JP2001253874A - Pyrimidine compound, their manufacturing method and herbicide including them - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain pyrimidine compounds useful as active ingredients for a herbicide. SOLUTION: Pyrimidine compounds or their salts expressed by formula (I); [A is A-1 or A-2 expressed by the formula, R1 is a halogen, an alkyl, or the like, R2 and R3 are each H, a halogen, or the like, R4 is hydroxy, a halogen, or the like, R5 is an alkyl, a haloalkyl, or the like, R6 and R7 are each H, a alkyl, or the like, (n) is 0-5].

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a novel pyrimidine compound useful as an active ingredient of a herbicide.

[0002]

BACKGROUND OF THE INVENTION JP-A-7-173141, although compounds similar to the pyrimidine compound represented by formula (I) given hereinafter are disclosed, in the after-mentioned formula (I) A or R ₁ A distinction is made in the substituents.

[0003]

DISCLOSURE OF THE INVENTION Problems to be Solved by the Invention The present inventors have conducted various studies on pyrimidine compounds in order to find a better herbicide, and as a result, completed the present invention. That is, the present invention provides a compound represented by the formula (I):

[0004]

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[Where A is

[0006]

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Wherein R ₁ is halogen, alkyl, haloalkyl, alkenyl, haloalkenyl, alkynyl, haloalkynyl, cycloalkyl, cycloalkenyl,-
_{OR 8, -S (O) m} R 8, amino, monoalkylamino, phenyl which may be dialkylamino or substituted, R ₂ and R ₃ are each hydrogen atom, halogen, alkyl or alkoxy, R ₄ Is hydroxy, halogen, alkyl,
_{Haloalkyl, -OR 8, -S (O)} m R 8, nitro or cyano, R ₅ is alkyl, haloalkyl, alkenyl, haloalkenyl, alkynyl, haloalkynyl, cycloalkyl, cycloalkenyl, 1,2 Epokishietani ,
1,3-epoxypropan-1-yl, 1,3-epoxypropan-2-yl or optionally substituted phenyl, wherein R ₆ and R ₇ are each a hydrogen atom, alkyl, haloalkyl, alkenyl, haloalkenyl, Alkynyl or haloalkynyl, R ₈ is alkyl, haloalkyl, alkenyl, haloalkenyl, alkynyl, haloalkynyl, cycloalkyl or cycloalkenyl, m is 0-2, n is 0-5, and n is R _{4 for} 2 or more
May be the same or different, provided that A is A-1 and R ₁ is alkyl, haloalkyl, cycloalkyl or phenyl which may be substituted.] Or a salt thereof, a method for producing them, and a herbicide containing them.

The substituent of the optionally substituted phenyl in R ₁ and R ₅ includes, for example, halogen, C 1-6 alkyl,
C1-6 haloalkyl, C1-6 alkoxy, C1-6 alkylthio, C1-6 alkylsulfinyl, C1-6 alkylsulfonyl and the like. The number of substitution of these substituents may be 1 or 2 or more, and when they are 2 or more, they may be the same or different.

The alkyl or alkyl moiety in R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ and R ₈ is a straight or branched one having 1 to 6 carbon atoms. E.g., methyl, ethyl, propyl, isopropyl, butyl, tert-butyl, pentyl,
Hexyl and the like.

The alkenyl or alkenyl moiety in R ₁ , R ₅ , R ₆ , R ₇ and R ₈ is a straight or branched one having 2 to 6 carbon atoms, for example, vinyl, propenyl, isopropenyl, Butenyl, pentenyl, hexenyl and the like.

The alkynyl or alkynyl moiety in R ₁ , R ₅ , R ₆ , R ₇ and R ₈ is a straight or branched one having 2 to 6 carbon atoms, for example, ethynyl, propynyl, butynyl, isobutynyl Pentynyl, hexynyl and the like.

The cycloalkyl in R ₁ , R ₅ and R ₈ includes those having 3 to 6 carbon atoms, for example, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl and the like.

The cycloalkenyl in R ₁ , R ₅ and R ₈ includes those having 3 to 6 carbon atoms, for example, cyclopropenyl, cyclobutenyl, cyclopentenyl, cyclohexenyl and the like.

Examples of the halogen or the halogen as a substituent in R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ and R ₈ include fluorine, chlorine, bromine and iodine. Can be The number of halogens as a substituent may be 1 or 2 or more, and in the case of 2 or more, each halogen may be the same or different. Also,
The halogen may be substituted at any position.

The pyrimidine compound represented by the above formula (I) can form a salt. Examples of the salt include any salt that is agriculturally acceptable. Examples thereof include alkali metal salts such as sodium salt and potassium salt; alkaline earth metal salts such as magnesium salt and calcium salt; dimethylamine And ammonium salts such as triethylamine salts.

The pyrimidine compound represented by the formula (I) includes optical isomers and geometric isomers, and the present invention includes both isomers and isomer mixtures.

The pyrimidine compound represented by the above formula (I) or a salt thereof (hereinafter abbreviated as the compound of the present invention) can be produced according to the reaction [A] to [C] or a usual method for producing a salt.

[0018]

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In the reaction [A], R ₁ , R ₂ , R ₃ , R ₄ , R ₅ and n
Is as described above, and X is Cl, Br or I.

The reaction [A] is usually performed in the presence of a solvent.
The solvent may be any solvent as long as it is inert to the reaction, but ethers such as diethyl ether and tetrahydrofuran are preferred.

The reaction [A] is performed in the presence of an inert gas, if necessary. Examples of the inert gas include nitrogen, helium, and argon.

The reaction [A] is carried out in the presence of a catalyst if necessary. Examples of the catalyst include copper halide.

The reaction temperature of the reaction [A] is usually -100 to +30.
° C, desirably -80 to + 25 ° C, and the reaction time is usually
It is 1 to 12 hours, preferably 2 to 6 hours.

The compound represented by the formula (II) in the reaction [A] is disclosed in JP-A-7-173141 or Heterocycles, vol.43, No.1,1.
It can be produced according to the method described on pages 996, 151-172.

[0025]

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In the reaction [B], R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , n and X are as described above. As alkyl lithium,
Methyl lithium, normal butyl lithium, tertiary butyl lithium and the like can be mentioned.

The reaction [B] is usually performed in the presence of a solvent.
The solvent may be any solvent as long as it is inert to the reaction, but ethers such as diethyl ether and tetrahydrofuran are preferred.

The reaction [B] is usually performed in the presence of an inert gas. Examples of the inert gas include nitrogen, helium, and argon.

The reaction temperature of the reaction [B] is usually -120 to +30
° C, preferably -100 to + 25 ° C, and the reaction time is usually 1 to 24 hours, preferably 2 to 18 hours.

[0030]

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In the reaction [C], R ₁ , R ₂ , R ₃ , R ₄ , R ₆ , R ₇ and n are as described above, and R ₅ ′ is alkyl, haloalkyl, alkenyl, haloalkenyl, alkynyl or Haloalkynyl.

The strong acid includes, for example, sulfuric acid, hydrochloric acid, nitric acid and the like.

The reaction [C] is carried out in the presence of a solvent, if necessary. Examples of the solvent include water, acetic acid, and acetic anhydride.

The reaction temperature of the reaction [C] is usually 0 to 150 ° C.,
The reaction temperature is desirably 20 to 110 ° C, and the reaction time is usually 1 to 12 hours, desirably 1 to 6 hours.

The compound of the present invention exhibits an excellent herbicidal effect when used as an active ingredient of a herbicide. The range of application is agricultural fields such as paddy fields, fields, orchards and mulberry fields, and non-agricultural land such as forests, agricultural roads, grounds, and factory sites.Application methods are also appropriate for soil treatment, foliage treatment, flooding treatment, etc. You can choose.

The compounds of the present invention include, for example, rice grasses, red-crowned grasses, red-crowned grasses, and red-crowned grasses, such as barnyardgrass, redgrass, Azegaya, Itoazegaya, red-bellied moss, and moss , Cyperaceae weeds such as scorpiongrass, stag beetle, pine bye, kurogwaii, etc. In addition to weeds, Ichibai, Malva Asagao, Shiroza, American sika deer, Purslane, Aobuyu, Ao-geito, Ebisu-gusa, Dogwood, Sasa It can control harmful weeds such as broadleaf weeds such as loblollys, chickweeds, firgrass, cornflowers, pokeweed, ragweed, yamgra, bilberry, Korean duckweed, sarcophaga fir, enokigusa, and useful crops such as maize, soybean, and soybean. , Wheat, rice, barley, oat, sorghum, rape, sunflower, sugar beet, sugar cane,
It is effectively used in the case of selectively controlling harmful weeds in the cultivation of turf, peanuts, flax, tobacco, coffee and the like, or in the case of non-selectively controlling harmful weeds. Particularly, the compound of the present invention is selectively harmful in cultivation of corn, soybean, cotton, wheat, rice, rape, sunflower, sugar beet, sugar cane, turf, peanut, flax, tobacco, coffee, etc. It is used effectively in controlling weeds.

The compound of the present invention is usually mixed with various agricultural auxiliaries to prepare powders, granules, wettable powders, wettable powders, aqueous suspensions, oily suspensions, aqueous solvents, emulsions, tablets, capsules. It is formulated in the form of a herbicide and used as a herbicide, but it can be in any form commonly used in the art as long as it conforms to the purpose of the present invention. Auxiliaries used in the formulation include diatomaceous earth, slaked lime, calcium carbonate,
Talc, white carbon, kaolin, bentonite,
Solid carrier such as a mixture of kaolinite and sericite, clay, sodium carbonate, sodium bicarbonate, sodium sulfate, zeolite, starch; water, toluene, xylene, solvent naphtha, dioxane, acetone, isophorone, methyl isobutyl ketone, chlorobenzene, cyclohexane, dimethyl Solvents such as sulfoxide, dimethylformamide, N-methyl-2-pyrrolidone, and alcohol; fatty acid salts, benzoates, alkylsulfosuccinates, dialkylsulfosuccinates, polycarboxylates, alkyl sulfates,
Alkyl sulfate, alkyl aryl sulfate, alkyl diglycol ether sulfate, alcohol sulfate, alkyl sulfonate, alkyl aryl sulfonate, aryl sulfonate, lignin sulfonate,
Alkyl diphenyl ether disulfonate, polystyrene sulfonate, alkyl phosphate ester salt, alkyl aryl phosphate, styryl aryl phosphate, polyoxyethylene alkyl ether sulfate, polyoxyethylene alkyl aryl ether sulfate, polyoxyethylene Alkyl aryl ether sulfate, polyoxyethylene alkyl ether phosphate, polyoxyethylene alkyl aryl phosphate,
Anionic surfactants and spreading agents such as salts of naphthalenesulfonic acid formalin condensate; sorbitan fatty acid ester, glycerin fatty acid ester, fatty acid polyglyceride, fatty acid alcohol polyglycol ether, acetylene glycol, acetylene alcohol, oxyalkylene block Polymer, polyoxyethylene alkyl ether, polyoxyethylene alkyl aryl ether, polyoxyethylene styryl aryl ether, polyoxyethylene glycol alkyl ether, polyoxyethylene fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene glycerin fatty acid ester, poly Nonionic surfactants such as oxyethylene hydrogenated castor oil and polyoxypropylene fatty acid esters Vegetable oils such as olive oil, kapok oil, castor oil, palm oil, camellia oil, coconut oil, sesame oil, corn oil, rice bran oil, peanut oil, cottonseed oil, soybean oil, rapeseed oil, linseed oil, cutting oil, liquid paraffin, etc. Is mentioned. These adjuvants can be selected from those known in the art without departing from the purpose of the present invention. In addition, various commonly used auxiliary agents such as a bulking agent, a thickener, an antisettling agent, an antifreezing agent, a dispersion stabilizer, a safener, and a fungicide can also be used.
The compounding ratio of the compound of the present invention and various adjuvants is 0.1: 99.9 to 9
5: 5, preferably 0.2: 99.8 to 85:15.

The application rate of the herbicide containing the compound of the present invention depends on weather conditions, soil conditions, preparation form, kind of target weed,
Although it cannot be specified unconditionally due to differences in the application time and the like, the compound of the present invention is generally applied in an amount of 0.5 to 5000 g, preferably 1 to 1000 g per hectare. The present invention also includes a method for controlling harmful weeds by applying such a herbicide.

The herbicides containing the compound of the present invention include:
It can be mixed or used in combination with other pesticides, fertilizers, safeners and the like, and in this case, more excellent effects and effects may be exhibited. Other pesticides include herbicides, fungicides, antibiotics, plant hormones, insecticides, and the like. In particular, one or two active compound compounds of the compound of the present invention and another herbicide
The mixed herbicidal composition in which or more species are mixed or used in combination can improve the range of applied grass species, the timing of chemical treatment, the herbicidal activity and the like in a preferable direction. The compound of the present invention and the active ingredient compound of the other herbicides may be prepared separately and mixed at the time of spraying, or both may be prepared together and used. The present invention also includes the above-mentioned mixed herbicidal composition.

The mixing ratio of the compound of the present invention to the active ingredient compound of another herbicide cannot be specified unconditionally due to differences in weather conditions, soil conditions, pharmaceutical preparation form, application time, application method and the like. With respect to 1 part by weight, other herbicides contain the active ingredient compound in an amount of 0.001 to 10,000 parts by weight, preferably 0.01 to 1000 parts by weight, per compound. Also, the appropriate dosage is 1
0.1-10000 as the total amount of active compound per hectare
g, preferably 0.2 to 5000 g. The present invention also includes a method for controlling harmful weeds by applying such a mixed herbicidal composition.

Examples of the active ingredient compounds of other herbicides include the following compounds (general names; some of which are under ISO application). And the like, if they exist, they are naturally included.

(1) 2,4-D, MCPA, MCPB,
Phenoxys, such as naproanilide, 2,3,6-TBA, dicamba
amba), picloram, aromatic carboxylic acids such as clopyralid, benzazolin, quinclorac, quinmerac, diflufenzopyr (di)
Flufenzopyr, thiazopyr (thiazopyr)
(pyr), which are said to exhibit herbicidal efficacy by disrupting the hormonal action of plants.

(2) diuron, linuron, isoproturone (isop)
roturon), metobenzlon (metobenz)
urea such as uron, simazine
e), atrazine, atratone, simetryn
n), promethrin, dimethamethrin, metribuzin, terbutyrazine (terb)
utilazine), cyanazine (cyanazi)
ne), amethrin (ametryn), sibutrin (cybutryne), triaziflam (triaz)
iflam), triazines such as propazine, bromacil,
Uracils such as lenacil, propanil, cypromid (cypr)
omid), anilide-based,
p), phenmedifam
m), carbamates such as bromoxynil (bro
hydroxybenzonitrile, such as moxynil, bromoxynil-octanoate, ioxynil, and other pyridats.
e), bentazone, amicarbazone, etc., which are said to exhibit herbicidal efficacy by inhibiting photosynthesis of plants.

(3) Quaternary ammonium salts such as paraquat and diquat, which are themselves considered as free radicals in plants and generate active oxygen to exhibit a rapid herbicidal effect. system.

(4) Nitrophen
n), chloromethoxyphene
en), bifenox, acifluorfen sodium salt (acifluorfen-s)
odium), fomesafen (fomesafen),
Diphenyl ethers such as oxyfluorfen, lactofen, ethoxyphen-ethyl, and chlorophthalim
alim), flumioxazin (flumioxazine)
n), full micro rack pentyl (flumiclor)
ac-pentyl), furthiacet-methyl (flu)
cyclic imides such as thiacet-methyl, and other oxadiargyls
1), oxadiazon, sulfentrazone, carfentrazone-ethyl
thyl), thidiazimine (thidiazimi)
n), pentoxazone, azafenidin, pyraflufen-ethyl, benzfendizone, butafenacil, butafenzilon, methobenzlon (methobenzilon)
inidon-ethyl, flupoxam (flup)
oxam), fluazolate (fluazolate)
e) inhibits chlorophyll biosynthesis in plants, such as profluazole and pyraclonil, and is said to exhibit herbicidal efficacy by abnormally accumulating photosensitized peroxides in plants. What you have.

(5) Norflurazone
zon), metflurazon (metflurazon)
Pyridazinones such as pyrazolates
late), pyrazoxyfen
n), pyrazoles such as benzofenap, and other fluridones
ne), flurtamone, diflufenican, methoxyphenone, clomazone, sulcotrione (sulc)
otrine, mesotrione
e), isoxaflutol
e), difenzoquat,
Isoxachlortol
e), benzobicyclone
e), picolinofen, biflubutamide and the like, which inhibit the pigment biosynthesis of plants such as carotenoids and exhibit herbicidal activity characterized by a whitening effect.

(6) diclohop methyl (diclof)
op-methyl), pyriphenop-sodium, fluazifop-butyl, haloxyfop-methyl
1), quizalofop-e
thyl), cyhalofop butyl (cyhalofop)
-Butyl), fenoxapropethyl (feno)
aryloxyphenoxypropionic acids such as xaprop-ethyl, alloxydim-sodium, clethodym, cetoxydim
ydim), tralkoxydim (tralkoxydi)
m), butoxydim, tepraloxydim, caloxydim, clefoxydim (cl)
Those having strong herbicidal activity specifically on grasses such as cyclohexanedione such as efoxydim).

(7) Chlorimuron ethyl (chlori)
muron-ethyl), sulfometuron methyl (s
ulformuron-methyl, primisulfuron-methyl
yl), bensulfuron methyl (bensulfuro)
n-methyl), chlorsulfuron (chlors)
ulfuron), metsulfuron-methyl (metsu)
lfuron-methyl), sinosulfuron (ci)
nosulfuron), pyrazosulfuron-ethyl (p
yrazosulfuron-ethyl, azimsulfuron, flazasulfuron, rimsulfuron, rimsulfuron, nicosulfuron (nic)
osulfuron), imazosulfuron (imazo)
sulfuron), cyclosulfamuron (cycl)
osulfamuron), prosulfuron (pros)
ulfuron), flupilsulfuron (flupyr)
sulfuron), trisulfuron-methyl (tris)
ulfuron-methyl, halosulfuron-methyl, thifensulfuron-methyl
-Methyl), ethoxysulfuron (ethoxy)
sulfuron), oxasulfuron (oxasul)
furon), ethametsulfuron (ethamets)
ulfuron), flupilsulfuron (flupyr)
sulfuron), iodosulfuron (iodosu)
lfuron), sulfosulfuron (sulfosu)
lfuron), tritosulfuron (tritosul)
furon), forumsulfuron (formamsu)
lfuron), trifluoxysulfuron (trif)
sulfonylureas such as Loxysulfuron, flumetsulum, metosulum, dicloslam (dicl)
osulam), chloranslam methyl (cloran)
slam-methyl, floraslam
asulam), metosulfam (methosulfa)
m) triazolopyrimidinesulfonamides such as
Imazapyr, imazethapyr (im
azethapyr), imazaquin (imazaqui)
n), imazamox, imazameth, imazamethabenz (ima)
zamethabenza), imazapic (imaza)
pic), imidazolinones such as pyrithiobac-sodiu
m), bispyribac sodium salt (bispyrib)
ac-sodium), pyriminobac-methyl (pyr)
iminobac-methyl), pyribenzoxim, pyriftalide (pyr)
pyrimidinylsalicylic acid systems such as ifalid)
Flucarbazone, procarbazone-so
Sulfonylaminocarbonyltriazolinones such as D.dium, and other glyphosate ammonium salts (gl
yphosate-ammonium, glyphosate-isopropylamine salt (glyphosate-iso)
propamine, glufosinate ammonium salt (glufosinate-ammoniu)
m), such as bialaphos, which are said to exhibit herbicidal efficacy by inhibiting the biosynthesis of amino acids in plants.

(8) Trifluraline
lin), oryzalin, nitralin, pendimethalin (pend)
imetalin), ethalfluralin (ethalin)
dinitroaniline, such as fluralin, amiprofos-methy
l), butamifos, anilofos, piperophos
os), chlorpropham (chl)
or phenyl carbamates such as barban, daimulon (daimu).
ron), cumyluron, cumylamines such as bromobutide, other asuram, dithiopyr, thiazopyr
Such as yr), which are said to exhibit herbicidal efficacy by inhibiting plant mitosis.

(9) EPTC, butyrate (butyl)
ate), molinate, dimepiperate, fluazolate, esprocarb (espr)
ocarb), thiobencarb
b), pyributicarb,
Thiocarbamate systems such as triallate, alachlor, butachlor, pretilachlor, metolachlor (me)
tolachlor), S-metrachlor (S-me)
tolachlor, tenyl chlor (thenyl)
chlor), dimethenamide (dimethenamide)
d), chloroacetamides such as acetochlor, propachlor, and other etobenzanides
anid), mefenacet,
Flufenacet, tridiphane, cafenstrole, fentrazamide (fe)
ntrazamide), oxadichromemefon (ox
azicromefone), indanophane (ind)
ananofan), which are said to exhibit herbicidal efficacy by inhibiting plant biosynthesis or lipid biosynthesis.

(10) Xanthomonas cam
pestris, Epicoccosurus nem
atosurus, Exerohillum mono
seras, Drechslera monocera
It is said to show herbicidal efficacy by parasitic on plants such as s.

The compound of the present invention has safety against crops such as rice and soybean as shown in the test examples described below.
And, including those showing selectivity that can control weeds well, when using the compound of the present invention in the crop cultivation,
Among the active ingredient compounds of the other herbicides, for example, a synergistic effect may be obtained by mixing or using one or more of the following compounds.

Cultivation of rice; 2,4-D, MCPA, MC
PB, naproanilide, quinclorac, simetryn,
Promethrin, dimethamethrin, propanil, swep, bentazone, nitrofen, clomethoxyfen,
Bifenox, oxadialgyl, oxadiazon,
Sulfentrazone, carfentrazone ethyl, pentoxazone, pyrazolate, pyrazoxifene, benzofenap, methoxyphenone, cyhalofop butyl,
Bensulfuron-methyl, sinosulfuron, pyrazosulfuron-ethyl, azimsulfuron, imazosulfuron, cyclosulfamuron, ethoxysulfuron, bispyribac sodium salt, pyriminobac-methyl, anilophos, piperophos, dimuron, cumyluron, bromobutide, dithiopyr, molinate, Dimepiperate, esprocarb, thiobencarb, piributicarb, tenylchlor, pretilachlor, butachlor, etobenzanide, mefenacet, flufenacet, cafenstrole, fentrazamide, oxadichromeme,
Cultivation of indanophan, benzobicyclon, pyribenzoxime, triadiflam, clefoxydim, pyraclonil, pyriphthalide soybean; 2,4-D, linuron, metribuzin, cyanazine, bentazone, paraquat, acifluorfen sodium salt, fomesafen, lactofen,
Ethoxyphenethyl, Flumicrolacpentyl, Flumioxazine, Fluthiacetmethyl, Sulfentrazone, Norflurazon, Cromazone, Fluazifopbutyl, Quizalofopethyl, Fenoxapropethyl, Haloxyfopmethyl, Cresodim, Sethoxydim, Butroxidim , Tepraloxydim, chlorimuron-ethyl, thifensulfuron-methyl, oxasulfuron, flumeturam, cloranslam-methyl, dicloslam, imazapyr, imazethapyr, imazaquin, imazamox, imazapic, trifluralin, pendimethalin, etalfluralin, arachlor , Metolachlor, S-metolachlor, acetochlor, dimethenamide, flufenacet maize cultivation; 2,4-D, MCPA, dicamba , Clopiralide, Benazoline, Diflufenzopyr, Diuron, Linuron, Methobenzuron, Simazine, Atrazine, Atrathone, Metribuzin, Terbutyrazine, Cyanazine, Ametrine, Cipromid, Bromoxynil, Bromoxynil octanoate, Pyridate, Bentazone, Paraquat, Microflufen, Oxyfluorfen Lacpentyl, furthiacet-methyl, fluridone, sulcotrione, mesotrione, isoxaflutol, carfentrazone-ethyl, primisulfuron-methyl, rimsulfuron, nicosulfuron, prosulfuron, halosulfuron-methyl, thifensulfuron-methyl, flumeturum, Methoslam, Imazethapyr, Glyphosate ammonium salt, Glyphosate isopropylamine salt, Glufosine Ammonium salt, trifluralin, pendimethalin, EPTC, butylate, alachlor, metolachlor, S- metolachlor, acetochlor, prop crawl, dimethenamid,
Cultivation of Tridiphan, Floraslam, Methobenzuron, Methosulfan, Oxasulfuron, Tepraloxydim Wheat; MCPB, Kimmelac, Linuron,
Isoproturon, promethrin, bromoxynil, bromoxynil octanoate, pyridate, bifenox, carfentrazone-ethyl, thidiadimine, pyraflufen-ethyl, flurtamon, diflufenican, sulcotrione, diclohop-methyl, tralcoquidim, chlorsulfuron, metsulfuron-methyl, Prosulfuron, halosulfuron-methyl, flumeturam, methoslam, pendimethalin, barban, imazamethabenz, sinidone ethyl, ethoxyphenethyl, floraslam, fluazolate, flupoxam, iodosulfuron, metsulfam, pyribenzoxime, sulfosulfuron, tralkoxydim, flucarbazone sodium, Picolinofen, cyclosulfamuron, ethoxysulfuron, imaza Box

[0054]

EXAMPLES Next, examples of the present invention will be described, but the present invention is not limited to these examples. First, a synthesis example of the compound of the present invention will be described.

Synthesis Example 1 1- (4-fluorophenyl) -1- (4-methylthiopyrimidin-5-yl) -isobutanol (compound described below)
Synthesis of No. I-82) (1) A mixed solution of 5 g of 4-methylthio-5-bromopyrimidine and 75 ml of tetrahydrofuran cooled to −78 ° C.
17 ml of a hexane solution of n-butyllithium in a nitrogen atmosphere
(Concentration: 1.57 mol / l) was gradually added dropwise, followed by a reaction at the same temperature for 30 minutes. After gradually adding a mixed solution of 3.02 g of 4-fluorobenzaldehyde and 25 ml of tetrahydrofuran to this solution, the mixture was reacted for 3 hours at the same temperature, and further reacted for 12 hours while returning the liquid temperature to room temperature. After the reaction,
Ethyl acetate and aqueous ammonium chloride solution were added for extraction. The organic layer was washed with water and then with a saturated saline solution, and dried over anhydrous magnesium sulfate. The solvent was distilled off under reduced pressure, and the residue was purified by silica gel column chromatography (eluent: n-hexane / ethyl acetate = 2/3).
2.8 g of α- (4-fluorophenyl) -4-methylthiopyrimidin-5-ylmethanol at 121.1 ° C. was obtained. (2) 2 g of α- (4-fluorophenyl) -4-methylthiopyrimidin-5-ylmethanol and 100 m of methylene chloride
After slowly adding 10 g of manganese dioxide to the mixed solution with l at room temperature, the mixture was reacted at the same temperature for 12 hours. After completion of the reaction, insolubles were filtered off, and the filtrate was concentrated to obtain 1.66 g of (4-fluorophenyl)-(4-methylthiopyrimidin-5-yl) ketone having a melting point of 82.9 ° C. (3) 1.6 g of (4-fluorophenyl)-(4-methylthiopyrimidin-5-yl) ketone and tetrahydrofuran
9 ml of isopropylmagnesium bromide (concentration: 0.81 mol / l) was gradually added dropwise at −78 ° C. under a nitrogen atmosphere to a mixed solution of 40 ml and then reacted at the same temperature for 1.5 hours. The reaction was further performed for 3 hours. After completion of the reaction, extraction was performed by adding ethyl acetate and an aqueous solution of ammonium chloride. The organic layer was washed with water and then with a saturated saline solution, and dried over anhydrous magnesium sulfate. The solvent was distilled off under reduced pressure, and the residue was purified by silica gel column chromatography (eluent: n-hexane / ethyl acetate = 3/1) to obtain 0.6 g of the desired product having a melting point of 178.6 ° C.

Synthesis Example 2 Synthesis of 1- (4-fluorophenyl) -1- (4-methylthiopyrimidin-5-yl) -2-methyl-1-propene (Compound No. II-82) 1- (4 -Fluorophenyl)-(4-methylthiopyrimidin-5-yl) -isobutanol was added to concentrated sulfuric acid 1
After addition to a solution consisting of drops and 5 ml of acetic anhydride,
Allowed to react for hours. After completion of the reaction, ice water and ethyl acetate were added for extraction. The organic layer was washed with an aqueous solution of sodium hydrogen carbonate, water, and saturated saline in this order, and dried over anhydrous magnesium sulfate. The solvent was distilled off under reduced pressure, and the residue was subjected to silica gel column chromatography (eluent: n
-Hexane / ethyl acetate = 4/1) to obtain 0.2 g of the desired product.

Synthesis Example 3 Synthesis of α- (4-fluorophenyl) -α- (4-methylthiopyrimidin-5-yl) cyclopropylmethanol (Compound No. I-88) 4-Methylthio cooled to −78 ° C. In a mixed solution of 3 g of 5-bromopyrimidine and 70 ml of tetrahydrofuran, under a nitrogen atmosphere, 10.25 ml of a hexane solution of n-butyllithium
(Concentration: 1.57 mol / l) was gradually added dropwise, followed by a reaction at the same temperature for 30 minutes. After gradually adding a mixed solution of 2.4 g of cyclopropyl-4-fluorophenyl ketone and 10 ml of tetrahydrofuran to this solution, the mixture was reacted at the same temperature for 2 hours, and further reacted for 3 hours while returning the liquid temperature to room temperature. . After completion of the reaction, extraction was performed by adding ethyl acetate and an aqueous solution of ammonium chloride. The organic layer was washed with water and then with a saturated saline solution, and dried over anhydrous magnesium sulfate.
The solvent was distilled off under reduced pressure, and the residue was subjected to silica gel column chromatography (eluent: n-hexane / ethyl acetate = 3 /
Purification in 2) gave 1.1 g of the desired product having a melting point of 196.5 ° C.

Next, typical examples of the compounds of the present invention represented by the above formula (I) are shown in Tables 1 and 2. These compounds are the same as those in the above-mentioned Synthesis Examples or various preparations of the above-mentioned compounds of the present invention. It can be synthesized based on the method.

The abbreviations used in the table are as follows.

Me: methyl group, Et: ethyl group, i-Pr: isopropyl group, n-Bu: normal butyl group, i-Bu: isobutyl group, t-Bu: tertiary butyl group, cyclo-Pr: cyclopropyl group Group, cyclo-Bu: cyclobutyl group, Ph: phenyl group 4-Cl-Ph indicates a phenyl group in which Cl is substituted at the 4-position.

[0061]

[Table 1]

[0062]

[Table 2]

[0063]

[Table 3]

[0064]

[Table 4]

[0065]

[Table 5]

[0066]

[Table 6]

[0067]

[Table 7]

[0068]

[Table 8]

[0069]

[Table 9]

[0070]

[Table 10]

[0071]

[Table 11]

[0072]

[Table 12]

[0073]

[Table 13]

[0074]

[Table 14]

Next, test examples of the present invention will be described. Test Example 1 Upland soil was filled in a 1 / 170,000 ha pot, and seeds of various plants were sown. After that, the plants have a certain leaf age ((1) Nobie 1.8-3 leaf stage, (2) Meishishiba 1.6-2.4 leaf stage, (3) Ao-geito 0.1-1.3 leaf stage, (4) American stag 0.1-0.5
Leaf stage, (5) Malva morning glory 0.4-1.2 leaf stage, (6) Onami fir 0.
3 to 2.1 leaf stage, (7) rice 1.5 to 2.1 leaf stage, (8) wheat 2.5 to 2.8
Leaf stage, (9) maize 2.4-3.0 leaf stage, (10) soybean 0.1-
(0.3 leaf stage), a wettable powder or an emulsion prepared from the compound of the present invention according to a conventional formulation method was weighed so as to have a predetermined amount of the active ingredient, and diluted with 500 liters of water per hectare. Further, 0.1% by volume of an agricultural spreading agent was added to the diluted solution, and foliage treatment was performed with a small spray.

On the 21st day after the chemical treatment, the growth state of various plants was visually observed, and the herbicidal effect was evaluated at a weeding rate (%) of 0 (equivalent to the untreated area) to 100 (complete killing). The results in the table were obtained.

[0077]

[Table 15]

Test Example 2 Upland soil was filled in 1 / 170,000 hectare pots, and seeds of various plants (Nobie, Meishishiba, Ao-geitou, American stag, Malva Asagao, Onamimi, rice, wheat, corn and soybean) were sown. The day after sowing,
A wettable powder or emulsion prepared from the compound of the present invention in accordance with a usual preparation method was weighed so as to have a predetermined amount of the active ingredient, diluted with 1500 liters of water per hectare, and subjected to soil treatment with a small spray.

20 to 21 days after the chemical treatment, the growth state of various plants was visually observed, and the herbicidal effect was evaluated at a weeding rate (%) of 0 (equivalent to the untreated area) to 100 (complete killing). The results in Table 4 were obtained.

[0080]

[Table 16]

Test Example 3 A paddy field soil was filled in a 1 / 1,000,000 hectare pot, seeds of Nobie and firefly were sown, and the soil was lightly covered thereon. After that, the tube was allowed to stand still in a greenhouse at a waterlogging depth of 0.5 to 1 cm, and the tuber of Urikawa was planted the next day or two days later. After that, the flooding depth was kept at 3-4 cm, and the flies and fireflies were in the 0.5 leaf stage,
At the time when Urikawa reached the primary leaf stage, a water diluent of a wettable powder or an emulsion prepared according to a conventional method of preparing the compound of the present invention was uniformly dropped with a pipette so as to have a predetermined amount of the active ingredient. .

Further, a paddy field soil was filled in a 1 / 1,000,000 hectare pot, and paddy was padded, the flooding depth was set to 3 to 4 cm, and on the next day, a two-leaf rice (cultivar: Nipponbare) was transplanted to a transplanting depth of 3 cm.
Four days after transplantation, the compound of the present invention was treated in the same manner as described above.

On the 14th day after the chemical treatment, the growth status of Nobie, Firefly and Urikawa was visually observed on the 21st day after the chemical treatment, and the growth status of rice was visually observed. From 0 (equivalent to the untreated group) to 100 (completely withered) The herbicidal effect was evaluated based on the weed control rate (%), and the results shown in Table 5 were obtained.

[0084]

[Table 17]

Next, preparation examples of the present invention will be described. Formulation Example 1 (1) 75 parts by weight of the compound of the present invention (2) Geropon T-77 (trade name; manufactured by Rhone Poulin Co.) 14.5 parts by weight (3) 10 parts by weight of NaCl (4) 0.5 parts by weight of dextrin Into a high-speed mixing granulator, and
% Water is added and granulated and dried to obtain a wettable powder.

Formulation Example 2 (1) 78 parts by weight of kaolin (2) Labelin FAN (trade name; manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) 2 parts by weight (3) Solpol 5039 (trade name; manufactured by Toho Chemical Industry Co., Ltd.) 5 parts by weight (4) Carplex (trade name; manufactured by Shionogi & Co., Ltd.) 15 parts by weight The mixture of the components (1) to (4) and the compound of the present invention are 9: 1.
To obtain a wettable powder.

Formulation Example 3 (1) High Filler No. 10 (trade name; manufactured by Matsumura Sangyo Co., Ltd.) 33 parts by weight (2) Solpol 5050 (trade name; manufactured by Toho Chemical Industry Co., Ltd.) 3 parts by weight (3 ) Solpol 5073 (trade name; manufactured by Toho Chemical Industry Co., Ltd.) 4 parts by weight (4) Compound of the present invention 60 parts by weight The above components (1) to (4) are mixed to obtain a wettable powder.

Formulation Example 4 (1) The present compound 4 parts by weight (2) Bentonite 30 parts by weight (3) Calcium carbonate 61.5 parts by weight (4) Toxanone GR-31A (trade name; manufactured by Sanyo Chemical Industries, Ltd.) 3 Parts by weight (5) 1.5 parts by weight calcium ligninsulfonate (1), (2) and (3), which were previously ground, were mixed, and
(4), (5) and water are added, mixed, and extruded and granulated. Thereafter, the granules are dried and sized to obtain granules.

Formulation Example 5 (1) 30 parts by weight of the compound of the present invention (2) 60 parts by weight of Siegrite (trade name; manufactured by Siegrite Co., Ltd.) (3) Newcalgen WG-1 (trade name: Takemoto Yushi Co., Ltd. )) 5 parts by weight (4) New Calgen FS-7 (trade name, manufactured by Takemoto Yushi Co., Ltd.) 5 parts by weight (1), (2) and (3) are mixed, passed through a pulverizer, After adding (4) and kneading, the mixture is extruded and granulated. Thereafter, drying and sizing are performed to obtain a water dispersible granule.

Formulation Example 6 (1) 28 parts by weight of the compound of the present invention (2) 2 parts by weight of sopropol FL (trade name, manufactured by Rhone Poulin Co.) (3) Solpol 355 (trade name, manufactured by Toho Chemical Industry Co., Ltd.) 1 part by weight (4) IP Solvent 1620 (trade name; manufactured by Idemitsu Petrochemical Co., Ltd.) 32 parts by weight (5) Ethylene glycol 6 parts by weight (6) Water 31 parts by weight The above components (1) to (6) And a wet pulverizer (Dyno-
Milling) to obtain an aqueous suspension.

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Soichiro Nagayama 2-3-1, Nishi-Shibukawa, Kusatsu-shi, Shiga Prefecture Inside the Central Research Laboratory of Ishihara Sangyo Co., Ltd. (72) Makiko Sano 2-3-3, Nishi-Shibukawa, Kusatsu-shi, Shiga Prefecture No. 1 Ishihara Sangyo Co., Ltd. Central Research Laboratory (72) Inventor Ken Ohno 2-3-1, Nishi-Shibukawa, Kusatsu-shi, Shiga Prefecture Ishihara Sangyo Co., Ltd. Central Research Laboratory F-term (reference) 4H011 AB01 AB02 BA01 BC03 BC06 BC07 BC18 BC20 DA02 DA14 DA15 DD04

Claims (4)

[Claims] 1. A compound of the formula (I) Wherein A is Wherein R ₁ is halogen, alkyl, haloalkyl, alkenyl, haloalkenyl, alkynyl, haloalkynyl, cycloalkyl, cycloalkenyl, -OR ₈ , -S
(O) _m R ₈ , amino, monoalkylamino, dialkylamino or phenyl which may be substituted, R ₂ and R ₃ are each a hydrogen atom, halogen, alkyl or alkoxy, and R ₄ is each hydroxy, halogen , alkyl, _{haloalkyl, -OR 8, -S (O)} m R 8, nitro or cyano,
R ₅ is alkyl, haloalkyl, alkenyl, haloalkenyl, alkynyl, haloalkynyl, cycloalkyl,
Cycloalkenyl, 1,2-epoxyethanyl, 1,3
-Epoxypropan-1-yl, 1,3-epoxypropan-2-yl or optionally substituted phenyl,
Each hydrogen and R ₆ and R ₇ are alkyl, haloalkyl, alkenyl, haloalkenyl, alkynyl or haloalkynyl, R ₈ is alkyl, haloalkyl, alkenyl, haloalkenyl, alkynyl, haloalkynyl, cycloalkyl or cycloalkenyl , M is 0-2
Wherein n is 0 to 5, and when n is 2 or more, R ₄ may be the same or different, provided that A is A-1;
And R ₁ is alkyl, haloalkyl, cycloalkyl or optionally substituted phenyl] or a salt thereof. 2. A compound of formula (I): Wherein A is Wherein R ₁ is halogen, alkyl, haloalkyl, alkenyl, haloalkenyl, alkynyl, haloalkynyl, cycloalkyl, cycloalkenyl, -OR ₈ , -S
(O) _m R ₈ , amino, monoalkylamino, dialkylamino or phenyl which may be substituted, R ₂ and R ₃ are each a hydrogen atom, halogen, alkyl or alkoxy, and R ₄ is each hydroxy, halogen , alkyl, _{haloalkyl, -OR 8, -S (O)} m R 8, nitro or cyano,
R ₅ is alkyl, haloalkyl, alkenyl, haloalkenyl, alkynyl, haloalkynyl, cycloalkyl,
Cycloalkenyl, 1,2-epoxyethanyl, 1,3
-Epoxypropan-1-yl, 1,3-epoxypropan-2-yl or optionally substituted phenyl,
Each hydrogen and R ₆ and R ₇ are alkyl, haloalkyl, alkenyl, haloalkenyl, alkynyl or haloalkynyl, R ₈ is alkyl, haloalkyl, alkenyl, haloalkenyl, alkynyl, haloalkynyl, cycloalkyl or cycloalkenyl , M is 0-2
Wherein n is 0 to 5, and when n is 2 or more, R ₄ may be the same or different, provided that A is A-1;
And R ₁ is alkyl, haloalkyl, cycloalkyl or phenyl which may be substituted)] or a pyrimidine compound or a salt thereof,
(1) Formula (II); Wherein R ₁ , R ₂ , R ₃ , R ₄ and n are as described above, and a compound represented by the formula (III): Wherein R ₅ is as described above, and X is Cl, Br or I
Or a compound represented by the formula (2)
V); [Wherein R ₁ , R ₂ , R ₃ and X are as described above], an alkyl lithium, and a compound represented by the formula (V): Wherein R ₄ , R ₅ and n are as described above, or (3) a compound of the formula (I-1 ′); [Wherein, R ₁ , R ₂ , R ₃ , R ₄ and n are as described above, and R ₅ ′
Is an alkyl, haloalkyl, alkenyl, haloalkenyl, alkynyl or haloalkynyl], and a strong acid. 3. A herbicide comprising the pyrimidine compound or the salt thereof according to claim 1 as an active ingredient. 4. A method for controlling harmful weeds, to which the effective amount of the pyrimidine compound or its salt according to claim 1 is applied.