WO1998031665A1 - Derives de n-phenylthiouree, procede de fabrication, fongicides a usage agricole et horticole les contenant en tant qu'ingredient actif et intermediaires aux fins de leur elaboration - Google Patents

Derives de n-phenylthiouree, procede de fabrication, fongicides a usage agricole et horticole les contenant en tant qu'ingredient actif et intermediaires aux fins de leur elaboration Download PDF

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Publication number
WO1998031665A1
WO1998031665A1 PCT/JP1998/000049 JP9800049W WO9831665A1 WO 1998031665 A1 WO1998031665 A1 WO 1998031665A1 JP 9800049 W JP9800049 W JP 9800049W WO 9831665 A1 WO9831665 A1 WO 9831665A1
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Prior art keywords
group
halogenated
alkyl group
derivative
hydrogen atom
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PCT/JP1998/000049
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English (en)
Japanese (ja)
Inventor
Shinya Henmi
Seiji Kakinuma
Kiyoshi Takasuka
Hideyo Fujii
Syuichi Usui
Noriyoshi Katsuyama
Shunnosuke Watanabe
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Agro-Kanesho Co., Ltd.
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Priority to AU53425/98A priority Critical patent/AU5342598A/en
Publication of WO1998031665A1 publication Critical patent/WO1998031665A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D239/00—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings
    • C07D239/02—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings
    • C07D239/24—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members
    • C07D239/28—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, directly attached to ring carbon atoms
    • C07D239/32—One oxygen, sulfur or nitrogen atom
    • C07D239/34—One oxygen atom
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C335/00—Thioureas, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups
    • C07C335/04—Derivatives of thiourea
    • C07C335/16—Derivatives of thiourea having nitrogen atoms of thiourea groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton
    • C07C335/18—Derivatives of thiourea having nitrogen atoms of thiourea groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton being further substituted by singly-bound oxygen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C335/00—Thioureas, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups
    • C07C335/04—Derivatives of thiourea
    • C07C335/16—Derivatives of thiourea having nitrogen atoms of thiourea groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton
    • C07C335/20—Derivatives of thiourea having nitrogen atoms of thiourea groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton being further substituted by nitrogen atoms, not being part of nitro or nitroso groups

Definitions

  • the present invention relates to an N-phenylthiourea derivative, a method for producing the same, an agricultural and horticultural fungicide containing the same as an active ingredient, and an intermediate for producing the same.
  • N-phenyl perylene-related compounds or N-phenyl thioperrea-related compounds have been known. Previously unknown. Accordingly, it is an object of the present invention to provide an N-phenylthioperylene derivative having an excellent bactericidal effect, particularly at a low concentration. Disclosure of the invention
  • the present inventor has conducted extensive research and research on agricultural and horticultural fungicides, and as a result, found that among compounds having an N-fuunyl thiourea skeleton, compounds having a specific structure exhibit excellent fungicidal activity at low concentrations.
  • the invention has been completed.
  • an object of the present invention is to provide a compound represented by the following general formula (I).
  • R 1 represents a hydrogen atom, a hydroxyl group, an alkyl group, a halogenated aralkyl kill group, an alkoxy group, a halogenated C alkoxy group, C 3 - a 5 alkynyl group, - 5 alkenyl group or C 3
  • R ′ 2 is a hydrogen atom or a C, —3 alkyl group
  • R 3 is a d- 3 alkyl group
  • X and Y are independently hydrogen, halogen, On alkyl, halogenated
  • A represents — 0— A 1 , — CH 2 — 0— A 2 or — CH 2 ON2 C (R 4 ) —A 3 ,
  • R ' is a C, -3 alkyl group
  • X ′ and Y ′ are independently a hydrogen atom, a halogen atom, c, — :
  • Halogenated 3 alkyl group 1 alkoxy group, halogenated C an alkoxy group, an Shiano group or a nitro group,
  • U represents a hydrogen atom, a halogen atom, alkyl group, halogenated C doctor 6 alkyl group, 6 alkoxy group, halogenated - 6 alkoxylated group, Shiano group, a nitro group or A a,
  • R 5 is a hydrogen atom, C, - 6 alkyl group, a halogenated 0 6 alkyl group or A a,
  • R 6 is a hydrogen atom, an alkyl group, a halogenated d alkyl group, (: 3 -5 alkenyl group, halogenated C 5 alkenyl group, C 3 5 alkynyl group or a halogen of C 3 5 alkynyl, W is a hydrogen atom, a halogen atom, C, - t; alkyl group, a halogenated ds alkyl le group, C, - an e alkoxy group or a halogenated C Bok 6 alkoxy group,
  • R 1 is a hydrogen atom, a hydroxyl group, a C, -3 alkyl group, a nitrogenated d- 3 alkyl group,
  • Ca is an alkynyl group.
  • the alkyl group having 1 to 3 carbon atoms may be linear or branched, and examples thereof include a methyl group, an ethyl group, an n-propyl group, and an isopropyl group.
  • the halogen atom include a fluorine atom, a chlorine atom, and a bromine atom.
  • examples of the halogenated C 3 alkyl include a trifluoromethyl group, a difluoromethyl group, a 2-trifluoroethyl group, a 2-chloroethyl group, and the like.
  • Examples of the 3 alkoxy include a methoxy group, an ethoxyquin group, an n- or isopropoxy group, and the like.
  • the halogenated 3 alkoxy for example, and Jifurorome butoxy group, 2-click Roroetokin group.
  • the alkenyl group having 3 to 5 carbon atoms may be linear or branched, and includes, for example, an aryl group, a 2-butenyl group, 1-methyl-2-propenyl and the like.
  • the alkynyl group having 35 carbon atoms may be linear or branched, and examples thereof include a propargyl group and a 2-butynyl group.
  • the alkoxy group having 13 carbon atoms is an alkoxy group of an alkyl group having 13 carbon atoms, and the range of the alkyl group is as described above.
  • R 2 is a hydrogen atom or a 3-alkyl group.
  • the range of the Ci- 3 alkyl group is as described above.
  • R 2 is preferably a hydrogen atom.
  • Is a d alkyl group the range of which is as described above.
  • X and Y are independently a hydrogen atom, a halogen atom, a —3 alkyl group, a halogenated
  • the ranges of the C alkyl group and the halogen atom are as described above.
  • R 4 is a C, -3 alkyl group, and its range is as described above.
  • a 1 is a group represented by the following formula.
  • X ′ and Y 2 independently represent a hydrogen atom, a halogen atom, a 3 alkyl group, a halogenated 3 alkyl group, a 3 alkoxy group, a halogenated 3 A oxy group, a cyano group, or a nitro group (the range of a halogen atom, an alkyl group, an alkoxy group, etc. is as defined above (
  • a 2 is the following functional group. Aa,
  • Z is N or CH
  • U is a hydrogen atom, a halogen atom, d - s ⁇ alkyl group, a halogenated - 6 alkyl group, - 6 alkoxy groups, halogenated C i alkoxylated group, Shiano group, It is a nitro group or Aa.
  • alkyl group include a methyl group, an ethyl group, an n- or isopropyl group, an n-, iso-, s- or t-butyl group, and neopentyl.
  • the range of the halogen atom is as described above.
  • a halogenated C, - as the s alkyl for example, Torifuruoro or methyl, trichloromethyl, 2-Kuroroechiru, 3 black port propyl, 3-Bed Romopuropiru, 5-bromopentyl, like hexyl group into 6- black port No.
  • the 6 alkoxy group include a methoxy group, an ethoxyquin group, an n- or isopropoxy group, n- , an iso-, s-, or t-butoxy group, and a neopentoxy group.
  • nodulated d-s alkoxy examples include, in particular, trifluoromethoxy, difluoromethoxy, 2-chloroethoxy, 2-trifluoroethoxy, 3-chloropropyloxy, 3-bromopropyloxy and the like.
  • V is a hydrogen atom, a halogen atom, a ds s alkyl group, a halogenated C 6 alkyl group, a 6 alkoxy group, a halogenated s alkoxy group, a cyano group, a nitro group.
  • —C, — «alkylcarbonyl group, d—s alkoxycarbonyl group, —C (R 5 ) N 0 R ′′. C i— 1 in d—s alkylcarbonyl group and C n alkoxycarbonyl group ;.!
  • alkyl groups are as previously described C - 6 the alkyl force Ruponiru group, for example, a methyl group, E chill carbonyl group, flop port pills carbonyl group, an isopropyl group, a butyl group, Examples include an isobutylcarbonyl group, an S-butylcarbonyl group, a t-butylcarbonyl group, an n-heptylcarbonyl group, an isoheptylcarbonyl group, a hexylcarbonyl group, etc. Particularly, a methylcarbonyl group and an ethyl group A carbonyl group is preferred.
  • Examples of the C, -6 alkoxycarbonyl group include those corresponding to the above 6 alkylcarbonyl group.
  • the range of the other functional groups is as described above.
  • R 5 is a hydrogen atom, a ds alkyl group, a halogenated C 6 -6 alkyl group or A a.
  • the ranges of the Ci- 6 alkyl group and the halogenated Ci-6 alkyl group are as described above.
  • R 6 is a hydrogen atom, d-6 alkyl group, a halogenated C, -6 alkyl group, C 5 alkenyl group, halogenated C 3-5 alkenyl group, C 3 5 alkynyl group or a halogen of C 3-5 alkynyl And the range of these functional groups is clear from the above.
  • the halogenated C 3 5 alkenyl group e.g., 3-Kuroroari Le and the like.
  • Examples of the halogenated C 3 5 alkynyl group for example, 3- ® chromatography Dopronogill can be mentioned.
  • w is a hydrogen atom, a halogen atom, a 6 alkyl group, a halogenated C alkyl group, a C, —s alkoxy group or a halogenated C 6 alkoxy group, and the range of these functional groups is clear from the above. It is.
  • diphenylthiourea derivatives of the present invention particularly, one CH: 0—A, and A 2 is
  • U And N-phenylthiodialea derivatives which are -C (R 5 ) 2 NOR 6 groups are preferred.For example, even at a low concentration of 64 ppm or less, preferably 16 ppm J It has an excellent germicidal effect for agriculture and horticulture as compared with the above compound.
  • the N-phenylthioperia derivative of the present invention can be produced by a known method.
  • the N-phenylthioperia derivative of the present invention can be produced as a mixture of E / Z isomers, geometric isomers, optical isomers, diastereomers, and the like.
  • the N-fluorothiodiarea derivative of the present invention is obtained as a mixture of isomers, it may be obtained by an ordinary method, for example, by recrystallization or chromatography. Can be separated into various isomers (
  • the compound represented by the formula (II) is reacted with the compound represented by the formula (II) usually in the presence of a solvent and a base.
  • the solvent include aromatic hydrocarbons such as benzene, toluene, xylene, and benzene; halogenated aliphatic hydrocarbons such as carbon form, carbon tetrachloride, methylene chloride, dichloroethane, and trichloroethane; Cyclic or acyclic aliphatic hydrocarbons such as n-hexane and cyclohexane; ethers such as getyl ether, dioxane, and tetrahydrofuran; ketones such as acetoneton, methyl ethyl ketone, and methyl isobutyl ketone
  • Nitriles such as acetate nitrile and propionitrile; and aprotic polar solvents such as dimethylformamide, N-methyl-12-pyrrolidone, dimethyl sulfoxide and sulfolane.
  • the base may be either an inorganic base or an organic base.
  • the inorganic base for example, sodium hydroxide, potassium hydroxide metal oxide such as potassium hydroxide hydroxide; sodium carbonate carbonate free, potassium hydroxide metal such as anhydrous calcium carbonate or potassium earth metal Carbonates; alkaline metal hydrides such as sodium hydride; alkaline metals such as sodium metal, and the like.
  • organic base examples include, for example, pyridine, triethylamine, diisopropylethylamine and the like.
  • the reaction temperature is usually from 120 ° C to the boiling point of each solvent, preferably from 0 to
  • the reaction time is generally 0.1 to 24 hours, preferably 0.5 to 12 hours.
  • the compound represented by the formula (II) is reacted with thiophosgene, usually in the presence of a solvent, optionally in combination with a base.
  • Solvent and base The same ones used in the method (A-1) can be used.
  • the reaction temperature and reaction time are also the same as those described above.
  • the compound represented by the formula (II) is usually reacted with an isothiosocyanate represented by the formula (V) in the presence of a solvent and optionally in the presence of a catalyst to obtain the compound represented by the formula (II).
  • a solvent include the same solvents as those used in the above-mentioned method (A-1).
  • the catalyst include boron trifluoride, acids such as hydrochloric acid, aluminum chloride, alkyltin chloride, and alkyltin acetate; triethylamine, pyridine, dimethylaniline, dimethylaminopyridine, 1,4-diazabicyclo (2.2).
  • the reaction temperature is usually from 120 ° C to the boiling point of the solvent, preferably from 0 to 50 ° C, and the reaction time is preferably from 0.5 to 24 hours, particularly preferably from 1 to 12 hours. Time is appropriate.
  • the intermediate represented by the general formula (II) can be produced according to the following production route (B) or (C).
  • nitrobenzene derivatives obtained by standard methods are reduced, for example, using hydrogen or a hydrogen source such as ammonium formate in the presence of a catalyst such as Pd, Pt or Ni.
  • a catalyst such as Pd, Pt or Ni.
  • Anirin derivative (II one 1) is obtained, resulting Anirin derivative (II- 1), by reaction with R 1 '-Hal in the usual manner to obtain compound (pi-2) be able to.
  • R 1 '- R "s is Hal, preferably, C, - 3 alkyl group, a halogenated C 3 alkyl group, C 3 - 5 alkenyl group or C 3 -. Shows the 5 alkynyl group other functional groups , X, Y, A, and Hal are as described above.
  • R 1 ′′ represents a 3- alkyl group or a halogenated C alkyl group, and the range is as described above.
  • Other X, Y, A, and Hal are as described above.
  • it can be reacted with ammonium chloride in the presence of zinc to obtain a phenylhydroxyamine derivative (III-3) (Organic Syntheses Collective Vol III p668 (1955)).
  • formylation is performed with formic acid and acetic anhydride to obtain an N-hydroxyformanilide derivative (other than a formyl group, if appropriate as a protecting group).
  • N-hydroxyformanilide derivative is reacted with R '"-Hal to obtain an N-alkoxyformanilide derivative, which is then hydrolyzed under alkaline or acidic conditions to give N-hydroxyformanilide derivative.
  • An alkoxyaniline derivative (II-4) can be obtained.
  • an N-alkoxyanilin derivative can be easily and inexpensively produced from an N-alkoxyformanilide derivative. Conventional methods have not found such a simple and inexpensive manufacturing method.
  • an organic solvent mixture of an aqueous solution is preferable.
  • examples of such an organic solvent include methanol, ethanol, dioxane, tetrahydrofuran, acetone, methyl ethyl ketone, acetonitrile, and dimethylformamide. , N-methyl-12-pyrrolidone, dimethylsulfoxide, sulfolane and the like.
  • the aqueous solution of sodium hydroxide includes sodium hydroxide, potassium hydroxide, carbonate carbonate, sodium carbonate, monomethylamine, etc., for example, 0.1 to 50%, preferably 1 to 30%. % Solutions are used.
  • the acidic aqueous solution it is suitable to use hydrochloric acid, sulfuric acid, nitric acid, acetic acid, formic acid, phosphoric acid, etc., for example, having a concentration of 0.1 to 50%, preferably 1 to 30%. It is.
  • the hydrolysis is preferably carried out at a temperature of from ⁇ 20 ° C. to the boiling point of the solvent, particularly preferably from 0 to 50 ° C., and the reaction time is, for example, from 0.1 to 24 hours, preferably from 0.1 to 24 hours. 1 to 12 hours is appropriate.
  • the N-alkoxyaniline derivative (II-4) can be produced, for example, according to the following production route (D). .
  • This route can be produced from a nitrobenzene derivative to an N-alkoxyformylaniline derivative by the same method as in Production Route C.
  • a free-radical initiator for example, azobisdisoptyronitrile, for example, with N-promosuccinimid, bromine, chlorine or SO 2 C 12 , or by free-radical halogen exposure to ultraviolet light
  • a free-radical initiator for example, azobisdisoptyronitrile, for example, with N-promosuccinimid, bromine, chlorine or SO 2 C 12
  • free-radical halogen exposure to ultraviolet light a hydride derivative can be obtained.
  • N-alkoxyaniline ( ⁇ -4) can be obtained by hydrolysis.
  • the N-funinylthioperia derivative represented by the general formula (I) of the present invention is useful as a fungicide for agricultural and horticultural use, for example, rice blast (Pyricularia oryzae), rice sheath blight (Rhizoctonia solani), and rice Sesame leaf blight (Crochl iobolus miyabeanus), oats, oat spot disease (Pseudocercosporel la herpotrichoides; oats, barley powdery mildew (Erysip he graminis), powdery mildew (Sphaerotheca ful iginea), buttocks (Uncinula necator), powdery mildew on various host plants, crown rust of enbac (Puccinia coronata) and Rust on other plants, Botryt is cinerea on grape and Botryt is cinerea on other plants, Sclerot i nia scle
  • the fungicide for agricultural and horticultural use of the present invention has a remarkable bactericidal effect on the above-mentioned diseases that damage paddy field crops, field crops, fruit trees, vegetables, other crops, flowers and the like. Treatment of paddy fields, fields, fruit trees, vegetables, other crops, flowers and other paddy water, foliage or soil, seeds, and bulbs before or at the time when the disease is predicted By doing so, the desired effect of the agricultural and horticultural fungicide of the present invention is exhibited.
  • the concentration of the compound of the present invention used Z varies depending on the target crop, the method of use, the formulation form, the application rate, etc., and cannot be specified unconditionally. However, in the case of foliage treatment, it is usually 0.1 to 10 per active ingredient. It is in the range of 0.000 ppm, preferably 1-2 ppm.
  • the compound of the present invention may be used in combination with other pesticides, if necessary, such as insecticides, acaricides, nematicides, fungicides, antiviral agents, attractants, herbicides, plant growth regulators, etc. In this case, the effect may be even better.
  • pesticides such as insecticides, acaricides, nematicides, fungicides, antiviral agents, attractants, herbicides, plant growth regulators, etc. In this case, the effect may be even better.
  • Examples of the active ingredient compound of the insecticide, acaricide, or nematicide include, for example, 1- (4-bromo-12-chlorophenyl) 0-ethyl S-propylphosphorothioate (generic name: profenophos) , Poly (2,2-dichlorovinyl) 0,0-Dimethylphosphonate (generic name: dichlorvos), 0-Ethyl 0— [3-Methyl 4- (methylthio) phenyl] N-Isopropyl phosphoramidate Generic name: phenamiphos), ⁇ , 0-dimethyl 0— (412-m-tolyl) phosphorothioate (generic name: dinitrothion), 0-ethyl 0— (4-nitrophenyl) phenylphosphonothio Aeto (generic name: EPN), 0, 0—Jetil
  • 0-(2-Isopropyl-6-methylpyrimidine-14-yl) phosphorothioate (generic name: diazinon), 0,0-dimethyl 0- (3,5,6-trichloro-1-2-pyridyl) phosphoro Thioate (generic name: chlorpyrifosmethyl), 0, S-dimethyl N-acetyl phosphoroamidothioate (generic name: acephate), 0— (2,4-dichlorophenyl) 0-ethyl S-propylphospho dithioate Organics (generic name: protifos), (RS) —S—sec—butyl diethyl 2—oxo-1,3—thiazolidine-13—ylphosphonothioate (generic name: phosthiazate) Phosphate ester compounds;
  • Carbamate compounds such as 2-sec-butylphenyl N-methylcarbamate (generic name: phenocarb);
  • S S '— 2-dimethylamino trimethylenebis (thiocarbamate) (general name: cartap), N, N-dimethyl_1,2,3-trithian-15-ylamine (generic name: thiocyclam) Nereistoxin derivative;
  • Organometallic compounds such as bis [tris (2-methyl-2-phenylpropyl) tin] oxide (generic name: fenbutatin oxide);
  • Pyridazinone compounds such as 2 — t-butyl-5 — (4 — t — butylbenzylthio) 1-4 1-chloro-3 (2 H) — pyridazinone (generic name: pyridaben); t-butyl 4 _ [ Pyrazole-based compounds such as (1,3-dimethyl-15-phenoxyvirazole-4-yl) methyleneaminooxymethyl] benzoate (generic name: phenylpyroximate);
  • Dinitro compounds, organic sulfur compounds, urea compounds, triazine compounds, hydrazine compounds, and other compounds such as 2-tert-butylimino-13-isopropyl-1-5-phenyl-1,3,5,6- Tetrahi draw 2 H— 1, 3,
  • 5-Thiadiazine 4-one (generic name: bubrophedin), trans- (4-chlorophenyl) -1-N-cyclohexyl-1-4-methyl-1-2-oxothiazolidinone
  • Examples of the active ingredient compound of the above bactericide include 2-anilino-4-methyl-6- (1-propynyl) pyrimidine (generic name: mepanipyrim), 4,6-dimethyl-2-N-phenyl-2-pyrimidinamine (general) Name: pyrimidinamine-based compounds such as pyrimesanil);
  • Quinoxaline-based compounds such as quinoxaline-2-one (generic name: quinomethionate); polymer of manganese ethylene bis (dithiocarbamate) (generic name: Maneb, a polymer of zinc ethylene bis (dithiocarbamate) (general name: zineb), complex compound of zinc (zinc) and manganez ethylene bis (dithiocarbamate) (manneb)
  • Organochlorines such as 4,5,6,7-tetrachlorophthalide (generic name: fusaride), tetrachloride isophthalonitrinole (generic name: chlorothalonil), and pentachloroditrobenzen (generic name: kintozen)
  • Pyridinamides such as 3-chloro-N— (3-chloro-2,6-dinitro-141-a, a, trifluorotrifluoro) -5-trifluoromethyl-12-pyridinamine (generic name: fludinam)
  • Cyanoacetamide compounds such as 1_ (2-cyano-2-methoxyiminoacetyl) -13-ethylethylurea (generic name: simoxanil);
  • a phenylamide compound such as i-to (general name: flaxyl), (c) i-ct-CN- (3-chlorophen
  • Sulfenic acid compounds such as N-dichlorofluoromethylthio-N ', N'-dimethyl-N-phenylsulfamide (generic name: dichlorofluoride); cupric hydroxide (generic name: cupric hydroxide) Copper-based compounds, such as KIKKOR 8-quinolinolate (generic name: organic copper);
  • Isoxazole-based compounds such as 5-methylisoxazol-3-ol (generic name: hydroxyisoxazole); aluminum tris (ethylphosphonate)
  • N- (trichloromethylthio) cyclohexyl 4--1,2-dicarboximide (generic name: captan)
  • N-halogenothioalkyl compounds such as 1,2-dicarboxymide (generic name: captaphol) and N- (trichloromethylthio) phthalimid (generic name: phthalide);
  • Dicarboxyimide compounds such as 5-methyl-5-vinyl-1,3-oxazolidine-12,4-dione (generic name: vinclozolin);
  • Benzanilide compounds such as a, a, 1-trifluoro-3 '-isopropoxy-o-toluanilide (generic name: flutolanil) and 3'-isopropoxy-o-toluanilide (generic name: mepronil) ;
  • Benzamide-based compounds such as the compounds described in JP-A-63-135354; ⁇ , ⁇ '-[piperazine-11,4-diylbis [(trichloromethyl) methylene] diformamide (generic name) : Piperazine compounds such as trifolin); 2 ',
  • Trifiniltin hydroxide (generic name: pentine hydroxide): an organic tin-based compound such as triphenylnitine acetate (generic name: fentin acetate);
  • Urea compounds such as 1- (4-cyclopentyl) 1-1-cyclopentyl-3-phenylperyl (generic name: peniculone);
  • Phenylcarbamate-based compounds such as isopropyl 3,4-ethoxycarbanilate (generic name: jetfancarb);
  • the appropriate mixing weight ratio of the N-phenylthiourea derivative represented by the general formula (I) and the counterpart agent to be used in combination is generally 1: 300 to 300: 1. Or 1: 100 to 100: 1.
  • this benzyloquinbenzene derivative is mixed with a pyrimidinamine-based compound, an organochlorine-based compound, a pyridinamine-based compound or a cyanopyrrole-based compound, an excellent effect of controlling various types of gray mold can be expected.
  • the N-phenylthioperia derivative of the present invention When the N-phenylthioperia derivative of the present invention is actually used as an active ingredient of a bactericide, it is usually mixed with a solid carrier, a solvent, a surfactant, and other pharmaceutical auxiliaries to form a powder, emulsion, or microparticle. They can be formulated into capsules, microemulsions, wettable powders, aqueous and oily suspensions, wettable powders and the like. These preparations contain the N-phenylthiodiurea derivative used in the present invention as an active ingredient in an amount of 0.002 to 80% by weight, preferably 0.01 to 70% by weight. Is appropriate.
  • solid carrier examples include fine powders and granules such as kaolin clay, attapuljait clay, bentonite, acid clay, virofluorite, talc, diatomaceous earth, calcite, walnut shell powder, urea, ammonium sulfate, and synthetic hydrated silica.
  • Can be Solvents include aromatic and aliphatic hydrocarbons such as quinylene, naphthas, methylnaphthalene, paraffins, and machine oil; alcohols such as isopropanol, butanol, propylene glycol, ethylene glycol, cellosolve, and carbitol; Examples include ketones such as acetone, cyclohexanone and isophorone, vegetable oils such as soybean oil and cottonseed oil, dimethyl sulfoxide, N, N-dimethylformamide, N-methylpyrrolidone, and acetonitrile.
  • Surfactants used for emulsification, dispersion, wet spreading, etc. include lignin sulfonate, alkyl naphthalene sulfonate, naphthalene sulfonate formaldehyde condensate, alkyl sulfate ester salt, alkyl sulfonate , Alkyali
  • formulation aids include alginates, polyvinyl alcohol, arabic gum, carboxymethylcellulose, xanthan gum, peran gum, isopropyl phosphate and the like.
  • a water-dispersible powder contains about 5 to 70 parts by weight of the N-phenylthiodiurea derivative of the present invention, 2 to 5 parts by weight of an anionic surfactant, and 5 to 5 parts by weight of a synthetic hydrous silicate carrier. It is prepared by mixing and grinding with 20 parts by weight and a solid carrier in an amount sufficient to make the whole 100 parts by weight.
  • the emulsion contains 1 to 70 parts by weight of the N-phenylthiourea derivative of the present invention, 5 to 15 parts by weight of a nonionic surfactant, 1 to 10 parts by weight of an anionic surfactant, and the whole.
  • the aqueous suspension contains 5 to 50 parts by weight of the N-phenylthioperia derivative of the present invention, 1 to 5 parts by weight of a nonionic surfactant or anionic surfactant, and 0.1 to 1 part by weight of a thickener. 0.3 parts by weight and a sufficient amount of water to make the whole 100 parts by weight, and wet-pulverize to a particle size of 0.1 to 3 urn, preferably 0.5 to 2 m.
  • the water-dispersible granules may contain 5 to 50 parts by weight of a finely divided N-fluorothiourea derivative of the present invention, 90 to 40 parts by weight of inorganic salt mineral powder, 5 to 10 parts by weight of a binder and a surfactant. These granules, which disintegrate and disperse quickly when administered in water.
  • a finely divided N-fluorothiourea derivative of the present invention 90 to 40 parts by weight of inorganic salt mineral powder, 5 to 10 parts by weight of a binder and a surfactant.
  • N- [2- [2-Methyl-1-41 [(E)-1- (Methoxyimino) ethyl] phenoxymethyl] aniline 2.8 g of a 3 O ml tetrahydrofuran solution was cooled to 10 ° C or less, and tiophosgene was added. After adding 1.2 g, 1.5 g of triethylamine was added, and the mixture was returned to room temperature and stirred for 30 minutes. 5 ml of a 40% monomethylamine methanol solution was quickly added. After stirring for 1 hour, 100 ml of water was added, and the mixture was extracted with ethyl acetate.
  • N- [2- [2-methyl-1-41 (: (E)- 1- (Methoxyimino) ethyl] phenoxymethyl] phenyl] 1 N-hydroxyamidine was added at 30 to 40 ° C.
  • the mixture was diluted with 300 ml of dichloromethane, and a 5% aqueous sodium hydroxide solution was added.
  • the organic layer was washed with water, dried over anhydrous magnesium sulfate, and evaporated to give N-hydroxy N- [2- [2-methyl-4. — (: (E) —1— (methoxymino) ethyl] phenoxymethyl]] formanilide 21 g of an oil was obtained.
  • Comparative Compound A The comparative compound A is not a thioperia compound but a mere perea compound.
  • the physical properties of the comparative compound are as follows.
  • Test example 1 Test example 1
  • a two-leaf barley (cultivar: Akagi nijo) grown in a pot with a diameter of 6 cm was uniformly sprayed with a water dilution of the compound of the present invention prepared in an emulsion using a spray gun.
  • conidiospores of barley powdery mildew Erys iphe graminis
  • Control rate (%) (1 number of lesions in one treatment area, number of non-treatment areas) X 100 (a) Table 7
  • a water-diluted solution of the compound of the present invention prepared in an emulsion was evenly sprayed on wheat at the second leaf stage (cultivar: Norin 61) grown in a pot having a diameter of 6 cm using a spray gun. After natural drying 1, the uredospore suspension of wheat leaf rust (Pucci ni a recondi ta) was sprayed and inoculated, left in a room with a high humidity of 24 ° C for 24 hours, and then controlled in a greenhouse. Seven days after the inoculation, the number of lesions formed on the leaves was examined, and the control rate was calculated according to the formula (a) in Test Example 1. Table 8 shows the results. Table 8
  • a two-leaf tomato (cultivar: large fukuju) grown in a pot with a diameter of 6 cm was uniformly sprayed with a water dilution of the compound of the present invention prepared in an emulsion using a spray gun.
  • a zoospore suspension of the phytotoxin fungus (Phy tophthora inf estans) was spray-inoculated, left in a room with a high humidity of 20 ° C for 24 hours, and controlled in a greenhouse.
  • Five days after the inoculation the area ratio of lesions formed on the leaves was examined, and the control rate was calculated according to the following formula (b). Table 9 shows the results.
  • Control rate (%) (1—area ratio of treated lesion area z area rate of untreated area) X 10 0 (b) Table 9
  • a water-diluted solution of the compound of the present invention prepared in an emulsion was sprayed evenly onto a 5-leaf stage tomato (cultivar: large fukuju) grown in a 6 cm diameter bottle using a spray gun.
  • Natural drying One day after drying, a conidia suspension of tomato ring spot fungus (Alternaria solani) was sprayed and inoculated, left in a room with a high humidity of 24 ° C for 24 hours, and then controlled in a greenhouse. Seven days after the inoculation, the area ratio of lesions formed on the leaves was examined, and the control rate was calculated according to the formula (b) in Test Example 3. Table 13 shows the results.
  • an N-phenyl thioperrea derivative having an excellent agricultural and horticultural fungicide at a low concentration can be obtained.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

L'invention a trait à des dérivés de N-phénylthiourée efficaces comme fongicides à usage agricole et horticole et très actifs même à faible concentration. Ces dérivés sont représentés par la formule générale (I). Parmi les composés représentés, A représente CH2-O-A2, A2 représentant la formule (1). Il est, en outre hautement préférable que V représente -C(R5)=NOR6.
PCT/JP1998/000049 1997-01-16 1998-01-09 Derives de n-phenylthiouree, procede de fabrication, fongicides a usage agricole et horticole les contenant en tant qu'ingredient actif et intermediaires aux fins de leur elaboration WO1998031665A1 (fr)

Priority Applications (1)

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AU53425/98A AU5342598A (en) 1997-01-16 1998-01-09 N-phenylthioura derivatives, process for the preparation thereof, fungicides foragricultural and horticultural use containing the same as the active ingredient , and intermediates for the preparation thereof

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JP9/5482 1997-01-16
JP548297 1997-01-16

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WO1998031665A1 true WO1998031665A1 (fr) 1998-07-23

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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0065668A2 (fr) * 1981-05-22 1982-12-01 CELAMERCK GmbH & Co. KG Dérivés d'urée, leur préparation et usage
JPS58208261A (ja) * 1982-05-05 1983-12-03 Sumitomo Chem Co Ltd Ｎ―フェニルカーバメート系化合物を有効成分とする農園芸用殺菌剤
JPS59167556A (ja) * 1983-02-28 1984-09-21 Sumitomo Chem Co Ltd Ｎ―フェニルカーバメート系化合物およびそれを有効成分とする農園芸用殺菌剤
JPH07502747A (ja) * 1992-01-29 1995-03-23 ビーエーエスエフ　アクチェンゲゼルシャフト カルバメートおよびそれらを含む作物保護剤
WO1996001256A1 (fr) * 1994-07-06 1996-01-18 Basf Aktiengesellschaft 2-[(dihydro)pyrazolyl-3'-oxymethylene]-anilides utilises comme pesticides et comme fongicides
WO1996016030A1 (fr) * 1994-11-23 1996-05-30 Basf Aktiengesellschaft Anilides d'iminooxymethylene, procede et produits intermediaires de preparation de celles-ci, et pesticides les contenant

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0065668A2 (fr) * 1981-05-22 1982-12-01 CELAMERCK GmbH & Co. KG Dérivés d'urée, leur préparation et usage
JPS58208261A (ja) * 1982-05-05 1983-12-03 Sumitomo Chem Co Ltd Ｎ―フェニルカーバメート系化合物を有効成分とする農園芸用殺菌剤
JPS59167556A (ja) * 1983-02-28 1984-09-21 Sumitomo Chem Co Ltd Ｎ―フェニルカーバメート系化合物およびそれを有効成分とする農園芸用殺菌剤
JPH07502747A (ja) * 1992-01-29 1995-03-23 ビーエーエスエフ　アクチェンゲゼルシャフト カルバメートおよびそれらを含む作物保護剤
WO1996001256A1 (fr) * 1994-07-06 1996-01-18 Basf Aktiengesellschaft 2-[(dihydro)pyrazolyl-3'-oxymethylene]-anilides utilises comme pesticides et comme fongicides
WO1996016030A1 (fr) * 1994-11-23 1996-05-30 Basf Aktiengesellschaft Anilides d'iminooxymethylene, procede et produits intermediaires de preparation de celles-ci, et pesticides les contenant

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
NAGARAJAN K., SHAH R. K.: "NMR SPECTRA OF 2-AMINO-4-PHENYLBENZOTHIAZOLES.", INDIAN JOURNAL OF CHEMISTRY, JODHPUR, IN, vol. 11., 1 September 1973 (1973-09-01), IN, pages 879 - 881., XP002912327 *

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