JP2001181262A - Thioester compound and its use - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a compound having excellent herbicidal activities. SOLUTION: This thioester compound is represented by the general formula [wherein, R1 is a 1-8C alkyl group, a 1-8C haloalkyl group, a 3-8C alkenyl group, a 3-8C haloalkenyl group, a 3-8C alkynyl group, a 3-8C haloalkynyl group, a 3-8C cycloalkyl group, a (substituted) phenyl group or a (substituted) benzyl group; R2 is a hydrogen atom or the like; and R3 is a hydrogen atom or the like]. The herbicide contains the thioester compound as an active ingredient.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a thioester compound and a herbicide containing the thioester compound as an active ingredient.

[0002]

2. Description of the Related Art At present, many herbicides are commercially available and used. However, since weeds to be controlled are of many types and are long-term, they have a higher herbicidal effect and a broader herbicidal spectrum. However, there is a need for herbicides that do not cause phytotoxicity problems for crops. JP-A-63-41466 discloses that certain phenyluracil compounds have herbicidal activity, but these phenyluracil compounds do not necessarily have sufficient performance required as herbicides.

[0003]

An object of the present invention is to provide a compound having excellent performance as a herbicide.

[0004]

Means for Solving the Problems The present inventors have conducted intensive studies to find a compound having excellent performance as a herbicide. As a result, a thioester compound having a phenyluracil skeleton represented by the following general formula 2 is used as a herbicide. The inventors have found that they have excellent performance, and have reached the present invention. That is, the present invention provides a compound represented by the general formula:

Embedded image [Wherein, R ¹ represents a C1-C8 alkyl group, a C1-C8 haloalkyl group, a C3-C8 alkenyl group, a C3-C8 haloalkenyl group, a C3-C8 alkynyl group, a C3-C8 haloalkynyl group, a C3-C8 cycloalkyl R ² represents a hydrogen atom, a C1-C4 alkyl group or a phenyl group; R ³ represents a hydrogen atom or a C 1 -C 4 alkyl group or a phenyl group;
Represents a 1-C4 alkyl group. (Hereinafter referred to as the present compound) and a herbicide containing the same as an active ingredient.

[0005]

BEST MODE FOR CARRYING OUT THE INVENTION The compound of the present invention may have a stereoisomer relating to a double bond and an asymmetric carbon atom, and each of the stereoisomers and a mixture thereof are also included in the compound of the present invention. . In the present invention, the C represented by R ¹
Examples of the 1-C8 alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group,
t-butyl group, pentyl group, isopentyl group, t-pentyl group, hexyl group, heptyl group, octyl group and the like. Examples of the C1-C8 haloalkyl group include a bromomethyl group, a chloromethyl group, a fluoromethyl group and a dichloro group. Methyl group, difluoromethyl group, chlorodifluoromethyl group, bromodifluoromethyl group, trifluoromethyl group, pentafluoroethyl group, 1,1-difluoroethyl group, 3,3,3-trifluoropropyl group and the like, As the C3-C8 alkenyl group, an allyl group, 1-
A methyl-2-propenyl group, a 2-methyl-2-propenyl group, a 2-butenyl group, a 3-butenyl group, and the like;
Examples of the C3-C8 haloalkenyl group include a 1-chloroallyl group, a 1-bromoallyl group, a 2-chloroallyl group,
Examples of the C3-C8 alkynyl group include a propargyl group, a 1-methyl-2-propynyl group, a 1,1-dimethyl-2-propynyl group, and a 2-dichloroallyl group.
-Butynyl group, 3-butynyl group and the like, and C3-C
8-haloalkynyl groups include 3-chloro-2-propynyl group, 3-bromo-2-propynyl group, 1-chloro-
2-propynyl group, 1-bromo-2-propynyl group, 1
-Chloro-2-butynyl group and the like, and the C3-C8 cycloalkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, and the like. Examples of the phenyl group include a phenyl group optionally substituted with a C1-C3 alkyl group or a halogen atom (for example, a phenyl group, a 4-methylphenyl group,
2-chlorophenyl group, 3-chlorophenyl group, 4-chlorophenyl group and the like. And the benzyl group which may be substituted includes a benzyl group which may be substituted by a C1-C3 alkyl group or a halogen atom (for example, benzyl group, α-methylbenzyl group, 1-methyl-1 -Phenylethyl group, 4-chlorobenzyl group, etc.)
And examples of the C1-C4 alkyl group represented by R ² include a methyl group, an ethyl group, and a propyl group.
The C1-C4 alkyl group represented by R ^3, a methyl group, an ethyl group, a propyl group.

Of the compounds of the present invention, R ¹ is preferably a C1-C8 alkyl group or a C3-C8 alkenyl group, and R ² and R ³ are preferably methyl groups, The other is a combination of hydrogen atoms.

Next, a method for producing the compound of the present invention will be described. The compound of the present invention can be produced, for example, by the production methods described in the following [Production Method 1] to [Production Method 3]. [Production Method 1] Formula 3

Embedded image 2-chloro-4-fluoro-5- {3-methyl-2,6-dioxo-4- (trifluoromethyl)-
1,2,3,6-tetrahydropyrimidin-1-yl}
Phenol (hereinafter referred to as ArOH) and a compound represented by the general formula

Embedded image [Wherein, R ¹ , R ² and R ³ represent the same meaning as described above, and X represents a leaving group such as a chlorine atom, a bromine atom, an iodine atom, a methanesulfonyloxy group, and a p-toluenesulfonyloxy group. Represent. And a compound represented by the formula: This method is carried out, for example, by reacting ArOH with a compound represented by the general formula 4 in a solvent or without a solvent in the presence of a base. Reaction temperature: -10 to 150 ° C Reaction time: instantaneous to 24 hours Type of base: organic bases such as pyridine and triethylamine, inorganic bases such as sodium hydroxide and sodium hydride Amount of reagents used in the reaction: general The theoretical amount of the compound represented by Formula 4 is 1 mole per 1 mole of ArOH, but it can be arbitrarily changed within a range of 1 mole to an excess amount depending on the reaction situation. The amount of the base is ArOH1
The ratio of 1 mole to the mole is a theoretical amount, but can be arbitrarily changed within a range of 1 mole to an excess amount depending on the reaction situation. Type of solvent: N, N-dimethylformamide (hereinafter referred to as D
MF. ), Etc., and hydrocarbons such as toluene. After the reaction, the reaction solution is added with water as necessary, and the resulting crystals are collected by filtration or subjected to a conventional method such as extraction with an organic solvent and concentration. The compound of the present invention can be obtained by performing the post-treatment operation. The compound of the present invention can also be purified by operations such as chromatography and recrystallization.

[Production method 2]

Embedded image [Wherein, R ² and R ³ represent the same meaning as described above. And a carboxylic acid compound represented by the general formula R ¹ -SH wherein R ¹ has the same meaning as described above. And a compound represented by the formula: In this method, for example, an acid chloride of a carboxylic acid compound represented by the general formula 5 is obtained by reacting a carboxylic acid compound represented by the general formula 5 with a chlorinating agent (hereinafter referred to as step 1). )), Followed by reacting the acid chloride with a compound represented by the general formula R ¹ -SH in the presence of a base (hereinafter, referred to as step 2). (Step 1) The reaction is carried out without a solvent or in a solvent, the reaction temperature is usually from 0 to 150 ° C, and the reaction time is usually from instantaneous to 24 hours. The amount of the reagent used in the reaction is a theoretical amount of 1 mole of the chlorinating agent to 1 mole of the carboxylic acid compound represented by the general formula 5, but depending on the reaction situation, 1 mole to excess It can be arbitrarily changed within the range of the amount. Examples of the chlorinating agent used in the reaction include thionyl chloride, sulfuryl chloride, phosgene,
Examples of the solvent include oxalyl chloride, phosphorus trichloride, phosphorus pentachloride, and phosphorus oxychloride. Examples of the solvent include ethers such as tetrahydrofuran (hereinafter, referred to as THF) and aromatic hydrocarbons such as toluene. After completion of the reaction, the reaction solution is generally concentrated under reduced pressure, and the concentrated residue is used as it is as a raw material in step 2.

(Step 2) The reaction is carried out in the presence of a base without solvent or in a solvent, and the reaction temperature is usually in the range of -20.
To 100 ° C., and the reaction time is usually from instant to 24 hours. The amount of the reagent used in the reaction is based on the ratio of 1 mol of the base and 1 mol of the compound represented by the general formula R ¹ -SH to 1 mol of the carboxylic acid compound represented by the general formula 5 used in the step 1. The amount can be arbitrarily changed within the range of 1 mol to an excess amount depending on the reaction conditions. Examples of the base used in the reaction include inorganic bases such as sodium carbonate and potassium carbonate, and organic bases such as pyridine and triethylamine. Examples of the solvent include ethers such as THF and aromatic hydrocarbons such as toluene. Can be After completion of the reaction, the reaction solution is added with water as needed, and the resulting crystals are collected by filtration or subjected to a usual post-treatment operation such as extraction with an organic solvent and concentration to obtain the compound of the present invention. Can be. The compound of the present invention can also be purified by operations such as chromatography and recrystallization.

A carboxylic acid compound represented by the general formula (5) and a general formula R ¹ -SH [wherein R ¹ has the same meaning as described above. The method for producing the compound of the present invention from the compound represented by the formula (1) is not limited to the above method, but may be based on a known method such as a method of reacting using a condensing agent (for example, carbonyldiimidazole, dicyclohexylcarbodiimide, etc.). It is also possible to carry out.

[0011] ArOH can be produced according to the method described in JP-A-63-41466. Also,
The carboxylic acid compounds represented by the general formulas (5) and (6) correspond to the corresponding methyl esters and ethyl esters (JP-A-63-4
No. 1466) can be produced by acid hydrolysis.

[Production method 3] ArOH and the general formula 6

Embedded image [Wherein, R ¹ , R ² and R ³ represent the same meaning as described above. And a compound represented by the formula: The method is carried out, for example, by reacting ArOH with a compound represented by the general formula 6 in a solvent in the presence of a phosphine compound and an azodicarboxylic acid ester. Reaction temperature: -10 to 50 ° C Reaction time: instantaneous to 24 hours Phosphine compound: triarylphosphine such as triphenylphosphine Azodicarboxylate: ethyl azodicarboxylate
Isopropyl azodicarboxylate, etc. Amount of reagent used in the reaction: The theoretical amount of the compound represented by the general formula 6 is 1 mol per 1 mol of ArOH. It can be arbitrarily changed within an excessive amount. The theoretical amount of the phosphine compound and the azodicarboxylic acid ester is 1 mol per 1 mol of ArOH, but can be arbitrarily changed within a range of 1 mol to an excess amount depending on the reaction situation. Type of solvent: ethers such as terahydrofuran and hydrocarbons such as toluene are reacted. After the reaction, the reaction solution is concentrated and then subjected to post-treatment such as column chromatography to obtain the compound of the present invention. it can. The compound of the present invention can be purified by an operation such as recrystallization.

The compound of the present invention has excellent herbicidal activity,
Some show excellent selectivity between crops and weeds. That is, the compound of the present invention has a herbicidal effect on various weeds, which are the following problems, in foliage treatment and soil treatment in the field. Red-bellied weed: Oenother
a erythrosepala), Oenothera laciniata Ranunculaceae weeds: Togemino foxne button (Ranu)
nculus muricatus, Ibomi buttercup (Ranunculus sardous) Polygonaceae Weed: Polygonum con
volvulus), Polygonum (Polygonum)
lapathifolium), Polygonum pensylvanicu
m), Hartade (Polygonum persica)
ria), Rumex crisp
s), Rumex obtusifo (Rumex obtusifo)
lius) and knotweed (Polygonum csp)
idatum) Purslanaceae Weed: Purslane (Portulaca)
oleracea) Weeds of the family Coleoptera: Chickweed (Stellaria med)
ia), Dutch Cerastium g
lomeratum) Acalyaceae Weed: Shiroza (Chenopodial al)
bum), Butterfly (Kochia scopari)
a) Amaranthaceae weed: Amaranthus r
etroflexus)
lanthus hybridus Brassicaceae Weed: Wild Radish (Raphan)
us raphanistrum)
inapis arvensis, Capsicum (Caps)
bur bursa-pastoris) and Mamegunbainazu (Lepidium virginicu)
m) Legume weeds: Sesbania
exaltata), Ebisugusa (Cassia ob)
tusifolia), Florida Vega Weed (De)
smodium tortuosum, white clover (Trifolium repens), giant rape (Vicia sativa), and red maggot (Medicago lupulina) Malvaceae weed: Abitil
hrusti), American deer (Sida sp.)
inosa) Violet weeds: Field panji (Viola ar)
vensis), Wild Panji- (Viola tr)
icor) Rubiaceae Weed: Gallium apari
ne) Convolvulaceae weed: American morning glory (Ipomoea)
hederacea), Malva Asagao (Ipomoe)
a purpura), Malva American morning glory (I
pomoea hederacea var integ
riuscula) and bean sagao (Ipomoea)
lacunosa), Convolvulus convolvulus (Convol)
vulus arvensis Lamiaceae Weeds: Lameur pur
puree), Photohenosa (Lamium ampl)
exicaule) Solanaceae weeds: Datura japonicus (Data)
a Stramonium), Dog Physalis (Sola)
num nigrum Scrophulariaceae Weed: Veronica
ca persica), Tachiinoufuguri (Vero)
nica arvensis)
onica hederaefolia Asteraceae Weed: Xanthium pensy
lvanicum), wild sunflower (Helianth)
us annuus), chamomile (Matricari)
a chamomilla), dog chamomile (Matr)
icaria performata or inodor
a), Common Mary Gold (Chrysanthem)
um segetum), savory ostrich (Matrica)
ria matricarioides, Ragweed (Ambrosia artemisiifoli)
a), Ambrosia trifid
a), Artemisia cana
densis), mugwort (Artemisia pri)
nceps), Solidago (Solidag)
o altissima), Dandelion (Tar)
axacum officinale Weaselaceae Weed: Forget-me-nots (Myosotis a)
Ravensis (Coleoptera: Chrysomelidae): Asclepias
syriaca spurges weed: Euphorbi
a helioscopia), Onishikisou (Eu)
phorbia maculata Anthracidae Weed: Geranium
carolinianum Oxalis Weed: Oxalis c.
orymbosa) Cucurbitaceae Weed: Arechiuri (Sicyos angula)
tus) Grass weed: Echinochloa cr
us-galli), Enokorogosa (Setaria)
viridis), Aquinoe nokorogosa (Setari)
a faberi), Meishishiba (Digitalias)
anguinalis), Hawkgrass (Eleusine)
indica), Poa annua (Poa annu)
a), Blackgrass (Alopecurus myo)
suloides), oats (Avena fat)
ua), Sorghum sorghum (Sorghum hale)
pense), barley (Agropyron rep)
ens), Umanohashiki (Bromus tecto)
rum), Cynodone dact (Cynodone dact)
ylon), cane millet (Panicum dich)
otomiflorum), Texas honeycomb (Pan)
icum texanum), Shata cane (Sor
ghum vulgare)
opecurus geniculatus Cyperaceae Weed: Commelina co
mmunis) Rhododendron weeds: horsetail
nse) Cyperaceae Weeds: Cygous Cyperus
ilia)
us), yellowtail sedge (Cyperus esculen)
tus)

Moreover, some of the compounds of the present invention include corn (Zea mays) and wheat (Tritic).
um aestivum), barley (Hordeum)
vulgare), rice (Orysa sativ)
a), Sorghumcolor, soybean (Glycine max), cotton (Gossip)
ium spp. ), Sugar beet (Beta vulgar)
is), peanuts (Arachis hypogae)
a) Sunflower (Helianthus annuu)
s), and does not show any phytotoxicity that would be a problem for main crops such as rapeseed (Brassica napus) and horticultural crops such as flowers and vegetables. Further, the compound of the present invention, soybean,
In non-tillage cultivation of corn, wheat and the like, various weeds which are problematic can be effectively eliminated. Moreover, some of the compounds of the present invention do not exhibit any harmful effects on crops. In addition, the compound of the present invention has herbicidal effects on various weeds which are problematic in the flooding treatment of paddy fields. Grass weeds: Echinochloa o
ryzicola) Scrophulariaceae Weed: Azena (Lindernia p.
rocumbens) Loxodontaceae Weeds: Rota indi
ca), hamemisohagi (Ammannaia multi)
flora) Dipterocarpaceae Weeds: Dictyostelium
iandra) Cyperaceae Weeds: Cyperus
diffirmis), fireflies (Sirpus j)
uncoides, pine trees (Eleocharis)
Acicularis) and Cyperus (Cyper)
us serotinus, Krogwai (Eleoc)
haris kuroguwai Water-lily Weeds: Monochoria v
aginalis) Weeds: Urikawa (Sagittaria p.
ygmaea), Omodaka (Sagittariat)
rifolia), Spiderfish (Alismacan)
aliculatum Weevil: Weevil (Potamogeto)
N distinctus Apiaceae Weed: Api (Oenanthe Javanic)
a) Moreover, some of the compounds of the present invention do not show any phytotoxicity that would cause a problem for transplanted rice.

Further, some of the compounds of the present invention include a dike slope, a riverbed, a road shoulder and a slope, a railway bedding,
Non-cultivated land, orchards, which need to control the growth of weeds such as park green lands, grounds, parking lots, airports, sites for industrial facilities such as factories and storage facilities, fallow lands, and idle lands in cities, etc.
A wide range of weeds that occur on pastures, lawns, forestry areas, etc. can be removed. Some of the compounds of the present invention include water hyacinth (Eich) which is generated in rivers, waterways, canals, reservoirs and the like.
hornia crassipes) and other herbicides against aquatic weeds. The compound of the present invention has properties similar to those of the herbicidal compound described in International Patent Application Publication No. WO95 / 34659, and the herbicide resistance gene and the like described in the specification are introduced. In the case of cultivating crops imparted with herbicide tolerance, it becomes possible to use the compound of the present invention in a larger dose than that used when cultivating normal crops without tolerance, which is not preferable. Weeds can be effectively removed.

When the compound of the present invention is used as an active ingredient of a herbicide, a solid carrier, a liquid carrier, a surfactant,
It is mixed with other formulation auxiliaries to form emulsions, wettable powders, suspensions, granules, concentrated emulsions, wettable granules and the like.
These preparations contain the compound of the present invention as an active ingredient in a weight ratio of 0.001 to 80%, preferably 0.005 to 7%.
It contains 0%. As solid carriers, kaolin clay, attapulgite clay, bentonite, acid clay, pyrophyllite, talc, diatomaceous earth, mineral fine powder such as calcite, organic fine powder such as walnut shell powder, water-soluble organic fine powder such as urea Examples thereof include fine powders of inorganic salts such as ammonium sulfate and the like and fine powders of synthetic hydrous silicon oxide. As the liquid carrier,
Aromatic hydrocarbons such as alkylbenzene such as methylnaphthalene, phenylxylylethane and xylene, isopropanol, ethylene glycol, 2-ethoxyethanol
Alcohols such as chlorobenzene, esters such as dialkyl phthalate, ketones such as acetone, cyclohexanone and isophorone, mineral oils such as machine oil, vegetable oils such as soybean oil and cottonseed oil, dimethyl sulfoxide, N, N -Dimethylformamide, acetonitrile, N-methylpyrrolidone, water and the like. Surfactants used for emulsification, dispersion, wet spreading, etc. include alkyl sulfates, alkyl sulfonates, alkyl aryl sulfonates, dialkyl sulfosuccinates, polyoxyethylene alkyl aryl ether phosphates. Anionic surfactants such as ester salts, polyoxyethylene alkyl ethers, polyoxyethylene alkyl aryl ethers, polyoxyethylene polyoxypropylene block copolymers, sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters, etc. Nonionic surfactants and the like can be mentioned. Other pharmaceutical auxiliaries include lignin sulfonate, alginate, polyvinyl alcohol,
Gum arabic, CMC (carboxymethylcellulo-
And PAP (acidic isopropyl phosphate). The compound of the present invention is usually formulated and subjected to soil treatment, foliage treatment or flooding treatment before or after emergence of weeds. The soil treatment includes a soil surface treatment and a soil admixture treatment. The foliage treatment includes a treatment from above a plant body and a local treatment for treating only weeds so as not to adhere to crops. In addition, the use of a mixture with other herbicides may enhance the herbicidal efficacy. In addition, insecticides,
Miticides, nematicides, fungicides, plant growth regulators, fertilizers,
It can be mixed with or used in combination with a soil conditioner or the like.

Examples of such herbicides are shown below. Atrazine, cyanazine
ne), dimethametry (dimethametry)
n), metribuzin, promethrin, simazine
ine), simetryn, chlorotoluron, diuron (d)
iron), fluometuron
n), isoproturon,
Linuron, metabenzthiazuron, propanil, bentazone
ne), bromoxynil, ioxynil, pyridate (pyr)
idate) butamifos, dithiopyr (d
ithiopyr), etalfluralin (ethalf)
luralin), pendimesalin (pendime)
thalin), thiazopyr,
Trifluralin, acetochlor, arachlor (al
achlor, butachlor
r), diethatyl-ethyl
yl), dimethenamide (dimethenamide)
d), fluthiamide, mefenacet, metrachlor, pretilachlor (pr)
etilachlor), propachlor (propa)
chlor), cinmethililine (cinmethyli)
n) Acifluorfen, acifluorfen-Na salt (acifluorfen-so)
dim), benzfendizone
zone), bifenox, butafenacil, chlomethoxynil, fomesafen, lactofen
fen), oxadiazon, oxadiargyl, oxyfluorfen, carfentrazone-ethyl
l), fluazolate, fullmicrolacpentyl (flumiclorac-pe)
ntyl), flumioxazin (flumioxazi)
ne), fluthiacet methyl
-Methyl), isopropazole (isoprop)
azol), sulfentrazone (sulfentra)
zone), thidiazimine
n), azafenidin, pyraflufen-ethyl
l), sinidone-ethyl difenzoquat, diquat, paraquat
t)

2,4-D, 2,4-DB, clopyralid, dicamba
a), fluroxypyr, MC
PA, MCPB, mecoprop,
Quinclorac, triclopyr azimsulfuron, bensulfuron-meth
yl), chlorimuron ethyl
-Ethyl), chlorsulfuron (chlorsul)
furon), cloranslam methyl (clorans)
ulam-methyl), cyclosulfamuron (c
iclosulfamuron, dicloslam (di)
Closlam), ethoxysulfuron (ethox)
ysulfuron), flazasulfuron (flaza)
sulfuron), flucarbazone (flucarb)
azone), flumetsura (flumetsula)
m), flupyrsulfur (flupyrsulfur)
on), halosulfuron methyl (halosulfur)
on-methyl), imazosulfuron (imazo)
sulfuron), iodosulfuron (iodos)
ulfuron), metosura (methosula)
m), metsulfuron-methyl (metsulfuron-
methyl), nicosulfuron (nicosulfu)
ron), oxasulfuron
n), primisulfuron methyl (primisulfu)
ron-methyl), procarbazone Na salt (pr
ocarbazone-sodium, prosulfuron, pyrazosulfuron-ethyl, rimsulfuron, sulfometuron-methyl
l), sulfosulfuron (sulfosulfuron)
n), triasulfuron
n), tribenuron-methyl (tribenuron-
methyl), tritosulfuron (tritosul)
furon), thifensulfuron-methyl (this)
nsulfuron-methyl, triflusulfuron-methyl
yl), pyribenzonoxi
m), bispyribac-Na salt (bispyribac-
sodium, pyriminobac-methyl (pyrimi)
nobac-methyl, pyrithiobac-sodium, imazameth, imazamethabenz-methyl, imazamox, imazapic (i)
mazapic), imazapyr (imazapyr),
Imazaquin (imazaquin), imazethapyr (i
mazethapyr) Tepraloxydim, alloxydim-Na salt (alloxydim-sodiu)
m), clethodim, clodinahop-propargyl (clodinafop-prop)
argyl), cyhalofobutyl (cyhalofo)
p-butyl, diclohopmethyl (diclof)
op-methyl), fenoxaprop-ethyl, fenoxaprop-ethyl (fenoxaprop-p-et)
hyl), fluazifop butyl (fluazifop)
-Butyl), fluazifop-p-butyl (fl
uazipop-p-butyl, haloxyfop-methyl, quizalofop-p-ethyl (quizalofop-p-eth)
yl), sethoxydim, traloxydim diflufenican, flurtamone, norflurazone, benzofenap (b)
enzofenap), isoxaflutole (isox)
aflutole, pyrazolate
te), pyrazoxyfen
n), sulcotrione, clomazone, mesotrione (me)
sotrione), isoxachlortol (isox)
achlortole)

Bialaphos, glufosinate ammonium salt (glufosinat)
e-ammonium), glyphosate (glyph)
osate, sulfosate dichlobenil, isoxaben benthiocarb, butyrate
(Butylate), dime pipette (dimep)
iperate), EPTC, esprocarb (esp)
rocarb, molinate, pyributicarb, trilatelate diflufenzopyr bromobutide, DSMA,
MSMA, cafenstrol
l), daimuron, epoprodan, flupoxam (flupox)
am), metobenzuron
n), pentoxazone, piperophos, triaziflam

Beflubutamid (beflubutami)
d), benzobicyclo
on), clomeprop, fentrazamide, flufenacet, florasram, indanophan (inda)
nofan), isoxadifen
n), mesotrione, naproanilide, oxazicromefone, pesoxyamide, phenothiol, pyridafol
afol) The above compounds were obtained from Farm Chemicals Handbook (Meister Publishing Company) [Farm Chem.
Ial Handbook (MeisterPubl
ising Company)] Catalog of 1995 edition, Agchemy-Compound Review 1995
Edition (Agchem Information Service) [AGC
HEM NEW COMPOUND REVIEW, VO
L. 13, 1995 (AG CHEM INFORMA
TAGON SERVICE)], Agchem New Compound Review 1997 Edition (Agchem Information Service) [AG Chem New Company]
D REVIEW, VOL. 15, 1997 (AG CH
EM INFORMATION SERVICE)], Agchem Information Review 1998 Edition (Agchem Information Service) [AG CHEM NE
W COMPOUND REVIEW, VOL. 16,1
998 (AG CHEM INFORMATION SE
RVICE)], Agrou No. 296 22 pages (AG
ROW No. 296 p22), Agrou No. 297
Page 21 (AGROW No. 297 p21); 308, page 22 (AGROW No. 308 p.
22), Agrou No. 32426-27 (AGR
OW No. 324 pp 26-27) or "Herbicide Research Directory (Hakutosha)".

When the compound of the present invention is used as an active ingredient of a herbicide, the amount of treatment varies depending on weather conditions, preparation form, treatment time, treatment method, soil conditions, target crops and target weeds. (Ha; 10,000 m ² ) Usually, 0.01 g to 20,000 g, preferably 1 g to
Emulsion, wettable powder, suspending agent, thick emulsion, wettable powder, etc. are usually prepared in a predetermined amount of 10 to 1000 liters per hectare (if necessary, It is diluted with water (with the addition of an agent), and the granules and certain suspending agents are usually processed without any dilution. Here, as an auxiliary agent used as needed, in addition to the above-mentioned surfactant, polyoxyethylene resin acid (ester), lignin sulfonate, abietic acid salt, dinaphthylmethane disulfonate, crop oil concentrate ( crop oil conc
and vegetable oils such as soybean oil, corn oil, cottonseed oil, sunflower oil and the like. Further, the compound of the present invention can be used as a cotton defoliant / desiccant, potato (Solanu).
mtuberosum) can be used as an active ingredient of a harvesting aid such as a desiccant. In this case, the compound of the present invention is usually formulated in the same manner as when used as an active ingredient of a herbicide, and foliage treatment is performed alone or in combination with other harvesting aids before harvesting the crop.

[0022]

EXAMPLES The present invention will be described in more detail with reference to Production Examples, Preparation Examples and Test Examples, but the present invention is not limited to these Examples. The compound numbers given to the individual compounds of the present invention are the compound numbers shown in Table 1 below. First, Production Examples of the compound of the present invention will be shown. Production Example 1 [Production of Compound 1-1 of the Present Invention] 2- [2-chloro-4-fluoro-5- {3-methyl-
2,6-dioxo-4- (trifluoromethyl) -1,
2,3,6-tetrahydropyrimidin-1-yl {phenoxy] propionate chloride 3.8 g and pyridine 0.8
g was dissolved in 15 ml of THF and stirred at 0 ° C. A separate MeSNa aqueous solution (MeSNa1.
MeSH generated by 5 g and 10 g of water) and diluted hydrochloric acid was blown. After the generation of MeSH stopped, the THF solution was stirred at room temperature for 2 hours. The THF
The solution was poured into water and extracted with ethyl acetate. The organic layer was washed sequentially with diluted hydrochloric acid and a saturated aqueous solution of sodium hydrogen carbonate,
Dry over anhydrous magnesium sulfate. After concentration under reduced pressure, the residue was subjected to silica gel column chromatography.
(Developing solvent; hexane: ethyl acetate = 10: 1),
2- [2-chloro-4-fluoro-5- {3-methyl-
2,6-dioxo-4- (trifluoromethyl) -1,
2,3,6-tetrahydropyrimidin-1-yl {phenoxy] methyl propanethioate (Compound 1-1 of the present invention)
1.6 g were obtained. ¹ H-NMR (250 MHz, CDCl ₃ , TMSδ (p
pm)): 1.63 (3H, d, J = 6.7 Hz),
2.29 (3H, s), 3.55 (3H, t, J = 1.
0 Hz), 4.68 to 4.78 (1H, m), 6.35
(1H, s), 6.76 (1H, d, J = 6.3H)
z), 7.34 (1H, d, J = 8.9 Hz)

Production Example 2 [Preparation of Compound 1-2 of the Present Invention] 2.0 g of 2-chloropropionate chloride and 1 ml of ethanethiol were dissolved in 10 ml of THF, and 2 ml of pyridine was slowly added dropwise under ice-cooling. After the dropwise addition, the mixture was stirred at room temperature for 1 hour, then the reaction solution was poured into water, diluted hydrochloric acid was added, and the mixture was extracted with ethyl acetate. The organic layer was sequentially washed with water, a saturated aqueous solution of sodium hydrogencarbonate, and a saturated saline solution, and dried over anhydrous magnesium sulfate. Concentrate under reduced pressure,
-2.1 g of ethyl chloropropanethioate were obtained. This was used for the next reaction as it was. 1.0 g of 2-chloro-4-fluoro-5- {3-methyl-2,6-dioxo-4- (trifluoromethyl) -1,2,3,6-tetrahydropyrimidin-1-yl} phenol and 2 0.50 g of ethyl-chloropropanethioate was dissolved in 10 ml of DMF, 0.50 g of potassium carbonate was added, and the mixture was stirred at 80 ° C for 4 hours. The reaction solution was poured into diluted hydrochloric acid and extracted with ethyl acetate. The organic layer was washed sequentially with water and saturated saline, and dried over anhydrous magnesium sulfate. After concentration under reduced pressure,
The residue was subjected to silica gel column chromatography (developing solvent; hexane: ethyl acetate = 5: 1) to give 2- [2
-Chloro-4-fluoro-5- {3-methyl-2,6-
Dioxo-4- (trifluoromethyl) -1,2,3
6-tetrahydropyrimidin-1-yl @ phenoxy]
Ethyl propanethioate (Compound 1-2 of the present invention) 0.47
g was obtained. ¹ H-NMR (300 MHz, CDCl ₃ , TMSδ (p
pm)): 1.21-1.28 (3H, m), 1.62
(3H, d, J = 6.5 Hz), 2.84 to 2.92
(2H, m), 3.54 (3H, t, J = 1.0H
z) 4.66-4.74 (1H, m), 6.34 (1
H, s), 6.73-6.77 (1H, m), 7.33
(1H, d, J = 8.9Hz)

Production Example 3 [Compound 1-6 of the present invention
Method for producing a compound rich in a compound in which the configuration of carbon substituted with R ² and R ³ in general formula 2 is R (hereinafter, referred to as compound 1-6-R of the present invention)] (2R) as a raw material compound -2- [2-chloro-4-fluoro-5- {3-methyl-2,6-dioxo-4-
Using (trifluoromethyl) -1,2,3,6-tetrahydropyrimidin-1-yl {phenoxy] propion chloride and 2-methylpropanethiol according to the method described in Production Example 1, (2R) -2- [2-chloro-4-fluoro-5- {3-methyl-2,6-dioxo-4- (trifluoromethyl) -1,2,3,6-tetrahydropyrimidin-1-yl} phenoxy] 2-methylpropyl propanethioate (Compound 1-6-R of the present invention) was obtained. ¹ H-NMR (250 MHz, CDCl ₃ , TMS
δ (ppm)): 0.94 (6H, m), 1.63 (3
H, d, J = 6.7 Hz), 1.72-1.92 (1
H, m), 2.72 to 2.87 (2H, m), 3.54
(3H, m), 4.71 (1H, dd, J = 1.9H)
z, 6.7 Hz), 6.35 (1H, s), 6.75
(1H, d, J = 6.3 Hz), 7.34 (1H, d, J
J = 8.9 Hz)

Production Example 4 [Compound 1-7 of the present invention
Method for producing a compound rich in a compound in which the configuration of carbon substituted with R ² and R ³ in general formula 2 is R (hereinafter, referred to as compound 1-7-R of the present invention)] (2R) as a raw material compound -2- [2-chloro-4-fluoro-5- {3-methyl-2,6-dioxo-4-
Using (trifluoromethyl) -1,2,3,6-tetrahydropyrimidin-1-yl {phenoxy] propion chloride and 2-propenethiol, according to the method described in Production Example 1, (2R)- 2- [2-chloro-4-
Fluoro-5- {3-methyl-2,6-dioxo-4-
Allyl (trifluoromethyl) -1,2,3,6-tetrahydropyrimidin-1-yl {phenoxy] propanethioate (Compound 1-7-R of the present invention) was obtained. ¹ H-NMR (250 MHz, CDCl ₃ , TMSδ (p
pm)): 1.63 (3H, d, J = 6.6 Hz),
3.51-3.55 (2H, m), 4.67-4.76
(1H, m), 5.10 (1H, d, J = 9.9H
z), 5.24 (1H, d, J = 16.4 Hz), 6.
35 (1H, s), 6.76 (1H, d, J = 6.3H)
z), 7.34 (1H, d, J = 8.9 Hz)

Production Example 5 2-chloro-4-fluoro-5- [3-methyl-2,6
-Dioxo-4- (trifluoromethyl) -1,2,2
3,6-tetrahydropyrimidin-1-yl] phenol, ethyl 2-hydroxyisobutanethioate and triphenylphosphine are dissolved in tetrahydrofuran, and the solution obtained by dissolving diisopropyl azodicarboxylate in tetrahydrofuran is gradually stirred with ice cooling. To be dropped. Thereafter, after stirring at room temperature, ice water is added to the reaction solution, and ethyl acetate and saturated saline are added, followed by liquid separation. The organic layer is washed with brine, dried over magnesium sulfate, and concentrated. The residue was subjected to silica gel column chromatography to give 2- [2-chloro-4-fluoro-5-
{3-methyl-2,6-dioxo-4- (trifluoromethyl) -1,2,3,6-tetrahydropyrimidine-
Ethyl 1-yl {phenoxy] isobutanethioate is obtained (Compound 1-22 of the present invention).

Next, a method for producing a starting compound of the compound of the present invention will be described as a reference production example. Reference Production Example 1 2- [2-chloro-4-fluoro-5- {3-methyl-
2,6-dioxo-4- (trifluoromethyl) -1,
77,29 g of ethyl 2,3,6-tetrahydropyrimidin-1-yl {phenoxy] propionate was dissolved in 350 ml of 1,4-dioxane, 130 ml of water and 130 ml of concentrated hydrochloric acid were added, and the mixture was heated and stirred under reflux for 4 hours. .
After allowing the reaction solution to cool, ice water was added to the reaction solution, and ethyl acetate and saturated saline were added, followed by separation. The organic layer was washed with saturated saline, dried over magnesium sulfate, and concentrated. The residue was subjected to silica gel column chromatography (developing solvent; hexane: ethyl acetate = 1: 4) to give 2-
[2-chloro-4-fluoro-5- {3-methyl-2,
6-dioxo-4- (trifluoromethyl) -1,2,2
72.63 g of 3,6-tetrahydropyrimidin-1-yl {phenoxy] propionic acid were obtained. ¹ H-NMR (300 MHz, CDCl ₃ , TMSδ (p
pm)): 1.70 (3H, d, J = 6.8 Hz),
3.52 (1.5H, d, J = 1.2Hz), 3.55
(1.5H, d, J = 1.2Hz), 4.7 to 4.6
(1H, m), 6.33 (0.5H, s), 6.35
(0.5H, s), 6.83 (0.5H, d, J = 5.
0 Hz), 6.86 (0.5H, d, J = 5.1H)
z), 7.32 (1H, d, J = 8.9 Hz)

Reference Production Example 2 2-chloro-4-fluoro-5- [3-methyl-2,6
-Dioxo-4- (trifluoromethyl) -1,2,2
3,6-Tetrahydropyrimidin-1-yl] phenol (40 g), methyl S-lactate (18.5 g, manufactured by Merck) and triphenylphosphine (46.5 g) were dissolved in tetrahydrofuran (100 g), and stirred under ice-cooling with stirring. A solution of 35.8 g of diisopropyl acid dissolved in 32 g of tetrahydrofuran was gradually added dropwise over 3 hours and 15 minutes (the temperature of the reaction solution at this time was 0 to 10 ° C.). Thereafter, after stirring at room temperature, ice water was added to the reaction solution, and ethyl acetate and saturated saline were added, followed by liquid separation. The organic layer was washed with brine, dried over magnesium sulfate, and concentrated. The residue was added to a mixed solvent of ethyl acetate and hexane,
It was left at room temperature. Thereafter, the solid that did not dissolve was removed by filtration. The filtrate was concentrated, and the residue was subjected to silica gel column chromatography (twice) to give (2R)-
2- [2-chloro-4-fluoro-5- {3-methyl-
2,6-dioxo-4- (trifluoromethyl) -1,
49 g of methyl 2,3,6-tetrahydropyrimidin-1-yl {phenoxy] propionate were obtained. ¹ H-NMR (300 MHz, CDCl ₃ , TMSδ (p
pm)): 1.67 (3H, d, J = 6.6 Hz),
3.55 (3H, t, J = 1.2 Hz), 3.74 (3
H, s), 4.69 (1H, q, J = 6.8 Hz),
6.35 (1H, s), 6.81 (0.5H, d, J =
6.4 Hz), 6.82 (0.5 H, d, J = 6.6 H)
z), 7.31 (1H, d, J = 9.1 Hz) [α] _D ²⁰ : + 25.8 ° (C = 1.0, CH ₃ OH)

(2R) -2- [2-chloro-4-fluoro-5- {3-methyl-2,6-dioxo-4- (trifluoromethyl) -1,2,3,6-tetrahydropyrimidine- 1-yl {phenoxy] methyl propionate 4
8.5 g was dissolved in 480 ml of 1,4-dioxane, 83 ml of water and 83 ml of concentrated hydrochloric acid were added, and the mixture was heated and stirred under reflux for 8 hours and 45 minutes. After allowing the reaction solution to cool, ice water was added to the reaction solution, and ethyl acetate and saturated saline were added, followed by separation. The organic layer was separated by adding 979 g of a 2.9% aqueous sodium hydrogen carbonate solution, and the separated aqueous layer was made acidic by adding aqueous hydrochloric acid and then extracted with ethyl acetate. Next, the extracted organic layer was dried over magnesium sulfate and concentrated, and then (2R) -2- [2-chloro-4-fluoro-5-
{3-methyl-2,6-dioxo-4- (trifluoromethyl) -1,2,3,6-tetrahydropyrimidine-
1-yl @ phenoxy] propionic acid was obtained in an amount of 41.0 g. ¹ H-NMR (300 MHz, CDCl ₃ , TMSδ (p
pm)): 1.69 (3H, d, J = 6.6 Hz),
3.52 (1.5H, s), 3.54 (1.5H, d,
J = 1.1 Hz), 4.7-4.6 (1H, m), 6.
33 (0.5H, s), 6.34 (0.5H, s),
6.84 (0.5 H, d, J = 6.58 Hz), 6.8
7 (0.5 H, d, J = 6.51 Hz), 7.31 (1
(H, d, J = 8.9 Hz)] (2R) -2- [2-chloro-4-fluoro-5- {3-methyl-2,6-dioxo-4- (trifluoromethyl) under a nitrogen stream. -1,2,3,6-tetrahydropyrimidin-1-yl {phenoxy] propionic acid 41.0
g was dissolved in 246 ml of tetrahydrofuran, 41.0 ml of thionyl chloride was added, and the mixture was heated and stirred under reflux conditions for 1 hour and 40 minutes. Thereafter, the mixture was allowed to cool, and the reaction solution was concentrated as it was. The residue was poured into hexane, and the precipitated crystals were filtered, dried, and dried with (2R) -2- [2-chloro-4-fluoro-5.
-{3-Methyl-2,6-dioxo-4- (trifluoromethyl) -1,2,3,6-tetrahydropyrimidin-1-yl} phenoxy] propion chloride 32.7
g was obtained. ¹ H-NMR (300 MHz, CDCl ₃ , TMSδ (p
pm)): 1.80 (3H, d, J = 6.9 Hz),
3.56 (3H, d, J = 1.1 Hz), 4.87 (1
H, q, J = 6.8 Hz), 6.35 (0.5H,
s), 6.36 (0.5H, s), 6.83 (0.5
H, d, J = 6.3 Hz), 6.87 (0.5 H, d,
J = 6.4 Hz), 7.35 (1H, d, J = 8.9H)
z))

Next, examples of the compound of the present invention are shown in Table 1 together with the compound numbers, but the compound of the present invention is not limited to these examples. General formula Compound represented by

[Table 1]

Next, formulation examples are shown. The compounds of the present invention are indicated by the compound numbers in Table 1. Parts are parts by weight. Formulation Example 1 50 parts of each of the present compounds 1-1 to 1-21, 3 parts of calcium ligninsulfonate, 2 parts of sodium lauryl sulfate 2
Parts and 45 parts of synthetic hydrous silicon oxide are crushed and mixed well to obtain each wettable powder. Formulation Example 2 10 parts of each of the compounds 1-1 to 1-21 of the present invention, 14 parts of polyoxyethylene styrylphenyl ether, 6 parts of calcium dodecylbenzenesulfonate, 35 parts of xylene and 35 parts of cyclohexanone are mixed well and each To obtain an emulsion of Formulation Example 3 2 parts of each of the present compounds 1-1 to 1-21, 2 parts of synthetic hydrous silicon oxide, 2 parts of calcium ligninsulfonate, 30 parts of bentonite and 64 parts of kaolin clay are thoroughly pulverized and mixed, and water is added. After kneading, the mixture is granulated and dried to obtain each granule. Formulation Example 4 25 parts of each of the present compounds 1-1 to 1-21, 50 parts of a 10% aqueous solution of polyvinyl alcohol, and 25 parts of water were mixed,
Each suspension is obtained by wet pulverization until the average particle size becomes 5 micrometers or less. Formulation Example 5 Five parts of each of the present compounds 1-1 to 1-21 are added to 40 parts of a 10% aqueous solution of polyvinyl alcohol, and the mixture is emulsified and dispersed with a homogenizer until the average particle size becomes 10 μm or less. Then, 55 parts of water are added to obtain each concentrated emulsion.

Next, Test Examples show that the compounds of the present invention are useful as active ingredients of herbicides. The compounds of the present invention are indicated by the compound numbers in Table 1. Test Example 1 Field foliage treatment test Cylindrical plastic pots having a diameter of 10 cm and a depth of 10 cm were filled with soil, and seeds of dogwood, American morning glory, and strawberries were sowed and grown in a greenhouse for 14 days. Thereafter, the compounds 1-1, 1-2, 1-6 of the present invention were prepared according to Formulation Example 2.
R and 1-7-R were each made into an emulsion, and a predetermined amount thereof was 1
The mixture was diluted with water containing a spreading agent equivalent to 1000 liters per hectare, and the whole foliage was uniformly treated from above the plant with a sprayer. After the treatment, the plants were raised in a greenhouse for 8 days, and the herbicidal efficacy was examined. As a result, compounds 1-1, 1-2 of the present invention,
1-6-R and 1-7-R completely inhibited the growth of dog millet, American morning glory, and strawberry at a dose of 32 g / ha.

Test Example 2 Upland Soil Surface Treatment Test A cylindrical plastic pot having a diameter of 10 cm and a depth of 10 cm was filled with soil, and seeds of dog millet, blackgrass, morning glory, and straw were sowed. Each of Compounds 1-1, 1-2, 1-6-R and 1-7-R of the present invention was made into an emulsion according to Formulation Example 2, and the predetermined amount thereof was adjusted to 10 per hectare.
It was diluted with 00 liters of water and sprayed evenly over the soil surface with a sprayer. Nine days after the treatment, the plants were raised in a greenhouse, and their herbicidal efficacy was investigated. As a result, the present compound 1-1, 1-
2, 1-6-R and 1-7-R completely inhibited budding of dog millet, blackgrass, American morning glory and strawberry at a dose of 500 g / ha.

[0034]

By using the compound of the present invention, an excellent herbicidal effect can be obtained.

 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 4H011 AB01 BA01 BB09 BC01 BC05 BC07 BC19 BC20 DA14 DA15 DA16 DC05 DD03 DD04 DE15 DF04 DG08 DH03 DH25

Claims (5)

[Claims] 1. A compound represented by the general formula: [Wherein, R ¹ represents a C1-C8 alkyl group, a C1-C8 haloalkyl group, a C3-C8 alkenyl group, a C3-C8 haloalkenyl group, a C3-C8 alkynyl group, a C3-C8 haloalkynyl group, a C3-C8 cycloalkyl R ² represents a hydrogen atom, a C1-C4 alkyl group or a phenyl group; R ³ represents a hydrogen atom or a C 1 -C 4 alkyl group or a phenyl group;
Represents a 1-C4 alkyl group. ] The thioester compound shown by these. 2. In the general formula 1, R ² is a methyl group,
The thioester compound according to claim 1, wherein R ³ is a hydrogen atom. 3. In the general formula 1, R ¹ is C1-C8.
The thioester compound according to claim 1 or 2, which is an alkyl group. 4. In the general formula 1, R ¹ is C3-C8
3. The thioester compound according to claim 1, which is an alkenyl group. 5. A herbicide comprising the thioester compound according to claim 1 as an active ingredient.