KR820000134B1 - Process for the preparation of carbanilic acid esters - Google Patents

Abstract

Title compds. (I; R1 = substituted or non-substituted aliphatic hydrocarbon; R2 = cyanoalkyl; R3 = substituted or non-substituted aromatic hydrocarbon; Y = O or S) were prepd. by reaction of II and amine of III in the presence of acid acceptor. Thus, 43.9g 3-anilinopropionic nitrate was reacted with 68.7g chloroformic acid-3-methoxycarbonylamino-phenylester and 41.4g potassium carbonate to give 76.6g N-(2-cyanoethyl)-carbanilic acid-[3-(methoxycarbabonylamino)-phenyl - ester. I showed excellent herbicidal activity against 24 weeds at 3 kg/ha with no damage to cotton.

Description

Method for producing carbanic acid ester

The present invention relates to a process for the preparation of novel carbanic acid esters of the general formula (I), which is useful as a selective herbicide.

In the above general formula, R ₁ is an unsubstituted or substituted aliphatic hydrocarbon group, R ₂ is a cyanoalkyl group, R ₃ is an unsubstituted or substituted aromatic hydrocarbon group, and Y is oxygen or sulfur.

The herbicidal action of the urethane is already known. (Note: German Patent Specification No. 1, 567, 151) However, this drug usually does not have a satisfactory and widespread action since some important weeds cannot be removed.

In particular, they were hardly expected to have excellent herbicidal effect by treating them before or after germination. These known herbicides have proven to be not selectable for cotton and other cultivated plants, and therefore these herbicides cannot be used for these plants.

Thus, an object of the present invention is to develop a herbicide having a wide range of activities on monocotyledonous and dicotyledonous plants and particularly having high selectivity for cotton and other cultivated plants.

This problem was solved by the compound according to the present invention of general formula (I).

Among the compounds according to the invention, in particular, having the following groups has excellent wide range action and selectivity.

R ₁ is C ₁ -C ₆ alkyl, C ₂ -C ₆ alkenyl, or C ₂ -C ₃ alkynyl group, R ₂ is cyanoalkyl having 1 to 4 carbon atoms in the alkyl site, and R ₃ is unsubstituted Phenyl or a phenyl group substituted with one or two (identical or different) substituents selected from C ₁ -C ₆ alkyl, C ₁ -C ₆ alkoxy, C ₁ -C ₃ alkylthio, halogen or trifluoromethyl Is oxygen or sulfur atom.

The best associated with this property is N- (2-cyanoethyl) -carbanoic acid- [3- (methoxycarbonylamino) -phenyl] -ester.

The compounds according to the invention are excellent for weeding unnecessary plants, and have a wide range of actions:

Gramineae: Festuca sp., Alopecurus sp., Agrotis sp., Oven (Avena sp.), Echinochloa, Puppy grass (Setaria sp.), Sorghum ( Sorghum sp.), Poa sp, Lolium sp., Arhenaterum sp., Phalaris sp., Phleum sp, Eleucine sp. Eleusine sp.), Bromus sp, Hordeum sp and the like.

Cyperaceae: Cyperus sp.

Liliaceae: Allium sp.

Amaranthaceae: Amaranthus sp.

Borageaceae: Ankusa sp., Amsinckia sp., Myosotis sp.

Caryophylaceae: Stellaria sp., Spergula sp., Cerastium sp.

Chenopodiaceae: Chenopodium sp., Salsola kali., Atriplex sp., Kochia sp.

Convolvulaceae: Ipomea sp.

Compositae: Ambrosia sp., Lactuca sp., Seneccio sp., Santhium sp., Galinsoga sp., Centaurea Species (Centaurea sp.), Matricaria sp., Helianthus sp., Chrysanthemum sp., And Cycorium intybus.

Cruciferae: Brassica sp, Cherantrants cheiri, Capsella sp., Thlaspi sp., Sinapis sp.

Labiatae: Lamium sp., Galeopsis sp.

Legumes (Leguminosae): Medigo sp., Trifolium sp., Vicia sp., Cassia sp.

Malvaceae: Abutilon theophrasti, Sida sp., Hibiscus sp.

Papaveraceae: Papaver sp.

Polygonaceae: Polygonum sp.

Purslane (Portulacaceae): Purslane (Portulaca sp.).

Rubiaceae: Galium sp, Richardia sp.

Ranunculaceae: Delphinium sp., Adonis sp.

Scrophulariaceae: Linaria sp., Digitalis sp., Veronica sp.

Solanaceae: Datura sp., Solanum sp., Physalis sp.

Nettle (Urticaceae): Urtica sp.

Umbelliferae: Daucus carota, etc.

The compounds can be used for these plants before and after germination treatment. The compounds according to the invention have the particular advantage of exhibiting a particularly high resistance to agricultural wells, in particular cotton and other cultivated plants.

It has also been found that the use of the compound according to the invention in combination with an interfacial ring agent in an amount exceeding the usual amount of use can increase its herbicidal action.

At this time, the weight ratio of the cyclic substance and the interfacial cyclization agent is 1: 10 to 1: 0.4, and particularly preferably the weight ratio of 1: 1 to 1: 2.

Accordingly, the present invention provides a composition consisting of a compound of formula (I) and a surfactant, wherein the composition ratio of the compound of formula (I) and a surfactant is from 1: 10 to 1: 0.4 and preferably from 1: 1 to 1: 2. to be. When two or more compounds of formula (I) and / or two or more surfactants are present in the composition, the composition ratio relates to the total amount of each compound.

The present invention also provides a herbicidal formulation consisting of a compound of formula (I) and a suitable carrier. This formulation may, of course, contain one or more compounds of the general formula (I) and may contain one or more surfactants in this proportion.

The present invention also provides a method of protecting a plant from weeds by treating the surroundings of a living plant with a compound of formula (I).

The compounds according to the invention can be used alone or in admixture with other active substances.

If desired according to the desired purpose, the following herbicide actives can be added directly before use.

Substituted aniline,

Substituted aryloxycarbonyl acids and salts thereof, esters and amides,

Substituted ether,

Substituted arsenic acid and salts thereof, esters and amides thereof,

Substituted benzimidazoles,

Substituted benzisothiazoles,

Substituted benzthiadiazinone dioxide,

Substituted benzoxazines,

Substituted benzoxazinones,

Substituted benzthiazoles,

Substituted benzthiadiazoles,

Substituted biuret,

Substituted quinoline,

Substituted carbamate,

Substituted aliphatic carboxylic acids, salts thereof, esters and amides,

Substituted aromatic carboxylic acids, salts thereof, esters and amides thereof,

Substituted carbamoylalkyl-thio- or dithiophosphates,

Substituted quinazolines,

Substituted cycloalkyl-amido carbonthiol acids and their salts, esters and amides,

Substituted cycloalkylcarbonamido-thiazoles,

Substituted dicarboxylic acids and salts thereof, esters and amides,

Substituted dihydrobenzofuranyl sulfonates,

Substituted disulfide,

Substituted dipyridium salts,

Substituted dithiocarbamate,

Substituted dithiophosphoric acid and salts thereof, ester amides thereof,

Substituted urea,

Substituted hexahydro-1H-carbothionate,

Substituted hydantoin,

Substituted hydrazide,

Substituted hydrazonium salts,

Substituted isoxazolepyrimidone,

Substituted imidazole,

Substituted isothiazolpyrimidone,

Substituted ketones,

Substituted naphthoquinones,

Substituted aliphatic nitriles,

Substituted aromatic nitriles,

Substituted oxadiazoles,

Substituted oxadiazinone,

Substituted oxadiazolidinediones,

Substituted oxadiazinedione,

Substituted phenols and salts and esters thereof;

Substituted phosphonic acids, salts thereof and esters and amides thereof,

Substituted phosphonium chlorides,

Substituted phosphonalkylglycines,

Substituted phosphites,

Substituted phosphoric acid and salts thereof, esters and amides,

Substituted piperidine,

Substituted pyrazoles,

Substituted pyrazolealkyl carboxylic acids and salts thereof, esters and amides,

Substituted pyrazolium salts,

Substituted pyrazolium alkyl sulfates,

Substituted pyridazines,

Substituted pyridazones,

Substituted pyridinecarboxylic acids and salts thereof, esters and amides,

Substituted pyridine,

Substituted pyridinecarboxylates,

Substituted pyridinones,

Substituted pyrimidone,

Substituted pyrrolidinecarboxylic acids, salts thereof, esters and amides thereof,

Substituted pyrrolidines,

Substituted arylsulfonic acids and salts thereof, esters and amides,

Substituted styrene,

Substituted tetrahydrooxadiazinedione,

Substituted tetrahydromethanoindenes,

Substituted tetrahydro-diazole-thione,

Substituted tetrahydro-thiadiazine-thione,

Substituted tetrahydro-thiadiazoledione,

Substituted thiadiazoles,

Substituted aromatic thiocarboxylic acid amides,

Substituted thio carboxylic acids and salts thereof, esters and amides,

Substituted thiol carbamates,

Substituted thio forphonic acid and salts thereof, esters and amides,

Substituted triazines,

Substituted triazoles,

Substituted uracils

Substituted uretidinediones.

As mixed components, in particular, the following active substances are listed.

4- (1, 1-dimethylethyl-2, 6-dinitro-N- (1-methylpropyl) -aniline,

,

,

-트리플루오로-3,5-디니트로 톨루엔-2,4-디아민,N ⁴ , N ⁴ -diethyl-

,

,

-Trifluoro-3,5-dinitro toluene-2,4-diamine,

2, 2-dichloropropionic acid,

4- (methylsulfonyl) -2, 6-dinitro-N, N-dipropylaniline,

,

,

-트리플루오로-2, 6-디니트로-N, N-디프로필-p-톨루이딘,

,

,

-Trifluoro-2, 6-dinitro-N, N-dipropyl-p-toluidine,

3- (3,4-dichlorophenyl) -1, 1-dimethylurea,

,

,

-트리플루오로-톨릴)-우레아,1, 1-dimethyl-3- (

,

,

-Trifluoro-tolyl) -urea,

3-tetrafluoroethoxyphenyl-N, N-dimethyl-urea,

2, 4-bis- (isopropylamino) -6- (methyldio) -S-triazine,

Mono-sodium-methanearsonate,

Di-sodium-methanearsonate,

Herbicide oil (naphtha)

3- (3,4-dichlorophenyl) -1-methoxy-1-methyl-urea,

4-phenylsulfonyl-trifluoromethanesulfono-0-toluidine,

Trichloracetic Acid,

Sodium- and potassium azide,

1, 1'-dimethyl-4,4'-bipyridylium-salt,

5-chloro-3- (2-tetrahydropyranyl) -6-methyluracil,

3- (4-brom-3-chlorophenyl) -1-methoxy-1-methylurea,

3- (p-chlorophenyl) -1, 1-dimethylurea,

3- (hexahydro-4, 7-methanoindan-5-yl) -1, 1-dimethylurea,

2-ethylrio-4, 6-bis (isopropylamino) -S-triazine,

Dimethyl-tetrachlor-terephthalate,

2-tert-butyl-4, 6-dinitrophenol,

N, N-dimethyl-2, 2-diphenylacetamide,

N-propyl-N- (2-chloroethyl) -α, α, α-trifluor-2, 6-dinitro-p-toluidine,

N-n-propyl-N-cyclopropylmethyl-4-trifluoromethyl-2, 6-dinitroaniline,

N-tert-butyl-2, 6-dinitro-3,4-xyldine,

N-tert-butyl-4-3-tert-butyl-2, 6-dinitro-aniline,

1, 1-dimethyl-3- (m-chlor-p-trifluoromethoxyphenyl) -urea,

Methyl-5- (2 ', 4'-dichlorphenoxy) -2-nitro-benzoate,

2- (3,4-dichlorophenyl) -4-methyl-1, 2, 4-oxadiazolidine-3, 5-dione,

N- (1-ethylpropyl) -2, 6-dinitro-3, 4-xyldine,

N-1-naphthylphthalamine acid,

2-[(4-chloro-6-ethylamino-triazin-2-yl) -amino] -2-methylpropionitrile,

,

,

-트리플루오르-m-톨릴)-3(2H)-피리다지논,4-chloro-5- (methylamino) -2- (

,

,

-Trifluoro-m-tolyl) -3 (2H) -pyridazinone,

2-chloro-2 ', 6'-diethyl-N- (methoxymethyl) -acetanilide,

N- (phosphomethyl) -glycine,

3,5-dinitro-N ⁴ , N ⁴ -dipropyl-sulfaniylamide,

r-2-ethyl-5-methyl-C-5- (2-methylbenzyloxy) -1, 3-dioxane,

C-5- (2-chlorbenzyloxy) -r-2-ethyl-5-methyl-1, 3-dioxane,

N-chloracetyl-N- (2, 6-diethylphenyl) -glycineethyl ether,

2- (1-allyloxyamino) -butylidene-5, 5-dimethyl-4-methoxy-carbonyl-cyclohexane-1,3-dione,

(1-methylethyl) -phosphoamidothioate,

2- [4- (4-chlorophenoxy) -phenoxy] -propionic acid-isobutyl ester,

2- [4- (2,4-dichlorophenoxy) -phenoxy] -propionic acid-methylester,

N ³ , N ³ -di-n-propyl-2, 4-dinitro-6-trifluoromethyl-m-phenylenediamine,

2-ethoxy-2,3-dihydro-3,3-dimethyl-5-benzofuranylmethane sulfonate,

C-5- (2-chlorobenzyloxy) -r-2-isopropyl-5-methyl-1,3-dioxane and r-2-isopropyl-5-methyl-C-5- (2-methylbenzyl Oxy) -1, 3-dioxane,

It is also possible to use other adducts which have no detrimental action and increase herbicidal action, ie wetting agents, emulsifiers, solvents and oily adducts.

The active compounds and mixtures containing them may be added in the form of herbicidal preparations, for example liquid and / or solid weight agents, or diluents and, if desired, by addition of surfactants such as wetting agents, adhesives, emulsifiers and / or dispersants, powders, It is used as a preparation such as spray, granule, solution, emulsion or suspension.

Suitable liquid extenders are, for example, water, aliphatic hydrocarbons, aromatic hydrocarbons such as benzene, toluene and xylene, cyclohexanone, isophorone, dimethylsulfoxide and dimethylformamide, and light fractions.

As the solid weight agent, for example, soils, ie, tonsil, silica gel, talc, kaolin, ataclei, limestone, silicic acid and vegetable products such as siliceous powder are suitable.

Surfactants include, for example, calcium lignin sulfonate, polyoxyethylene-alkyl-phenylether, naphthalene sulfonic acid and salts thereof, phenolsulfonic acid and salts thereof, formaldehyde condensates, fatty alcohol sulfates and substituted benzenesulfonic acids and salts thereof Etc. can be mentioned.

The content of active compounds in various formulations can vary widely. For example, each formulation contains approximately 10 to 80% (by weight) of active compound, approximately 90 to 20% (by weight) of liquid or solid weight, as well as up to 20% (by weight) of surfactant if necessary. The active compound can be used in a conventional manner, for example, as a spraying solution of about 100 to 1000 liters per hectare using water as an extender.

The active compounds may be used in the so-called "low dose method" and "ultra low dose method", and may also be used in the so-called fine granular form.

The compound of general formula (I) according to the present invention may be prepared by treating the compound of general formula (II) with an acid acceptor such as an excess of amine or inorganic base such as sodium hydroxide, sodium carbonate, calcium carbonate or tertiary organic base, For example, it is prepared by reacting with an amine of the following general formula (III) in the presence of triethylamine.

In the general formula, R ₁ , R ₂ , R ₃ and Y are as described above.

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

Example 1

N- (2-cyanoethyl) -carbanoic acid- [3- (methoxycarbocarbonylamino) -phenyl] -ester

100 mL of water was added to a solution of 43.9 g of 3-anilinopropionate nitrile in 100 mL of ethyl acetate, followed by 68.7 g of chloroformic acid-3-methoxycarbonylamino-phenylester in 250 mL of ethyl acetate. The solution and a solution of 41.4 g of potassium carbonate dissolved in 250 ml of water are added over 25 minutes with cooling to about 10-14 ° C. under stirring.

The mixture is stirred for 30 minutes at 10 ° C., then the organic layer is separated and washed with dilute sodium hydroxide solution, dilute hydrochloric acid and water at 0 ° C. Dehydrated with magnesium sulfate and concentrated under reduced pressure. The oily residue is crystallized by adding ether.

Yield: 76.6g (75% of theory)

Melting Point: 98-99 ℃

Elemental Analysis Value: Calculation Value: C 63.71 H 5.05 N 12.38%

Found: 63.98 5.65 12.19%

In a similar manner, compounds like 2 to 52 in the following table are prepared.

These compounds are, for example, soluble in acetone, cyclohexanone, ethylacetate, isophorone, retrahydrofuran, dioxane, dimethyl foramide and hexamethyl phosphate triamide and are almost insoluble in water and light gasoline.

The next test details the availability of the compounds according to the invention.

[Test Example 1]

In the greenhouse, the compounds according to the present invention listed in the table above are emulsified in 600 l of water per hectare at the use rate of 5 kg of active substance per hectare, before germination and after germination of mustard and eggplant plants, which are test plants. Perform a series of tests to process.

After 3 weeks of treatment, the treatment result is evaluated from 0 to 4.

0 = if no action

4 = when all plants are damaged

-= Indicates not tested.

As can be seen from the following table, the test plants are generally all damaged.

[Test Example 2]

In a greenhouse, a series of tests are carried out by pre-germination of the compounds according to the invention to the plants shown in the following table at a rate of 3 kg per hectare.

Control herbicides: 3-methoxycarbonylaminophenyl-N- (3-methylphenyl) -carbamate

(German Federal Republic of Patent No. 1, 567, 151)

Plants are used young and the test substance is applied as an emulsion. The amount of liquid sprayed is 500 liters per hectare.

After 14 days, the treatment results are evaluated. (0 = when all plants are damaged, 10 = when plants are not damaged at all)

From the following table it can be clearly seen that the compounds according to the invention are excellent in resistance and effect to crops, while the known control herbicides are ineffective.

[Test Example 3]

In a greenhouse, a series of tests are carried out by post-germination treatment of the compounds according to the invention at a rate of 3 kg per hectare in the plants shown in the following table.

Control herbicides: 3-methoxycarbonylaminophenyl-N- (3-methylphenyl) -carbamate

(German Federal Republic of Patent No. 1, 567, 151)

Plants are used young and the test substance is applied as an emulsion. The amount of liquid used is 500 liters per hectare.

After 14 days, the treatment results are evaluated. (0 = when all plants are damaged, 10 = oral with little damage)

While the compounds according to the invention have good crop resistance, the known control herbicides can damage the crops or exhibit less extensive herbicidal activity, which is clearly shown by the evaluation index given in the following table.

Claims (1)

A method for preparing a compound of formula (I) by reacting a compound of formula (II) with an amine of formula (III) in the presence of an acid acceptor.

In the above general formula, R ₁ is an unsubstituted or substituted aliphatic hydrocarbon group, R ₂ is a cyanoalkyl group, R ₃ is an unsubstituted or substituted aromatic hydrocarbon group, and Y is oxygen or sulfur.