KR820001214B1 - Process for the preparation of n-phenyl-n-methyl ureas - Google Patents

Abstract

One hundred forty-four title compds. (I; R1 = H, Me, MeO; R2 = H, lower alkyl; R3 = the same or different halo, lower alkyl, alkoxy, alkylthio, CF3; X = H, halo; Y = O, S; Z = C1-8 alkylene, optionally contg. a terminal or internal O, S) useful as herbicides, were prepd. by reaction of II and III. Thus, 2 g III(R1 = OMe) reacted with 5.2 g II(R2 = H; R3 = MeO; X = H ; Y = O ; Z = Me) to give 4.3 g I, which showed strong herbicidal activity against a variety of undesirable plants.

Description

Method for preparing N'-phenyl-N-methyl urea derivative

The present invention, general formula (I):

Since R ₁ is a hydrogen atom, a methyl group or a methoxy group, R ₂ is a hydrogen atom or a lower alkyl group, and R ₃ is the same or different. A halogen atom, a lower alkyl group, a lower alkoxy group, a lower alkylthio group or a trifluoromethyl group, n is an integer of 0 to 5, X is a hydrogen atom or a halogen atom, Y is an oxygen atom or a sulfur atom, and Z is a C ₁ -C ₃ alkylene group which is a straight or branched chain which may have one or more oxygen and / or sulfur atoms inside and / or at the end of the alkylene chain.

The compound of (I) has a significant bactericidal activity against a wide range of plant pathogens that cause a wide range of weeds for the cultivation of crops without any chemical damage to mammals and fish and no chemical damage to crops. Indicates.

In general formula (I) R ₂ comprises, for example, hydrogen, methyl and ethyl, and R ₃ contains, for example, methyl, ethyl, propyl, butyl, fluorine, chlorine, cancelled, methoxy, ethoxy, pro Foxy, butoxy, methylthio, ethylthio, propylthio, butylthio and trifluoro, methyl, X includes, for example, hydrogen, fluorine, chlorine and cancellation, and Z, for example, Ethylene, ethylidene, trimethylene, 2-methyl ethylene, 1-methyl ethylene, tetra methylene, 1-methyl-trimethylene, 1,2-dimethyl trimethylene, 2,2-dimethyl ethylene, pentamethylene, 2-methyl tetra Methylene, 3-methyl tetra methylene, 2,3-dimethyl trimethylene, 2,2-dimethyl trimethylene, 3-ethyl trimethylene, hexamethylene, 5-methyl pentamethylene, 2,5-dimethyl tetramethylene, 3-ethyl Tetra methylene, 2,3,3-trimethyl trimethylene, 3-propyl trimethylene, hepta methylene, 2-methylhexamethylene, 4-meth Methyl hexamethylene, 5-methyl hexamethylene, 2,5-dimethyl pentamethylene, 3,5-dimethyl pentamethylene, 5,5-dimethyl pentamethylene, 4-ethyl pentamethylene, 2,3,4-trimethyl tetramethylene, 2,4,4-trimethyl tetra methylene, 2-propyl tetra methylene, octa methylene, 6-methyl hepta methylene, 4,6-dimethyl hexamethylene, 4-ethyl hexamethylene, 2,4,5-trimethyl pentamethylene, 2-methyl-5-ethyl pentamethylene, methyleneoxy, methylenethio, 2-oxa ethylene, 2-thiaethylene, 1-ethyl-2-oxa ethylene, 3-oxa trimethylene, 3-thiatrimethylene, 1-oxa Trimethylene, 2-oxa trimethylene, 2-thiatrimethylene, 4-oxa tetramethylene, 4-thia tetramethylene, 1-methyl-3-oxa trimethylene, 3-oxa tetramethylene, 2,5-dioxapenta Methylene, 5-thia-2-oxa pentamethylene, 5-oxa pentamethylene, 1-methyl-4-oxa tetra methylene, 1-ethyl-3-oxa trimethyltyl, 4-thi Pentamethylene, 2,5-dioxane hexamethylene, 6-oxhexamethylene, 6-thiahexahexamethylene, 1,3-dimethyl-4-oxa tetramethylene, 2,6-dioxa hexamethylene, 2,6-di Thiahexamethylene, 4-oxa hexamethylene, 3-ethyl-4-oxapenta methylene, 2,5,8-trioxa octamethylene, 7-oxa hepta methylene, 5-oxa hepta methylene, 8-oxa octamethylene and 8 -Thiaoctamethylene (number refers to the numbered position from the side of the half of the phenyl urea).

Rice, wheat, corn, soybeans, cotton, sugar beet, etc. are important agricultural products, and the use of herbicides is essential to prevent damage to weeds and increase yields.

Research efforts have been made to find herbicides that have a strong herbicidal action on weeds with high selectivity for these crops and low toxicity for mammals.

Among the urea-based compounds, N'-4-chlorophenyl-N, N-dimethyl urea (monotone) and N'-3,4-dichlorophenyl-N, N-dimethylurea (di-diol) have strong herbicidal action as is well known. Wootone).

It is also well known that the herbicidal action of these urea compounds is due to their inhibitory effect on photosynthesis. Photosynthesis is a unique physiological function of higher plants and does not work in mammals.

Therefore, inhibitors corresponding to photosynthetic processes do not cause significant damage to mammals, but are likely to eradicate higher plants.

In fact N'-4-chlorophenyl-N, N-dimethyl urea, N'-3,4-dichlorophenyl-N, N-dimethyl urea, 5-bromo-3- agent 2-butyl uracil (bromasil) Photosynthetic inhibitors, such as and the like are all low toxicity of mammals.

As described above, photosynthetic inhibitors generally have the advantage of low mammalian toxicity, but since photosynthesis is common to all higher plants, they have the potential to exert herbicidal action on all higher plants.

In practice, however, most photosynthetic inhibitors are non-selective and damage crops.

There is now a need for selective herbicides that do not harm planned crops and have strong herbicides on weeds only. However, it is very difficult to find selective herbicides having both high selectivity and strong herbicidal action, and thus cannot be easily found systematically only by the similarity and modification of known chemical compositions.

Therefore, it is necessary to find such selective herbicides in more detailed studies with trial and error.

For example, among the urea-based compounds, N'-3,4-dichlorophenyl-N-methoxy-N-methyl urea (linutone) has a selectivity in the apiaceae, but it is methyl instead of the methoxy group of linutone. Compounds with ethyl groups lose selectivity completely in the plants described above (American Weed Science Society, Herbicide Handbook, 3rd edition, pages 172-176 and pages 221-225 (1974)).

As described above, the mechanism of selective herbicidation is so unique that a slight difference in chemical structure causes a large difference in the degree and type of selectivity. In view of low toxicity and strong herbicidal activity in mammals, we attempted to prepare derivatives with improved selectivity while paying attention to urea compounds.

As a result, the compounds of general formula (I) exhibited potent herbicidal action on many types of weeds by inhibiting photosynthesis, and in addition, these compounds have high selectivity for various important crop plants depending on their type. .

In a closer examination of the herbicidal action of compounds (I), these compounds have potent herbicidal action on a broad range of weeds, both pre-emergency and post-coagulation.

For example, these compounds include Rotala indica, Waterstarwort (Callitriche verna), Grassy turf (Linderna pyxidaria), Stiletto (Monochoria vaginalis), Dopatri-um junceum, Vandellia angustifolia Benth., Echinochioa Crus-galli), Cyperus difformis, etc., have powerful herbicidal effects on weeds such as genus.

However, these compounds have a high degree of selectivity for tap water crops as described above.

Compounds (I) also have potent herbicidal activity on a wide range of highland weeds when used by post-emergency treatment.

Highland weeds include, for example, Xanthium pennsylvanicum, Sunflower (Halianthus annuus), Tusk (Amaranthus retroflexus), Chen-opodium album, Ipomoea purpurea, Datura stramonium, Solanum nigrum, Sida spinosa, Sacrifice obsidi-folia, Portulaca oleracea, Poligonum sp., Ambrosia tifida, Abtuon theophrasti, capsella bursa-pastoris, cardamine flexuosa, stellar media, gallium aparine L., cerastium glomerastum, sagina japomica ohwi, johnson Broad-leaved weeds and blood (Echinochloa crus-galli), Digitaria sanguinalis, Setaria viridis, 1-year-old Brugrus (Sorghum halepense), Sisbania spp. Poa annua, Avena fatua L. It includes. As described below, compounds (I) have a high degree of selectivity for soybeans, cotton, beets, corn and wheat.

Several of the compounds of compound (I) are novel, and N '-(3-benzyl-oxyphenyl) -N, N-dimethylurea (hereinafter referred to as control compound (a)) in US Pat. No. 3,819,697 is described above. Compounds and chemical structures are known to be similar.

However, the herbicidal action of compound (I) is extremely potent than that of control compound (a) as shown in the examples.

That is, the herbicidal action extends the chain of -CH ₂ -of the benzyl group in the control compound (a), in other words, the benzyl group, such as phenethyl, phenylpropyl, phenylbutyl, or phenyl- (C ₂ -C) ₉ ) Significantly improved by substitution with an alkyl group or a phenyl (C ₂ -C ₈ ) alkyl group containing oxygen or sulfur such as phenoxy ethyl, phenyl thioethyl or phenoxy propyl.

In addition, the following unexpected findings were found, and the selectivity and / or herbicidal action of various compounds (I) can be increased by introducing a substituent to the benzene ring.

As mentioned above, it is clear that the various compounds of the present invention are very effective as selective herbicides for cropland.

These compounds are also excellent herbicides that can be used in non-cultivated land because of their potent herbicidal action.

In addition, the compound (I) of the present invention is a bacterium such as apples, grapes, oranges, cucumbers, melons, wheat, powdery mildew, grapes, oranges, cucumbers, melons, etc. It is effective in preventing and suppressing plant diseases caused by various plant pathogens on agricultural plants such as diseases and fruit trees.

These compounds are Puccinia striiformis, barley and wheat streaks, Puccinia graminis barley and wheat stem rust, Puccinia recondita Leaf rust on wheat, Puccinia coronata, flicker on Yeonmec, rust on soybeans in Uromyces sojae, and Uromuces appendiculatus. It is particularly effective in preventing and suppressing rust, such as rust caused by Gangnam beans and Hemileia vastatrix.

Compared with the conventional fungicides, these compounds (I) are characterized not only in the prophylactic effect but also in the therapeutic effect.

Therefore, the compounds (I) of the present invention are useful as fungicides.

In particular, when these compounds are used for the cultivation of rice crops, upland crops, cotton, soybeans, corn, wheat, barley, etc., it is a product that can be expected at the same time herbicidal action and sterilization.

Compound (I) can be manufactured by the following method.

(a) Formula (II)

The phenyl isocyanate derivative of is reacted with an amine, ie, monomethylamine, dimethylamine, N, O-dimethylhydroxylamine or the like.

Where R ₂ , R ₃ , n, x, y and z are each as defined above.

The reaction is carried out with an organic solvent (e.g., benzene, toluene, xylene, diethyl ether, tetra hydrofuran, dioxane, N, N-dimethylformamide, chloroform, carbon tetrachloride), water or mixtures thereof. .

This reaction is generally achieved at 1 to 10 hours at a temperature of 0 to 50 ° C. to obtain a high yield of the desired compound.

(b) general formula (III)

Method for methylation of N'-phenyl-N-hydroxy urea derivatives.

Where R ₂ , R ₃ , n, x, y and z are each as defined above.

As the methylating agent, for example, methyl oxide, dimethyl sulfate or diazomethane can be used.

When using dimethyl sulfate, for example, the reaction is carried out in a solvent in the presence of alkali.

This alkali comprises sodium hydroxide and potassium hydroxide, and the solvent is an organic solvent (for example, benzene, toluene, xylene, methanol, ethanol, isopropanol, diethyl ether, tetrahydrofuran, dioxane, methylene chloride), water and Mixtures thereof.

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

This reaction is usually achieved in 1 to 10 hours at temperatures between 0 and 100 ° C. so that the desired compound is obtained in high yield.

(c) general formula (IV)

A method of reacting with an aniline derivative, methyl isocyanic acid, N-methoxy-N-methylcarbamyl, or N, N-dimethylcarbamyl.

Where R ₂ , R ₃ , n, x, y and z are each as defined above.

This reaction is carried out in an organic solvent (for example, benzene, toluene, xylene, diethyl ether, tetra hydrofuran, dioxane, chloroform, carbon tetrachloride, ethyl acetate, pyridine, dimethylformamide). The yield of this reaction can be increased using dechlorination agents such as pyridine, triethylamine, sodium hydroxide and potassium hydroxide.

This reaction can usually be achieved in 1 to 10 hours at a temperature of 0 to 150 ° C. to obtain the desired compound in high yield.

(d) General formula (Ⅴ)

A method by reacting a halide of N with a N'-phenyl-N-methylurea derivative represented by the general formula (VI).

Where R ₂ , R ₃ , n and z are each as defined above and A is a halogen atom.

General formula (Ⅵ)

Wherein R ₁ and X are as defined above, respectively, and Q is a hydroxyl group or a metcapto group.

This reaction is carried out in a solvent in the presence of a dehalogenating agent. Examples of dehalogenating agents include pyridine, triethylamine, sodium hydroxide, potassium hydroxide, sodium carbonate and the like.

Examples of the solvent include organic solvents (e.g., benzene, toluene, xylene, diethyl ether, tetra hydrofuran, dioxane, chloroform, carbon tetrachloride, methylene chloride, ethyl acetate, methanol, ethanol, isopropanol, N, N- Dimethylformamide) and mixtures thereof.

In the method (a), the phenyl isocyanic acid derivative of the general formula (II) can be easily obtained by the reaction between the aniline derivative of the general formula (IV) and the phosgene.

In the method (b), the N'-phenyl-N-hydroxy urea derivative of the general formula (III) is formed between the phenyl isocyanate derivative of the general formula (II) (the corresponding aniline derivative of the general formula (IV) and phosgene). Obtained by the reaction of) with a hydroxyl amine.

Some examples of compounds of formula (I) are shown below, although the compounds of the invention are not limited to these examples.

For practical use of compounds (I), these compounds can be used in any form of manufacture, such as wetting agents, emulsion concentrates, particles and powders.

In producing such a manufacturing form, a solid or liquid carrier is used.

As a solid carrier, mineral powder (for example, kaolin, bentonite, clay, montmorillonite, talc, diatomaceous earth, mica, burmekite, gypsum, calcium carbonate and apatite) vegetable powder (for example, soy flour, flour, wood powder) , Tobacco powder, starch, crystalline cellulose) high molecular weight compounds (eg, petroleum resins, polyvinyl chloride, dammar gum, ketone resins) are known as alumina, wax, and the like.

Examples of liquid carriers include alcohols (e.g. methanol, ethanol, ethylene glycol, benzyl alcohol), aromatic hydrocarbons (e.g. toluene, benzene, xylene, methylnaphthalene), halogens and hydrocarbons (e.g. chloroform, tetrachloride). Carbon, monochlorobenzene), ethers (e.g. dioxane, tetra hydrofuran), ketones (e.g. acetone, methyl ketone, cyclohexanone), esters (e.g. ethyl acetate, butyl acetate, acetic acid Ethylene glycol), acid amide (e.g., dimethyl formamide), nitrile (e.g. acetonitrile), ether alcohol (e.g., ethylene glycol ethyl ether), water and the like.

The surfactant used for emulsification, dispersion, and diffusion can use any of anionic, anionic, cationic and amphoteric active agents. Examples of the surfactant include polyoxyethylene alkyl ether, polyoxy ethylene alkylaryl ether, poly oxyethylene fatty acid ester, sorbitan fatty acid ester, polyoxy ethylene sorbitan fatty acid ester, oxy ethylene polymer, oxy propylene polymer, polyoxy ethylene alkyl Phosphates, fatty acid salts, alkyl sulfates, alkyl sulfonates, alkyl sulphonates, alkyl phosphates, polyoxyethylene alkyl sulfates, quaternary ammonium salts, oxy alkylamines and the like.

However, the surfactant is, of course, not limited to these compounds.

If necessary, gelatin, casein, sodium alginate, starch, agar, polyvinyl alcohol and the like can be used as an adjuvant.

Examples of the herbicide composite according to the present invention are shown below. In these examples, parts are expressed by weight.

Example A

80 parts of compound (I) (compound No. 65)), 5 parts of polyoxyethylene alkylaryl ether, and 15 parts of synthetic silicon oxide hydrate are ground while mixing well to obtain a powder.

Example B

30 parts of compound (I) (compound No. 2 or 70), 7 parts of polyoxyethylene alkylaryl ether, 3 parts of sulfonic acid alkyl aryl, and 60 parts of xylene are mixed well. Thus an emulsion concentrate is obtained.

Example C

1 part Compound (I) (Compound No. 49) 1 part white carbon, 5 parts lignosulfonate and 93 parts of clay are mixed and ground, and the mixture is kneaded well with water, granulated and dried to obtain fine particles. Get

Example D

40 parts of bentonite, 5 parts of lignosulfonate and 55 parts of clay are mixed to make powder.

The mixture is kneaded well with water, granulated and dried to obtain fine particles containing no active ingredient.

95 parts of this particulate is impregnated with 5 parts of compound (I) (compound No. 8.44 or 55). Thus you gain fine grain.

Example H

3 parts of compound (I) (compound No. 57), 0.5 parts of isopropyl phosphate, 66.5 parts of clay, and 30 parts of talc are mixed and ground to obtain a powder.

Example I

25 parts of compound (I) (compound No. 1 or 35) 2.5 parts of dodecylbenzene sulfonate, 2.5 parts of lignosulfonate and 70 parts of diatomaceous earth are mixed to obtain a powder.

Thus a hydrate is obtained.

The compound (I) of the present invention can be used together with other herbicides to improve herbicidal action, and in some cases aerodynamic effects can be expected.

Other herbicides include phenoxy-based herbicides such as 2,4-dichloro phenoxy butyrate (including its esters and salts), 2,4-dichlorophenyl-4'-nitrophenyl ether, 2,4,6-trichloro Phenyl-4'-nitrophenylether, 2,4-dichlorophenyl-4'-nitro-3'-methoxyphenylether and 2,4-dichlorophenyl-3'-methoxycarbonyl-4 Diphenyl ether herbicides such as' -nitrophenyl ether, 2-chloro-4,6-bisethylamino-1,3,5-triazine, 2-chloro-4-ethylamino-6-isopropylamino-1 Such as 3,5-triazine, 2-methylthio-4.6-bisethyl amino-1,3,5-triazine and 2-methylthio-4,6-bisisopropylamino-1,3,5-triazine Triazine herbicides, triazine herbicides such as 4-amino-6-tertbutyl-3- (methylthio) -1,2,4-triazine-5 (4H) -one, 3- (3,4 -Dichlorophenyl) -1,1-dimethylurea, 3- (3,4-dichlorophenyl) -1-methoxy-1-methylurea, 3- (3-chloro-4-diflo Chloromethylophenyl) -1,1-dimethylurea, 3-4- (4-chlorophenoxy) phenyl-1,1-dimethylurea and 3- (α, α, α, -trifluoro-m- Urea herbicides such as tolyl) -1,1-dimethylurea, isopropyl N- (3-chlorophenyl) carbamate, methyl N- (3,4-dichlorophenyl) carbamate, and 4-chloro-2 Carbamate-based herbicides such as -butynyl-mM-chlorocarbanirate, S- (4-chlorobenzyl) -N, N-diethylthio carbamate, S-ethyl-N, N-hexamethylenethiol carba Mate, thiocarbamate-based herbicides such as S-ethyl dipropylthiol carbamate, 3,4-dichloro propionanilide, N-methoxymethyl-2,6-diethyl-2-chloroacet anilide, 2 Acid anhydride herbicides such as -chloro-2 ', 6'-diethyl-N- (butoxymethyl) acet anilide, 5-bromo-3- agent 2-butyl-6-methyluracil and 3-cyclohexyl Uracil, such as -5,6-trimethylene uracil Family herbicides, pyridinium salts Rp thermal herbicides such as 1,1'-dimethyl-4,4'-bispyridinium dioxide, N- (phosphonomethyl) glycine, 0-ethyl 0- (2-nitro-5- Phosphorus herbicides such as methylphenyl) -N-second 2-butyl phosphoramido thioate and 0-methyl 0- (2-nitro-4-methylphenyl) -N-isopropyl phosphoroamido thioate, α, α, α-trifluoro-2,6-dinitro-N, N-dipropyl-P-toluidine and N- (cyclopropylmethyl) -α, α, α-trifluoro-2,6-di Toluidine based herbicides such as nitro-N-propyl-P-toluidine, N-second 2-butyl-4-second 3-butyl-2,6-dinitroaniline, 3,5-dinitro-N ⁴ , N ^4- Dipropyl sulfanamide, 5-third-butyl-3- (2,4-dichloro-5-isopropoxyphenyl) -1,3,4-oxadiazolin-2-one, 3-isopropyl-1H -2,1,3-benzothiadiazine- (4) -3H-one-2,2-2 oxides (including their salts), α- (β-naphthoxy) propionanilide, 2- (α -Naphthoxy) -N, N-diethyl Pionamide, 3-amino-2,5-dichlorobenzoic acid, 2-tert-butyl-4,6-dinitrophenol, N-1-naphthylphthalic acid, 2- (1-allyloxyamino), butyl Den-5,5-dimethyl-4-methoxycarbonyl-cyclohexane-1,3-dione, including salts thereof, and the like.

However, these herbicides are of course not limited to the above examples.

Herbicides of the present invention can be used in combination with fungicides, microbial pesticides, organo-phosphate insecticides, carbamate insecticides, pyrethrin insecticides, plant culture modifiers, chemical fertilizers and the like.

The present invention will be described in more detail with reference to the following examples.

Example 1 (Method (a))

A solution of 3- (2- (3-methoxyphenyl) ethoxy) -phenyl isocyanate (5.2 g) in benzene (100 mL) was added N, O-dimethyl hydroxyamine (50 mL). 2g) was added dropwise at a temperature of minus 30 ° C. The reaction mixture was left at room temperature for 30 minutes and the solvent was removed under reduced pressure.

The residue was recrystallized from ethanol to obtain 4.3 g of N'-3- (2- (3-methoxyphenyl) ethoxy) phenyl-N-methoxy-N-methyl urea (Compound No. 11) as a white needle. . Melting Point 53 ~ 54 ℃

Elemental Analysis: Calcd for C ₁₈ H ₂₂ O ₄ H ₂ (%): C, 65.44; H, 6.71; N, 8.48

Found (%): C, 65.23; H, 6.83; N, 8.52;

NMR δ CDCl ₃ : 3.02 (t, 2H); 3.15 (s, 3 H); 3.72 (s, 3 H); 3.78 (s, 3 H); 4.17 (t, 2 H); 6.40-7.35 (8H); 7.60 (2, 1H).

Compounds (I) such as compounds No. 7, 13, 15, 17, 19, 21, 23, 27 and 30 were synthesized in the same manner as described above.

Example 2 (Method (a))

A solution of dimethylamine (6 g) in benzene (100 mL) was added dropwise to a solution of benzene (3-phen ethyloxyphenyl isocyanate (15 g) in 200 mL) dropwise at 30 ° C.

The reaction mixture was left to stand at room temperature for 1 hour, and the solvent was removed under reduced pressure.

This residue was recrystallized from ethanol to obtain 13.6 g of N'-3-phenethyloxyphenyl-N, N-dimethyl urea (Compound No. 2) as a white needle. Melting Point 100 ~ 101 ℃

Elemental Analysis: Calcd for C ₁₇ H ₂₀ O ₂ N ₂ (%): C, 71.80; H, 7.09; N, 9.85.

Found (%): C, 71.84; H, 7.06; N, 9.84.

NMR δ CDCl ₃ : 2.94 (s, 6H); 3.02 (t, 2H); 4.10 (t, 2 H); 6.20-7.40 (10 H).

Compounds (I) such as compounds No. 4, 6, 8, 10, 12, 18, 22, 24 and 31 were synthesized in the same manner as described above.

Example 3 (Method (a))

To a solution of 3- [2- (4-chlorophenyl) ethoxy] -phenyl isocyanate (10 g) in benzene (500 mL) was added a solution of monomethylamine in benzene (100 mL) at minus 30 ° C. It was added dropwise.

The reaction mixture was left to stand at room temperature for 1 hour and the solvent was removed under reduced pressure.

This residue was recrystallized from ethanol to obtain 7.3 g of N'-3 (2- (4-chlorophenyl) ethoxy) -phenyl-N-methylurea (Compound No. 33) as a white needle. Melting point 126 ~ 127 ℃

Elemental Analysis: Calcd for C ₁₆ H ₁₇ O ₂ CI (%): C, 63.05; H, 5.62; N, 9.19; C, 11.63.

Found (%): C, 63.09; H, 5.58; N, 9.16; C, 11.67.

NMR δ CDCl ₃ : 2.69 (s, 6H); 3.00 (t, 2 H); 4,06 (t, 2H); 5.80 (m, 1 H); 6.20-7.30 (8H); 8.17 (s, 1 H).

Compound (I) like Compound No. 32 was synthesized in the same manner as described above.

Example 4 (Method (b))

Hydroxylamine hydrochloride (5 g) and sodium hydroxide (2.8 g) in a solution of 3-phenethyloxyphenyl isocyanate (4.8 g) in methylene chloride (60 mL) were added to water (10 mL) at -20 ° C. It was added dropwise to a solution of.

The charged crystals were collected by filtration and dried to give 4 g of N'-3-phenethyl oxyphenyl-N-hydroxy-urea. To an aqueous solution of hydroxyurea derivative (4 g) in a mixture of benzene / methanol (1: 1) (150 mL) was added an aqueous solution of dimethyl sulfate (2.8 mL) and sodium hydroxide (10 N, 6 mL) at -30 ° C. Alternately.

After stirring at room temperature the reaction solution was diluted with water and extracted with benzene.

The solvent was removed from the extract under reduced pressure and the residue was recrystallized from ethanol to obtain 1.8 g of white prism N'-3-phenethyloxy phenyl-N-deoxy-N-methylurea (Compound No. 1). Melting Point 82.0 ~ 82.5 ℃

Elemental Analysis: Calcd for C ₁₇ H ₂₀ N ₂ C ₃ (%): 7C, 6.98; H, 6.71; N, 9.33.

Found (%): C, 67.83; H, 6.82; N, 9.31.

NMR δ CDCl ₃ : 3.04 (t, 2H); 3.12 (s, 3 H); 3.69 (s, 3 H); 4.14 (t, 2 H); 6.40-7.40 (9H); 7.60 (s. 1 H).

Compounds (I) such as compounds Nos. 9 and 25 were synthesized in the same manner as described above.

Example 5 (Method (a))

To the solution of sodium ethoxide (2 g) in N, N-dimethylformamide (100 mL) was added N'-3-hydroxyphenyl-N-methoxy-N-methylurea (4 g).

To this was then added dropwise a solution of 2- (2-methylphenyl) ethyl bromide (4 g) in N, N-dimethyl formamide (50 mL).

The reaction mixture was slowly heated to hold at 90 ° C. to 100 ° C. for 3 hours, poured into ice water and extracted with benzene. The solvent was removed under reduced pressure and the residue was recrystallized from ethanol to give 3.2 g of N'-3- [2- (2-methylphenyl) ethoxy] phenyl-N-methoxy-N-methyl urea (compound) as a white needle. No. 3) was obtained.

Melting Point 88 ~ 89 ℃

Elemental Analysis: Calcd for C ₁₈ H ₂₂ O ₃ N ₂ (%): C, 68.77; H, 7.05; N, 8.91.

Found (%): C, 68.46; H, 7.03; N, 8.92.

NMR δ CDCl ₃ : 2.35 (s, 3H); 3.09 (t, 2 H); 3.15 (s, 3 H); 3.70 (s, 3 H); 4.13 (t, 2 H); 6.40-7.30 (8 H); 7.55 (s. 1 H).

In the same manner as described above, compounds (I) such as compounds No. 5, 14, 16, 20, 26, 28 and 29 were synthesized.

Example 6 (Method (a))

To a solution of 3-phenethylthiophenyl isocyanate (25.5 g) in benzene (300 mL) was added dropwise a solution of N, O-dimethyl hydroxylamine (8 g) in benzene (10 mL) at 20 to 30 ° C. Was added.

After stirring for a while at room temperature, the solvent was removed under reduced pressure. This residue was recrystallized from ethanol to obtain 30.5 g of N'-3-phenethyl thiophenyl-N-deoxy-N-methyl urea (Compound No. 34) as a white needle.

Melting Point 76 ~ 77 ℃

Elemental Analysis: Calcd for C ₁₇ H ₂₀ O ₂ N ₂ S (%): C, 64.53; H, 6.37; N, 8.86; S, 10.13.

Found (%): C, 64.30; H, 6.44; N, 8.69; S, 9.90.

NMR δ CDCl ₃ : 3.01 (m, 4H); 3.10 (s, 3 H); 3.68 (s, 3 H); 6.80-7.50 (9H); 7.59 (s. 1 H).

Compounds (I) such as compounds Nos. 35, 36, 41, 43, 44 and 46 were synthesized in the same manner as described above.

Example 7 (Method (a))

A solution of hydroxylamine hydrochloride (7 g) and sodium hydroxide (4 g) in a solution of 3- (4-chlorophenethylthio) phenyl isocyanate (15 g) in methylene chloride (500 mL) in water (15 mL) Was added dropwise at a temperature of minus 20 ℃.

After dilution with water, the precipitated crystals were collected by filtration and dried to obtain 16.3 g of N'-3- (4-chlorophenethylthio) phenyl-N-hydroxy urea.

Then 16.3 g of hydroxy urea derivative was dissolved in a mixture of benzene / methanol (1: 1), and 10 ml of 10N aqueous sodium hydroxide solution and 12 g of dimethyl sulfate were added dropwise at 30 ° C.

After stirring at room temperature the reaction mixture was diluted with water and extracted with benzene.

The solvent was removed from the extract under reduced pressure and the residue was recrystallized from ethanol to give 13.4 g of N'-3- (4-chlorophenethylthio) phenyl-N-methoxy-N-methyl urea (Compound No.) as a white needle. .45).

Melting Point 88 ~ 89 ℃

Elemental Analysis: Calcd for C ₁₇ H ₁₉ O ₂ N ₂ (%): C, 58.19; H, 5.46; N, 8.00; C, 10.11; S, 9.14.

Found (%): C, 57.99; H, 5.55; N7.89; C, 10.13; S, 9.01.

NMR δ CDCl ₃ : 2.97 (m, 4H); 3.11 (s, 3 H); 3.68 (s, 3 H); 6.70-7.55 (8H); 7.65 (s. 1 H).

Example 8 (Method (a))

N'-3-mercaptophenyl-N, N-dimethylurea (20 g) was added to a solution of sodium ethoxide (6.8 g) in N, N-dimethylformamide (200 mL), and N, N was added thereto. A solution of 2-methylphenethyl bromide (20 g) in -dimethylformamide (100 mL) was added dropwise.

The reaction mixture was gradually heated to hold at 100 ° C. for 5 hours, poured into ice water, and then extracted with benzene. The solvent was removed from the extract under reduced pressure, and the residue was recrystallized from ethanol to give 24.5 g of N "-3- (2-methylphenethylthio) phenyl-N, N-dimethyl urea (Compound No. 38) as a white needle. Get)

Melting point 128 ~ 129 ℃

Elemental Analysis: Calcd for C ₁₈ H ₂₂ OH ₂ S (%): C, 68.75; H, 7.05; N, 8.91; S, 10.20.

Found (%): C, 68.49; H, 7.26; N8.63; S, 9.99.

NMR δ CDCl ₃ : 2.22 (s, 3H); 2.919 (m, 4 H); 2.93 (s, 6 H); 6.41 (s, 1 H); 6.60-7.40 (8 H).

Mixture No. in the same manner as described above. Compounds (I) such as 40, 42, 47 and 48 were synthesized.

Example 9 (Method (a))

To a solution of 3- (3-phenylpropoxy) phenyl isocyanate (12.7 g) in benzene (100 mL) was added 20 to 20 to a solution of N, O-dimethyl hydroxyl amine (5 g) in benzene (50 mL). It was added dropwise at 30 ℃.

The reaction mixture was further stirred at the same temperature for 30 minutes. The solvent was removed under reduced pressure and the residue was recrystallized in ethanol to obtain 11.5 g of N'-3- (3-phenylpropoxy) phenyl-N-methoxy-N-methylurea (Compound No. 49) as a white needle. . Melting Point 82 ~ 83 ℃

Elemental Analysis: Calcd for C ₁₈ H ₂₂ N ₂ O ₃ (%): C, 68.77; H, 7.05; N, 8.91.

Found (%): C, 68.79; H, 7.06; N, 8.88.

NMR δ CDCl ₃ : 2.05 (m, 2H); 2.75 (t, 2 H); 3.09 (s, 6 H); 3.61 (t, 2 H); 3.88 (t, 2 H); 6.85-7.30 (9H); ; 7.61 (s, 1 H).

Compound No. in the same manner as described above. 55, 51, 52, 53, 56, 58, 63, 64, 70, 71, 74, 75, 76, 77, 78, 79, 80, 93, 94, 101, 102, 109, 110, 111, 112, Compounds such as 113, 114, 115, 118, 119, 120, 121, 122, 123, 124, 125, 126, 127, 128, 129, 134, 135, 138, 139, 140, 141, 143 and 144 ) Were synthesized.

Example 10 (Method (b))

Hydrochloric acid hydroxylamine (3.5 g) and hydroxide in a solution of 3- [3,4-dichlorophenylpropoxy] -phenylisocyanate (16.1 g) in methylene chloride (50 mL) in water (15 mL) To a solution of sodium (2.1 g) was added dropwise at a temperature of minus 20 ℃.

After dilution with water, the precipitated crystals were collected by filtration and dried to give 15.3 g of N'-3- [3- (3,4-dichlorophenyl) propoxy] -phenyl-N-hydroxy urea.

To a solution of hydroxyurea derivative (15.3g) sulfuric dimethyl (22g) and tetra-n-butyl ammonium bromide (0.15g) in toluene (240ml) was added dropwise an aqueous solution of sodium hydroxide (10N 17.0ml). Was added.

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

The benzene layer was washed with water and then the solvent was removed under reduced pressure. This residue was recrystallized from ethanol to give 13.6 g of N'-3- [3- (3,4-dichlorophenyl) -propoxy] phenyl-N-methoxy-N-methyl urea as a white needle (Compound No. 55 ) Melting Point 68 ~ 69 ℃

Elemental Analysis: Calcd for C ₁₈ H ₂₀ Cl ₂ N ₂ O ₃ (%): C, 5.40; H, 5.26; N, 7.31; C, 18.50.

Found (%): C, 56,46; H, 5.25; N, 7.30; C, 18.50.

: 2.01(m,2H); 2.72(t,2H); 3.11(s,3H); 3.66(s,3H); 3.89(t, 2H); 6.3C-7.30(7H); 7.55(s,1H).

: 2.01 (m, 2H); 2.72 (t, 2 H); 3.11 (s, 3 H); 3.66 (s, 3 H); 3.89 (t, 2 H); 6.3C-7.30 (7H); 7.55 (s, 1 H).

Compound No. in the same manner as described above. Compounds (I) such as 59,65,69,81,83,87,89,81,95,99,107.116,130 and 136 were synthesized.

Example 11 (Method (C))

A solution of 3- (4-phenylbutoxy) aniline (25 g), 40% aqueous sodium hydroxide solution (100 ml) and N, N-dimethyl carbamyl chloride (17 g) in toluene (200 ml) was heated under reflux for 10 hours. It was.

The reaction mixture was allowed to stand at room temperature. The toluene layer was washed with water and the solvent was removed under reduced pressure. This residue was recrystallized from ethanol to obtain 20.6 g of N'-3- (4-phenylbutoxy) phenyl-N and N-dimethyl urea (Compound No. 66) as white needles. Melting Point 115 ~ 116 ℃

Elemental Analysis: Calcd for C ₁₉ H ₂₄ N ₂ O ₂ (%): C, 73.04; H, 7.74; N, 8.97.

Found (%): C, 72.89; H, 7.88; N8.80.

NMR ^δ CDCl ₃ : 1.72 (m, 4H); 2.62 (t, 2 H); 2.90 (s, 6 H); 3.86 (t, 2 H). 6.40-7.30 (10 H).

Compound No. in the same manner as above. Compounds (I) such as 54, 60, 82, 88, 92, 100, 108, 117, 131, 137 and 142 were synthesized.

Example 12 (Method (a))

To a solution of sodium ethoxide (6.8 g) in N, N-dimethyl formamide (200 mL) was added 20 g of N '-(3-hydroxyphenyl) -N-methoxy-N-methyl urea, to which A solution of 3- (4-methylphenyl) propyl bromide (21 g) in N, N-dimethyl formamide (100 mL) was added dropwise. The reaction mixture was gradually heated, held at 100 ° C. for 5 hours and poured into ice water.

The precipitated crystals were collected by filtration, washed sequentially with water, ethanol and ether, dried in air and recrystallized from ethanol to give a white needle of 27 g of N'-3-3- (4-methylphenyl) propoxyphenyl-N. -Methoxy-N-methylurea (Compound No. 57) was obtained. Melting Point 75 ~ 75 ℃

Elemental Analysis: Calcd for C ₁₉ H ₂₄ H ₂ O ₃ (%): C, 69.49; H, 7.37; N, 8.53.

Found (%): C, 69.23; H, 7.53; N8.49.

NMR ^δ CDCl ₃ : 2.01 (m, 2H); 2.30 (s, 3 H); 2.25 (t, 2 H); 3.11 (s, 3 H); 3.67 (s, 3 H); 3.90 (t, 2 H); 6.40-7.30 (8 H); 7.62 (s, 1 H)

Compound No. in the same manner as described above. Compounds (I) such as 61, 62, 67, 68, 72, 73, 84, 85, 86, 90, 96, 97, 98, 103, 104, 105, 106, 132 and 133 were synthesized.

The use of compounds (I) as herbicides is illustrated in the following examples, where the phytotoxicity of the crops and the herbicidal action against weeds were evaluated as follows.

The aerial exposure of the treated test plants was cut and weighed to determine the percentage of the new weight of the untreated and the new weight of the untreated. Phytotoxicity against cultivated plants and herbicidal action against weeds were expressed in a class of integers from 0 to 5 according to the criteria shown in the following table.

Classifications 5 and 4 are generally recognized as satisfactory for preventing weeds in cultivated plants.

The classification value of the crop test alone was calculated from the dry weight of the plant.

The following control compounds were used in the examples.

Example 13 (Workpiece Test)

Wagner's jars (1/5000 are) were filled with 1.5 kg of oar soil containing weed seeds and dipped under flooded water.

To this the seedlings were seeded in the third leaf stage and grown for 5 days.

The required amount of hydrating agent of each test compound was then diluted with water and used in soil under flooded conditions.

25 days after this, weeding and phytotoxicity were evaluated for crop blood, broad-leaved weeds (for example, stilt, grass of grass, node flower) and algae.

These results are shown in Table 1.

TABLE 1

Example 14 (Herbicidal Action by Post- Germination Treatment)

Fill the plastic trays (35 × 25 × 10 cm) with topsoil, trays with bream, radishes, red mallow, white mallow, black walnut, sunflower, annual morning glory, zombies, ragweed and blood seeds. Sprinkled in water and grown in greenhouse for 2-3 weeks. The requirement of the test compound was sprayed on the leaves of the test plants from above with a small hand sprayer. After the share price on the leaves, these plants were further grown in the greenhouse for three weeks. Then the herbicidal action was examined. When the share price on the above-mentioned leaves was used, these test compounds were formulated as emulsified concentrates, respectively, and a humectant was added and dispersed in water for use at a spraying capacity of 5 liters per each are. The height of the plant at the time of share price on the leaves is different depending on the type, but was carried out at the stage of 2 to 4 leaves and the height of 2 to 10 cm.

The results are shown in Table 2.

[Table 2]

Example 15 (Selectivity to Crops by Post- Germination Treatment)

Wagner's jars (1 / 5,000 are) were filled with topsoil each and seeded separately from corn, wheat, crops, cotton, soy and beet, and grown in greenhouses for two to three weeks.

The required amount of test compound was then sprayed onto the leaves of the test plant with a small hand sprayer. After spraying, the test plants were grown for three more weeks in the greenhouse and then examined for phytotoxicity for each plant.

In the cycles to the leaves described above, the test compounds were formulated as emulsified concentrates, respectively, and added to the humectant and dispersed in water for use in a volume of 5 liters per each arena.

Maize leaves are 2-leaf stages, wheat is 2-leaf stages, crops are 3-leaf stages, cotton is 1-leaf stages, soybeans is 2-3 stages, and beets are 2-leaf stages. This was.

The results are shown in Table 3.

TABLE 3

Example 16 (Process before germination)

Fill the topsoil with plastic trays (35 × 25 × 10 cm) and use the beans, cotton, beets, corn, wheat, rice, red rooted mallow, white mallow, radish, comon pure sarane Seeds were sprinkled separately on these trays. For use at a capacity of 3 liters per each areal, a small volume of the hydrating agent of each test compound was dispersed in water and sprayed onto the front of the soil with a small manual sprayer.

After spraying, the test crops were grown in a greenhouse for 20 days and tested for phytotoxicity and herbicidal activity.

Inspection was carried out on the same criteria as described above. The results are shown in Table 4.

Table 4

The use of compounds (I) as fungicides is illustrated in the following examples, which were used to compare fungicides known under the general name "Trisoline" and obtained as a commodity having the following general formula.

Example 17 (Protective Effect of Leaf Rust on Wheat)

Wheat (excitation: Nohrin No. 61) was grown in pots 9 cm in diameter up to the one-leaf stage, inoculated with Puccinia recondita and placed in a wet room for 18 hours. Each emulsion concentrate containing test compounds was then diluted with water and sprayed at the rate of 15 ml / jar for test plants. These test plants were placed in a room kept at 20 ° C, and further grown for 10 days under fluorescent lamps. The infectious state was observed and the degree of disease was calculated based on the following standards.

The results are shown in Table 5.

Table 5

Claims (1)

A method for producing an N'-phenyl-N-methylurea derivative represented by the general formula (I), which is reacted with a phenyl isocyanate derivative represented by the following general formula (II) and an amine of the general formula (III).

Wherein R ₁ is a hydrogen atom, a methyl group or a methoxy group, R ₂ is a hydrogen atom or a lower alkyl group, R ₃ is a halogen atom, a lower alkyl group, a lower alkoxy group, a lower alkylthio group, Or a trifluoro methyl group, n is an integer from 0 to 5, X is a hydrogen atom or a halogen atom, Y is an oxygen atom or a sulfur atom, Z is one oxygen at the end of the carbon chain or at its inner axis And or a straight or branched C ₁ -C ₈ alkylene group having a sulfur atom)