JPH03227976A - Imidazolidine-2-one derivative - Google Patents

Abstract

NEW MATERIAL:A compound of the formula (R is alkyl, haloalkyl, alkenyl, cycloalkyl, substitutable benzyl, alpha-alkyl benzyl). EXAMPLE:3-Methylimidazolidine-2,5-dione-1-carboxy-ethylamide. USE:A herbicide. The compound of the formula exhibits a strong horlvicidal activity against weeds such as Eclipta, Amaranthus, Aeschynomene, Panicum crusgalli or Alopeurus. PREPARATION:Methyl hydantoin is reacted with an isocyanate of formula: RNCD in the presence of a basic catalyst (e.g. triethyl amine) in a solvent such as dichloroethane at 0-50 deg.C to prepare an imidazolidine-2,5dione derivative. The derivative is reduced with sodium borohydrate to provide the compound of the formula.

Description

DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application The present invention relates to a novel imidazolidin-2-one derivative, a method for producing the same, and a herbicide containing the derivative as an active ingredient.

BACKGROUND OF THE INVENTION Some imidazolidin-2-one derivatives and their herbicidal activity are known. For example, U.S. Patent No. 4,
No. 578,107 discloses imidazolidin-2-one derivatives represented by the general formula and herbicidal activity of the derivatives. However, in the derivatives disclosed in the above specification, the carbamoyl group at position 1 of the imidazolidine ring, that is, the R2 group, is -CONHAr, and the amine moiety of the carbamoyl group is limited to aromatic amines, such as alkyl amines, cyclo alkylamines,
Benzylamine and the like are not described at all. Furthermore, although these derivatives exhibit strong herbicidal activity, they are not necessarily fully satisfactory in selectivity and herbicidal power.

DISCLOSURE OF THE INVENTION The compound of the present invention is a novel compound that has not been described in any literature, and is represented by the following formula (I).

[In the formula, R is an alkyl group, haloalkyl group, alkenyl group, cycloalkyl group, benzyl group, alkyl group, Place Represents a substituted benzyl group or an α-alkylbenzyl group. ]

In this specification, the alkyl group represents a straight chain or branched alkyl group, such as a methyl group, an ethyl group, an n-
Examples include propyl group, isopropyl group, n-butyl group, isobutyl group, 5ee-butyl group, n-pentyl group, isopentyl group, n-hexyl group, n-octyl group, and the like. As the haloalkyl group, monochloroethyl group,
Examples include monobromoethyl group, dichloroethyl group, monochloropropyl group, monochlorobutyl group, monobromopropyl group, and monobromobutyl group. Examples of the cycloalkyl group include a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, and a methylcyclohexyl group.

Examples of the substituted benzyl group include 2-chlorobenzyl group, 4-
Chlorobenzyl group, 2,4-dichlorobenzyl group, 3,
4-dichlorobenzyl group, 2-bromobenzyl group, 2-
Examples include methylbenzyl group, 4-methylbenzyl group, 2-methoxybenzyl group, 4-methoxybenzyl group, and 4-nitrobenzyl group. Examples of the α-alkylbenzyl group include α-methylbenzyl group, α,α-dimethylbenzyl group, and α-ethylbenzyl group.

The compound of the present invention represented by the above-mentioned -Kakuju CI) can be produced by various methods, but one preferred example thereof is produced according to the following reaction formula.

Reaction formula () [[) Reaction formula [■] (IV) Reaction formula-3 0 [In the formula, R is the same as above] The reaction shown in the above reaction formula-1 is carried out without a solvent or in a solvent. The solvent to be used may be any solvent that does not adversely affect the reaction, such as aromatic solvents such as toluene, xylene, and chlorobenzene, ethers such as ethyl ether, isopropyl ether, and dioxane, dichloromethane, and dichloroethane. , chloroform, carbon tetrachloride, and other halogenated hydrocarbons. Although this reaction can be carried out without a catalyst, it is preferable to use a basic catalyst in order to obtain the target product in good yield. Basic catalysts used include tertiary amines such as triethylamine, tributylamine, dimethylaniline, hexamethylenetetramine, etc.
Preferably triethylamine is used. The basic catalyst is used in an amount of 0.001 to 1.0 times the amount of methylhydantoin represented by the formula [■], preferably 0.05 to 0.5 times the amount by mole. be done.

The ratio of the hydantoin of formula (II) to the isocyanate represented by formula [III'l is usually about 3 times the molar equivalent of the former, preferably about 3 times the molar amount of the latter.
It is used in an amount of about 1.5 times the mole.

If the reaction temperature is too high, side reactions will occur, and if it is too low, the yield will decrease, so the reaction temperature is carried out in the range of 0 to 50°C. The reaction time is about 10 to 20 hours.

The reaction represented by Reaction Formula-2 is carried out in a solvent. Examples of the solvent used include halogenated hydrocarbons such as dichloromethane, dichloroethane, and chloroform. In this reaction, methylhydantoin represented by formula [II] and trichloromethylchloroforme-1-(TCP) are reacted in the presence of a dehydrochlorination agent, and -killing (IV) is performed without further isolation. This is carried out by reacting the amines represented by in the presence of a dehydrochlorination agent. Examples of the dehydrochlorination agent used here include tertiary amines such as triethylamine, tributylamine, and dimethylaniline, and pyridines such as pyridine and picoline. The dehydrochlorination agent is preferably used in an amount corresponding to the amount of hydrogen chloride generated by the reaction.

The ratio of formula []II and trichloromethyl chloroformate used is usually about 0.25 to 0.75 moles. The ratio of the amines represented by formula [■] and general formula [v] to be used is about 0.5 to 3.0 times the former by mole, preferably about equimolar to 2.0 times the latter by mole. It is. The reaction temperature is generally 0 to 50°C, and the reaction temperature is 10 to 2
Completed in about 0 hours.

The reduction reaction shown by Reaction Formula-3 is carried out using sodium borohydride. The proportion of sodium borohydride used is -imidazolidine indicated by [IV]
The amount is 0.001 to 2.0 times the amount of the 2,5-dione derivative, preferably about 30.05 to equimole times. This reaction is carried out in a solvent, and the solvents used include water, alcohols such as methyl alcohol, ethyl alcohol, and isopropyl alcohol, or alcohols and halogenated hydrocarbons such as dichloromethane, chloroform, and dichloroethane. A mixed solvent with The reaction temperature is -10~5
At 0°C, the reaction is completed in about 0.5 to 3 hours.

The compounds obtained by the various methods described above are purified by conventional means such as recrystallization, solvent extraction, column chromatography, etc.

The present invention also relates to a herbicide containing the imidazolidin-2-one derivative represented by the above-mentioned -killing [■] as an active ingredient.

The compounds of the present invention include Takasaburou, Aobiyu, Kusanemu, Sparrow gnome, Polygonum, Mugwort, A.
4) It has a strong herbicidal effect on weeds, so the growth of those weeds is harmful to the production and landscape of agricultural crops such as tangerines, apples, soybeans, corn, mulberries, tea, and paddy rice. It is effective in controlling weeds.

When applying the compound of the present invention as a herbicide, the compound of the present invention may be used as it is, but it is generally mixed with an adjuvant commonly used in the formulation of agricultural chemicals and used in any dosage form. be able to.

Among these, emulsion, wettable powder, and granule forms are preferably used. At this time, examples of auxiliary agents to improve stability and effectiveness include fillers such as diatomaceous earth, kaolin, clay, bentonite, white carbon, and talc, polyoxyethylene alkyl ether, and polyoxyethylene alkyl ether. Phenyl ether, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene fatty acid ester, sodium alkylbenzene sulfonate,
Nonionic or anionic surfactants such as sodium lignin sulfonate, sodium alkyl sulfate, sodium polyoxyethylene alkyl sulfate, quidylol, acetone, methanol, ethanol, isopropanol, dioxane, dimethylformamide, dimethyl sulfonate. Organic solvents such as Kizide and carbon tetrachloride are used.

The herbicide composition of the present invention is formulated so that the active ingredient is about 1
It is formulated by adding adjuvants to 90% by weight, preferably about 5 to 70% by weight. The appropriate amount to be applied depends on the formulation form of the drug, the application method, the application time, the type of target weed, and the weather conditions that tend to affect the herbicidal effect.
They differ depending on soil conditions, etc., and are appropriately selected from a wide range, but - For boat fishing, the amount of active ingredients is about 0.1 to 100 g/a, preferably 1 to 80 g.
Approximately /a is sprayed.

Examples The following examples, formulation examples, and test examples are given to explain the misfire 6 in more detail. Note that the test compound numbers in the test examples correspond to the numbers in the examples.

Example 1 Preparation of 3-methylimidazolidine-2,5-dione 1-carboxyethylamide 4.6 ml of methylhydantoin was added to a 300-meter 4 flask.
g (0.04 mol), dichloroethane 50Inf11
Triethylamine 0. 2.8 g (0.04 mol) of ethyl isocyanate J dissolved in 3 mfl dichloroethane was added dropwise over 5 minutes under stirring at room temperature.
After the dropwise addition was completed, the mixture was stirred at room temperature for 15 hours. The reaction mixture was washed with water and saturated brine, dried over anhydrous magnesium sulfate,
Concentrate under reduced pressure.

The resulting residue was recrystallized from ether to obtain 4.5 g (yield: 61%) of the above-mentioned target compound as white crystals.

Melting point: 101.9°C NMR: δ(CDCρ3) 7 1, 14 (3H), 2. 93 (3H)
, 3, 25 (2H) , 3.85 (2H
), 7, 72 (IH) Example 2 Production of 3-methylimidazolidine-2,5-dione 1-carboxy-(○-chlorobenzylamide) 5.7 ml of methylhydantoin was added to a 300-volume 4-head flask.
(0.05 mol), 4.0 g (0.05 mol) of pyridine, 49 mQ of dichloroethane, and 1 portion of ethyl acetate were added to the trichloromethyl chloroformate while stirring in a water bath.
1-3.1 mfl (0,025 mol) was added dropwise. 1
After stirring at room temperature for 5 hours, it was cooled again and 7.1 g (0.05 mol) of O-chlorobenzylamine and 4.0 g of pyridine were added.
(0.05 mol) was added and stirred at room temperature for 7 hours. .

The reaction mixture was washed with water and saturated brine, dried over magnesium sulfate, and concentrated under reduced pressure. The resulting residue was recrystallized from methanol to obtain the desired compound as white crystals (6.8 g, yield 48.5%).

Melting point: 95.2°C NMR: δ (CDCβ3) 2.90 (3H), 3.80 (2H), 4.45
(2H), 6.957.40 (4H), 8.33
(IH) Example 3 In the same manner as in Example 1 or 2, a compound of general formula (IV) in which R is a 2-chloroethyl group was obtained.

Melting point: 118.9°C Example 4 In the same manner as in Example 1 or 2, a compound of general formula (TV) in which R is an isopropyl group was obtained.

Melting point: 107.6°C Example 5 In the same manner as in Example 1 or 2, a compound of general formula (TV) in which R is an n-butyl group was obtained.

9 Melting point: 81.4°C Example 6 In the same manner as in Example 1 or 2, a compound of general formula [IV) in which R is an isobutyl group was obtained.

Melting point: 120.9°C Example 7 In the same manner as in Example 1 or 2, a compound of the general formula [IVI] in which R is a 5ec-butyl group was obtained.

Melting point: 85.8°C Example 8 In the same manner as in Example 1 or 2, a compound of general formula [IV) in which R is an n-pentyl group was obtained.

Melting point: 97.3°C Example 9 A compound of the general formula (IVI) in which R is a cyclohexyl group was obtained in the same manner as in Example 1 or 2.

Melting point: 115.5°C Example 10 0 In the same manner as in Example 1 or 2, a compound of general formula (IV) in which R is a (2-methyl)cyclohexyl group was obtained.

Properties Example 11 of Oily Product In the same manner as in Example 1 or 2, a compound of the general formula [■] in which R is a benzyl group was obtained.

Melting point: 88.3°C Example 12 In the same manner as in Example 1 or 2, a compound of general formula (IV) in which R is a (1-phenyl)ethyl group was obtained.

Properties: Oil Example 13 Preparation of 3-methyl-5-hydroxy imidazolidine-2-one-1-carboxy ethylamide 3-methylimidazolidine-2,5-dione 1 1-carboxy ethylamide 3.7 g (0,02 mol) was suspended in a mixed solvent of 45 ml of chloroform and 5-mole of methanol. After cooling to 10° C., 0.4 g (0.01 mol) of sodium borohydride was added under stirring, and the mixture was returned to room temperature and stirred for 30 minutes. The reaction mixture was washed with water and saturated brine, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure.

The obtained residue was recrystallized from methanol/ether to obtain 2.6 g of white crystals (yield: 69.4%).

Melting point: 116.9℃ Elemental analysis value (as C7H1aN303) HN Calculated value (%) 44.91 7.00 22.4
5 Actual value (%) 44.87 7.03 22.
47NMR: δ(CDCβ3) 1.12 (3H), 2.80 (3H), 3.17
(IH), 3.20 (2H), 3.50 (IH)
, 5.05 (LH), 2 5, 75 (IH), 7. 93 (IH) Example 14 Preparation of 3-methyl-5-hydroxy imidazolidin-2-one-1-carboxy-(0-chlorobenzylamide) 3-methylimidazolidine-2,5-dione 1-carboxy-( 0-chlorobenzylamide)2,8 (0,0
1 mol) of ooform 45 mfl and methanol 5
The suspension was suspended in a standard mixed solvent. After cooling to 10°C and stirring, add 0.2 g of sodium borohydride: (0.01 mol)
was added, the temperature was returned to room temperature, and the mixture was stirred for 30 minutes. the reaction mixture with water,
The mixture was washed with saturated brine, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The obtained residue was recrystallized from methanol/ether to obtain 2.2 g of white crystals (yield 77.7%).

Melting point: 12B, 7°C Elemental analysis value 3 HN Calculated value (%) 50.80 4.97 14.8
1 Actual value (%) 50.84 4.96 14.
79NMR: δ (CDCρ3) 2.78 (3H), 3. 10 (LH)
, 3.40 (LH) , 4.42 (2H)
, 4, 90 (LH) , 5. 65 (I
H), 6, 90-7. 30 (4H), 8
．． 4'7' (IH) Examples 15-24 The compounds of Examples 15-24 were synthesized in the same manner as in Example 13.14. Physical properties and NMR data are shown in Table 1.

4 Table 5 6 7 28 Formulation example 1 (30% emulsion) (parts by weight) Compound of Example 13 30 Polyoxyethylene nonyl 1° Phenyl ether dimethylformamide 20 Xylene
40 Prescription Example 2 (50% water use agent) Compound of Example 14 50 Sodium ligninsulfonate 1 Sodium dodecylbenzenesulfonate 4 Clay
45 Formulation Example 3 (10% powder) Compound of Example 15 10 Sodium ligninsulfonate 0° Sodium dodecylbenzenesulfonate 2 Diatomaceous earth
27゜bentonite 60
9 In the case of an emulsion, each component can be uniformly mixed and dissolved, and in the case of a wettable powder, each component can be uniformly mixed and ground to obtain them. In the case of granules, the ingredients are uniformly mixed, water is added and thoroughly kneaded, and then granulated, then finely cut into granules and dried.

Test Example 1 (Stem and Leaf Treatment Test) Sterilized alluvial soil was placed in a 1/2000 a Wagner pot, and the seeds of the test plants shown in Table 2 were sown. -3 leaf stage), an emulsion containing the compound obtained by the method shown in the example as an active ingredient was prepared according to Formulation Example 1, and the active ingredient was 5.
The solution was diluted with water to give a concentration of 1.g, 1.a and was sprayed so that the entire surface of the stems and leaves of the plant was thoroughly wetted. After spraying 3
The herbicidal activity against each plant was examined every week. The results are shown in Table 2. The herbicidal activity was evaluated by visual observation using an index compared to that of no treatment according to the following criteria.

0 (herbicidal activity) no change 1-24% inhibition 25-49% inhibition 50-74% inhibition 75-90% inhibition complete withering 1 弗 table Test plants A-H are as follows.

A... Green millet B... Kusanemu D... Radish E... Buckwheat G... Wheat
H... Takasaburou C... Novie F... Asaga No. 2 Test Example 2 (Soil Treatment Test) Sterilized alluvial soil was placed in a Wagner pot of 1/2000 a, and the test plants shown in Table 3 were sow the seeds,
The soil was covered with approximately 0.5 to 1.0 cm of soil. Next, an irrigation agent containing the compound obtained by the method shown in the example as an active ingredient was prepared according to Formulation Example 2, diluted with water so that the active ingredient was 5 g/a, and the soil surface was uniformly coated. It was sprayed so that it was wet. Herbicidal activity against each plant was examined three weeks after spraying. The results are shown in Table 3 below. The evaluation criteria were the same as in Test Example 1.

3 No. table (Hereafter Up) 4

Claims (4)

[Claims] (1) General formula▲ Numerical formula, chemical formula, table, etc.▼ [In the formula, R represents an alkyl group, a haloalkyl group, an alkenyl group, a cycloalkyl group, a benzyl group, a substituted benzyl group, or an α-alkylbenzyl group. ] An imidazolidin-2-one derivative represented by: (2) Methylhydantoin and the general formula RNCO [wherein R represents an alkyl group, a haloalkyl group, an alkenyl group, a cycloalkyl group, a benzyl group, a substituted benzyl group, or an α-alkylbenzyl group. ] Imidazolidine-2,5-dione represented by the general formula ▲ Numerical formula, chemical formula, table, etc. ▼ [In the formula, R is the same as above] by reacting with isocyanates represented by the above in the presence of a basic catalyst. After obtaining the derivative, it is further reduced to obtain an imidazolidin-2-one derivative represented by the general formula ▲ Numerical formula, chemical formula, table, etc. ▼ [In the formula, R is the same as above] Method for producing lysin-2-one. (3) After reacting methylhydantoin and trichloromethyl chloroformate, a compound of the general formula R-NH_2 [wherein R is an alkyl group, a haloalkyl group, an alkenyl group, a cycloalkyl group, a benzyl group, a substituted benzyl group, or an α- Represents an alkylbonzyl group. ] After reacting with amines represented by the general formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [In the formula, R is the same as above] An imidazolidin-2-one derivative characterized in that it is reduced to obtain an imidazolidin-2-one derivative represented by the general formula ▲ Numerical formula, chemical formula, table, etc. ▼ [In the formula, R is the same as above] Production method. (4) General formula▲ Numerical formula, chemical formula, table, etc.▼ [In the formula, R represents an alkyl group, a haloalkyl group, an alkenyl group, a cycloalkyl group, a benzyl group, a substituted benzyl group, or an α-alkylbenzyl group. ] A herbicide characterized by containing an imidazolidin-2-one derivative represented by the following as an active ingredient.