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