JPS5962571A - Imidazolidin-2-one derivative - Google Patents

Abstract

NEW MATERIAL:The imidazolidin-2-one derivative of formula I [R is H, lower alkyl, lower alkoxy (lower alkyl), or lower alkoxycarbonyl(lower alkyl); Ar is phenyl which may have substituent group (halogen, NO2, lower alkyl, lower alkoxy, or lower haloalkyl)]. EXAMPLE:3-Methyl-4-hydroxyimidazolidin-2-one-1-carboxyanilide. USE:Herbicide. PROCESS:The compound of formula IV which is compound of formula I can be prepared by reducing the hydantoin derivative of formula II or formula III. If necessary, the product is made to react with the compound of formula R'X (R' is R excepting H; X is halogen) to obtain the compound of formula V which is another compound of formula I .

Description

[Detailed description of the invention]

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. The imidazolidin-2-one derivative of the present invention has the following general formula [I] (-
shown. (]R (in the formula, 1 or represents a hydrogen atom, a lower alkyl group, a lower alkoxy lower alkyl group, or a lower alkoxycarbonyl lower alkyl group. Δr) represents an upperyl group, and the phenyl group has a halogen atom, C may be substituted with a lower alkyl group, a lower alkyl group, a lower alkyl group, or a lower haloalkyl group. In the present invention, +3 and lower alkyl groups include, for example, Meboul Rev. 4.] nitrogen, +1-propyl group. , isopropyl group, 11-butyl group, 5ea-methyl group, isomethyl group, tert-methyl group, etc. Examples of lower alkoxy lower alkyl groups include Examples of the lower alkoxycarbonyl lower alkyl group include methoxycarbonylmethyl, methoxycarbonylmethyl, methoxycarbonyl, methoxycarbonyl, methoxycarbonyl, methoxycarbonyl, methoxycarbonyl, methoxycarbonyl, methoxycarbonyl, methoxycarbonyl, and methoxycarbonyl. Examples of the halogen atom include fluorine, chlorine, iodine, and iodine.Lower alkoxy groups Examples of the lower haloalkyl group include monochloromethyl group, monochloromethyl group, monochloromethyl group, etc. group, monochloropropyl group, dichloromethyl group, monobromomethyl group, monobromoethyl group, monobromopropyl group, monofluoromethyl group, j-lifluoromethyl group, triflu A
Examples include loethyl group. Noryl group having a halogen atom, nitro group, lower alkyl group, lower alkoxy group or lower haloalkyl group as a substituent U
fJ It u1el, r 2-ri[1ruphenyl L(,
3.
+, 2-norA (-1futonirufu, 2-21-lov)
～-ru J11.3---' 1 u 7-i nil;z
(,2-Methylphenol J: (,3-methylphenol group, 4-methylphenol group, 1,3,4-dimethylphenol group, 2-isozo(1biru-)onyl group , 2-meth:
1-diphenyl group, 33-meth-1-diphenyl group, 2
Examples include -11-propyloxynoenyl, 2-isobutyloxynoenyl, 3-1-lifluoromethylphenyl, and the like. "Mokukomei's compound represented by general formula [I] is fi
I+J can be manufactured by various methods, but one preferred example is manufactured according to the following anti-r16 formula. (1!] [16,) (m) (lb)11 Indicates a lower alkyl group or a lower alkoxycarbonyl lower alkyl group. X represents a halogen atom. Ar is the same as above. ] In the above reaction formula, the general formula [I
The hydan I-yne derivatives represented by I] or [1] are known compounds, such as 1-methylhytantoin and 3-
It can be obtained by a conventional method from methyl danyl hene and 7lyl isocyanate i-. 1-Methyl dan-1-yne and allyl isocyanatonon σ:)
The opposite of 1. (Also, Article 1'1 may be used, without solvent or (
(-17', c 4] in J solvent.
For example, Anikichi IA solvents such as 1-silene, 1-silene, and 1-rubengen are used. The ratio of the isocyanate 1- to be used is not limited to 11 and can be appropriately selected within a wide range, but it is generally about 1:1 molar ratio of the latter to 10 times molar molar ratio of the former, preferably equal to mol to 3 (J: 8 mol at most).The reaction temperature for this reaction is not particularly limited, but is usually 100 to 2 mol.
The reaction proceeds appropriately at about 00°C, and the reaction is generally completed in about 3 to 5 hours. The compound represented by the general formula [I] is reduced to form a compound represented by the general formula [1a].
] Compound shown by 1! Reaction and general formula [■]C
The reaction to obtain the compound represented by the general formula [, I: b ] by 3ψ elements of the shown compound can be carried out in a solvent (j). Examples of the solvent used include water, methyl alcohol, ethyl Alcohols such as alcohol, propyl alcohol, butyl alcohol, or ethers such as diethyl ether, dibutyl ether, dihydrofuran, diochirin, and the like can be used together with general formula [11] or [I Based on the compound represented by [l], the U-nv formula [Ia 1 or

【Yo[
A compound represented by the general formula [II] or [lI] is used as a reducing agent in a reaction (for example, borohydride is used. The ratio of boron to 1-lium is not particularly limited and can be selected as appropriate from a wide range;
v The latter is used in an amount of about 0.1 to 5 times the mole of the former, preferably j=0.25 to about the same mole as J:0. The reaction temperature for the reaction is not particularly limited. The reaction is completed when the general formula [Ia ] or [Ill] r is shown. 7., 3
The reaction between the 4B combined force and the alkyl halide represented by the general formula [IV] may be carried out without a solvent or in an appropriate solvent. Water, alcohols such as methyl alcohol, alcohol, alcohol, diethyl 1-fluor, dibutyl alcohol, dibdelny 7-
/S,A)-Halogenated carbons (arsenic compounds, hempine, 1- to luene, etc.) Aromatic D
X-based solvent, pyridine, At M = L del, Are1-
Di[~lyl, dimethyl small lumamide, etc. can be mentioned. The proportion of the compound represented by the general formula [ia] or [Ib] and the compound represented by the general formula E IV is not particularly limited and can be selected from a wide range as appropriate; The latter is preferably used in an amount of equimolar to 5 times the molar amount, preferably equimolar to 2 times the molar culm. The reaction between the compound represented by the general formula [Ia] and the compound represented by the general formula [IV] (, (, t
A base is used to scavenge the hydrogen halide that accompanies itΣ. The base used is, for example, hydroxide,
Negative 131 and amines such as -lium, potassium hydroxide, sodium carbonate, potassium carbonate, 1-ethylamine, 1-heributylamine, pyridine such as pyridine, vinyl phosphorus, luzidine>: n, metal boolean 1- lium, hydrogenated 1~
Liu 1\, sodium alcohola-1, etc. can be mentioned. The ratio of the compound represented by the general formula [Ia] or [Ib]/hydrogen scavenger is not particularly limited and can be appropriately selected from a wide range; It is preferable to use about equimolar to 5 times the mole, preferably equimolar to about 2 times the mole. The reaction temperature for this reaction is not particularly limited, but is usually O to 100
The reaction proceeds suitably at a temperature of about Examples of the compounds of the present invention that can be purified by the above method are as follows: 3-Methyl-4-hydroxyimitazolidin-2-one-1-carboxyanilide 5-Human '-Chloranilide 33-methyl-5-hydroxyimidazolidine-2-
F1-1-carboxy-(2'-chloranilide) 3-methyl-4-hy1:roxyimigzolidine-2-A
-1-carboxy-(3'-chloranilide) 3-methyl-5-human[]]ximitazolidine-2-A-1carboxy-(3'-chloranilide) 3-methyl-5-hysiloxy Imitazolicin-2-7
1-1-carboxy-(2',/l'-dichloro1nilide) 3-, methyl-4-hydroxyimitazolidine-2-,
+C'1-Carboxy(3'-methylanilide) 3-Methyl-5-hyroxyimitazolidine-2-one-1-carboxy-(3'-methylanilide) 3-Methyl-5-hydroxyimidazolidine- 2-one-1-carboxy-(2'-me-1-xyanilide) 3-methyl-5-hydroxyimitazolidin-2-one-1-carboxy-(3'-1-lifluoromethylanilide) 3-methyl- 5-Hydroxyimitazolidine-2-A Sea 1-no J Rubo 4 Ni-di-ku 3'-21-Roani 1 Nod) 3-Medyl-4-Mel-Ximidazolidine-2-one-1-carboxyanilide 3 -Methyl-5-methoxyimidazolidin-2-one-1-carboxyanilide 3-methyl-5-methyl-5-methyloxyimidazolidin-2-one-1-carboxy-(2'-chloroanilide)3-methyl -5-ethoxycarbonylmethylimidazolidine-2
-one-1-carboxyanidine-1-Z3-methyl-5-methyl-xintoxyimidazolidine-2-A-1-carboxyanidine-2 -Relates to a herbicide containing an A derivative as an active ingredient. The compounds of the present invention include 711 plants such as Takanobu [Kola, Aobiyu, Klinem, Psyllium psyllium, Polygonum, Polygonum, A.A. Since it shows a strong herbicidal effect on grasses, the growth of these 711 flowers is harmful to the production of agricultural crops such as oranges, apples, dice, corn, mulberry, tea, and paddy rice. It is useful in controlling old weeds. When applying the present Komei compound as a herbicide, you may use the same compound as the herbicide, but in general,
Le I! It can be mixed with adjuvants used in the formulation of mulberry and used in any dosage form.Among them, emulsion, aqueous phase, and granule forms are preferably used.In this case, Examples of auxiliary agents for stabilizing the effect and improving the effect include diatomaceous earth, kaolin, clay, 11!1 stone agents such as Ben]-Nai]~, Why1~Cahone, and talc, polyurethane, etc. Upper ethylene alkyl ether, polyoxyethylene alkylphenyl ether, polyΔxyethylene sorbitan fatty acid ester, polyoxyethylene fatty acid ester, mono-lithium alkylbenzene sulfonate, sodium lignin sulfonate, n9-lithium alkyl sulfonate, Nonionic or anionic surfactants such as poly(Axy-1-dylene algyl sulfate), pheasantol, amine, methanol, ethanol, isopropanol, dioxane, dimethylformamide, dimethyl sulfate, tetrachloride Organic solvents such as carbon are used.When formulating the weed control composition of the present invention, an adjuvant is added so that the active ingredient is about 1 to 90% by weight, preferably about 5 to 70% by weight. The application M depends on the tit formulation of the drug, the application method, the application time, the type of target weeds, and especially the herbicidal effect, and the weather condition 4'1, ±10 conditions based on A5. The color of the active ingredient is approximately 5 to 100 mm/a;
Preferably about 10 to 100 u/a)
．． I will be attacked. Reference examples, examples, prescription examples, and test examples are listed in 1 page C.
Honkomyo further n'r IJ riN! Illuminated. Note that the test example is J3Rir111, and the excipient compound number corresponds to the number in the example. Reference Example 1 Production of 33-methylimidazolidine-2,4-dione-1-lupogycyanilide 3-methylhytan-1-yne 5.7 g (0,057)
and 5.9 g of phenyl sacyanate in an oil bath at 150°C.
The mixture was melted for 3 hours. The melt was recrystallized from dimethylformamide and colorless crystals of 9.00% (yield 78%) were obtained as I+'7
Ta. R1i point 219-220°C NMR of the crystal in DMSO-de was shown as follows. δ 3. OOppm (31-1), δ /1.33
1'lr)m (21-1>67.00~7.GO1+
pm < 5H) Yuan Cumulative Analysis (Scions (C+ 1H+ 1N
303) Analysis value % C5G, 90 1-14.7
5 N+8.10 theory (11T% C5G, 89 1
-14.77 N18.09 or above. Reference Example 2 Production of 3-methylimidazolidine-2,5-diA-C-1-carboxyanilide 1-methyl dan-1-yne 5.7 g (0.05 mol)
and isocyan n) phenyl 5.9 g (0.05 mol)
was melted at 180°C for 3 seconds at rt. The melt was thoroughly washed with water and then recrystallized with ethanol to yield 3.79 (IUy, ratio 3296) of colorless crystals. Melting point: 160-160.5°C Crystals of NMII in DMSO-de are shown below. ('5 3, +13 January +m (3H),
δ LoopHm (2N) ('3 7.
00 ~7.70 old + m (51-1) elemental analysis fin
(CI + 1-111 N303 +!:L/ ()
bu,)''in1((96C5G, 91 1-14
．． 76 N 18.07 buried ii21111 solo
05G, 89 I-14,77N 18.09 and above-
Example 1 3-Methyl-4-hydroxyimidazolidine-2-'A
Preparation of syncarboxyanilide 3-medylimidazolidine-2,4-dione-1-carboxyanilide
7.0(+(0.03 mol)) was suspended in methanol 5Qn+1. After cooling to 10°C, it was added to a hydrogenation bowl under stirring.
-Added 1.2g of January rim. After stirring for 30 minutes, the mixture was returned to seedling temperature and further stirred for 10 hours. After the reaction was completed, the reaction solution was concentrated, and water was added to the residue to precipitate crystals. 8mm crystal
After recrystallization with ethanol, colorless crystals of 5.4 (+ (
+1176%) lrf. The N fvI R of the crystals in deuterated chloroform was shown as follows: 62.70 ppm (3H), δ 3.85 ppm
(2H)δ 5. OOppm (11-1), δ 7
．． 00~7.70pp+++ (5H) Elemental analysis value (C+ + 1-113N303 etc.) Analysis value % C5G, 13 1-15.59 N17.8
7 Theoretical value% C5G, 16 H5, 57N17.8+
The results of 3 or more were confirmed. Example 2 Preparation of 3-methyl-5-hydroxyimidazolidine-2-A-1-carboxyanilide 3-methylimidazolidine-2,5-diane-1-carbo:1 dianilide
7.0 μl (0.03′El) was suspended in 50 ml of methanol. After cooling to 10'C, borohydride 1 was added under stirring.
・Added 1.2 J (0.03 mol) per unit. After 30 minutes, the mixture was returned to air temperature and stirred for an additional 2 hours. After the reaction 11 was completed, the reaction solution was concentrated, and water was added to the residue to precipitate crystals. After filtering the crystals. Ethanol J was recrystallized to give 6.40 colorless crystals (yield 90%).
) was 10. Midwifery 178-178.5°C NMR of the crystal in deuterated chloroform was shown as follows. - 62,90ppm (31-1), 63.3011
11m (11-1)δ 3. (351111111
(71-1), δ 4.47Dpm (
1t]) δ G, 001+ p m (Si(),
67.10~7.701)l)m(5LI) Elemental analysis 11n (C+ + H+ 3 N303 LT) analysis 1in96 (:, 56.18 days 5.
54 N17.89 Theoretical value% C56,16H5,5
7N17.86 or higher result J: confirmed. Example 3 3-Methyl-5-methoxyimidazolidin-2-one-
Preparation of 1-carboxy-(3-methylanilide) 3-methyl-5-hydroxy-f midazolidine=2-one-1-carboxy-(3-methylanilide) 2.5(
1 (0.01 mol) was dissolved in 40 ml of dimethylbormamide. After cooling to 10°C, 0.5 (1 (0.01 mol)) of sodium hydride was added under stirring. After stirring for 30 minutes,
1.5 g (0.01 mol) of methyl iodide was added dropwise. After stirring for 2 hours, water was added to the reaction solution to precipitate crystals. ml of crystals, recrystallized from ethanol to obtain colorless crystals 2. 4!7 l of Ou (yield 76%):. Melting point: 104-105°C [7] NMR of the crystals obtained in nail chloroborum showed the following. δ 2,32ppm (31-1), δ 2,90p
pm (31-1) δ 3,24ppm (11-1)
, δ 3.52+111m (31-1>δ 3.
GOppm (ll-1), 65.651] 1
1 m (month) 5 G, 97pton (11-1
), δ 7.20 ~ 7.50ppm (31-1) Elemental analysis fifl (as CI 31117 N30s) Analysis tin 9 (l C59,2880,54N
15.98 theoretical value% C59,30@G,51
The results of N15.9+3 or higher were confirmed. Examples 4 to 18 Compounds of Examples 4 to 18 were synthesized by the same operations as in Examples 1 to 3. The chemical properties and NMR data are shown in Table 1. Table 1 Formulation Example 1 (30% Emulsion) (Heavy Use Part) Compound of Example 1 30 PolyA xylene dylene nonyl 10 Onyl supra-dercindyl small lumamide 20 Xylene
40 Formulation Example 2 (50% hydrating powder) Compound of Example 2 50 Rikuninsulfone thorium 1 Dodecylbenzenesulfone r+
'U 4s 1-lium clay 45 tal +t!
I 3 (10% granules) Compound of Example 3
10 ligninsulfonic acid 1-lium 0
．． 5 Dodecylbenzene sulfonic acid 27.5 Ben 1 - N 1 - 60 In the case of an emulsion, each component is mixed and dissolved uniformly, and in the case of a wettable powder, each component is uniformly mixed and dissolved. You can crush them and make 1q of them. In the case of granules, they are manufactured by uniformly mixing each component, adding water and thoroughly kneading, granulating, and then cutting into small pieces to form granules and drying. Test Example 1 (Stem Treatment Test) ~) Sterilized alluvial soil was placed in a '1/2000 a Wagner Bot, and seeds of the test plants shown in Table 2 were sown.
When each plant reaches a certain size (approximately 2 to 3' leaf stage), an emulsion containing the compound obtained by the method shown in the example as an active ingredient is prepared according to Formulation Example 1, and each plant has an active ingredient. The solution was diluted with water to a concentration of 100 g/a and sprayed so that the entire stem and leaves of the plant were sufficiently and uniformly wetted. The herbicidal activity against each plant was examined three weeks after spraying. The results are shown in Table 2. In addition, the herbicidal activity was determined by visual observation using the following group 1:
．． % and evaluated as an index compared to the case without treatment. (Indexton (herbicidal activity 1l-) 0 No change 1 1-24% flJl damage 2 25-49% inhibition 3 50-74% inhibition/1 75-90% ToH damage 5
Table 2: Incarbamide rN- * (2-Methylpropyl) xamide" In the above table, test plants A~)-1 are the following plants. A... Aobiyu B... Ri] Nonem C... Nobie D... Radish I Yo... Buckwheat F.
...A4 Hemlock AG...Wheat 1-1...Takari flow test example 2 (Soil 18 treatment test 1-) Alluvial soil sterilized to Wagner Bot 1 of 1/2000a +
1, and the seeds of the test plants shown in Table 3 were sown and covered with soil to a depth of about 0.5 to 1.0 cm. Next, the compound obtained by the method shown in the example was added to the active ingredient Tozuro hydrating agent in Formulation Example 2 (Do 1).
1), diluted with water so that each active ingredient was 100 g/a, and sprayed this so that the soil If4 surface was evenly wet. Three weeks after spraying, the herbicidal activity against each plant was determined. The results are shown in Table 3. The evaluation criteria are the same as in Test Example 1. The reference compounds in Table 3 and 1 are the same as in Table 2. Also, the test plants Δ
~G 1. L ffi 2 tables and turns. Test Example 3 (Flooding treatment test) Add 1 liter of water to a 1/5000a Wagner Bottle, and add 1 liter of water and 17 liters of soil to the surface layer of (respectively).
After adding soil containing -C mixed with seeds of Japanese tree, Ajisu, and Gikasig4no, the water depth was maintained at 3 cm. Next, granules containing 1 q of the compound as an active ingredient obtained by the method shown in Example C were prepared according to Formulation Example 3, and the active ingredient was 50 g/a each.
The herbicidal activity on each plant was determined 3 weeks after application. The results are shown in Table 71. The evaluation criteria are the same as in Test Example 1. Table 4 Control compounds are the same as in Table 2. In addition, test plants C and I
− is as follows. C... Nobie I... 7 trees to Tamaga J... Azena 1 Ku... Kinoko Shigurii (and above) Agent Patent attorney Eiji Saegusa ・'\. ! No ゛

Claims (1)

[Claims] ■ General formula [wherein R represents a hydrogen atom, a lower alkyl group, a lower alkoxy lower alkyl group or a lower alko:1-dicarbonyl lower alkyl group]; Ar represents ) engineering, and the phenyl group may be substituted with a halogen atom, a di]-ro group, a lower alkyl group, a lower alkoxy group, or a lower haloalkyl group. ] An imidazolidin-2-one derivative represented by: (2) General (1) [In the formula, Ar represents a phenyl group, and the phenyl group may be substituted with a halogen atom, a di]--ro group, a lower alkyl group, a lower alkoxy group, or a lower haloalkyl group. ] By reducing the hytantoin derivative represented by the general formula [wherein Ar is the same as above]. ] A method for producing an imidazolidin-2-one derivative, which comprises obtaining an imidazolidin-2-one derivative shown in the following. (2) General formula [In the formula, r represents a phenyl group, and the phenyl group may include a halogen atom, a lower alkyl group, a lower alkoxy group, or a lower haloalkyl group. ] The -rmigsylidin-2-one derivative represented by the general formula [wherein R' represents a lower alkyl group, a lower alkoxy lower alkyl group, or a lower alkoxycarbonyl lower alkyl group]. X represents a halogen atom. ] by reacting with an alkyl halide represented by the general formula [where R' and Ar are the same as above]. A method for producing an imidazolidin-2-one derivative, which comprises removing an imidazolidin-2-one derivative represented by the following. R [In the formula, R represents a hydrogen atom, a lower alkyl group, a lower alkoxy lower alkyl group, or a lower alkoxycarbonyl lower alkyl group. 8r represents a nyl group, and the phenyl group may be substituted with a halogen atom, a nitro group, a lower alkyl group, a lower alkoxy group, or a lower haloalkyl group. ] A herbicide characterized by containing an imidazolidin-2-one derivative represented by the following as an active ingredient.