KR810002058B1 - Process for the preparation n-phenyl-n-methyl-urea derivatives - Google Patents

Abstract

Title compds.(I; R1, R2 and R3 are H, lower alkyl, lower alkoxy, lower alkylthio, halogen, trifluoromethyl; R4 = lower alkyl, H; A = methyl, methoxy; X = O, S; Y = H, halogen; Z = C1-8 alkylene; n=1-3), useful as herbicides, were prepd. by the reaction of II and III. Thus, 100 ml 4-≮2-(4-chlorophenyl)ethoxy≉-phenylisocyanate and 1.5 g N,O-dimethylhydroxylamine were mixed at 20-30≰C in benzene, stirred for 30 min to give 2.9 g N'-4-2-(4-chlorophenyl)ethoxyphenyl-N-methoxy-N-methyl-urea.

Description

Method for preparing derivatives of N'-phenyl-N-methyl-urea

The present invention relates to the preparation of N'-phenyl-N-methyl-urea derivatives.

N'-phenyl-N-methyl-urea derivative of the present invention is represented by the following general formula [I]

Where R ¹ , R ² and R ³ are each hydrogen, lower alkyl, lower alkoxy, lower alkylthio, halogen or trifluoro methyl, R ⁴ is hydrogen or lower alkyl, and A is methyl or methyl Oxy, X is oxygen or sulfur, Y is hydrogen or halogen, Z is a linear or branched alkylene chain having up to 8 carbon atoms (having one or more oxygen and / or sulfur inside and / or at the end of the alkylene chain) And n is an integer of 1 to 3, and has the following conditions.

(a) when R ¹ is lower alkyl or lower alkoxy, R ² is hydrogen or methyl, R ⁴ is hydrogen, A is methoxy, X is oxygen, Y is hydrogen, and Z is methylene R ³ is lower alkyl, lower alkoxy, halogen or trifluoro methyl,

(b) R ¹ is hydrogen, halogen or trifluoro methyl, R ⁴ is hydrogen, A is methoxy, X is oxygen, Y is hydrogen, and when Z is methylene, R ² and R ³ Are hydrogen, lower alkyl, lower alkoxy, halogen or trifluoro methyl,

(c) R ⁴ is hydrogen, A is methoxy, X is oxygen, Y is halogen, and when Z is methylene, R ¹ , R ² and R ³ are each hydrogen, lower alkyl, lower alkoxy, Halogen or trifluoro methyl,

(d) when R ⁴ is hydrogen, A is methyl, X is oxygen, and Z is methylene, then R ¹ , R ² and R ³ are each hydrogen, lower alkyl, lower alkoxy, halogen or trifluoro methyl ego,

(e) when R ⁴ is hydrogen, X is sulfur and Z is methylene, then R ¹ , R ² and R ³ are each hydrogen, lower alkyl, lower alkoxy, halogen or trifluoro methyl,

(f) R ⁴ is lower alkyl and 1 wherein Z is straight or branched alkylene having 1 to 8 carbon atoms, or may have one or more oxygen and / or sulfur inside and / or at the end of the alkylene chain; In the case of linear or branched alkylene having from 7 to 7 carbon atoms R ² and R ³ are each hydrogen, lower alkyl, lower alkoxy, lower alkylthio, halogen or trifluoromethyl, and

(g) ¹ to ^{7 in} which R ⁴ is hydrogen and Z is linear or branched alkylene having 2 to 8 carbon atoms, or may have one or more oxygen and / or sulfur inside and / or at the end of the alkylene chain; In the case of linear or branched alkylene having 2 carbon atoms, R ² and R ³ are each hydrogen, lower alkyl, lower alkoxy, lower alkylthio, halogen or trifluoromethyl.

The term " lower " used so far with respect to alkyl, alkoxy or alkylthio means a base having up to 8 carbon atoms, in particular up to 5 carbon atoms. Thus the term "lower alkyl" includes methyl, ethyl, propyl, butyl and the like, the term "lower alkoxy" includes methoxy, ethoxy, propoxy, butoxy and the like, and the term "lower alkylthio" is an example. For example, they are methylthio, ethylthio, propylthio, and butylthio.

The term "halogen" refers to chlorine, cancellation, fluorine, oxo and the like.

Examples of alkylene which is a straight or branched chain which may have one or more oxygen and sulfur inside or at the end of the alkylene chain are as follows.

Ethylene, ethylidene, trimethylene, 2-methylethylene, 1-methylethylene, tetramethylene, 1-methyltrimethylene, 1,2-dimethylethylene, 2,2-dimethylethylene, pentamethylene, 2-methyltetramethylene, 3-methyltetramethylene, 2,3-dimethyltrimethylene, 2,2-dimethyltrimethylene, 3-ethyltrimethylene, hexamethylene, 5-methylpentamethylene, 2,4-dimethyltetramethylene, 3-ethyltetramethylene , 2,3,3-trimethyltrimethylene, 3-propyltrimethylene, heptamylene, 2-methylhexamethylene, 4-methylhexamethylene, 5-methylhexamethylene, 2,5-dimethylpentamethylene, 3,5- Dimethylpentamethylene

, 5,5-dimethylpentamethylene, 4-ethylpentamethylene, 2,3,4-trimethyltetramethylene, 2,4,4-trimethyltetramethylene, 2-propyltetramethylene, octamethylene, 6-methylheptamethylene, 4,6-dimethylhexamethylene, 4-ethylhexamethylene, 2,4,5-trimethylpentamethylene, 2-methyl-5-ethylpentamethylene, methyleneoxy, methylenethio, 2-oxyethyl, 2-thioethyl, 1-oxyethyl, methylene oxyethyl, methylenethiomethyl, 3-oxy-propyl, 3-thiopropyl, 2-oxy-1-methylethyl, 2- (methylene-oxy) ethyl, (2-oxyethyl) oxymethyl , 4-oxybutyl, 3-oxy-1-methylpropyl, 2-oxy-1-ethylethyl, 3-methylenethiopropyl, (2-methyleneoxyethyl) oxymethyl, 5-oxypentyl, 5-thiopentyl , 3-oxy-1,3-dimethylpropyl, (3-oxypropyl) oxymethyl, (3-thiopropyl) oxymethyl, 3- (1-ethyleneoxy) propyl, 3-methoxypentamethylene, 2- ( 2-oxyethyloxy) ethyloxymethyl, 6-oxyhexyl, 3- (1-trimethyleneoxy) prop Peel, 7-oxy-heptyl, 7-thio-heptyl, such as the (number indicating the position Is calculated as the starting point side phenylurea from a carbon atom).

As is well known, soybeans, cotton, corn, wheat, rice, sugar beet etc. are important crops worldwide.

For the cultivation of these crop plants, chemical control of the weeds is absolutely necessary to prevent crop reduction.

In recent years, the selective use of herbicides that can eradicate weeds without chemically damaging the material to the desired crops is highly desirable.

Among the substituted urea derivatives are N'-4-chlorophenyl-N, N-dimethyl urea (Monuron) and N'-3,4-dichlorophenyl-N, N-dimethylurea (di There are compounds with powerful herbicides, such as Diuron.

It is also well known that the herbicidal action of these urea derivatives is due to the inhibition of photosynthesis. Photosynthesis is a physiological function unique to higher plants and is absent in mammals.

Therefore, inhibitors specific to photosynthetic processes are entirely possible to eradicate higher plants without significantly damaging mammals.

Herbicidal photosynthetic inhibitors, such as monuron and diuron, are all low toxicity to mammals.

However, since photosynthesis is common to higher plants, these detoxifiers exert herbicidal action on all higher plants.

Therefore, most photosynthetic inhibitors are non-selective and damage crops.

In order to make the compound a selective herbicide, it must have strong herbicidal activity against weeds and high selectivity against the planned crops.

However, these selective herbicides are very difficult to find and cannot be easily thought out systematically by simple similarities and modifications of known chemical structures.

Therefore, highly detailed studies with trial and error are needed to discover these selective herbicides.

For example, 2-chloro-4-ethylamino-6 with high selectivity to corn

In the case of isopropylamino-S-triazine (Atrazine), the chlorine atom in the 2-position is important for selectivity.

Instead of chlorine atoms, compounds with groups of methoxy or methylthio have very low selectivity for corn.

[H. Gysin: Insecticide Chemistry Vol. 5, pp. 1 to 27 (1972) 화학적 Chemical structure and biological relationship of S-triazine N] N'-3,4-dichlorophenyl-N -Methoxy-N-methyl urea (Linuron) is selective for several crops of the Umbelliferae family, such as carrots.

However, compounds having a methyl group instead of a methoxy group lack the selectivity for the above-mentioned plants. [Insecticide Handbook of the Weed Science Society of America, 3rd Edition, pages 172 to 176, and pages 221 to 225 (1974)] Selective herbicidation requires a very special chemical structure, and the selectivity is limited to only slight differences in the chemical structure. There is a big difference in frequency and type.

The present inventors have determined to focus on phenyl urea derivatives in view of low toxicity and potent production in mammals, and conducted a careful investigation of how to give selectivity to these derivatives.

As a result, N'-phenyl-N-methyl-urea [I] exhibits potent herbicidal activity against many types of weeds by inhibiting photosynthesis, and in addition to other important crops for rice plants. It was found to have a high selectivity by the type of.

N'-phenyl-N-methyl-urea [I] is novel and several compounds similar in structure to this are known, among which N '-(4-phenoxy methoxyphenyl) -2-methylurea [ Swiss Patent 532,891] N '-(4-benzyloxyphenyl) -N, N-dimethylurea [US Patent 3,819,697] N'-(4-benzylthiophenyl) -N, N-dimethylurea [US Patent 3,819,697] N ' -(4-benzyloxyphenyl) -N-methoxy-N-methylurea (Japanese Patent Laid-Open No. 1977-111542) and the like.

Compared with their known N'-phenyl-N-methyl-urea derivatives, N'-phenyl-N-methyl-urea [I] is much more potent for herbicidal action.

Due to this high herbicidal capacity, N'-phenyl-N-methyl-urea [I] is used as a herbicide in arable lands that require high selectivity and in non-arable lands that do not necessarily require high selectivity. .

As described above, the N'-phenyl-N-methyl-urea [I] of the present invention has a high selectivity for rice plants and exhibits generally strong herbicidal activity against a wide range of weeds. Low toxicity.

Their selectivity for a variety of non-crop crops varies somewhat with their varieties. Some examples are:

Regarding the herbicidal action of N'-phenyl-N-methyl-urea [I], they are used for both weeds of high altitude fields and weeds of cultivated fields by the use of both cases before and after weeds. Has herbicidal action.

For example, they are broad-leaved weeds: Amaranthus retroflexus, Chenopodium alubum, Xanthium pennsylvanicum, Ipomoea purpurea, Stellaria media, Radishes sativus, Polygonum lapathifolium, Rotalia indica, Pinnacle (Monochoria vaginalis), Widder (Linderna pyxidaria), Pit hawk (Sidula frondosa), Solaum nigrum, Sunflower (Helianthus annus) (Datura stramonium), Abutilon theophrasti, etc. Grassy weeds, for example, Eleusine indica, Digitaria sanguinalis, Echinochloa crusgalli, Setaria viridis, etc. Seeds, for example, have strong herbicidal activity at low concentrations in various weeds, such as Cyperus difformis.

N'-phenyl-N-methyl-urea [I] is prepared by various processes, among which are as representative in the following schemes.

Wherein G is hydrogen or methyl, Q is hydroxy or metcapto, Hal is halogen (e.g. chlorine, cancelled), and R ¹ , R ² , R ³ , R ⁴ , A, X, Y , Z and n are as defined above.

That is, N'-phenyl-N-methyl-urea [I] is prepared by reacting phenylisocyanate [II] with amine [III].

This reaction is usually carried out over a wide range of temperatures, i.e. at room temperature under cooling or during heating (usually up to 100 ° C), with or without solvent.

The reaction time varies in the range of about 1 to 10 hours depending on the reaction temperature, the reagent and the like. As a solvent, water or an organic solvent (e.g., benzene, toluene, xylene, diethyl ether, tetra hydrofuran, dioxane, chloroform, carbon tetrachloride, ethyl vinegar, pyridine, dimethylformamide) or a mixture thereof can be used. Can be.

When water is used as the solvent, the amine [III] can be used in the form of an aqueous solution so that the desired compound can be obtained in good yield.

Alternatively, N'-N-phenyl-N-methyl-urea [I] is prepared by reacting N-hydroxyurea [IV] with a methylating agent [V].

Examples of methylating agents are methyl oxide, dimethyl sulfate, diazomethane and the like.

This reaction is carried out in an inert solvent at a wide range of temperatures, ie, at room temperature or under heating (usually up to 100 ° C.).

If the methylating agent is dimethyl sulfate, the inert solvent is water or an organic solvent (e.g., benzene, toluene, xylene, methanol, ethanol, isopropanol, diethyl ether, tetrahydrofuran, dioxane) or mixtures thereof .

The presence of alkalis such as sodium hydroxide and potassium hydroxide is advantageous for carrying out the reaction smoothly.

The presence of a phase transfer catalyst such as benzyl triethyl ammonium chloride or tetra-n-butyl ammonium embrittlement is also advantageous for the reaction.

The reaction time depends on the reaction temperature, the methylating agent and the like, and usually takes about 0.5 to 10 hours.

In another method, N'-phenyl-N-methyl-urea [I] is prepared by reacting phenylamine [VI] with halogenated carbamyl [VII].

This reaction is carried out at a wide range of temperatures, i.e., at room temperature or in heating (usually up to 150 ° C), with or without an inert solvent, suitably in the presence of an acid scavenger.

As an inert solvent, water or an organic solvent (for example, benzene, toluene, xylene, diethyl ether, tetrahydrofuran, dioxane, chloroform, carbon tetrachloride, methylene chloride, ethyl vinegar, methanol, ethanol, isopropanol, dimethylform Amides) or mixtures thereof.

Examples of acid removers are organic bases (eg pyridine, triethylamine), inorganic bases (eg sodium hydroxide, potassium hydroxide, sodium carbonate) and the like.

The reaction time is usually about 0.5 to 10 hours depending on the reaction temperature.

Alternatively, N'-phenyl-N-methyl-urea [I] is prepared by reacting halogenated alkyl [VIII] with phenyl urea [IX].

This reaction is usually carried out over a wide range of temperatures in the presence of an acid scavenger in an inert solvent, i.e. at room temperature or under heating (usually up to 150 ° C) under cooling.

As an inert solvent, an organic solvent (for example, benzene, toluene, xylene, diethyl ether, tetra hydrofuran, dioxane, chloroform, carbon tetrachloride, methylene chloride, ethyl acetate, methanol, ethanol, isopropanol, dimethylformamide) ), Water, or a mixture thereof.

Examples of the acid remover include pyridine, triethylamine, sodium hydroxide, potassium hydroxide, sodium carbonate and the like.

The reaction time usually takes about 0.5 to 10 hours depending on the reaction temperature.

In the above process, isocyanate phenyl [II] is obtained by reacting phenylamine [VI] with phosgene.

N-hydroxy urea [IV] is obtained by reacting phenyl isocyanate phenyl [II] with hydroxylamine or N-methyl hydroxylamine.

Several forms of the preparation of N'-phenyl-N-methyl-urea [I] are clearly shown in the following examples.

Example 1

A solution of 4- [2- (4-chlorophenyl) ethoxy] -phenyl isocyanate (100 ml) in benzene (100 ml) of N, O-dimethyl hydroxyl amine (1.5 g) in benzene (50 ml) The solution was added dropwise at a temperature of 20 to 30 ° C.

After the addition was completed, the resulting mixture was further stirred at the same temperature for 30 minutes.

The reaction mixture was concentrated under reduced pressure and the residue was crystallized in ethanol to give N'-4-2- (4-chlorophenyl) ethoxy phenyl-N as a white needle (2.9 g) which melted at 77 to 78 ° C. -Methoxy-N-methylurea (Compound No. 9) was produced.

Example 2

N, O-dimethyl hydroxylamine in benzene (50 ml) in a solution of 3-chloro-4- [2- (4-chlorophenyl) -ethoxy] phenyl isocyanate (4 g) in benzene (100 ml) ( 2g) was added dropwise at a temperature of 30 占 폚 or lower.

The resulting mixture was left to stand at room temperature for 30 minutes and then concentrated under reduced pressure.

This residue was crystallized in ethanol and melted at 99-100 ° C. (2.7

g) N'-3-chloro-4- [2- (4-chlorophenyl) ethoxy] phenyl-N-methoxy-N-methylurea (Compound No. 28) was produced.

Example 3

To a solution of 4- [2- (4-methylphenyl) ethoxy] phenyl isocyanate (30 g) in benzene (300 ml) was added dropwise a solution of dimethylamine (11 g) in benzene (100 ml) at a temperature of 30 ° C. or lower. Was added.

The resulting mixture was allowed to stand at room temperature for 1 hour and then concentrated under reduced pressure.

This residue was crystallized from ethanol and melted at 152 to 153 ° C. White needle (20 g) N'-4- [2- (4-methylphenyl) -ethoxy] phenyl-N, N-dimethyl urea (Compound No. 30 ).

Example 4

To a solution of 4-phenethyl thiophenyl isocyanate (25.5 g) in benzene (100 ml), benzene (

A solution of N, O-dimethyl hydroxylamine (9 g) in 50 ml) was added dropwise at a temperature of 30 deg.

The resulting mixture was left at room temperature for 30 minutes and then concentrated under reduced pressure.

This residue was crystallized in ethanol and melted at 85 to 85.5 ° C.

.4 g) was produced N'-4-phenethyl thiophenyl-N-methoxy-N-methylurea (Compound No. 56).

Example 5

Benzene (50 ml) in a solution of 4- (5-phenylpentoxy) phenyl isocyanate (28.1 g) in benzene

), A solution of N, O-dimethyl hydroxylamine (9.1 g) was added dropwise at a temperature of 20 to 30 ℃.

The resulting mixture was stirred at the same temperature for 30 minutes and then concentrated under reduced pressure.

This residue was determined in ethanol and dissolved in white needles at 82.5 to 83 ° C (30

.3 g) was produced N'-4- (5-phenylpentoxy) -phenyl-N-methoxy-N-methyl urea (Compound No. 95).

Example 6

4-2- (2-methoxy phenyl) ethoxy phenyl isocyanate (4.7) in methylene chloride (50 ml)

To the solution of g), a solution of hydroxylamine hydrochloride (7 g) and sodium hydroxide (4 g) in water (15 ml) was added dropwise at a temperature of 20 deg.

The precipitated crystals were collected by filtration and dried to give N'-4- [2- (2-methoxyphenyl) ethoxy] phenyl-N-hydroxy urea (4.5 g).

Aqueous solution of sodium hydroxide (10N, 5.4 ml) was added to a solution of this hydroxyurea derivative (4.5 g), dimethyl sulfate (4.2 g), and tetra-N-butyl ammonium embrittlement (0.05 g) in toluene (60 ml). It was dripped and added at the temperature below ° C.

The resulting mixture was stirred at rt, diluted with water and extracted with benzene.

N'-4- [2- (2-methoxyphenyl) ethoxy] phenyl-N-methoxy, a white needle (4.4 g), obtained by removing the solvent under reduced pressure and then determining the residue in ethanol and melting at 63 to 64 ° C. -N-methylurea (Compound No. 4) was produced.

Example 7

Hydroxylamine hydrogen chloride (7 g) and hydroxide in water (15 ml) in a solution of 3-chloro-4-2- (4-methoxyphenyl) -ethoxyphenyl isocyanate (6 g) in methylene chloride (80 ml) A solution of sodium (4 g) was added dropwise at a temperature of 20 ° C or lower.

The precipitated crystals were collected by filtration and dried to obtain N'-3-chloro-4-2- (4-methoxyphenyl

) Ethoxyphenyl-N-hydroxy urea (5.6 g) was produced.

This hydroxy urea derivative (5.6 g) was dissolved in a mixture of benzene and methanol (volume 1: 1) (250 ml), and 10N sodium hydroxide solution (4 ml) and dimethyl sulfate (3.2 ml) were added thereto at 30 ° C or less. It was added dropwise at temperature.

The resulting mixture was stirred at rt, diluted with water and extracted with benzene.

N'-3-chloro-4-2- (4-methoxyphenyl) ethoxyphenyl-N, which is a white needle (3.2 g) which is crystallized in ethanol and is then melted at 51 to 52 DEG C after removing the solvent under reduced pressure. -Methoxy

-N-methylurea (Compound No. 43) was produced.

Example 8

To a solution of 4- [2- (4-methylphenyl) ethylthio] -phenyl isocyanate (13.5 g) in methylene chloride, a solution of hydroxylamine hydrogen chloride (7 g) and sodium hydroxide (4 g) in water (15 ml) Was added dropwise at a temperature of 20 ° C. or lower.

The resulting mixture was diluted with water.

The precipitated crystals were collected by filtration and dried to give N'-4- [2- (4-methylphenyl) ethylthio] phenyl-N-hydroxy urea (14.5 g).

This hydroxy urea derivative (14.5 g) was dissolved in a mixture of benzene and methanol (volume 1: 1) (200 ml), and a 10N sodium hydroxide solution (10 ml) and dimethyl sulfate (12 g) were added thereto at 30 ° C or less. It was added dropwise at temperature.

The resulting mixture was stirred at rt, diluted with water and extracted with benzene.

The solvent was removed under reduced pressure, and the residue was then determined in ethanol. N'-4- [2- (4-methylphenyl) ethylthio] phenyl-N-methoxy-N, a white needle (11.9 g), dissolved at 74.5 to 75 ° C. -Methyl urea (Compound No. 58) was produced.

Example 9

Hydroxylamine hydrogen chloride (8.9 g) and hydroxide in a solution of 4- [3- (3,4-dichlorophenyl) propoxy] phenyl isocyanide (32.2 g) in methylene chloride (50 ml) in water (20 ml) Sodium (5

2 g) was added dropwise at a temperature of 20 DEG C or lower.

The reaction mixture was diluted with water and the precipitated crystals were collected by filtration and dried to give N'-4- [3- (3,4-dichlorophenyl) -propoxy] -phenyl-N-hydroxy urea (34.3 g). ).

This hydroxy urea derivative was dissolved in a mixture of benzene and methanol (volume 1: 1) (200 ml), and 10N sodium hydroxide solution (19 ml) and dimethyl sulfate (25.2 g) were alternately added dropwise thereto at a temperature of 30 ° C. or lower. Was added, and stirring was continued at room temperature.

The reaction mixture was diluted with water and extracted with benzene.

The benzene extract was washed with water, concentrated under reduced pressure, crystallized in ethanol and melted at 95 to 96 ° C., N'-4- [3- (3,4-dichlorophenyl) propoxy, a white crystal (35.3 g). ] -N-methoxy-N-methyl urea (Compound No. 75) was produced.

Example 10

N'-4-hydroxyphenyl-N-methoxy-N-methylurea (15 g) was added to a solution of sodium ethoxide (5.2 g) in N, N-dimethylformamide (100 ml), and N, A solution of 2- (2,5-dimethylphenyl) ethyl embrittlement (16.3 g) in N-dimethyl formamide (50 ml) was added dropwise.

The resulting mixture was heated gradually to 90 ° C. and held at this temperature for 3 hours.

The reaction mixture was poured into ice-water and extracted with benzene.

The benzene extract was concentrated under reduced pressure, and the residue was determined in ethanol. The white needle (8.8 g) dissolved at 115 to 115.5 ° C. was N'-4-2- (2,5-dimethylphenyl) ethoxyphenyl-N-meth. Toxoxy-N-methyl urea (Compound No. 10) was produced.

Example 11

To a solution of sodium ethoxide (2.7 g) in N, N-dimethylformamide (100 ml) was added N '-(3-chloro-4-hydroxy) phenyl-N, N-dimethyl urea (8.6 g), To this was added dropwise a solution of 2- (3-methyl-4-methoxyphenyl) ethyl embrittlement (9.2 g) in N, N-dimethyl formamide (50 ml).

The resulting mixture was gradually heated to 90-100 ° C. to hold this temperature for 3.5 hours.

The reaction mixture was poured into ice-water and extracted with benzene.

The benzene extract was concentrated under reduced pressure, and the residue was crystallized in ethanol, and N'-3-chloro-4- [2- (3-methyl-4-methoxyphenyl) as a white needle (5.2 g) which was melted at 114 to 116 ° C. ) Ethoxy] phenyl-N, N-dimethyl urea (Compound No. 53) was produced.

Example 12

A solution of 4- [2- (3-chlorophenyl) ethylthio] -aniline (26.4 g), N, N-dimethyl carbamyl chloride (11.3 g) and pyridine (50 ml) in toluene (300 ml) was added under reflux. Heated for hours.

The reaction mixture was diluted with water, the toluene layer was separated, washed with dilute hydrochloric acid and water, dried over anhydrous sodium sulfate and concentrated under reduced pressure.

This residue was crystallized from ethanol and melted at 107 to 108 DEG C. White needle (25 g), N'-4- [2- (3-chlorophenyl) ethylthio] phenyl-N, N-dimethyl urea (Compound No. 65 ).

Example 13

To a solution of 4- (9-phenyl-n-nonyloxy) aniline (14.8 g) in toluene (300 ml), 40% sodium hydroxide solution (55 ml) and N, N-dimethyl carbamyl chloride (8 g) were added. The mixture was refluxed for 10 hours.

After cooling to room temperature, the toluene layer was separated, washed with water, and then concentrated under reduced pressure.

This residue was crystallized in ethanol and dissolved as a white crystal (13.7 g) at 79 to 81 DEG C. N'-4- (9-phenyl-N-nonyloxy) phenyl-N, N-dimethyl urea (Compound No. 106) Produced.

Example 14

N'-4-mercaptophenyl-N, N-dimethyl urea (20 g) was added to a solution of sodium ethoxide (6.8 g) in N, N-dimethylformamide (200 ml), and N, N-dimethyl was added thereto. A solution of 2- (2,4-dimethylphenyl) ethyl embrittlement (22 g) in formamide (100 ml) was added dropwise.

The resulting mixture was gradually heated to 100 ° C. and held at this temperature for 5 hours.

The reaction mixture was poured into ice-water and extracted with benzene.

The benzene extract was concentrated under reduced pressure, and the whole substance was determined by ethanol, and the acicular needle (25.8 g), N'-4-2- (2,4-dimethylphenyl) ethylthiophenyl-N, N-dimethyl urea (Compound No. 61) was produced.

Example 15

To a solution of sodium ethoxide (6.8 g) in N, N-dimethyl formamide (200 ml) was added N '-(4-hydroxyphenyl) -N, N-dimethyl urea (18 g), to which N, N -A solution of 2- (3-trifluoromethyl phenoxy) ethyl embrittlement (29.5 g) in dimethyl formamide (100 ml) was added dropwise.

The temperature was gradually raised to 100 ° C. and the reaction mixture was held at this temperature for 5 hours before being poured into ice water. The precipitated crystals were collected by filtration, washed with water, ethanol and ether, dried and recrystallized from ethanol to melt at 127 to 128 ° C., N'-4- [2- (3-tree). Fluoromethyl phenoxy) ethoxy] phenyl-N, N-dimethyl urea (Compound No. 113) was produced. Specific examples of N'-phenyl-N-methyl-urea [I] which can be prepared by the same method as described above are as follows.

For the actual use of N'-phenyl-N-methyl urea [I], it is used in any form of standard such as wet powder, emulsion concentrate, granular powder, or the like. Is suitable for.

A solid or liquid carrier is used to produce such a standard product.

As for the solid carrier, mineral powders (e.g. kaolin, bentonite, clay, montmorillonite, talc, diatomaceous earth, mica, vermiculite, gypsum, calcium carbonate, apatite) Stone powder], plant powder (eg soy flour, flour, wood flour, tobacco powder, starch, crystalline capulose), polymer compound [eg petroleum resin, polyvinyl chloride, damar gum (dammar gum), ketone resin] and alumina wax is used.

Regarding liquid carriers, alcohols (eg methyl alcohol, ethyl alcohol, ethylene glycol, benzyl alcohol), aromatic hydrocarbons (eg toluene, benzene, xylene, methyl naphthalene), halogenated hydrocarbons (eg chloroform, Carbon tetrachloride, mono chlorobenzene), ethers (eg dioxane, tetra hydrofuran), ketones (eg acetone, methyl ethyl ketone, cyclohexanone), esters (eg ethyl acetate, acetic acid) Butyl, ethylene acetate), acid amide (e.g., dimethyl formamide), nitrile (e.g. acetonitrile), ether alcohol (e.g., ethylene glycol ethyl ether), water and the like can be used. Surface active agents used for emulsion dispersion and development can be any of nonionic, anionic, cationic and amphoteric forms of the active agent.

Examples of surface active agents include polyoxyethylene alkyl ethers, polyoxyethylene alkylaryl ethers, polyoxyethylene fatty acid ethers, sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters, oxyethylene, polymers, oxypropylene polymers, polyoxyethylenealkyls Phosphates, fatty acid salts, alkyl sulfates, alkyl sulfonates, alkylaryl sulfonates, alkyl phosphates, polyoxyethylene alkyl sulfates, quaternary ammonium salts, oxyalkyl amines and the like.

However, the surface active agent is not limited to these compounds as well.

If necessary, gelatin, casein, sodium alginate, starch, agar and polyvinyl alcohol can be used as a supplement.

The practical example of the herbicidal composite according to the present invention is clearly shown in the following examples, in which parts and percentages are by weight.

Compound numbers correspond to those shown above.

Example A

Compound No. 1 or No. 25 parts of 56, 2.5 parts of dodecyl benzenesulfonate, 2.5 parts of lignin sulfonate and 70 parts of diatomaceous earth are mixed well to be a wet powder standard product.

Example B

80 parts of compound No. 28, 5 parts of a surface active agent (polyoxyethylene alkaline aryl ether type), and 15 parts of talc are finely mixed while being milled to become a wet powder standard product.

Example C)

5 parts of 80 parts of the surface active agent (polyoxyethylene alkylaryl ether type) of compound No. 85 and 15 parts of synthetic silicic acid are mixed well while milling to become a standard product of wet powder.

Example D

30 parts of Compound No. 4 emulsifier 10 parts of Sopol SM (trade name, manufactured by Toho Chemical Co., Ltd.) and 60 parts of xylene are mixed well to be a standard product of the emulsion concentrate.

Example E

5 parts of compound No. 30, 20 parts of a surface active agent (polyethylene glycol ether type), and 75 parts of benzene are mixed well so as to become a standard product of an emulsified concentrate.

Example F

30 parts of compound No. 57 or 87, 7 parts of polyoxy ethylene alkylaryl ether, 3 parts of alkylaryl sulfonate and 60 parts of xylene are mixed well so as to be a standard product of the emulsion concentrate.

Example G

5 parts of compound No. 9 or 59, 1 part of white carbon, 5 parts of sulphonic acid green, and 89 parts of clay are mixed well.

This mixture is then kneaded well with water, granulated and dried to form a granular standard.

Example H

5 parts of compound No. 43, 40 parts of bentonite, 50 parts of clay and 5 parts of sodium lignin sulfonate are mixed well during powdering.

The mixture is then kneaded well with water and granulated and dried to obtain a granular standard.

Example J

1 part of compound No. 89, 1 part of white carbon, 5 parts of lignin sulfonate and 93 parts of clay are mixed well during powdering.

The mixture is then kneaded with water, granulated and dried to form a granular standard.

Example K

5 parts of 40 parts lignin sulfonate of bentonite and 55 parts of clay are mixed well while powdered.

This mixture is then kneaded well with water and granulated and dried to obtain a granular product.

This granular material (95 parts) is impregnated with 5 parts of compound No. 63 or 69 to obtain a granular standard product.

Example L

3 parts of compound No. 12,65 or 77, 1 part of isopropyl diacid, 66 parts of clay and 30 parts of talc are mixed well during powdering to obtain a powder standard product.

Example M

Three parts of compound No. 53 and 97 parts of clay are mixed well as powder to obtain a powder standard product.

N'-phenyl-N-methyl-urea [I] can be used as a herbicide in combination with other herbicides in order to improve these functions, and in some cases a synergistic effect can be expected.

-트리 플루오로-m-톨릴)-N,N-디메틸 우레아와 같은 치환한 우레아 제초제, 이소 프로필-N-(3-클로로페닐) 카르바민산염, 메틸-N-(3,4-디클로로페닐) 카르바민산염, 및 4-클로로-2-부티닐-N-(3-클로로페닐) 카르바민산염과 같은 카르바민산 제초제, S-(4-클로로벤질)-N,N-디에틸 티올 카르바민산염, S-에틸-N,N-헥사 메틸렌 티올 카르바민산염, 및 S-에틸 디 프로필티올 카르바민 산염과 같은 티올 카르바민산염 제초제, 3,4-디 클로로 프로피온 아닐리드, N-메톡시 메틸-2,6-디에틸-2-클로로 아세트 아닐리드 및 2-클로로-2',6'-디에틸-N-(부톡시 메틸)아세트 아닐리드와 같은 산 아닐리드 제초제, 5-브로모-3-제2부틸-6-메틸 우라실, 및 3-스클로 헥실-5,6-트리 메틸렌 우라실과 같은 우라실 제초제, 1,1'-디메틸-4,4'-비스 피리디늄 2염화 물과 같은 피리디늄염 제초제, N-(포스포노메틸)글리신, O-에틸-O-(2-니트로-5-메틸페닐)-N-제2부틸 포스포로 아아미도 티오에이트 및 O-메틸-O-(2-니트로-4-메틸페닐)-N-이소프로필 포스포로 아미도 티오에이트와 같은 유기-인(燐)제초제,

-트리 플루오로-2,6-디 니트로-N,N-디 프로필-p-톨루이딘 및 N-(시클로 프로필 메틸)-

-트리 플루오로-2,6-디 니트로-N-프로필-p-톨루이딘과 같은 톨루이딘 제초제, N-제2부틸-4-제3부틸-2,6-디니트로 아닐린, 3,5-디 니트로-N,N-디프로필 술파닐 아미드, 5-제3부틸-3-(2,4-디 클로로-5-이소 프로폭시 페닐)-1,3,4-옥사디 아졸린-2-온, 3-이소프로필-1H-2,1,3-벤조티아디아진-(4)-3-온-2,2-2산화물(이것의 염을 포함하여),

-(

-나프톡시) 프로피온 아닐리드, 2-(

-나프톡시)-N,N-디에틸 프로피온 아미드, 3-아미노-2,5-디 클로로 안식향산, 2-제2부틸-4,6-디 니트로페놀, N-1-나프틸 프탈라믹산, 2-(1-알릴 옥시아미노)부틸리덴-5,5-디 메틸-4-메톡시 카르보닐 시클로헥산-1,3-디온(이들의 염을 포함하여)등 속을 사용할 수 있다. 그러나 이들 제초제는 이들의 실시예에 물론 한정되는 것은 아니다.Other herbicides include phenoxy herbicides such as 2,4-dichloro phenoxy acetic acid, 2-methyl-4-chloro phenoxy acetic acid and 2,4- dichloro phenoxy-butyric acid (including esters and salts thereof), 2,4-dichlorophenyl-4'-nitrophenyl ether, 2,4,6-trichlorophenyl-4'-nitro phenyl ether, 2,4-dichlorophenyl-4'-nitro-3'-methoxy Diphenyl ether herbicides such as phenyl ether and 2,4-dichlorophenyl-3'-methoxycarbonyl-4'-nitrophenyl ether, 2-chloro-4,6-bisethylamino-1,3,5- Triazine, 2-chloro-4-ethyl amino-6-isopropylamino-1,3,5-triazine, 2-methylthio-4,6-bisethylamino-1,3,5-triazine and 2 Triazine herbicides such as -methylthio-4,6-bis isopropyl amino-1,3,5-triazine, 4-amino-6-third-butyl-3-methylthio-1,2,4-triazine Triazinone herbicides such as -5 (4H) -one, N '-(3,4-dichlorophenyl) -N, N-dimethyl urea, N'-(3,4 -Dichlorophenyl) -N-methoxy-N-methyl urea N '-(3-chloro-4-difluorochloromethylthiophenyl) -N, N-dimethyl urea, N'-[4- (4- Chlorophenoxy) phenyl] -N, N-dimethyl urea, and N '-(

Substituted urea herbicides such as -trifluoro-m-tolyl) -N, N-dimethyl urea, isopropyl-N- (3-chlorophenyl) carbamate, methyl-N- (3,4-dichlorophenyl) Carbamic acid herbicides such as carbamate, and 4-chloro-2-butynyl-N- (3-chlorophenyl) carbamate, S- (4-chlorobenzyl) -N, N-diethyl thiol carbamine Thiol carbamate herbicides such as acid salts, S-ethyl-N, N-hexamethylene thiol carbamate, and S-ethyl dipropylthiol carbamate, 3,4-dichloropropion anilide, N-methoxy methyl- Acid anilide herbicides such as 2,6-diethyl-2-chloro acetanilide and 2-chloro-2 ', 6'-diethyl-N- (butoxy methyl) acet anilide, 5-bromo-3-second Uracil herbicides such as butyl-6-methyl uracil, and 3-sklohexyl-5,6-trimethylene uracil, and pyridinium salt herbicides such as 1,1'-dimethyl-4,4'-bispyridinium dichloride , N- (phosphonome Glycine, O-ethyl-O- (2-nitro-5-methylphenyl) -N-secondary butyl phosphoramido thioate and O-methyl-O- (2-nitro-4-methylphenyl) -N-iso Organic-phosphorus herbicides such as propyl phosphoro amido thioate,

-Trifluoro-2,6-dinitro-N, N-dipropyl-p-toluidine and N- (cyclopropyl methyl)-

Toluidine herbicides such as -trifluoro-2,6-dinitro-N-propyl-p-toluidine, N-tert-butyl-4-tert-butyl-2,6-dinitroaniline, 3,5-dinitro -N, N-dipropyl sulfanyl amide, 5-tertbutyl-3- (2,4-dichloro-5-isopropoxy phenyl) -1,3,4-oxadiazolin-2-one, 3-isopropyl-1H-2,1,3-benzothiadiazine- (4) -3-one-2,2-2 oxide (including its salts),

-(

-Naphthoxy) propion anilide, 2- (

-Naphthoxy) -N, N-diethyl propionamide, 3-amino-2,5-dichloro benzoic acid, 2-tert-butyl-4,6-di nitrophenol, N-1-naphthyl phthalamic acid, 2- (1-allyl oxyamino) butylidene-5,5-dimethyl-4-methoxy carbonyl cyclohexane-1,3-dione (including their salts) and the like can be used. However, these herbicides are not limited to these examples, of course.

菊) 계통의 살충제, 그외의 합성 살충제, 식물성장 조정제 또는 비료와 함께 사용할 수 있다. 제초합성물의 활성성분으로서 N'-페닐-N-메틸-우레아[I]의 농도는 보통으로는 중량으로 약 1내지 80%인데, 이보다 높거나 낮은 농도로도 사용할수 있다.Herbicides of the present invention, fungicides, pesticides of microorganisms, insect pests

Iii) Can be used together with line insecticides, other synthetic insecticides, plant growth regulators or fertilizers. The concentration of N'-phenyl-N-methyl-urea [I] as the active ingredient of the herbicidal compound is usually about 1 to 80% by weight, and can be used at higher or lower concentrations.

When N'-phenyl-N-methyl-urea [I] is used as a herbicide, the method of use and the amount of use depends on the type of standard product of the active ingredient, the type of crop planted, the type of weeds to be removed, and the weather conditions. . It is justified for use on these plants in weeds and crop plants that are processed after germination, at any time during the distribution stage. The application amount is about 2 to 80 grams, suitably 5 to 40 grams of active ingredient per each are.

For example, the use on arable land is carried out on weeds, about 1 to 15 cm in height, with an application of about 2 to 80 grams per malar by treatment on leaves.

In addition, for example, the use of paddy fields can be carried out within 4 weeks after the rice wool is transplanted with the amount of active ingredient applied in an amount of about 2 to 80 grams for each arena by water treatment. have.

The following examples show some representative test data showing good herbicidal action of N'-phenyl-N-methyl-urea [I].

Compound numbers correspond to those indicated above.

Compounds for comparison are as follows.

Example 1

Herbicides and selectivity for rice plants in paddy fields:

Wagener's complex (1 / 5000ares) was filled with paddy soil (1.5kg / acre) and kept in water.

Rice seedlings were transplanted to it in the trifoliate stage, and the seed of the blood was sown and grown for 5 days.

The planned amount of test compound was then used for the aqueous layer.

To use the test compound, the planned amount of this was normalized to wet powder, diluted with water and used by the pipette in a water layer at a rate of 15 ml for each jar.

25 days after use, weeding and crop damage were assessed on rice and cultivated blood, as well as on naturally-presented algae and broad-leaved weeds (ie, stilts, perillas, and flowers). The results are shown in Table 1.

Herbicidal action and crop damage were evaluated as follows.

Cut the aerial portion of the test plant to weigh it (new weight); The percentage of the new weight of the treated plant to the weight of the untreated plant was calculated by making 100 the new weight of the untreated plant.

Crop damage and herbicidal activity were evaluated according to the criteria shown in the table below.

TABLE 1

Example 2

Herbicidal action by use on leaves:

Fill the plastic jars (35 × 25 × 10 cm) with highland soils, planting otters, radishes, hairy scallops, white tuna, crows, sunflowers, morning glory, zombies, ragweed, and blood seeds in each jar Grown for 3 weeks.

The planned amount of test compound was sprayed onto the leaves on the test plants with a small hand sprayer.

When using the test compound, the test plants were in the 2 to 4 leaf stage and were 2 to 10 cm in height with variation by the type of test plant.

After spraying, the test plants were placed in the greenhouse for three more weeks, and the herbicidal action was evaluated as in Example 1.

The results are shown in Table 2.

In use on the leaves described above, the desired amount of the test compound was normalized to an emulsion concentrate dispersed in water containing a humectant and sprayed at a volume of 5 liters for each ar.

TABLE 2

Example 3

Phytotoxicity to crop plants by use on leaves:

Wagder's jars (1/5000 are) were filled with high-altitude field soil, and each jar was seeded with corn, wheat, cotton or soybean seeds.

After 2 to 3 weeks of incubation in the greenhouse, the planned amount of test compound was sprayed onto the leaves above the test plants with a small hand sprayer.

After spraying test plants were further grown for three weeks, and damage to the crop plants was assessed by the criteria shown in Example 1. The results are shown in Table 3.

The planned amount of test compound in use on the leaves described above was normalized to an emulsified concentrate dispersed in water containing a humectant and sprayed at a volume of 5 liters for each ar.

The growth stage of each test plant at the time of use was as follows.

Maize, 2-leaf stage; Wheat, bilobal phase; Cotton, 1-lobed; Soybean, 2-lobed; Beet, two-lobed stage.

TABLE 3

Example 4

Herbicidal Activity and Crop Selectivity of Compound I of the Present Invention by Soil Use:

Wagner's jars (15,000 are) were filled with highland soils, and seeds of soybeans, cotton, corn wheat, beets, rice, hair agar, white tuna, radishes, purslane and scabbard were sown in each jar.

The planned amount of test compound normalized to wet powder was dispersed in water and sprayed onto the soil surface with a small hand sprayer at a volume of 10 liters per each arena.

After spraying, the test plants were placed in a greenhouse for 20 days to assess crop damage and herbicidal activity.

This evaluation was performed according to the criteria shown in Example 1.

The results are shown in Table 4.

TABLE 4

Example 5

Phytotoxicity of the rest:

Fill the high-velocity soil with a plastic jar (35 × 25 × 10 cm), disperse the planned amount of the test compound, a wet powder product, in water to a volume of 5 liters per malt, and disperse the soil with the aid of a small hand sprayer. Sprayed on. The jars were left outdoors, and after one or three months they were sown seeds of wheat and soybeans. The test plants were then grown outdoors and the aerial portions of the test plants were cut out.

The dry weight of the cut portion was weighed and the plants in the untreated places grown under the same conditions as described above were compared with the weight.

Plant toxicity was evaluated based on the same criteria as in Example 1.

The results are shown in Table 5.

TABLE 5

Claims (1)

A method for producing an N'-phenyl-N-methyl-urea derivative represented by general formula (I) by reacting a compound represented by general formula (II) with a compound represented by general formula (III).

[Wherein, R ¹ , R ² and R ³ are each hydrogen, lower alkyl, lower alkoxy, lower alkylthio, halogen or trifluoromethyl, R ⁴ is hydrogen or lower alkyl, A is methyl or methoxy, X is oxygen or sulfur, Y is hydrogen or halogen and Z is a straight or branched alkylene chain having up to 8 carbon atoms (may have one or more oxygen and / or sulfur inside and / or at the end of the alkylene chain) And n is an integer of 1 to 3 and has the following conditions. (a) when R ¹ is lower alkyl or lower alkoxy, R ² is hydrogen or methyl, R ⁴ is hydrogen, A is methoxy, X is oxygen, Y is hydrogen and Z is methylene R ³ is lower alkyl, lower alkoxy, halogen or trifluoromethyl, (b) R ¹ is hydrogen, halogen or trifluoromethyl, R ⁴ is hydrogen, A is methoxy, X is oxygen, Y is hydrogen, and when Z is methylene, R ² and R ³ is hydrogen, lower alkyl, lower alkoxy halogen or trifluoro methyl, (c) R ⁴ is hydrogen, A is methoxy, X is oxygen, Y is halogen, and when Z is methylene, R ¹ , R ² and R ³ are each hydrogen, lower alkyl, lower alkoxy, Halogen or trifluoromethyl, (d) when R ⁴ is hydrogen, A is methyl, X is oxygen and Z is methylene, then R ¹ , R ² and R ³ are each hydrogen, lower alkyl, lower alkoxy, halogen or trifluoro methyl ego, (e) when R ⁴ is hydrogen, X is sulfur and Z is methylene, then R ¹ , R ² and R ³ are each hydrogen, lower alkyl, lower alkoxy, halogen or trifluoro methyl, (f) R ⁴ is a lower alkyl group, and from 1 to 7 wherein Z is linear or branched alkylene having 1 to 8 carbon atoms or may have one or more oxygen and / or sulfur inside and / or at the end of the alkylene chain; In the case of linear or branched alkylene having carbon atoms, R ² and R ³ are each hydrogen, lower alkyl, lower alkoxy, lower alkylthio, halogen or trifluoromethyl, and (g) R ⁴ is hydrogen And Z is a linear or branched alkylene having one to seven carbon atoms which may have one or more oxygen and / or sulfur inside and / or at the end of the alkylene or alkylene chain having two to eight carbon atoms. R ² and R ³ are each hydrogen, lower alkyl, lower alkoxy, lower alkylthio, halogen or trifluoro methyl.