CH618321A5 - Herbicidal composition containing N,N-disubstituted alanine derivatives - Google Patents

Description

The invention also relates to herbicidal compositions comprising a carrier and / or a surface-active agent and as active ingredient at least one compound of the general formula I. Weeds can be destroyed or combated with the aid of the new compounds by adding a herbicidally effective amount of the compositions according to the invention the weeds or the place where they grow.

The term "carrier" as used here means a substance, which can be inorganic or organic and synthetic or natural, with which the active compound 5

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618 321

is mixed or prepared in order to facilitate the application to the plants, seeds, the soil or other objects to be treated or their storage, transport or handling. The carrier can be solid or liquid. All of the carriers usually used for the production of pesticides, herbicides or fungicides can also be used here.

Suitable solid carriers are natural and synthetic clays and silicates, e.g. B. natural silicas such as diatomaceous earth; Magnesium silicates, e.g. B. Talke; Magnesium aluminum silicates, e.g. B. Attapulgite and Vermiculite; Aluminum licenses, e.g. B. kaolinites, montmorillonites and mica; Calcium carbonates; Calcium sulfate; synthetic hydrated silicas and synthetic calcium and aluminum silicates; Elements, e.g. B. carbon and sulfur; natural and synthetic resins, e.g. B. coumarone resins, polyvinyl chloride and styrene polymers and copolymers; solid polychlorophenols; Bitumens; Waxes, e.g. B. beeswax, paraffin wax and chlorinated mineral waxes and solid fertilizers, e.g. B. Superphosphates.

Suitable liquid carriers are water, alcohols, e.g. B. iso-propanol and glycols; Ketones, e.g. B. acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone; Ether; aromatic hydrocarbons, e.g. B. benzene, toluene and xylene; Petroleum fractions, e.g. B. kerosene and light mineral oils; chlorinated hydrocarbons, e.g. B. carbon tetrachloride, perchlorethylene and trichloroethane; and liquefied, usually gaseous perchlorethylene and trichloroethane; and liquefied, usually gaseous compounds. Mixtures of different liquids are often suitable.

The surfactant can be an emulsion or dispersion or a wetting agent. It can be non-ionic or ionic. Any of the surfactants commonly used to prepare pesticides, herbicides or fungicides can also be used here. Examples of suitable surface-active agents are the sodium or calcium salts of polyacrylic acids and lignosulfonic acids; the condensation products of fatty acids or aliphatic amines or amides containing at least 12 carbon atoms in the molecule, with ethylene oxide and / or propylene oxide; Fatty acid esters of glycerin, sorbitan, sucrose and pentaeiythritol; Condensates of these substances with ethylene oxide and / or propylene oxide; Condensation products of fatty alcohols or alkylphenols, e.g. B. p-octylphenol or p-octylcresol with ethylene oxide and / or propylene oxide; Sulfates or sulfonates of these condensation products; Alkali or alkaline earth metal salts, preferably sodium salts, of sulfur or sulfonic acid esters containing at least 10 carbon atoms in the molecule, e.g. B. sodium lauryl sulfate, sodium sec-al-alkyl sulfates, sodium salts of sulfonated castor oil and sodium alkylaiyl sulfonates such as sodium dodecylbenzenesulfonate; and polymers of ethylene oxide and copolymers of ethylene oxide and propylene oxide.

The agents according to the invention can be produced as wettable powders, dusts, granules, solutions, emulsifiable concentrates, emulsions, suspension concentrates and aerosols. Wettable powders are usually composed such that they contain 25, 50 or 75% by weight of active ingredient and usually, in addition to the solid carrier, 3 to 10% by weight of dispersing agent and, if necessary, 0 to 10% by weight of stabilizers) and / or other additives such as Penetrants or tackifiers included. Dusts are usually produced as dust concentrates with a similar composition to that of the wettable powders, but without a dispersing agent, and are diluted in the field with another solid carrier in order to obtain an agent which is usually 0.5 to 10% by weight of active ingredient contains. Granules are usually made so that they are

Have particle sizes from 0.152 to 1.676 mm and can be obtained by agglomeration or impregnation processes. Grains generally contain 0.5 to 25% by weight of active ingredient and 0 to 10% by weight of additives such as stabilizers, slow release agents and binders. In addition to the solvent and, if necessary, the second solvent, emulsifiable concentrates usually contain 10 to 50% (weight / volume) active ingredient, 2 to 20% (weight / volume) emulsifiers and 0 to 20% (weight / volume) suitable additives such as stabilizers, Penetrants and corrosion inhibitors, suspension concentrates are composed in such a way that a stable, non-settling, flowable product is obtained and usually contain 10 to 75% by weight of active ingredient, 0.5 to 15% by weight of dispersing agent, 0.1 to 10% by weight of suspending agent such as Protective colloids and thixotropic agents, 0 to 10% by weight of suitable additives such as anti-foaming agents, corrosion inhibitors, stabilizers, penetrants and tackifiers and as a carrier water or an organic liquid in which the active ingredient is essentially insoluble. Certain organic solids or inorganic salts may be dissolved in the carrier to prevent settling or as an anti-freeze when water is the carrier.

The invention also relates to dispersions and emulsions, e.g. B. Agents that have been obtained by diluting a wettable powder or a concentrate according to the invention with water. These emulsions can be in the form of water-in-oil or oil-in-water emulsions and have a thick mayonnaise-like consistency.

The agents according to the invention can also contain other components, e.g. B. contain other compounds with pesticider, herbicide or fungicidal activity.

The invention is illustrated by the following examples:

example 1

Preparation of 2- (N-benzoyl-N- (3-chloro-4-fluorophe-

nyl)) - amino-N '- (4-chlorophenyl) propionohydrazide 6.4 g of N-benzoyl-N- (3-chloro-4-fluorophenyl) alanine were stirred with a suspension of 3.6 g of 4-chlorophenylhy -drazinhydrochlorid in 50 ml of methylene chloride, to which 2.8 ml of triethylamine had been added. The mixture was stirred at room temperature for a further 30 minutes. Then 5 g of dicyclohexylcarbodiimide in 20 ml of methylene chloride were added and the mixture was stirred for a further hour. The precipitated N, N-dicyclohexylurea was filtered off and the filtrate was evaporated. The residue was triturated with ether, giving the desired product as a white solid, mp. 88 to 89 ° C, yield 72%.

Analysis for C ^ H ^ C ^ FN-jC ^:

calculated: C 59.2 H 4.0 N 9.4%

found: C 59.5 H 4.1 N 9.3%

Example 2

Preparation of 2- (N-benzoyl-N- (3-chloro-4-fluorophenyl)) amino-N '- (methyl) propionohydrazide 6.4 g of N-benzoyl-N- (3-chloro-4-fluorophenyl ) Alanine were dissolved in 70 ml of methylene chloride and 1 ml of N-methylhydrazine was added. The mixture was stirred for 15 minutes to give a clear solution, then 5 g of dicyclohexylcarbodiimide was added and the precipitated urea was filtered off. The methylene chloride solution was evaporated and the residue triturated with ether to give the desired product, mp. 135-138 ° C, yield 20%.

Analysis for C17H17C1FN302:

calculated: C 58.4 H 4.9 N 12.0%

found: C 58.7 H 4.9 N 12.1%

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618 321

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Example 3

Preparation of 2- (N-benzoyl-N- (3-chloro-4-fluoro-phenyl)) amino-N '- (tert-butoxycarbonyl) propionohydrazide 6.4 g of N-benzoyl-N- (3-chloro -4-fluorophenyl) alanine were dissolved in 70 ml of methylene chloride containing 2.7 g of tert-butyl carbazate. Then 5 g of dicyclohexylcarbodiimide in 20 ml of methylene chloride were added at room temperature with stirring, a clear solution being formed. N, N'-dicyclohexylurea precipitated almost immediately and the reaction mixture was left to stand for an additional hour. The solid was filtered off and after evaporation of the filtrate, the residue was recrystallized from petroleum ether (60 to 80 ° C) to give the desired product, mp. 78 to 80 ° C, yield 84%.

Analysis for C21H23CIFN3O4:

calculated: C 58.0 H 5.5 N 9.6%

found: C 58.9 H 5.9 N 9.5%

Example 4

Preparation of 2- (N-benzoyl-N- (3-chloro-4-fluorophenyl)) aminopropionohydrazide 11g 2- (N-benzoyl-N- (3-chloro-4-fluorophenyl)) amino-N '- ( Tert-butoxycarbonyl) propionohydrazide were dissolved in 110 ml of ethyl acetate and dry hydrogen chloride was passed into the solution, which was cooled with ice. The solution was left overnight and then evaporated to a resinous product. After treatment with ether, the solid was washed with sodium bicarbonate solution, extracted with ether and the ether solution was evaporated to give the desired product, mp 135 to 137 ° C., yield 64%.

Analysis for C16H1SC1FN302:

calculated: C 57.5 H 4.5 N 8.3%

found: C 57.5 H 4.3 N 8.2%

Example 5

Preparation of 2- (N-benzoyl-N- (3-chloro-4-fluorophenyl)) amino-N-morpholinopropionamide 6.4 g of N-benzoyl-N- (3-chloro-4-fluorophenyl) alanine were in 100 ml of methylene chloride dissolved and 2 ml of N-aminomorpholine added. The mixture was stirred for 15 minutes to give a clear solution. Then 5 g of dicyclohexylcarbodiimide in 20 ml of methylene chloride were added and the mixture was stirred for a further 12 hours. The precipitated urea was filtered off and the filtrate was evaporated to half the volume and left at 0 ° C. overnight. The precipitated solid was filtered off, dried and the ethanol recrystallized, giving the desired product, mp. 205 to 207 ° C., yield 93%.

Analysis for C20H21CIFN3O3:

calculated: C 58.9 H 5.1 N 10.3% 5 found: C 58.7 H 5.3 N 10.1%

Example 6

Preparation of 2- (N-benzoyl-N- (3-chloro-4-fluorophenyl)) amino-N '- (trimethyl) propiono-hydrazinium iodide 10 1.1 g2- (N-benzoyl-N- (3- chlor-4-fluorophenyl)) amino-N '- (dimethyl) propionohydrazide were dissolved in 50 ml ether / acetone and excess methyl iodide was added. The mixture was refluxed for 6 hours and the solvent was evaporated. The residue was dissolved with 20 ml of Et-15 her / acetone, whereby pale yellow crystals of the desired product were obtained, yield 60%.

Analysis for C19H22CIFN3O2:

calculated: C 45.1 H 4.3 N 8.3% 20 found: C 45.1 H 4.5 N 8.1%

Example 7

Preparation of 2- (N-benzoyl-N- (3-chloro-4-fluorophenyl)) aminopropionyl azide 25 16.0 g of N-benzoyl-N- (3-chloro-4-fluorophenyl) alanine were added in 7 ml of water stirred and sufficient acetone (30 ml) added to achieve a solution. The solution was cooled to 0 ° C and 7 ml of triethylamine in 90 ml of acetone was added keeping the temperature at 0 ° C. Then 6 ml of ethyl chloroformate in 20 ml of acetone were slowly added and the mixture was stirred at 0 ° C. for 40 minutes. Then 4.3 g of sodium azide in 15 ml of water were added dropwise and the mixture was stirred at 0 ° C. for one hour and then at room temperature for a further 5 hours. The reaction mixture 35 was poured into 11 ice water, extracted with 2 × 250 ml of ether and the ether solution was evaporated. The desired product, mp. 88-91 ° C., yield 22% was obtained.

Analysis for C16Hi2ClFN402:

calculated: C 55.4 H 3.5 N 16.1% 40 found: C 55.1 H 3.5 N 15.8%

Examples 8 to 18 Further processes were prepared by methods similar to those given in Examples 1 to 7, the 45 physical properties and analyzes of which are shown in Table I below.

For example

No.

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9

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11

12

13

14

15

16

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5

Table I

618 321

connection

R

Mp. ° C from analysis booty

2- (N-benzoyl-N- (4-fluoro-

phenyl)) - amino-N '- (di-

methyl) propionohydrazide

2- (N-Benzoyl-N- (3,4-di-chlorophenyl)) amino-N '■ - (dimethyl) propionohydrazide

2- (N-benzoyl-N- (4-chloro

phenyl)) amino-N '- (di-

methyl)) propionohydrazide

2- (N-benzoyl-N- (3-chloro

4-fluorophenyl)) amino

N '- (methyl-ethoxy-

carbonyl) propionohydrazide

2- (n-benzoyl-N- (3-chloro

4-fluorophenyl)) amino

N '- (ethoxycarbonyl) -

propionohydrazide

2- (N-benzoyl-N- (3-chloro

4-fluorophenyl)) amino-N '-

(dimethyl) propiono-

hydrazide

2- (N-Benzoyl-N- (3-chloro-4-fluorophenyl)) amino-N '- (diphenyl) propionohydrazide

2- (N-Benzoyl-N- (3-chloro-4-fluoro-phenyl)) amino-N-pyrrolidinyl-propionamides chicken (ch3) 2 123-105 81

cl cl nhn (ch3) 2 rubber 76

Cl H NHN (CH3) 2 105-107 74

Cl

Cl

, CH,

Rubber 72

NHN

COOC2H5 Cl NHNHCOOC2H5 162-164 82

Cl NHN (CH3) 2 123-125 80

Cl NHN (C6Hs) 2 148-150 47

V

144-146 87

Calculated for C 65.7 Calculated: C 65.7 Calculated for C 56.9 Calculated: C 56.7 Calculated for C 62.5 Calculated: C 62.8 Calculated for C 57.5 Calculated .: C 58.4 calc. For C 56.0 calc .: C 56.4 calc. For C 59.5 calc .: C 59.1 calc. For C 69.0 calc .: C 68.8

C18H20FN3O2:

H 6.1 N 12.8%

H 6.0 N 12.6% C18H19C12N302: H 5.0 N 11.0%

H 5.3 N 10.6% C18H20ClN3O2:

H 5.8 N 12.2 Cl 10.3%

H 5.8 N 12.0 Cl 10.3% C20H21ClFN3O4: H 5.0 N 9.9%

H 5.3 N 9.9% C19H19C1FN304: H 4.7 N 10.3%

H 5.1 N 10.6% C18H19C1FN302: H 5.2 N 11.6%

H 5.4 N 11.3% C28H23C1FN302: H 4.8 N 8.6%

H 5.7 N 8.7%

for C20H21ClFN3O2: C 61.6 H 5.5 N 10.8% found:

C 61.8 H 5.9 N 11.0%

2- (N-Benzoyl-N- (3-chloro-4-fluorophenyl)) amino-N-piperidino-propionamides

Cl

NH-N

/

V

178-180 91 calc. For c21h23c1fn302:

c 62.5 h 5.8 n 10.4% found:

c 62.6 h 6.1 n 10.3%

2- (N-Benzoyl-N- (3-chloro-4-fluorophenyl)) amino-N- (1,2,4-triazol-4-yl) propionamide

Cl

NH-

/

—N 204-208 51

for C18H15C1FNS02: C 55.8 H 3.9 N 18.1% found:

C 55.6 H 4.2 N 18.3%

2- (N-Benzoyl-N- (3-chloro-4-fluorophenyl)) amino-N '- (trimethyl) propiono-hydrazinium methosulfate cl nhn (ch3) 3

ch3so4

208-210 50 calc. For C19H22C1FN302 • S04CH3: C 49.0 H 5.1 N 8.6%

found:

C 49.0 H 5.1 N 8.6%

618 321

6

Example 19 Herbicidal Efficacy 25 seedlings of cultivated oats were planted in 7 cm pots containing John Innes Compost No. 1. When the plants had reached 1V2 to 21/2 leaves, the pots were sprayed with a solution of the compound to be examined in a 1: 1 mixture of acetone and water containing added wetting agent / tackifier. Each compound was applied at 1 and 5 kg / ha. The pots were kept in the greenhouse at 21 ° C. under 16 hours of daylight.

Investigations were carried out 7 days after spraying. The percentage suppression of oat growth was determined visually on a percent scale, with 100% meaning no growth after treatment. The results obtained are shown in Table II below:

Table II

Percent inhibition of growth after the treatment of grown oats

Compound dose according to example 1 kg / ha 5 kg / ha

No.

7 100 100

8 60 90 13 75 90 17 60 60

Example 20

In order to further investigate the herbicidal activity, the compounds according to the invention were compared with the aid of a representative number of plants, namely maize, zea mays (MZ); Rice, Oryza sativa (R); Chicken millet, Echi-

nochloa crusgalli (BG); Peas, Pisum sativum (P); Linseed, Linum usitatissimum (L); Mustard, Sinapis alba (M) and sugar beet, Beta vulgaris (SB).

The experiments were divided into two groups, namely experiments 5 before emergence and after emergence. In the pre-emergence experiments, a liquid preparation of the compound was sprayed onto the soil in which the seeds of the plants had been sown just before. In the experiments after emergence, the leaves of the young plants were sprayed with a liquid preparation comprising a compound according to the invention.

The soil used in the experiments was a steam-sterilized, modified John Innes compost mix in which half of the peat in the bulk was replaced by vermiculite.

The preparations used in the tests were prepared by diluting the compounds in acetone containing 0.4% by weight of an alkylphenol-ethylene oxide condensate (Triton X-155) with water. The acetone solutions were diluted with an equal volume of water and the resulting preparations were sprayed in two doses corresponding to 5 and 1 kg of active ingredient / ha in a volume corresponding to 4001 / ha.

The herbicidal activity of the compounds according to the invention was assessed visually 7 days after spraying on the leaves and 11 days after spraying on the soil and rated on an O to 9 scale.

A rating of 0 means no effect on the treated plants, a rating of 2 means a reduction in the fresh weight of stems and leaves of the plants of approximately 25%, a rating of 5 means a reduction of approximately 55% and a rating 9 means a reduction of 95%.

The results of these tests are given in Table 35 below III.

Table III

Compound dose After emergence Before emergence after kg / ha spraying the leaves spraying the soil Example

No.MZ R BG P L M SB MZ R BG P L M SB

1

5

0

0

0

0

0

0

0

0

6

0

0

4th

7

0

1

0

0

0

2nd

5

0

3rd

0

0

2nd

0

0

0

6

0

0

3rd

5

0

1

0

0

0

0

7

2nd

3rd

6

7

6

3rd

4th

0

2nd

1

0

3rd

2nd

1

0

0

0

5

6

0

0

0

0

0

0

0

8th

5

0

0

0

0

5

1

0

2nd

6

0

0

2nd

4th

0

1

3rd

0

0

2nd

0

0

9

5

0

0

0

0

4th

2nd

0

0

3rd

0

0

0

3rd

0

1

0

0

1

3rd

17th

5

1

0

0

0

4th

5

0

0

0

0

0

0

0

0

0

2nd

0

Claims (5)

618 321 1. Herbicidal agent, characterized in that it contains at least one new N, N-disubstituted alanine derivative of the general formula y as active ingredient r- ° // \\ - N-CH-COR (I) \ - / ch3 contains, in which X represents a halogen atom and n represents an integer from 1 to 5, Y represents an optionally substituted aryl group, R represents an azido group or a group of the formula -NHNR * R2, in which R1 and R2 each represent a hydrogen atom, an optionally substituted alkyl - or aryl group or an alkoxycarbonyl group or R1 and R2 together represent a polymethylene group which may be interrupted by one or more non-carbon atoms and, in the case of derivatives which are capable of forming salts, the salts of these compounds. 2. Composition according to claim 1, characterized in that X is a chlorine or fluorine atom, n 1 or 2, Y is a phenyl group and R is an azido group or a group of the formula —NHNR1R2, where R1 and R2 are each a hydrogen atom, a Alkyl group with 1 to 4 carbon atoms, a phenyl group, a halophenyl group, an alkoxycarbonyl group with up to 4 carbon atoms or R1 and R2 together represent a polymethylene group with up to 5 carbon atoms, which is optionally interrupted by 1 or more non-carbon atoms, and if that Derivatives salts can form the salts of these compounds. 2nd PATENT CLAIMS 3. Composition according to claim 1 or 2, characterized in that X is a fluorine or chlorine atom, n 1 or 2, Y is a phenyl group and R is an azido group or a group of the formula —NHNR1R2, where R1 and R2 are each a hydrogen atom, a Means a methyl group or a chlorophenyl group and salts of these compounds. Herbicidal compositions which contain N, N-disubstituted alanine derivatives as active ingredient are known. The present invention aims to provide such derivatives with improved effectiveness. This object is achieved by the means defined in claim 1. The preferred compounds are those of the formula I in which X is a chlorine or fluorine atom, n 1 or 2, Y is a phenyl group and R is an azido group or a group of the formula -NHNR1R2, where R1 and R2 are each a hydrogen atom, an alkyl group 1 to 4 carbon atoms, preferably a methyl group, a phenyl group, a halophenyl group, e.g. B. a chlorophenyl group, an alkoxycarbonyl group of up to 4 carbon atoms, e.g. represent an ethoxy or butoxycarbonyl group or R1 and R2 together form a polymethylene group with up to 5 represent carbon atoms which may be interrupted by one or more non-carbon atoms, e.g. B. a tetramethylene or pentamethylene group, which is optionally interrupted by an oxygen atom or one or more nitrogen atoms, and, if the derivatives can form salts, the salts of these derivatives. A particularly preferred connecting group of the general formula I are those in which X is a fluorine or Chlorine atom, n 1 or 2, Y is a phenyl group and R is an azido group or a group of the formula -NHNR1R2, where R1 and R2 each represent a hydrogen atom, a methyl group or a chlorophenyl group and salts of these derivatives. The N, N-disubstituted alanine derivatives can show geometric and / or optical isomers. The individual isomers and their mixtures also fall under the invention. The derivatives of the formula I in which R is a substituted hydrazine group can be prepared by reacting a compound of the formula Y (X) CH in which X, n and Y have the meaning given above, with a compound of the formula (III) in which R1 and R2 have the meaning given above. The reaction is essentially a condensation reaction in which water is split off and is carried out in the presence of a suitable dewatering agent, e.g. B. of N, N'-dicyclohexylcarbodiimide. The reaction takes place at room temperature and is carried out in an inert reaction medium such as methylene chloride. During the reaction, the dehydrating agent is converted into dicyclohexyl urea and then filtered off and the resulting reaction mixture is worked up in a conventional manner. Those compounds of formula I in which R is an unsubstituted hydrazine group can be prepared by treating a compound of formula I in which R is an alkoxycarbonyl, preferably a tert-butoxycarbonyl group, with dry hydrogen chloride. The reaction is carried out in a suitable solvent such as ethyl acetate. Salts of N, N-disubstituted alanine derivatives of the formula I can be prepared by reacting a compound of the formula I in which R is a group of the formula -NHNR1R2 with a mineral acid, for. B. hydrochloric acid or sulfuric acid, or an alkyl halide, e.g. B. methyl or ethyl bromide or iodide, or with an alkyl sulfate, e.g. B. dimethyl sulfate. Such derivatives of the formula I in which R is an azido group are prepared by reacting sodium azide with the corresponding mixed carboxylic acid hydride, which has preferably been obtained in situ by reacting a compound of the formula II with ethyl chloroformate. The reaction solvent is conveniently aqueous acetone.