JP2000319264A - Optically active uracil compound - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a new compound, an optically active specific uracil compound with the absolute steric configuration at the 2-position of the propionic acid site being R-configuration, having high herbicidal activity, therefore useful as a herbicide. SOLUTION: This new compound is a compound of formula I (R1 is a 1-8C alkyl or 3-8C alkenyl; * denotes an asymmetric carbon atom) with the absolute steric configuration of the 2-position (C atom marked with *) of the propionic acid site being R-configuration, e.g. methyl (2R)-2- 2-chloro-4-fluoro-5-[3- methyl-2,6-dioxo-4-(trifluoromethyl)-1,2,3,6-terahydropyrimidin-1-yl]p henoxy) propionate. The compound of formula I is obtained byreaction between a compound of formula II and a compound of formula III[ e.g. methyl (S)-lactate] in the presence of a triarylphosphine or the like and a di(lower alkyl) azodicarboxylate pref. at 0-100 deg.C.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to an optically active uracil compound and its use.

[0002]

2. Description of the Related Art JP-A-63-41466 discloses that certain uracil compounds have herbicidal activity. However, no mention is made as to whether the herbicidal activity is the same or different between the optical isomers, and which of the optical isomers is more useful as a herbicide.
Generally, in the field of agrochemicals, it is known that certain optical isomers have almost the same activity as the racemic form, and that certain optically active forms have almost twice the activity of the racemic form. It has been known. This phenomenon that the biological activities are the same or different seems to be due to the structure of the portion near the asymmetric carbon atom in the compound. However, it is extremely difficult to predict without experiment whether the biological activity of the optical isomers is the same or different. If one optical isomer shows little activity, the other optical isomer should theoretically have twice the activity of the racemate. This is because the racemate has the active isomer at 1 /
Because it contains only two.

[0003]

An object of the present invention is to provide a compound having an excellent herbicidal activity.

[0004]

Means for Solving the Problems The present inventors have conducted intensive studies to find a compound having excellent herbicidal activity.

Embedded image [Wherein, R ¹ is a C1-C8 alkyl group or C3-C8
* Represents an alkenyl group, and * represents an asymmetric carbon atom. Uracil compound having an R configuration in the absolute configuration at the 2-position (the carbon atom marked with *) in the propionic acid site has excellent herbicidal activity, and thus completed the present invention. That is, the present invention provides a uracil compound represented by the general formula (2) in which the absolute configuration at the 2-position of the propionic acid site is an R configuration (hereinafter, referred to as the compound of the present invention), and a herbicide containing the same as an active ingredient. I do.

[0005]

BEST MODE FOR CARRYING OUT THE INVENTION The compound of the present invention has the above general formula
Among the uracil compounds represented by Chemical Formula 2, isomers whose absolute configuration is essentially a pure R configuration in the sense that the absolute configuration at position 2 of the propionic acid site is essentially not S, Alternatively, an isomer-rich compound in which the absolute configuration at the 2-position of the propionic acid moiety is the R configuration is included. In the present invention, an isomer having an essentially pure R configuration refers to an isomer having an absolute configuration of R configuration by 95%.
The compound containing the above is referred to, and the compound rich in isomers whose absolute configuration is in the R configuration generally means a compound containing 80% or more of the R configuration in the ratio of the R configuration to the S configuration. Since the compound of the present invention is an optically active compound, it is also possible to specify the compound of the present invention by optical rotation, which is a physical property of the compound. Optical rotation refers to the property of rotating the plane of polarization of linearly polarized light. Usually, the angle at which the plane of polarization is rotated when linearly polarized light passes through a certain thickness of a substance having optical rotation (specific rotation). , But usually measured using a pure liquid or solution. In order to measure the specific rotation of the compound of the present invention, the compound of the present invention is made into a homogeneous solution of methanol, and is measured using a D line of sodium.

In the present invention, C1-C represented by R ¹
8-alkyl groups include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, s-butyl, t-butyl, amyl, isoamyl, s-
Amyl group, t-amyl group, hexyl group and the like;
As the -C8 alkenyl group, for example, an allyl group, a 1-methyl-2-propenyl group, a 3-butenyl group, a 2-butenyl group, a 3-methyl-2-butenyl group, a 2-methyl-3-
Butenyl group and the like. In the present invention, R ¹ is preferably a C1-C6 alkyl group or a C3-C6 alkenyl group.

The compound of the present invention can be produced, for example, by the following production method. (Production method 1) Formula 3

Embedded image And a compound represented by the general formula

Embedded image [Wherein, R ¹ has the same meaning as described above. [S] -lactic acid derivative represented by the following formula: The reaction is carried out in the presence of a triarylphosphine or a trialkylphosphine such as triphenylphosphine, triethylphosphine or tributylphosphine, and a di (lower alkyl) azodicarboxylate such as diethylazodicarboxylate or diisopropylazodicarboxylate. Done in The reaction is usually carried out in a solvent, and the reaction temperature is usually from -20 to 150 ° C, preferably from 0 to 100 ° C, and the reaction time is from instant to
48 hours. The amount of the reagent used for the reaction is 1 to 3 mol, preferably 1 to 1. mol of the (S) -lactic acid derivative represented by the general formula 4 based on 1 mol of the compound represented by the formula 3.
2 mol, triarylphosphine or trialkylphosphine is 1-3 mol, preferably 1-1.2 mol, and di (lower alkyl) azodicarboxylate is 1 mol.
３3 mol, preferably 1-1.2 mol. As the solvent used for the reaction, for example, hexane, heptane,
Aliphatic hydrocarbons such as ligroin, cyclohexane, petroleum ether, aromatic hydrocarbons such as benzene, toluene, xylene, aromatic hydrocarbons such as chlorobenzene, dichlorobenzene, benzotrifluoride, diethyl ether, diisopropyl ether, dioxane , Tetrahydrofuran, ethers such as ethylene glycol dimethyl ether, and mixtures thereof. After completion of the reaction, the target compound of the present invention can be obtained, for example, by the method shown below. 1) The reaction solution is poured into water, extracted with an organic solvent, the organic layer is dried and concentrated, and the residue is subjected to chromatography. 2) The reaction solution is concentrated as it is, and the residue is subjected to chromatography. The compound of the present invention can be purified by an operation such as recrystallization.

(Production method 2) A compound represented by the formula 3 and a compound represented by the general formula 5

Embedded image [Wherein, R ¹ has the same meaning as described above. And (S) -2-chloropropionic acid derivative represented by the formula: The reaction is usually carried out in a solvent in the presence of a base, and the reaction temperature is usually in the range of -20 to 1
00 ° C, preferably 0 to 40 ° C, and the reaction time range is from instant to 240 hours. The amount of the reagent used in the reaction is such that 1 mol of the compound represented by the formula 3 and 1 to 2 mol of the (S) -2-chloropropionic acid derivative represented by the general formula 5, preferably 1 to 1 mol. .2 mol, base 1-3
Mole, preferably 1-1.2 mole. Examples of the base used in this reaction include inorganic bases such as lithium carbonate, sodium carbonate, potassium carbonate, and sodium hydride. As the solvent used in the reaction, for example, hexane, heptane, ligroin, cyclohexane, aliphatic hydrocarbons such as petroleum ether, benzene, toluene,
Aromatic hydrocarbons such as xylene, aromatic hydrocarbons such as chlorobenzene, dichlorobenzene, benzotrifluoride, ethers such as diethyl ether, diisopropyl ether, dioxane, tetrahydrofuran, ethylene glycol dimethyl ether, acetone, methyl ethyl ketone, methyl isobutyl ketone , Isophorone, ketones such as cyclohexanone, ethyl formate, ethyl acetate,
Esters such as butyl acetate and diethyl carbonate; nitriles such as acetonitrile, propionitrile and butyronitrile; acid amides such as formamide, N, N-dimethylformamide and acetamide; sulfur compounds such as dimethylsulfoxide and sulfolane; Mixtures are mentioned. After the completion of the reaction, for example, by the method shown below,
The desired compound of the present invention can be obtained. 1) The reaction solution is poured into water, extracted with an organic solvent, the organic layer is dried and concentrated, and the residue is subjected to chromatography. 2) The reaction solution is concentrated as it is, and the residue is subjected to chromatography.

The compound represented by Formula 3 is disclosed in
It is a compound known in -41466, and can be produced according to the production method described in the publication.

(Production method 3) Formula 6

Embedded image And a carboxylic acid compound represented by the general formula

Embedded image R ¹ OH [wherein, R ¹ are as defined above. The method of manufacturing by reacting with the alcohol compound shown by these.

(Production method 3-1) A method of producing by directly reacting a compound represented by the formula (6) with an alcohol compound represented by the formula (7). The reaction is usually carried out in the absence of a solvent or in a solvent in the presence of an acid, and the reaction temperature is usually from 20 to 150 ° C, preferably from 50 to 100 ° C, and the reaction time is from instant to 24 hours. . The amount of the reagent used in the reaction is such that the amount of the alcohol compound represented by the general formula 7 is 1 mol to a large excess with respect to 1 mol of the carboxylic acid compound represented by the chemical formula 6, and the amount of the acid is the amount of the catalyst. To 1 mole. Examples of the acid used for the reaction include inorganic acids such as sulfuric acid, sulfonic acids such as methanesulfonic acid, trifluoromethanesulfonic acid, p-toluenesulfonic acid, and benzenesulfonic acid, and acidic cation exchange resins. As the solvent used in the reaction, for example, hexane,
Aliphatic hydrocarbons such as heptane, nonane, decane, ligroin, cyclohexane, petroleum ether, and halogenated hydrocarbons such as methylene chloride, chloroform, carbon tetrachloride, 1,2-dichloroethane, 1,2,3-trichloropropane , Aromatic hydrocarbons such as benzene, toluene, xylene, mesitylene, halogenated aromatic hydrocarbons such as chlorobenzene, dichlorobenzene, benzotrifluoride, diethyl ether, diisopropyl ether,
Examples thereof include ethers such as methyl-t-butyl ether, dioxane, tetrahydrofuran, and ethylene glycol dimethyl ether, and mixtures thereof. After completion of the reaction, the target compound of the present invention can be obtained, for example, by the method shown below. 1) If necessary, concentrate the reaction solution, pour the reaction solution into water, extract this with an organic solvent, dry and concentrate the organic layer, and subject the residue to chromatography. 2) The reaction solution is concentrated as it is, and the residue is subjected to chromatography. This method can be applied as a known method using a dehydrating esterifying agent such as dicyclohexylcarbodiimide.

A carboxylic acid compound represented by the following formula:
The compound of the present invention represented by the general formula 2 can be produced by subjecting a certain compound to acid hydrolysis and, if necessary, purifying the compound. The reaction is carried out usually in a solvent in the presence of an acid and water, the reaction temperature is usually 20 to 150 ° C, preferably 70 to 110 ° C, and the reaction time is instantaneous to 4 ° C.
8 hours. The amount of the reagent used in the reaction is based on 1 mol of the compound of the present invention represented by the general formula (2).
The amount of acid is from a catalytic amount to an excess amount, preferably from a catalytic amount to 0.2 mol, and the amount of water is from 1 mol to a large excess amount. Examples of the acid used for the reaction include inorganic acids such as hydrochloric acid and sulfuric acid, and sulfonic acids such as methanesulfonic acid, trifluoromethanesulfonic acid, p-toluenesulfonic acid, and benzenesulfonic acid. After completion of the reaction, the desired compound represented by the formula (6) can be obtained, for example, by the following method. 1) If necessary, concentrate the reaction solution, pour the reaction solution into water, extract this with an organic solvent, dry and concentrate the organic layer, and subject the residue to chromatography. 2) The reaction solution is concentrated as it is, and the residue is subjected to chromatography. That is, the method of Production Method 3-1 gives a result equivalent to that of transesterification, and is particularly suitable as a method for converting the compound of the present invention in which R ¹ is a methyl group or an ethyl group into another ester.

(Production method 3-2) A method of producing a compound represented by the formula (6) by converting it into a reactive derivative such as an acid halide and then reacting the compound with an alcohol compound represented by the formula (7). In the method, for example, after a carboxylic acid compound represented by the formula 6 is reacted with a chlorinating agent to obtain an acid chlorinated product (hereinafter referred to as Step 3-2-1), the reaction is carried out in the presence of a base. The reaction is performed by reacting with an alcohol compound represented by the general formula (7) (hereinafter referred to as step 3-2-2). Step 3-2-1 is performed without a solvent or in a solvent, and the reaction temperature is usually in the range of 0 to 1
The reaction time is usually from instantaneous to 24 hours. The theoretical amount of the reagent used in the reaction is 1 mol of the chlorinating agent per 1 mol of the carboxylic acid compound represented by the formula 6, but depending on the situation of the reaction, 1 mol to excess It can be arbitrarily changed within the range of the amount. Examples of the chlorinating agent include thionyl chloride, sulfuryl chloride, phosgene, oxalyl chloride, phosphorus trichloride, phosphorus pentachloride, phosphorus oxychloride and the like. As the solvent used in the reaction, for example, hexane, heptane, nonane, decane, ligroin, cyclohexane, aliphatic hydrocarbons such as petroleum ether, benzene, toluene, xylene, aromatic hydrocarbons such as mesitylene, methylene chloride, chloroform ,
Aliphatic halogenated hydrocarbons such as carbon tetrachloride, 1,2-dichloroethane and 1,2,3-trichloropropane; aliphatic halogenated hydrocarbons such as monochlorobenzene, dichlorobenzene and benzotrifluoride; diethyl ether; Examples thereof include ethers such as diisopropyl ether, methyl-t-butyl ether, 1,4-dioxane, tetrahydrofuran, and ethylene glycol dimethyl ether, and mixtures thereof. After the completion of the reaction, the reaction solution is usually concentrated under reduced pressure, and the concentrated residue is used as it is in Step 3-2-2.

Step 3-2-2 is carried out in the presence of a base in the absence or presence of a solvent.
100 ° C., and the reaction time is usually from instant to 24 hours. The theoretical amount of the reagent used for the reaction is 1 mole of the base and 1 mole of the alcohol compound of the general formula with respect to 1 mole of the carboxylic acid compound of the chemical formula. 1 for each situation
It can be arbitrarily changed within the range of mol to excess.
As the base, for example, inorganic bases such as lithium hydrogen carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, lithium carbonate, sodium carbonate, potassium carbonate, pyridine, quinoline, 4-dimethylaminopyridine, 2-picoline, 3-
Picoline, 4-picoline, 2,3-lutidine, 2,4-
Lutidine, 2,5-lutidine, 2,6-lutidine, 3,
4-lutidine, 3,5-lutidine, 3-chloropyridine, 2-ethyl-3-methylpyridine, 5-ethyl-2
Nitrogen-containing aromatic compounds such as -methylpyridine, triethylamine, diisopropylethylamine, tri-n-propylamine, tri-n-butylamine, benzyldimethylamine, phenethyldimethylamine, N-methylmorpholine, 1,8-diazabicyclo [5. 4.0] Undec-7-ene, 1,5-diazabicyclo [4.3.
Tertiary amines such as [0] non-5-ene or 1,4-diazabicyclo [2.2.2] octane; As the solvent used for the reaction, for example, hexane,
Aliphatic hydrocarbons such as heptane, nonane, decane, ligroin, cyclohexane and petroleum ether; aromatic hydrocarbons such as benzene, toluene, xylene and mesitylene;
Aliphatic halogenated hydrocarbons such as methylene chloride, chloroform, carbon tetrachloride, 1,2-dichloroethane, 1,2,3-trichloropropane, and aliphatic halogenated hydrocarbons such as monochlorobenzene, dichlorobenzene and benzotrifluoride And ethers such as diethyl ether, diisopropyl ether, methyl-t-butyl ether, 1,4-dioxane, tetrahydrofuran, and ethylene glycol dimethyl ether, and mixtures thereof. After completion of the reaction, the target compound of the present invention can be obtained, for example, by the method shown below. 1) The reaction solution is poured into water, extracted with an organic solvent, and the organic layer is dried and concentrated. 2) Concentrate the reaction solution as it is or, if necessary, filter and concentrate the filtrate. In addition, the compound of the present invention can be purified by an operation such as chromatography. In this method, the compound of the present invention can be similarly produced by using carbonyldiimidazole instead of the chlorinating agent.

The compound of the present invention has an excellent herbicidal effect,
In addition, excellent selectivity between crops and weeds can be exhibited. For example, 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 a field. Polygonum convolvulus (Polygonum convolvulus), Polygonum
gonum lapathiolium), Polygonum
pensylvanicum), haradade (Polygonum persicaria), stag beetle (Rumex crispus), sedge beetle (Rumex
obtusifolius), knotweed (Polygonum cuspidatum), purslaneaceae weed, purslane (Portulaca oleracea), sarcophagidaceae weed, Stellaria media, akazaceae weed, Chenopodium album, Koukia scopari
a) Amaranthus retroflexus, Amaranthus hybridus, Brassica weed Wild radish, Raphanus raphanistrum, Sinapis arvensis, Capsella bursa
-Pastoris) Legume weeds Sesbania exaltata, Cassia obtusifolia, Florida Vega Weed (Des
modium tortuosum), white clover (Trifoliumrepens) Malvaceae weed, Abutilon theophrasti, American deer
(Sida spinosa) Violet Weeds Field Pansies (Viola rafinesqii), Wild Pansies (Viola tricolor) Rubiaceae Weeds (Galium aparine) Convolvulaceae Weeds
omoea hederacea var integriuscula)
(Ipomoea lacunosa), Convolvulus
arvensis) Labiatae Weed, Lamium purpureum, Photohenosa (Lam
ium amplexicaule) Solanaceae weed White Datura (Datura stramonium), Sornumnigrum (Solanumnigrum)
(Veronica hederaefolia) Asteraceae weed, Xanthium strumarium, wild sunflower (Helian
Thus annuus), dog chamomile (Matricaria perforata or
inodora), corn marigold (Chrysanthemum sege)
tum), orangwort (Matricaria matricarioides), ragweed (Ambrosiaartemisiifolia),
sia trifida) and Emugeron canadensi
s), Artemisia princeps, Artemisia princeps, Solidago altissima

[0016] Grass weed, Echinochloa crus-galli,
taria viridis), Achinoekorogosa (Setaria faber
i), crabgrass (Digitaria sanguinalis), crabgrass (Eleu
sine indica), Poa annua, Blackgrass (Alopecurus myosuroides), Oats (Avena)
fatua), sorghum sorghum (Sorghum halepense), barley (Elytrigia repens), and sea breeze (Bromus tect)
orum), Cynodon dactylon, Panax dichotomiflorum, Texas Panicum
cum texanum), shatter cane (Sorghum bicolor) and communisaceae Weedy communis (Commelina communis) and cynoaceae (Equisetum arvense) Cyperus weed (Cyperus iria) and Cyperus (Cyperus)
rotundus), yellow bean sedge (Cyperus esculentus) and some of the compounds of the present invention
(Zea mays), wheat (Triticum aestivum), barley
(Hordeum vulgare), rice (Oryza sativa), sorghum
(Sorghum vulgare), soybean (Glycine max), cotton (Gos
sypium spp.), sugar beet (Beta vulgaris), peanuts (Arachis hypogaea), sunflowers (Helianthus annuu)
s), and does not show any phytotoxicity that could cause problems for major crops such as rapeseed (Brassica napus) and horticultural crops such as flowers and vegetables.

The compound of the present invention can effectively eliminate various weeds which are problematic in non-tillage cultivation of soybean, corn, wheat and the like. 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 efficacy against various weeds which are the following problems in flooding treatment of paddy fields. Grass weeds Raspberry (Echinochloa oryzoides) Scrophulariaceae weed Azena (Lindernia procumbens) Berberidaceae weed Rixala (Rotala indica), Scrophularis (Ammannia)
multiflora) Dipterocarpaceae Weedweed (Elatine triandra) Cyperaceae Weed Cyperus difformis, Firefly (Scirpu
s juncoides), pine stalks (Eleocharis acicularis), Spodoptera cricket (Cyperus serotinus), Krogwai (Eleocha)
ris kuroguwai) Mallow Mallow Weed Konagi (Monochoria vaginalis) Omodaka Weed Urikawa (Sagittaria pygmaea), Omodaka (Sagittar
ia trifolia), Spider-moth (Alisma canaliculatum) Himebushi-family weed Hirume-shiro (Potamogeton distinctus) Apiaceae weed Seri (Oenanthe javanica)

Furthermore, some of the compounds of the present invention do not show any phytotoxicity which would be a problem for transplanted rice. In addition, the compounds of the present invention can control a wide range of weeds that occur in orchards, pastures, lawns, forestry or waterways, canals or other non-crop lands. In addition, the compound of the present invention can be used for water hyacinth (Eichhornia crass
It has herbicidal effect on aquatic weeds such as ipes). The compound of the present invention has the same properties as the herbicidal compound described in International Patent Application Publication No. WO95 / 34659, and is introduced by introducing the herbicide resistance gene and the like described in the specification. In the case of cultivating a crop to which tolerance has been imparted, the compound of the present invention can be used in a larger dose than that used when cultivating a normal crop to which tolerance has not been imparted. Can be weeded.

When the compound of the present invention is used as an active ingredient of a herbicide, it is usually mixed with a solid carrier, a liquid carrier, a surfactant and other auxiliaries for preparation to prepare an emulsion, a wettable powder, a suspension,
Formulated in granules, concentrated emulsions, wettable powders 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 70%.
contains. As a solid carrier, kaolin clay, attapulgite clay, bentonite, acid clay, pyrophyllite, talc, diatomaceous earth, mineral powder such as calcite,
Organic substance fine powders such as walnut shell powder, water-soluble organic substance fine powders such as urea, inorganic salt fine powders such as ammonium sulfate, and fine powders of synthetic hydrous silicon oxide, and the like.
Aromatic hydrocarbons such as alkylbenzenes such as methylnaphthalene, phenylxylylethane and xylene; alcohols such as isopropanol, ethylene glycol and 2-ethoxyethanol; esters such as dialkyl phthalate; acetone, cyclohexanone and isophorone Ketones, mineral oils such as machine oil, vegetable oils such as soybean oil, 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,
Anionic surfactants such as dialkyl sulfosuccinate, polyoxyethylene alkyl aryl ether phosphate ester salt, polyoxyethylene alkyl ether, polyoxyethylene alkyl aryl ether, polyoxyethylene polyoxypropylene block copolymer, sorbitan fatty acid ester, poly Nonionic surfactants such as oxyethylene sorbitan fatty acid esters and the like can be mentioned. Other auxiliaries for formulation include lignin sulfonate, alginate, polyvinyl alcohol, gum arabic, CMC (carboxymethylcellulose), 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. For soil treatment,
There are soil surface treatment, soil mixing treatment, etc.
In addition to the treatment from the top of the plant, there is a local treatment for treating only the weeds so as not to adhere to the crop. When the compound of the present invention is used as an active ingredient of a herbicide, the treatment amount is as follows:
Weather conditions, formulation, treatment time, treatment method, soil conditions,
Although it depends on the target crop, the target weed, etc., it is usually 0.01 g to 10000 g, preferably 1 g / ha.
g to 8000 g, and the emulsions, wettable powders, suspensions, concentrated emulsions, wettable powders and the like usually have 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 necessary, in addition to the above-mentioned surfactant, polyoxyethylene resin acid (ester), lignin sulfonate, abietic acid salt, dinaphthylmethane disulfonate, crop oil concentrate (Crop oil concentrate)
And vegetable oils such as soybean oil, corn oil, cottonseed oil and sunflower oil. The compound of the present invention can be used, for example, in a corn field, a wheat field, a barley field, a rice field, a sorghum field, a soybean field, a cotton field, a sugar beet field, a peanut field, a sunflower field, a rape field, or a paddy field. Further, the compound of the present invention can be used as an active ingredient of a harvesting aid such as a cotton defoliant / desiccant and a potato (Solanum tuberosum) 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.

[0020]

EXAMPLES The present invention will be described in more detail with reference to Production Examples, Formulation Examples and Test Examples, but the present invention is not limited to these Examples. First, Production Examples of the compound of the present invention will be shown. Production Example 1 17.0 g of the compound represented by Formula 3, 8.0 g of (S) -methyl lactate (manufactured by Merck), and 20.0 g of triphenylphosphine were dissolved in 50 ml of tetrahydrofuran, and the mixture was stirred with ice cooling. A solution in which 13.0 g of diethyl azodicarboxylate was dissolved in 15 ml of tetrahydrofuran was gradually added dropwise over 30 minutes (at this time, the temperature of the reaction solution was 8 to 15 ° C.). Then, after stirring at room temperature for 30 minutes, the reaction solution was poured into water, and this was extracted with ethyl acetate. The organic layer was washed with saturated saline, dried over magnesium sulfate, and concentrated. The residue is subjected to silica gel column chromatography (developing solvent: hexane / ethyl acetate = 3).
/ 1) and (2R) -2- [2-chloro-4-fluoro-5- {3-methyl-2,6-dioxo-4- (trifluoromethyl) -1,2,3,6 18.48 g of methyl [tetrahydropyrimidin-1-yl} phenoxy] propionate (hereinafter, referred to as the present compound 1) was obtained. ¹ H-NMR (CDCl ₃ , 300 Mz): δ (ppm)
7.31 (1H, d, J = 9.0 Hz), 6.82 (1
/ 2H, d, J = 6.42 Hz), 6.81 (1/2
H, d, J = 6.45 Hz), 6.35 (1H, s),
4.68 (1H, q, J = 6.9 Hz), 3.74 (3
H, s), 3.55 (3H, s, br), 1.66 (3
H, d, J = 6.9 Hz) [α] _D ²⁰ : + 25.8 ° (c 1.0, CH ₃ OH) R: S = 97.3: 2.7 (L using an optically active column)
C method)

Production Example 2 (2R) -2- [2-chloro-4-fluoro-5- {3
-Methyl-2,6-dioxo-4- (trifluoromethyl) -1,2,3,6-tetrahydropyrimidine-1-
Il @ phenoxy] propionic acid (described below, Reference Production Example 6)
Manufactured according to the method described in ) 10.0 g was dissolved in 150 ml of ethanol, 1.0 ml of sulfuric acid was added, and the mixture was heated under reflux for 3 hours. Thereafter, the reaction solution was partially concentrated, the concentrated solution was poured into water, and extracted with ethyl acetate. The organic layer was washed with brine, dried over anhydrous magnesium sulfate, and concentrated. The residue was subjected to silica gel column chromatography (developing solvent: hexane / ethyl acetate = 3/1), (2
R) -2- [2-Chloro-4-fluoro-5- {3-methyl-2,6-dioxo-4- (trifluoromethyl)
7.8 g of ethyl-1,2,3,6-tetrahydropyrimidin-1-yl {phenoxy] propionate (the present compound 2) was obtained. ¹ H-NMR (CDCl ₃ , 300 MHz): δ (pp
m) 7.31 (1H, d, J = 9.0 Hz), 6.83
(1 / 2H, d, J = 6.4 Hz), 6.81 (1/2
H, d, J = 6.4 Hz), 6.34 (1 / 2H,
s), 6.33 (1 / 2H, s), 4.67 (1H,
q, J = 7.0 Hz), 4.25 to 4.15 (2H,
m), 3.54 (3H, q, J = 1.3 Hz), 1.6
6 (3H, d, J = 7.0 Hz), 1.23 (1/2 ×
3H, t, J = 7.2 Hz), 1.22 (1/2 × 3
H, t, J = 7.1 Hz) R-form 99% or more (by LC method using an optically active column)

Production Example 3 (2R) -2- [2-chloro-4-fluoro-5- {3
-Methyl-2,6-dioxo-4- (trifluoromethyl) -1,2,3,6-tetrahydropyrimidine-1-
Il @ phenoxy] propionic acid (described below, Reference Production Example 6)
Manufactured according to the method described in 1.51 g) was dissolved in tetrahydrofuran (10 ml), and thionyl chloride (1.
After adding 5 ml, the mixture was heated and stirred under reflux conditions for 1 hour.
Thereafter, the mixture was allowed to cool, concentrated, dissolved in 6 ml of tetrahydrofuran, added with 1 ml of pyridine, and then added with 0.5 ml of allyl alcohol. After stirring at room temperature for 1 hour, ice water was poured into the reaction solution, ethyl acetate and saturated saline were added, and the mixture was separated. The organic layer was washed with saturated saline and dried over magnesium sulfate. And concentrated. The residue was subjected to silica gel column chromatography (developing solvent: hexane / ethyl acetate = 3/1) to give (2R) -2- [2-chloro-4-fluoro-5- {3-methyl-2,6-dioxo 1.02 g of allyl-4- (trifluoromethyl) -1,2,3,6-tetrahydropyrimidin-1-yl {phenoxy] propionate (Compound 3 of the present invention) was obtained. ¹ H-NMR (CDCl ₃ , 300 MHz): δ (pp
m) 7.31 (1H, d, J = 8.9 Hz), 6.84
(1 / 2H, d, J = 6.50 Hz), 6.82 (1 /
2H, d, J = 6.41 Hz), 6.34 (1H,
s), 5.91 to 5.80 (1H, m), 5.29 (1
H, ddd, J = 1.1 Hz, 1.1 Hz, 17.1 H
z), 5.22 (1H, dd, J = 1.1 Hz, 10.2).
7 Hz), 4.71 (1H, q, J = 7.1 Hz),
4.64 (2H, dd, J = 1.1 Hz, 5.6H
z), 3.55 (3H, t, J = 1.45 Hz), 1.6
8 (3H, d, J = 7.1 Hz) [α] _D ¹⁹ : + 24.7 ° (c 1.0, CH ₃ OH)

Production Example 4 (2R) -2- [2-chloro-4-fluoro-5- {3
-Methyl-2,6-dioxo-4- (trifluoromethyl) -1,2,3,6-tetrahydropyrimidine-1-
Il @ phenoxy] propionic acid (described below, Reference Production Example 6)
Manufactured according to the method described in 30.0 g) was dissolved in 360 g of N, N-dimethylformamide.
6.7 g was added, and the mixture was stirred at room temperature for 1 hour and 40 minutes. 18.96 g of isobutyl S-2-chloropropionate there
Was gradually added dropwise over 1 hour and 40 minutes, and after completion of the addition, the mixture was stirred at room temperature for 8 hours and 45 minutes. Thereafter, the reaction solution was poured into ice water and extracted with ethyl acetate. The organic layer was washed with saturated saline 2
It was washed twice, dried over magnesium sulfate and concentrated. The residue was subjected to silica gel column chromatography (developing solvent;
Hexane / ethyl acetate) to give (2R) -2- [2-
Chloro-4-fluoro-5- {3-methyl-2,6-dioxo-4- (trifluoromethyl) -1,2,3,6
-Tetrahydropyrimidin-1-yl {phenoxy] isobutyl propionate (Compound 4 of the present invention)
I got ¹ H-NMR (CDCl ₃ , 300 MHz): δ (pp
m) 7.31 (1H, d, J = 8.7 Hz), 6.81
(1 / 2H, d, J = 6.4 Hz), 6.80 (1/2
H, d, J = 6.3 Hz), 4.70 (1H, q, J =
6.6 Hz), 3.97 to 3.86 (2H, m),
54 (3H, q, J = 1.3 Hz), 1.97 to 1.8
2 (1H, m), 1.70 (3H, d, J = 6.6 Hz
HHH), 0.861 (3H, d, J = 6.5 Hz),
0.858 (3H, d, J = 6.5 Hz) [α] _D ²⁹ : + 24.5 ° (c 1.0, CH ₃ OH)

Production Example 5 41.5 g of the compound represented by Formula 3 and 13.5 methyl (S) -methyl lactate (Lot 42111033 manufactured by Merck & Co.)
g and 35.4 g of triphenylphosphine were dissolved in 350 ml of tetrahydrofuran, and 67.8 g of a 40% toluene solution of 13.0 g of diisopropyl azodicarboxylate was gradually added dropwise over 15 minutes under ice cooling. Thereafter, the mixture was stirred at room temperature for 2 hours and 45 minutes. Thereafter, the reaction solution was poured into water, and this was extracted with ethyl acetate. The organic layer was washed with saturated saline, dried over magnesium sulfate, and concentrated. The residue was subjected to silica gel column chromatography (eluent: hexane / ethyl acetate = 3/1) to give (2
R) -2- [2-Chloro-4-fluoro-5- {3-methyl-2,6-dioxo-4- (trifluoromethyl)
40.8 g of methyl-1,2,3,6-tetrahydropyrimidin-1-yldiphenoxy] propionate (hereinafter, referred to as the present compound 5) was obtained. R-form 99% or more (by LC method using optically active column)

Production Example 6 5.0 g of the present compound 5 was dissolved in tetrahydrofuran to prepare a 100 ml solution (hereinafter referred to as solution A). On the other hand, compound X produced according to Reference Production Example 5 described below
5.0 g was dissolved in tetrahydrofuran to prepare a 100 ml solution (hereinafter referred to as solution B). By mixing 9.0 ml of the solution A and 1.0 ml of the solution B and then concentrating, the R-form ratio is 90% (2R) -2-.
[2-chloro-4-fluoro-5- {3-methyl-2,
6-dioxo-4- (trifluoromethyl) -1,2,2
Methyl 3,6-tetrahydropyrimidin-1-yl {phenoxy] propionate (hereinafter referred to as the present compound 6) was obtained. 8.0 ml of solution A and 2.0 m of solution B
and then concentrated to obtain an R-isomer ratio of 80%.
(2R) -2- [2-chloro-4-fluoro-5
Methyl-{3-methyl-2,6-dioxo-4- (trifluoromethyl) -1,2,3,6-tetrahydropyrimidin-1-yl} phenoxy] propionate (hereinafter referred to as methyl
This is referred to as Compound 7 of the present invention. ) Got.

Next, as a reference production example, a production example of a compound used for comparison with a test example of the compound of the present invention will be described. Reference Production Example 1 8.5 g of the compound represented by Formula 3, 3.12 g of (R) -methyl lactate (manufactured by Tokyo Chemical Industry Co., Ltd.), and 7.9 g of triphenylphosphine were dissolved in 25 ml of tetrahydrofuran, and stirred while cooling with ice. A solution prepared by dissolving 5.2 g of diethyl azodicarboxylate in 5 ml of tetrahydrofuran was gradually added dropwise over 15 minutes (at this time, the temperature of the reaction solution was 8 to 20 ° C.). Then, after stirring at room temperature for 30 minutes, the reaction solution was poured into water, and this was extracted with ethyl acetate. The organic layer was dried over magnesium sulfate and concentrated. The residue was subjected to silica gel column chromatography (developing solvent: hexane / ethyl acetate = 3/1) to give (2S) -2- [2-chloro-4-fluoro-5-
{3-methyl-2,6-dioxo-4- (trifluoromethyl) -1,2,3,6-tetrahydropyrimidine-
9.91 g of methyl 1-yl {phenoxy] propionate (hereinafter referred to as comparative compound 1) was obtained. ¹ H-NMR (CDCl ₃ , 300 Mz): δ (ppm)
7.31 (1H, d, J = 9.0 Hz), 6.82 (1
/ 2H, d, J = 6.42 Hz), 6.81 (1/2
H, d, J = 6.45 Hz), 6.35 (1H, s),
4.68 (1H, q, J = 6.9 Hz), 3.74 (3
H, s), 3.55 (3H, s, br), 1.66 (3
H, d, J = 6.9 Hz) [α] _D ²⁰ : −23.5 ° (c 1.0, CH ₃ OH) R: S = 2.9: 97.1 (L using an optically active column)
C method)

Reference Production Example 2 20 g of the compound represented by the formula 3 was dissolved in 200 ml of N, N-dimethylformamide, and potassium carbonate 10.0 g was dissolved.
g and 12.1 ml of ethyl 2-bromopropionate were added, and the mixture was stirred at room temperature for 40 minutes. Thereafter, the reaction solution was poured into water and extracted with ethyl acetate. The organic layer was washed with saturated saline, dried over anhydrous magnesium sulfate, and concentrated. The residue was subjected to silica gel column chromatography (developing solvent:
Hexane / ethyl acetate = 3/1) to give 2- [2-
Chloro-4-fluoro-5- {3-methyl-2,6-dioxo-4- (trifluoromethyl) -1,2,3,6
-Ethyl tetrahydropyrimidin-1-yl {phenoxy] propionate (hereinafter referred to as comparative compound 2) 23.
46 g were obtained.

Reference Production Example 3 2- [2-chloro-4-fluoro-5- {3-methyl-
2,6-dioxo-4- (trifluoromethyl) -1,
1.32 g of 2,3,6-tetrahydropyrimidin-1-yl {phenoxy] propionic acid was dissolved in 15 ml of tetrahydrofuran, 1.0 ml of thionyl chloride was added, and the mixture was heated under reflux for 1 hour and 10 minutes. Thereafter, the reaction solution was concentrated, and the obtained residue was added with 15 ml of tetrahydrofuran. 1 ml of allyl alcohol and 1 ml of pyridine were added thereto, and the mixture was stirred at room temperature for 4 hours. Thereafter, the reaction solution was poured into water and extracted with ethyl acetate. The organic layer was washed with brine, dried over anhydrous magnesium sulfate, and concentrated. 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-
1.02 g of allyl (trifluoromethyl) -1,2,3,6-tetrahydropyrimidin-1-yl {phenoxy] propionate (hereinafter referred to as comparative compound 3) was obtained.

Reference Production Example 4 5.0 ml of solution A and 5.0 ml of solution B described in Production Example 5 were mixed and concentrated to give 2- [2-chloroform having an R-form ratio of 50%. -4-fluoro-5-
{3-methyl-2,6-dioxo-4- (trifluoromethyl) -1,2,3,6-tetrahydropyrimidine-
Thus, methyl 1-yl {phenoxy] propionate (hereinafter referred to as comparative compound 4) was obtained.

Reference Production Example 5 1.13 g of the compound represented by Formula 3, 0.4 ml of (R) -methyl lactate (manufactured by Tokyo Chemical Industry Co., Ltd.), and 1.0 g of triphenylphosphine were dissolved in 7.5 ml of tetrahydrofuran. Under ice cooling, 1.9 g of a 40% toluene solution of diisopropyl azodicarboxylate was gradually added dropwise over 15 minutes. After completion of the dropwise addition, the mixture was stirred at room temperature for 1 hour and 30 minutes.
Thereafter, the reaction solution was poured into water and extracted with ethyl acetate.
The organic layer was dried over magnesium sulfate and concentrated. The residue was subjected to silica gel column chromatography (eluent: hexane / ethyl acetate = 3/1) to give (2
S) -2- [2-Chloro-4-fluoro-5- {3-methyl-2,6-dioxo-4- (trifluoromethyl)
0.91 g of methyl-1,2,3,6-tetrahydropyrimidin-1-yl {phenoxy] propionate (hereinafter referred to as compound X) was obtained. S-form 99% or more (by LC method using optically active column)

A production example of the compound represented by the formula 6 which is a raw material compound for producing the compound of the present invention is described in Reference Production Example 6
Shown in

Reference Production Example 6 (2R) -2- [2-chloro-4-fluoro-5- {3
-Methyl-2,6-dioxo-4- (trifluoromethyl) -1,2,3,6-tetrahydropyrimidine-1-
Dissolve 3.01 g of methyl [Il [phenoxy] propionate (Compound 1 of the present invention) in 30 ml of 1,4-dioxane, add a mixed solution of 5 ml of concentrated hydrochloric acid and 5 ml of water with stirring, and then reflux for 2 hours and 30 hours. The mixture was heated and stirred for minutes. After cooling, ice water was added to the reaction solution, ethyl acetate and saturated saline were added, and the mixture was separated. The organic layer was washed with saturated saline.
After drying over magnesium sulfate, the mixture was concentrated. The residue was subjected to silica gel column chromatography (developing solvent: hexane / ethyl acetate) to give (2R) -2- [2-chloro-
4-fluoro-5- {3-methyl-2,6-dioxo-
2.42 g of 4- (trifluoromethyl) -1,2,3,6-tetrahydropyrimidin-1-yl {phenoxy] propionic acid were obtained.

Next, preparation examples of the compound of the present invention will be shown. Formulation Example 1 50 parts of Compounds 1 to 7 of the present invention, 3 parts of calcium ligninsulfonate, 2 parts of sodium lauryl sulfate and 45 parts of synthetic hydrous silicon oxide are thoroughly pulverized and mixed to obtain each wettable powder. Formulation Example 2 10 parts of Compounds 1 to 7 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 emulsion is prepared. Get. Formulation Example 3 2 parts of Compounds 1 to 7 of the present invention, 2 parts of synthetic hydrous silicon oxide, 2 parts of calcium ligninsulfonate, 30 parts of bentonite and 64 parts of Karion Klei are well pulverized and mixed, and water is added and kneaded well. After granulation and drying, each granule is obtained. Formulation Example 4 25 parts of Compounds 1 to 7 of the present invention, 50 parts of a 10% aqueous solution of polyvinyl alcohol and 25 parts of water are mixed and wet-pulverized until the average particle size becomes 5 μm or less. To obtain a suspension.

Next, Test Examples show that the compounds of the present invention are useful as active ingredients of herbicides. The evaluation of the herbicidal efficacy was made such that the growth state of the test plant (weed) at the time of the survey was completely or almost no difference compared to that of the untreated plant, and the test plant was completely withered or , Those whose growth is completely suppressed are defined as “5”, and “0” to
It is divided into 6 stages of "5", "0", "1", "2",
Indicated by “3”, “4” or “5”.

Test Example 1: Field foliage treatment test Field soil was filled in a plastic pot having an area (26.5 × 19) cm ² and a depth of 7 cm, and a fir tree was sown and grown in a greenhouse for 21 days. A test compound was used as an emulsion according to Formulation Example 2, and a predetermined amount thereof was diluted with water containing 1% of agridex equivalent to 1000 liters per hectare,
It was evenly sprayed over the whole foliage from above the plant with a sprayer.
The plants were grown in a greenhouse for 21 days after the treatment, and the herbicidal efficacy was evaluated.
Table 1 shows the results.

[Table 1]

Test Example 2: Upland soil surface treatment test Upland soil was filled in a plastic pot having an area (26.5 × 19) cm ² and a depth of 7 cm, and sorghum sorghum was sown. After seeding and before germination, the test compound was used as an emulsion in accordance with Formulation Example 2, and a predetermined amount thereof was diluted with water equivalent to 1000 liters per hectare, and uniformly sprayed on the entire surface of the soil with a sprayer. After the treatment, the plants were grown in a greenhouse for 25 days, and the herbicidal efficacy was evaluated. Table 2 shows the results.

[Table 2]

Test Example 3 Upland Soil Mixing Treatment Soil was packed in a cylindrical plastic pot having a diameter of 10 cm and a depth of 10 cm. A 3 cm soil was once taken out from the surface of the soil, and the test compound was made into an emulsion according to Formulation Example 2, and a predetermined amount thereof was uniformly mixed with a solution diluted with 606 liters of water per hectare. After returning this soil to the plastic pot, sorghum sorghum was sown at a seeding depth of 1.5 cm, and after the treatment, grown 19 days indoors to evaluate herbicidal efficacy. Table 3 shows the results.

[Table 3]

Test Example 4: Upland soil surface treatment test Upland soil was filled in a plastic pot having an area (26.5 × 19) cm ² and a depth of 7 cm, and sorghum sorghum was sown. After seeding and before germination, the test compound was used as an emulsion in accordance with Formulation Example 2, and a predetermined amount thereof was diluted with water equivalent to 1000 liters per hectare, and uniformly sprayed on the entire surface of the soil with a sprayer. After the treatment, the plants were grown in a greenhouse for 25 days, and the herbicidal efficacy was evaluated. Table 4 shows the results.

[Table 4]

Test Example 5: Field Soil Mixing Treatment The soil was packed in a cylindrical plastic pot having a diameter of 10 cm and a depth of 10 cm. A 3 cm soil was once taken out from the surface of the soil, and the test compound was made into an emulsion according to Formulation Example 2, and a predetermined amount thereof was uniformly mixed with a solution diluted with 606 liters of water per hectare. After returning this soil to the plastic pot, sorghum sorghum was sown at a seeding depth of 1.5 cm, and after the treatment, grown 19 days indoors to evaluate herbicidal efficacy. Table 5 shows the results.

[Table 5]

Test Example 6: Field Soil Surface Treatment Test The field soil was filled in a plastic pot having an area (26.5 × 19) cm ² and a depth of 7 cm, and sorghum sorghum was sown. After seeding and before germination, the test compound was used as an emulsion in accordance with Formulation Example 2, and a predetermined amount thereof was diluted with water equivalent to 1000 liters per hectare, and uniformly sprayed on the entire surface of the soil with a sprayer. After the treatment, the plants were grown in a greenhouse for 25 days, and the herbicidal efficacy was evaluated. Table 6 shows the results.

[Table 6]

[0041]

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

Claims (4)

[Claims] 1. A compound represented by the general formula: [Wherein, R ¹ is a C1-C8 alkyl group or C3-C8
* Represents an alkenyl group, and * represents an asymmetric carbon atom. And a uracil compound in which the absolute configuration at the 2-position (the carbon atom marked with *) of the propionic acid site is the R configuration. 2. A uracil compound represented by the general formula 1 and having a specific rotation of + (dextrorotary). 3. A uracil compound represented by the general formula 1 and having 80% or more of optical isomers in which the absolute configuration at the 2-position (the carbon atom marked with *) of the propionic acid moiety is the R configuration. 4. A herbicide containing the uracil compound according to claim 1, 2 or 3.