KR820000116B1 - Process for the preparation of carbamic acid ester - Google Patents

Abstract

Herbicidal carbamic acid-[3-(3-cyclopropyl-ureido)-phenyl -ester(I; R,R1 = H, substituted hydrocarbon) were prepd. by reaction of 1-cyclopropyl-3-(3-hydroxyphenyl)-urea(II) and carbamoylchloride(III) under acid coupling agent. Thus, 6.6g III(R = H; R1 = C4H9) and 3 drops of (C2H5)3N were added to 11.5 g II followed by filtering with diisopropylether to give 14.0 g I(m.p.; 154≰C). I had herbicidal activity at 5 kg/ha.

Description

How to prepare carbamate

The present invention relates to a process for producing novel carbamic acid-[3- (3-cyclopropyl-ureido) -phenyl] -ester having the following general formula (I), which is effective as a herbicide.

R and R ₁ in the general formula may be the same or different from each other, and each represent hydrogen, aliphatic hydrocarbon, substituted aliphatic hydrocarbon, alicyclic hydrocarbon, substituted substituted hydrocarbon, aromatic hydrocarbon, substituted aromatic hydrocarbon, heterocyclic group or R And R ₁ represents a heterocyclic group together with a nitrogen atom.

The herbicidal action of carbamic acid- [3- (3-alkylureido) -phenyl] -ester is known (German Publication 1518815), but the herbicidal action of this compound has not always been satisfactory. It is therefore an object of the present invention to make a herbicide having a stronger herbicide than any herbicide known in the art, which object is to contain a compound of formula (I) according to the present invention. Could be achieved.

The compounds according to the invention exhibit more potent herbicidal action and better selectivity than known structurally similar compounds which exhibit similar actions.

The compounds according to the present invention can be effectively used for monocotyledonous and dicotyledonous plants because they exhibit a wide range of herbicidal action, and because they are selective, they can be used without damaging many crops such as potatoes, rice, vegetables, peanuts, peas, etc. Can be.

The compounds according to the invention can be used before and after germination, for example, sunflowers, pine needles, chrysanthemums, wild herbs, cockscomb, blood, foxtail, humbus, mustard, matricaria, apomea, centaurea, Can remove weeds such as sageweed and lolium.

To remove weed seeds, the active substance is usually used at a rate of 0.5 kg / ha-5 kg / ha.

The compound according to the present invention can be effectively used as an extensive herbicide for extinction or suppression of weeds in wasteland in which weeds are grown in excess.

The compounds according to the invention can be used alone or in admixture with other active substances. As desired, the following herbicides may be used by direct mixing before using the compounds according to the invention.

Substituted aniline

Substituted aryloxycarboxylic acids and salts, esters and amides thereof

Substituted Etel

Substituted arsenic acids and salts thereof, esters and amides

Substituted benzimidazoles

Substituted Benzisothiazole

Substituted Benzthiadia Dioxide

Substituted benzoxazines

Substituted benzoxazide

Substituted Benzthiadiazine

Substituted Benzthiazole

Substituted Biuret

Substituted Quinoline

Substituted carbamate

Substituted aliphatic carboxylic acids and salts thereof, esters and amides

Substituted aromatic carboxylic acids and salts thereof, esters, amides

Substituted carbamoyl alkylthio- or dithiophosphates

Substituted Quinazolin

Substituted cycloalkylamido carbondiol acids and their salts, esters, amides

Substituted cycloalkyl carbon amido-thiazole

Substituted dicarboxylic acids and salts thereof, esters and amides

Substituted dihydrobenzofuranylsulfonates

Substituted disulfide

Substituted dipyridium salts

Substituted dithiocarbamates

Substituted dithiophosphoric acid and salts thereof, esters and amides

Substituted pyridine

Substituted pyridinecarboxylic acid salts

Substituted pyridinones

Substituted pyrimidones

Substituted pyrrolidinecarboxylic acids and salts thereof, esters, amides

Substituted pyrrolidines

Substituted arylsulfonic acids and salts thereof, esters, amides

Substituted styrol

Substituted Tetrahydrooxadiazinedione

Substituted tetrahydromethanoindenes

Substituted Tetrahydro-Diazole-Tion

Substituted Urea

Substituted hexahydro-1H-carbothioate

Substituted hydantoin

Substituted hydrazide

Substituted Hydrazonium Salts

Substituted isooxazole pyrimidone

Substituted imidazole

Substituted Isoziazole Pyrimidone

Substituted ketones

Substituted naproquinones

Substituted aliphatic natryl

Substituted aromatic nitriles

Substituted oxadiazoles

Substituted Oxadiazide

Substituted oxadiazolidinediones

Substituted Oxadiazine Dione

Substituted phenols and salts thereof, esters

Substituted phosphonic acids and salts thereof, esters, amides

Substituted phosphonium chlorides,

Substituted Phosphonalkyl Glycine

Substituted Phosphoric Acid

Substituted phosphoric acid and salts thereof, esters, amides

Substituted piperidine

Substituted pyrazoles

Substituted pyrazolealkylcarboxylic acids, salts, esters, amides

Substituted pyrazolium salts

Substituted pyrazoliumalkylsulfates

Substituted pyridazines

Substituted pyridazones

Substituted pyridinecarboxylic acids and salts thereof, esters, amides

Substituted tetrahydro-thiadiazine-thione

Substituted Tetrahydro-thiadiazinedione

Substituted Thiadiazole

Substituted Aromatic Thiocarboxylic Acid

Substituted thiocarboxylic acids and salts thereof, esters, amides

Substituted diol carbamates

Substituted thiophosphates and salts thereof, esters, amides

Substituted triazine

Substituted triazoles

Substituted uracil

Substituted uretidinediones

Other adducts which are not toxic to plants and which can cause synergism to herbicides, for example emulsifiers, wetting agents, solvents and oily adducts may be used.

The active substances or mixtures thereof of the present invention may be prepared by using liquid and / or solid carriers or diluents and, if necessary, wetting agents, adhesives, emulsifiers and / or dispersion aids, such as powders, dusting agents, granules, solutions, emulsions or suspensions. It may be formulated in the form of a formulation.

Suitable liquid carriers are, for example, water, aliphatic and aromatic hydrocarbons (eg benzene, toluene, xylene, cyclohexane, isophorone, dimethylsulfoxide, dimethylformamide) and petroleum fractions.

Solid carriers are, for example, plant products such as tonsil, silica gel, talc, cowlin, araclay, limestone, silicic acid and grain flour.

Examples of the surfactant include calcium lignin sulfonide, polyoxyethylene alkyl-phenylethyl, naphthalene sulfonic acid and salts thereof, phenol sulfonic acid and salts thereof, formaldehyde condensates, substituted benzene sulfonic acids and salts thereof, and aliphatic alcohols. . The concentration of active substance in various formulations can vary widely. For example, the formulation may contain 10 to 80% by weight of active substance and 90 to 20% by weight of a liquid or solid carrier, and may contain up to 20% by weight of surfactant as necessary.

Spraying of the preparation is carried out in a conventional manner, for example, at a rate of 100-1000 liters per hectare using water as a carrier. The active compound can also be used in the form of so-called "low dose method", "ultra low dose method" and so-called fine particles.

R. R ₁ in the compounds according to the invention are each hydrogen, C ₁ -C ₆ alkyl, C ₂ -C ₆ alkenyl, C ₂ -C ₆ alkynyl, C ₃ -C ₆ cycloalkyl, phenyl, C _1- C ₃ alkyl-phenyl, halogenophenyl, C ₁ -C ₃ alkoxy-phenyl, trifluoromethyl-phenyl, nitrophenyl or naphthyl groups (where phenyl and naphthyl groups are mono- or di-substituted with the same or different substituents). The compound of formula (I), which indicates that it can, exhibits particularly potent herbicidal action.

Examples of such groups of R and R ₁ are methyl, ethyl, porphyll, isopropyl, allyl, propionyl, cyclopropyl, butyl, isobutyl, secondary-butyl, tert-butyl, pentyl, isopentyl, hexyl , Cyclohexyl, phenyl, methylphenyl, dimethylphenyl, chlorophenyl, dichlorophenyl, methoxyphenyl, dimethylphenyl, chlorophenyl, dichlorophenyl, methoxyphenyl, dimethoxyphenyl, trifluoromethylphenyl, nitrophenyl, and naphthyl Wherein the phenyl group and the naphthyl group may be mono or disubstituted with the same or different substituents.

The compound of formula (I) is prepared by reacting 1-cyclopropyl-3- (3-hydroxyphenyl) -urea of formula (II) with carbamoyl chloride of formula (III) in the presence of an acid binder. do.

In the general formula, R and R ₁ are as described above.

Acid binders can be used for all materials conventional in the art. Suitable organic bases for this are tertiary amines such as triethylamine or N, N-dimethylaniline or pyridine and suitable inorganic bases are oxides, hydroxides and alkanates of alkali and alkaline earth metals. Liquid organic bases can be used as solvents at the same time.

1-Cyclopropyl-3- (3-hydroxyphenyl) -urea (melting point 154 ° C.) can be easily mowed from m-aminophenol and cyclopropyl isocyanate.

This reaction can be carried out at 0 ° -120 ° C. It is generally carried out at room temperature and the reaction reagents are used in the same amount when synthesizing the compound of the present invention.

Suitable reaction solvents should be solvents which are inert to the reaction reagents, for example aliphatic and aromatic hydrocarbons (eg petroleum ether, cyclohexane, benzene, toluene and xylene), halogenated hydrocarbons (eg methylene chloride, chloroform, carbon tetrachloride) , Halogenated ethylene, ethereal compounds (e.g. diethyl ether, tetrahydrofuran, dioxane), ketones (acetone, tiltylisobutyl ketone, isophorone), esters (e.g. tilme- and ethyl acetate), acidamide ( Such as ditylmeformamide, hexamethylphosphortriamide), carboxylic acid nitrile (eg acetonitrile) and the like.

If the compound according to the invention formed is a material that is difficult to melt, it is filtered and if it is a material that is easily soluble, evaporate the added solvent under atmospheric pressure or reduced pressure or apply it to an ether or hydrocarbon such as a less polar solvent such as petroleum ether or diisopropyl ether. Put it apart.

The following examples detail the preparation of the compounds according to the invention.

Example 1

To 11.5 g of 1-cyclopropyl-3- (3-hydroxyphenyl) -urea solution, 6.6 g of butyl isocyanate and three drops of triethylamine are added with stirring. Leaving overnight produces a colloidal material which is filtered off with suction and washed with diisopropyl ether. Butylcarbamic acid-[3- (3-cyclopropylureido) -phenyl] -ester of 14.0 g (80.3% of theory) is obtained. Melting Point: 154 ℃

Elemental Analysis: Calculation: C 61.84% H 7.27% N 14.42%

Found: 61.78% 7.68% 14.61%

Example 2

70 ml of a solution of 76.5 g of N-ethyl-N-phenyl-carbamoyl chloride dissolved in pyridine was suspended in 60 ml of pyridine with 19.2 g of 1-cyclopropyl-3- (3-hydroxyphenyl) -urea. Add. Stirring at 70 ° C. for 3 hours gives a transparent solution. After cooling to room temperature, the reaction mixture is poured into ice water, acidified by adding hydrochloric acid, and the separated material is extracted with methylene chloride. The organic layer was washed with dilute hydrochloric acid and water, dehydrated with magnesium sulfate, and the solvent was distilled off under vacuum. The remaining cinnabar is recrystallized from diisopropyl ether.

Product: 29.7 g (87.6% of theory) N-ethyl-N-phenylcarbamic acid- [3- (3-cyclopropylureido) -phenyl] -ester Melting point: 120 degreeC

Elemental Analysis: Calculated Value: C, 67.2% H, 6.24% N, 12.38%

Found: C, 67.35% H, 6.33% N, 11.99%

In a similar manner, the compounds according to the invention can be prepared as follows.

Compound Name Melting Point (℃)

Carbanic acid-(3- (3-cyclopropyl ureido) -phenyl)-ester 160 degrees Celsius

Methyl carbamic acid-(3- (3-cyclopropyl ureido) -phenyl)-ester 143 degrees Celsius

Ethyl carbamic acid-(3- (3-cyclopropyl ureido) -phenyl)-ester 170 degreeC

Cyclopropyl carbamic acid-(3- (3-cyclopropyl ureido) -phenyl)-ester 184 degrees Celsius

Tert-butylcarbamic acid-(3- (3-cyclopropylureido) -phenyl) -ester 137 degrees Celsius

Isopropyl carbamic acid-(3- (3-cyclopropyl ureido) -phenyl)-ester

180 ° C (decomposition)

3-Methylcarbanic acid-(3- (3-cyclopropyl ureido) -phenyl)-ester 155 degrees Celsius

Allyl carbamic acid-(3- (3-cyclopropyl ureido) -phenyl)-ester 153 degrees Celsius

Propyl carbamic acid-(3- (3-cyclopropyl ureido) -phenyl)-ester 160 degrees Celsius

Cyclohexyl carbamic acid-(3- (3-cyclopropyl ureido) -phenyl)-ester 182 degrees Celsius

3-Chlorocarbanilic acid-(3- (3-cyclopropyl ureido) -phenyl)-ester 161 degreeC

Dimethyl carbamic acid-(3- (3-cyclopropyl ureido) -phenyl)-ester 118 degrees Celsius

Diallyl carbamic acid-(3- (3-cyclopropyl ureido) -phenyl)-ester 66 degrees Celsius

N-methyl-N-phenylcarbamic acid-(3- (3-cyclopropyl ureido) -phenyl) -ester 155 degreeC

3-methoxycarbanic acid-(3- (3-cyclopropyl ureido) -phenyl)-ester 115 degreeC

3, 5-dichlorocarbanoic acid-(3- (3-cyclopropyl ureido) -phenyl)-ester 174 degreeC

Diphenyl carbamic acid-(3- (3-cyclopropyl ureido) -phenyl)-ester 190 degrees Celsius

3-nitrocarbanic acid-(3- (3-cyclopropyl ureido) -phenyl)-ester 185 degrees Celsius

1-naphthyl carbamic acid-(3- (3-cyclopropyl ureido) -phenyl)-ester 187 degrees Celsius

3-trifluoromethylcarbanoic acid-(3- (3-cyclopropyl ureido) -phenyl)-ester 179 degreeC

3, 4-dichlorocarbanoic acid-(3- (3-cyclopropyl ureido) -phenyl)-ester 179 degreeC

2-Methylcarbanic acid-(3- (3-cyclopropylureido) -phenyl)-ester 170 degrees Celsius

The compound according to the invention is a colorless, odorless crystalline substance, insoluble in water and nonpolar organic solvents (e.g. hydrocarbons), slightly soluble in ether, ketones, esters, carbonitriles and alcohols, dimethylsulfoxide, dimethylformamide and lower Soluble in organic solvents of the same polarity as carboxylic acids.

The following test examples detail the use of the compounds according to the invention.

[Test Example 1]

In a greenhouse, 5 kg / ha of the compound according to the present invention in the following table is suspended in 500 L / ha of water, and mustard and eggplant plants are sprayed before germination and after germination with test plants. Three weeks after the treatment, the treatment results were evaluated using the evaluation index, where 0 was the case where there was no damage to the plant and 4 was the case where all the plants were damaged. As can be seen from the following table, the test water is generally damaged.

0 = no damage

4 = All damage

[Test Example 2]

In a greenhouse, the compounds of the present invention are treated at a rate of 3 kg per hectare before the plants given in the following table germinate. N-propyl- [N '-(3-N "-methylcarbamoyloxy) -phenyl] -urea is used as a control substance, which is used as a suspending agent when the plant is young. The amount of sprayed water is hectare. 500 liters per day The treatment result is evaluated after 14 days (0 = when the whole is damaged, 10 = when little is not damaged).

The values in the following table show that the compounds according to the invention have excellent resistance to action while the known control material does not show any sufficient herbicidal action.

[Pre-germination treatment]

0 = totally damaged

10 = a little undamaged

[Test Example 3]

After germination of the plants given in the following table in the greenhouse, the compounds of the invention are treated at a rate of 3 kg per hectare. As a control substance, N-propyl- (N '-(3-N "-methylcarbamoyloxy) -phenyl] urea is used. As a suspending agent, the plant is sprayed when it is young. The amount of sprayed water is per hectare. 500 L. The result of the treatment is evaluated after 14 days (0 = all damaged, 10 = little damaged).

The values in the following table show that the compounds according to the invention have excellent resistance to crops, whereas the known control substances do not show any sufficient herbicidal action.

[Post-germination treatment]

0 = totally damaged

10 = a little undamaged

Claims (1)

1-cyclopropyl 3- (3-hydroxyphenyl) -urea of the following general formula (II) is reacted with carbamoyl chloride of the following general formula (III) in the presence of an acid binder to give the following compound of general formula (I) How to make ester.

R and R ₁ in the general formula may be the same or different from each other and each represent hydrogen, aliphatic hydrocarbon, substituted aliphatic hydrocarbon, alicyclic hydrocarbon, substituted alicyclic hydrocarbon, aromatic hydrocarbon, substituted aromatic hydrocarbon, heterocyclic group or R And R ₁ together with a nitrogen atom represent a heterocyclic group.