CH616560A5 - Herbicidal composition containing N,N-disubstituted alanine derivatives - Google Patents

Description

616 560

2nd

PATENT CLAIMS 1. Herbicides containing at least one active ingredient

N, N-disubstituted alanine derivative of the general formula:

COY

CD

CHCOON = CR1R2,

in which X each represents a hydrogen, fluorine, chlorine, bromine or iodine atom and n is a number from 1 to 5, while Y represents an optionally substituted aryl group and Z represents an alkyl group and where R 1 and R 2 can each mean: A hydrogen atom, a hydroxyl group, an optionally substituted alkyl, alkenyl, aryl, heterocyclic, alkoxy or alkylthio group or a group of the formula -NQ1Q2 or -PO (OQ1) (OQ2), in which Ch and Q2 are each a Hydrogen atom or an optionally substituted alkyl, alkenyl or aryl group, or wherein R 1 and R 2 together represent an alkylene bridge which is optionally interrupted by one or more heteroatoms.

2. Composition according to claim 1, characterized in that X is chlorine or fluorine, n is 1 or 2, Y is phenyl and Z is methyl.

3. Composition according to claim 1, characterized in that X is chlorine or fluorine, n is 1 or 2, Y is phenyl and Z is methyl and that Rt and R2 each mean: a hydrogen atom, a hydroxyl group, an alkyl group with

1 to 4 carbon atoms, a phenyl group, a benzyl group,

an alkoxy, alkylthio or cyanoalkylthio group with 1 to 4 C atoms, a pyridyl group, an amino group, a mono- or dialkyl-substituted amino group, in which each alkyl group contains 1 to 4 C atoms, or a —P0 (0-A1-alkyl ) 2 group, in which each alkyl group contains 1 to 4 carbon atoms; or wherein Rt and R2 together form an alkylene bridge

Represent 2 to 5 carbon atoms.

4. Use of the agent according to claim 1 for controlling unwanted vegetation.

5. Use according to claim 4 for controlling wind oats in grain fields.

4 carbon atoms, a pyridyl group, an amino group, a mono- or dialkyl-substituted amino group in which each alkyl group contains 1 to 4 carbon atoms, or a -P0 (0-A1-alkyl) 2 group in which each alkyl group contains 1 contains up to 4 carbon atoms; Rj and R2 can also jointly represent an alkylene group with 2 to 5 carbon atoms in these compounds.

Many of the new compounds obviously have a geometric and / or optical isomerism and the individual isomers of these compounds and their isomer mixtures io fall under the invention.

A process for the preparation of the compounds of the formula (I) consists in that a compound of the general formula:

15

20th

US Pat. No. 1,164,160 discloses certain alanine derivatives which are active against wild oats.

The object of the present invention is to provide new alanine derivatives which are more specifically active against weeds, in particular wild oats, than the known derivatives. This object is achieved by the means defined in claim 1.

Preferred compounds of the general formula (I) are those in which X is chlorine or fluorine, n is 1 or 2, while Y is phenyl and Z is methyl. Of particular interest among these compounds are the 3,4-dichloro, the 3-chloro-4-fluoro, the 4-chloro or the 4-fluorine derivatives.

Another preferred class of compounds has the general formula (I), wherein X is chlorine or fluorine, n is 1 or 2 and Y is phenyl and Z is methyl, while R and R 2 each have the following meaning: a hydrogen atom, a Hydroxyl group, an alkyl group of 1 to 4 carbon atoms, a phenyl group, a benzyl group, an alkoxy, alkylthio or cyanoalkylthio group with 1 to

\ / \ CHC (

(II)

CHCOOH

t z

reacted with a compound of the formula:

HCM = CS

R.

(III),

where X, Y, Z, n, Rt and R2 have the above meaning. Since the reaction is a condensation process with elimination of water, it is preferably carried out in the presence of a dehydrating agent to absorb the by-product; an example of such an agent is dicyclohexyldiimide. The reaction proceeds at room temperature and is preferably carried out in an inert liquid reaction medium in which the reactants and the dewatering agent are soluble. A preferred solvent is methylene chloride. During the reaction, the dicyclohexyldiimide is converted into dicyclohexylurea-40 substance, which is filtered off; the reaction mixture can then be worked up in a conventional manner.

The new compounds can be used in the manner known for herbicides, i.e. H. they are used e.g. B. on or with a suitable carrier and / or a 45 surfactant.

It has been found that the new compounds are of particular interest when it comes to selectively combating wind oat that has grown as weed in cereal fields, particularly wheat and barley fields.

The term "carrier" here means a solid or liquid substance, which can be inorganic or organic and an artificial or natural product and with which the active ingredient is mixed or made up in order to apply it to plants, seeds, soil or a to facilitate another object to be treated or to enable its storage, transport or handling. All substances that are usually used for the preparation of such agents are suitable as solid or liquid carriers. 60 Suitable solid supports are natural and synthetic types of clay and silicates, e.g. B. natural silica such as diatomaceous earth; Magnesium silicates, e.g. B. Talke; Magnesium aluminum silicates, e.g. B. Attapulgite and Vermiculite; Aluminum silicates, e.g. B. kaolinites, montmorillinites and mica; Cal-65 ciumcarbonate; Calcium sulfate; synthetic hydrated silicon oxides and synthetic calcium or aluminum silicates; Individual elements, e.g. B. carbon and sulfur; natural and artificial resins, e.g. B. coumarone resins, polyvinyl chloride

3rd

616 560

and styrene polymers and copolymers; solid polychlorophenols; Bitumen; Waxes, e.g. B. beeswax, paraffin and chlorinated mineral waxes; as well as solid fertilizers, e.g. B. Superphosphates.

Examples of suitable liquid carriers are water, alcohols, e.g. B. isopropanol or 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 such as kerosene or light oil; chlorinated hydrocarbons, e.g. B. carbon tetrachloride, per-chloroethylene or trichloroethane including liquefied, usually vapor or gaseous compounds. Mixtures of different liquids are often particularly suitable.

The surfactant can be an emulsifying or dispersing or wetting agent, which can be non-ionic or ionic. The agents common to herbicides or insecticides can be used. Examples of suitable surface-active agents are the sodium or calcium salts of polyacrylic acids and lignin sulfonic acids; the condensation products of fatty acids or aliphatic amines or amides with at least 12 carbon atoms in the molecule with ethylene oxide and / or propylene oxide; the fatty acid esters of glycerin, sorbitol, succrose or pentaerythritol; their condensates 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 sulfuric acid or sulfonic acid esters with at least 10 carbon atoms, e.g. B. sodium lauryl sulfate, sodium sec-alkyl sulfates, sodium salts of sulfonated castor oil and sodium alkylarylsulfonates such as sodium dodecylbenzene sulfonate; and polymers of ethylene oxide and copolymers of ethylene oxide and propylene oxide.

The agents according to the invention can be used as wettable powders, dusts, granules, solutions, emulsifiable concentrates, emulsions, suspension concentrates and aerosols and generally contain 0.5 to 95% by weight, preferably 0.5 to 75% by weight, of active ingredient. Wettable powders are usually made up to contain 25, 50 or 75% by weight of active ingredient, and usually they are, in addition to a solid carrier, 3 to 10% by weight of a dispersant and optionally 0 to 10% by weight of stabilizers) and / or others Additives such as penetrants or adhesives are added. Dusts are concentrates whose composition corresponds to that of the wettable powders, but without a dispersant; they are diluted with another solid carrier in use, so that the agent finally contains 0.5 to 10% by weight of active ingredient. Granules usually have a grain size of 0.13 to 1.3 mm and can be produced by agglomeration or impregnation. In general, the granules contain 0.5 to 25% by weight of active ingredient and 0 to 10% by weight of additives, such as stabilizers or binding or delaying agents. In addition to the solvent and optionally an auxiliary solvent, emulsifiable concentrates usually contain 10 to 50% w / v. Active ingredient, 2 to 20% w / v. Emulsifiers and up to 20% w / v. suitable additives, such as stabilizers or agents to facilitate penetration and to prevent corrosion. Suspension concentrates are prepared 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 agents for defoaming or preventing corrosion, stabilizers, penetrants and adhesives, and as a carrier water or an organic liquid in which the active ingredient is essentially insoluble; Certain organic salts may be dissolved in the carrier to prevent settling or, in the case of water, freezing.

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

The examples serve to explain the invention in more detail.

example 1

Preparation of N-Benzoyl-N- (3,4-dichlorophenyl) alanine acetoxime ester. N-Benzoyl-N- (3,4-dichlorophenyl) alanine (6.7 g) was dissolved in methylene chloride (80 ml) containing of acetoxime (1.5 g) followed by the addition of dicyclohexylcarbodiimide (4.2 g). The reaction mixture was stirred for 48 hours, after which the methylene chloride was evaporated and replaced with ether. After adding 5 ml of acetic acid, the mixture was left to stand for 12 hours. Then the N, N * -dicyclohexylurea was filtered off and the ether solution was washed with water, saturated sodium bicarbonate solution and again with water and dried over sodium sulfate. The residue remaining on evaporation was recrystallized from cyclohexane and gave the product sought, mp 90-92 ° C .; Yield 59%.

Analysis: C19Hi803N2Cl2

calc .: C 58.0 H 4.6 N 7.1%

found: C 58.4 H 4.9 N 6.8%

Example 2

Preparation of N-benzoyl-N- (4-fluorophenyl) alanine-cyclopentanone oxime ester N-benzoyl-N- (4-fluorophenyl) alanine (6.7 g) was dissolved in methylene chloride (80 ml) containing cyclopentane oxime (1.5 g). Dicyclohexylcarbodiimide (4.2 g) was added and the reaction mixture was stirred for 48 hours after which the methylene chloride was evaporated and replaced with ether. After adding 5 ml of acetic acid, the mixture was left to stand for 12 hours. Then the N, N1-dicyclohexylurea was filtered off and the ether solution was washed with water, saturated sodium bicarbonate solution and again with water and dried over sodium sulfate. After evaporation, the residue was recrystallized from cyclohexane and gave the desired product, mp. 110 to 112 ° C; Yield 68%.

Analysis: C21H21N2O3F

calc .: C 68.5 H 5.7 N 7.6%

found: C 68.9 H 5.8 N 7.6%

Examples 3 to 23 According to Examples 1 and 2, a series of compounds were prepared, the structure and physical properties of which are shown in the following table.

5

10th

15

20th

25th

30th

35

40

45

50

55

60

616 560 4

Example No.

X

A

ri ra

Mp

Yield in%

Analysis c

H

N

Cl

3rd

cl

Cl

-ch2

, ch2.ch2.ch2-

_

60

c21 h20n2o3ci2

calc.:

60.2

4.9

6.7

17%

found:

61.8

5.5

6.5

17.2%

4th

Cl

Cl ch3

c2h5

73-5

30th

c2oH2on203c12

calc .:

59.1

4.9

6.9%

found:

59.6

5.0

6.7%

5

Cl

Cl

-ch2

.ch2.ch2.ch2.ch2-

-

47

c22h22n2o3ci2

calc .:

61.0

5.1

6.5%

found:

60.8

5.5

6.4%

6

Cl

Cl c6h5

ch3

155-7

62

c24h20n2o3ci2

calc .:

63.3

4.5

6.2%

found:

63.4

5.1

6.4%

7

f

Cl ch3

ch3

-

71

c19h18n2o3fci ber .:

60.6

4.8

7.4%

found:

60.7

5.2

6.9%

8th

Cl

Cl c2hs c2hs

96-8

60

c2i h22n203c12

calc .:

59.9

5.2

6.6%

found:

59.6

5.6

6.4%

9

f h

ch3

ch3

80-2

52

c19h19n2o3f ber .:

66.6

5.6

8.2%

found:

66.5

5.4

8.0%

10th

f

Cl c2hs c2hs

71-3

70

c21h22n2o3cif ber .:

62.3

5.4

6.9%

found:

62.6

5.6

6.9%

11

f

Cl

-ch2

, ch2.ch2.ch2-

85-7

74

c2iH20n2o3fc1

calc .:

62.6

4.97

6.9%

found:

62.2

4.9

6.7%

12

f

Cl

-ch2

, ch2.ch2.ch2.ch2-

91-3

69

c22h22n2o3fci ber .:

63.4

5.3

6.7%

found:

63.2

5.2

6.6%

13

f h

c2h5

c2h5

64-6

72

c21h23n2o3f ber .:

68.1

6.2

7.6%

found:

68.1

6.2

7.5%

14

f h

-ch2

, ch2.ch2.ch2.ch2-

108-110

59

c22h23n2o3f calc .:

69.1

6.1

7.3%

found:

68.8

6.0

7.1%

15

Cl h

ch3

ch3

112-114

82

ci9H19n203c1

calc .:

63.6

5.3

7.8%

found:

63.9

5.5

7.7%

16

Cl h

c2hs c2hs

73-75

72

c21h23n2o3ci ber .:

65.2

5.9

7.3%

found:

64.8

6.1

7.3%

17th

Cl h

ch3

c2h5

87-89

90

c20H2in2o3c1

calc .:

64.5

5.6

7.5%

found:

64.7

5.9

7.3%

18th

Cl h

-ch2

, ch2.ch2.ch2-

112-114

74

c21h21n2o3ci ber .:

65.5

5.5

7.3%

found:

66.0

5.8

7.3%

19th

Cl h

-ch2

, ch2.ch2.ch2.ch2-

132-134

78

c22h23n2o3ci ber .:

66.2

5.8

7.0%

/; \

found:

66.5

5.9

7.2%

20th

f

Cl sch3

- // \)

112-114

15

c23h19n3so3ci ber .:

58.6

4.0

8.9%

\ /

found:

58.7

4.3

8.8%

\ N = /

O

21st

f

Cl c6hs ii

—P (oc2h5) 2

-

-

c27h27pn2o6cif calc .:

57.8

4.8

5.0%

O

found:

57.5

5.2

4.8%

22

f

Cl ch3

ii

-p (oc2h5) 2

_

c22h25pn2o6cif calc .:

52.9

5.0

5.6%

found:

52.0

5.2

5.8%

23

f

Cl ch3

-s (ch2) 3cn

94-96

c22h21n3o3scif ber .:

57.2

4.6

9.1%

found:

57.6

4.9

9.2%

Examples 24 to 27

According to Examples 1 and 2, further related compounds were prepared, the structure and physical properties of which are shown in the following table.

5

616 560

Example X Y Rj R2 mp. Yield

No. ("Cl (%)

24 F Cl CH3 SCH3 40-42 51

25 F Cl H C6Hs 100-103 30

26 F Cl CH3 OC2Hs rubber 51

27 F Cl CH3 NH, 133-135 57

Example 28

Evidence of the Effect as Selective Herbicides In 7 cm pots of compost (John Innes No. 1), 25 seeds of barley, 25 seeds of wheat and 30 seeds of wind oat (Avena Spp) were sown. After the plants had formed 1/2 to 2- 1/2 leaves, the pots were sprayed with a solution of the compound in equal parts of acetone and water, which contained a wetting agent and an adhesive. The crops were treated with a dosage of 10 to 0.6 kg / ha, while the wind oat was treated with a dosage of 2.0 to 0.15 kg / ha. The spraying was repeated four times in each case, after which the pots were kept in the greenhouse at about 21 ° C. and with an exposure of 16 hours per day.

Evaluation was carried out 10 to 14 days after spraying. For this, the plants were removed directly above the ground

10 cut and determined their weight, which was expressed as a percentage of the weight of untreated plants.

The percentage impairment of growth in wind oat plants was estimated visually. The values thus obtained were then used to calculate the dosage needed to affect growth. The dose that gave 50% inhibition for crops (GIDso) was compared to the dose (GIDS0) that also gave 50% growth inhibition in wind oat. The selectivity factor for the compound in question is then given by the ratio:

GID50 for crops GID50 for wind oats

The test results are shown in Table 25 below.

table

Compound of wind oat barley selectivity wheat selectivity

Example No.GIDS0 GIDä0 factor GIDS0 factor

9

0.68

4.79

7.0

12.4

18.2

13

1.14

4.93

4.3

19.8

17.4

2nd

1.23

5.99

4.9

14.2

11.5

14

1.28

5.74

4.5

16.7

13.0

7

0.60

2.26

3.8

7.6

12.7

10th

1.02

2.67

2.6

8.6

8.4

11

1.06

2.97

2.8

11.1

10.5

12

1.08

2.74

2.5

11.1

10.3

1

1.60

2.57

1.6

12.5

7.8