FR2495152A1 - NEW N-HALOGENACETYL-2-SUBSTITUENT-6-ACYLANILINES HERBICIDES AND THEIR APPLICATIONS - Google Patents

Abstract

The invention relates to N-haloacetyl-2-substituent-6-acylanilines. The compounds of the invention correspond to the formula: (CF DRAWING IN BOPI) in which X is a halo radical; m and n are equal to 0 or to 1; R ** 1 and R ** 3 represent hydrogen or an alkyl group or together form a carbocyclic ring; R ** 2 and R ** 4 represent hydrogen or an alkyl group; R ** 5 and R ** 6 represent hydrogen, an alkyl or alkoxyalkyl group; R ** 7 is hydrogen, a halo radical, a nitro, alkoxy or alkyl group; and Y is oxygen or an NR ** 8 group in which R ** 8 is hydrogen or an alkyl radical. The compounds of the invention are endowed with herbicidal activity and exert a growth regulating activity, in particular against weeds of the grass family.

Description

U.S. Patent No. 4,141,989

  discloses 3- (N-chloroacetyl) -N- (2,6-dialkylphenyl)

  amino) -gamma-butyrolactones having fungal properties

  cides. U.S. Patent No. 4,055,410 discloses bromacetamides and chloroacetamides

  substituted with herbicidal properties.

  O, O-dialkyl acetals of 3- / 3'-alkyl-2 '- (N-

  halogen acetylalkoxymethylamino) phenylpropionaldehydes are described in Chem. Abstr., 92: 58400W

(1980).

  The present invention relates to novel N-haloacetyl-2substituant-6-acylanilines and their methods of use as herbicides and as plant growth substances. It has now been found that the attachment of certain substituents acyl ketal, oxime,

  hydroxyalkyl and alkoxyalkyl at the 6-position of the N-halogen

  acetyl-2-substituent-anilines gives compounds having herbicidal activity and influencing the growth of plants. The compounds of the invention are

  particularly effective for pre-treatment

grass emergence.

  The compounds of the invention are represented by the formula:

R6 R R2

GOLD

R7 N-CCH2X

\ / O (CH2) m (I) / \ e t (CH2) n \ yJ

R5 R3

  wherein X is a halogeno radical; n and m represent

feel individually 0 or 1;

1 3

  R and R are individually hydrogen or an alkyl group of 1 to 4 carbon atoms or R 1 and R 3 together form a carbocyclic ring containing 10 carbon atoms; R2 and R4 are each hydrogen, an alkyl group having 1 to 4 carbon atoms, phenyl group or a phenyl group substituted with 1 to 4 halo, alkyl of 1 to 4 carbon atoms, alkoxy of 1 to 4, and 4 carbon atoms or nitro; R5 and R6 individually represent hydrogen, an alkyl group having 1 to 4 carbon atoms or an alkoxyalkyl group having 2 to 6 carbon atoms; R7 is hydrogen, halo, nitro, alkylthio having 1 to 4 carbon atoms, alkoxy having 1 to 4 carbon atoms or alkyl having 1 to 4 carbon atoms; and Y is oxygen or NR8, where R8 is hydrogen or an alkyl radical having 1 to 4 carbon atoms, provided that when R6 is H or alkyl and n is 0, R5 is group

  alkyl and Y is oxygen, (1) R1, R2, R3 and R are not

  not all of them are hydrogen and (2) if one of R1 and R2 is hydrogen and the other is an alkyl group and one of R3 and R4 is hydrogen, the other is

not the same alkyl group.

  Representative examples of R alkyl groups,

2 3 4 5 6 8

  R 2, R 3 R, R, R and R are methyl, ethyl, isopropyl, n-propyl, n-butyl, sec-butyl, isobutyl. Examples

  representative of carbocyclic bonds R 1 -R 3 are the groups

  -CH 2 CH 2, - (CH 2) 3, - (CH 2) 4-, - (CH 2) 6 - and - (CH 2) 8 -. of the

2 2 '2 4

  representative examples of phenyl groups R and R are the

  phenyl, p-chlorophenyl, 3,5-dichlorophenyl, 4-methyl-

  phenyl, 4-methoxyphenyl. Preferably, R1 is a group

2 3 4

  alkyl of 1 to 4 carbon atoms and R2, R and R are hy-

  or alkyl groups of 1 to 4 carbon atoms.

  Representative examples of alkoxy groups

  R5 and R6 are methoxymethyl, methoxy-

  ethyl, ethoxymethyl, ethoxyethyl, methoxypropyl,

ethoxybutyl and methoxypentyl.

  Preferably, R 5 is an alkyl group having 1

  to 4 carbon atoms and, in particular, R5 is the methyl group.

  R6 is preferably hydrogen.

  Other representative R7 groups are the

  chloro, bromo, fluoro, nitro, methoxy, methyl-

  thio, ethoxy, propoxy, propylthio, butoxy. Preferably, R is an alkyl group having 1 to 4 carbon atoms. Representative examples of X groups are the chloro, bromo, fluoro and iodo radicals. Preferably,

X is the chloro radical.

  Preferably, Y is oxygen and n and m are

both are equal to zero.

  The compounds of the invention may be prepared according to the following scheme: R7 o / O

/ \ NHCCH3

  (C2Jo - 8 (CH2) nCR5 R7 NH2 + o (CH2) nCR5 (Ia)

CH3CO2H

(II) o

II + XCH2CC1

) R7 o

HCCH2X + HC1

oCH2) R

(CH2>) R5

(III) (1) (2)

HO-CR1R2

III + (CH2) m

H-Y-C R3R4

(IV) R7 O

HP / \ NHCCH2X + H20

R1

(CH-)., O --- R2

(IVa) IVa + R6Z Z = Br, Cl>

I + HZ

  The above reactions are conventional reactions of deacetylation (1), acetylation (2), ketalization (3) and alkylation (4) and can be carried out

by known methods.

  In the case where R5 is hydrogen, the preferred process corresponds to the following scheme: ## STR2 ## )

R7 R1

w / \ R2

VII + XCH2CC1 NHCCH2X O (7)

(CH2) n CH (CH2) m YR3 R4

(VIII)

  VIII + R6Z Z = Br, Cl I + HZ (8) The reaction conditions for reactions (5), (7) and (8) are similar to the respective conditions of reactions (3), (2) and (4). The reaction (6) can be carried out under conventional hydrogenation conditions

with a platinum catalyst.

  The compounds of the present invention are generally herbicidal and affect plant growth in both pre-emergence and post-emergence applications, but are particularly effective in pre-emergence applications. For pre-emergent destruction of undesirable vegetation, the herbicidal compounds are applied in herbicidally effective amounts at the site or in the growth medium of the vegetation, for example, soil infested with seed and / or seedlings. of this vegetation. This application inhibits the growth of seeds, sprouts and seedlings or destroys them. For post-emergence applications, herbicide compounds are applied

  directly to foliage and other parts of plants.

  Generally, the herbicidal compounds of the invention are effective against weeds of the family

  grasses and weeds.

  Some may be selective with regard to the mode of application

  cation and / or type of weeds. The compounds of the invention are particularly effective as pre-emergence herbicides against

the family of grasses.

2495'52

  When the compounds are applied above.

  from the soil to growing plants in a quantity chosen so that they do not destroy plants

  useful, they also perform an effective and

  plant growth retardant and can be used advantageously, for example, for

  prevent or delay grass growth

  The compounds can be applied in the form of any of a variety of compositions. In general, the compounds can be diluted with a carrier of the type that is used and usually referred to in practice, for example

  inert solids, water and body fluids.

  The compounds are included in these compositions in an amount sufficient for them to exert

  herbicidal effect or to influence growth. customarily

  approximately 0.5 to 95% by weight of the

  compounds is included in these formulations.

  Solid compositions can be prepared with inert powders. The compositions can therefore be homogeneous powders which can be used as such, diluted with inert solid substances

  to form powders for dusting, or suspended

  in a liquid medium suitable for spray application. The powders usually contain the active ingredient in admixture with small amounts of a conditioning agent. Natural, absorbent clays such as attapulgite or relatively non-absorbent clays such as kaolin, diatomaceous earth, finely divided synthetic silica, calcium silicate and other solid inert carriers of the type commonly used in herbicidal compositions in powder, can be used. The active ingredient usually constitutes 0.5 to 90% of these powder compositions. Solids usually have to be very finely divided. For the conversion of powders into dusting powders, talc, pyrophyllite and the like are usually used. Liquid compositions comprising the active compounds defined above can be prepared

  by mixing the compound with a suitable liquid diluent.

  Examples of commonly used liquid media are methanol, benzene, toluene and the like. The active ingredient ordinarily constitutes about 0.5 to 50% of these liquid compositions. Some of these compositions are intended to be used as they are, and others

  must be diluted with large amounts of water.

  Compositions in the form of wettable powders or liquids may also contain one or more surfactants such as

  wetting, dispersing or emulsifying agents. The surfactants

  The active agents cause wettable powders or liquids to disperse or emulsify readily in water to form sprayable aqueous compositions. The surfactants used can be

  of the anionic, cationic or nonionic type. They understand

  For example, long-chain sodium carboxylates, alkylarylsulfonates, sodium lauryl sulphate, polyethylenes, lignosulfonates

and other surfactants.

  When used as a pre-treatment

  raised, it is desirable to include a fertilizer, insecticide

  a fungicide or other herbicide.

  The amount of compound or composition that is administered varies with the portion of the plant or growth medium of the plant to be affected, the general site of application - ie protected areas such as than greenhouses, compared to exposed areas such as fields, as well as

  desired type of struggle. Generally, for a herbicidal struggle

  In both pre-emergence and post-emergence, the compounds of the invention are applied at rates of 0.2 to 60 kg / ha and the recommended rate is in the range of 0.5 to kg / ha. . For regulating or retarding activity of plant growth, it is essential to apply the oximes at an insufficiently high concentration to destroy the plants. Therefore, application rates for regulatory or growth retarding activity of plants are generally lower than rates used to kill plants. These rates generally vary from 0.1 to 5 kg / ha and preferably from 0.1

at 3 kg / ha.

  Herbicide tests on compounds

  representative of the invention have been made using

following methods.

  Pre-emergence herbicidal test An acetone solution of the test compound was prepared by mixing 375 mg of the compound, 118 mg of a non-ionic surfactant and 18 ml of acetone. 10 ml of this solution was then added to 40 ml of water to form

the test solution.

  Seeds of the test vegetation were sown in a pot of soil and the test solution was sprayed uniformly to the soil surface at a dose of 27.5 g / cm 2. The pot was watered

  and installed in a greenhouse. We sprayed the pot through

  mittence, and the emergence of seedlings, the vigor of emerged seedlings, etc., for a period of three weeks. At the end of this period, efficiency

  herbicide of the compound was assessed on the basis of

  physiological conditions. We used a scale of 0-

  at 100 where 0 was no phytotoxicity and 100 was total kill. The results of these tests appear in Table I. The compounds were also tested at lower doses on

  weeds and cultivated plants. The results

  these tests appear in Table II.

  Post-emergence herbicide test The test compound was formulated in the same manner as for the pre-emergence test. This formulation was applied uniformly by spraying on two similar pots of 24-day old plants (about 25 plants per pot) at a dose of 27.5 μg / cm 2. After drying, the plants were placed in a greenhouse and then sprinkled intermittently at their base, if necessary. Plants were periodically observed for phytotoxic effects and physiological and morphological responses to treatment. After three weeks, the herbicidal efficacy of

  compound was evaluated on the basis of these observations.

  A scale of 0 to 100 was used, with 0 representing the absence of phytotoxicity and 100 representing complete destruction. The results of these tests appear on the

Table I.

  Plant growth regulation test Four lawn grass species listed in Table III were grown in rows in 16.5 x 24.1 cm pots to a height of 10.2 to 15.2. cm,

  then they were cut to a height of 2.54 cm.

  Each test compound was applied uniformly by

  spraying on lawn grass species, concentrating

  testing. After a stay of 20 days in a greenhouse

  under normal conditions of watering and fertilization

  each species was cut 2.54 cm above the ground and weighed. Weights are expressed as percent growth inhibition compared to untreated control species. We used four

tests by treatment.

EXAMPLE 1

  Preparation of N-chloroacetyl-2-methyl-6-acetylaniline A. 76.1 g of N-acetyl-2-methyl-6-acetylaniline are refluxed for 24 hours in 300 ml of water and 300 ml of ethanol. 300 ml concentrated hydrochloric acid and 15 ml concentrated sulfuric acid. The solution is cooled and concentrated ammonium hydroxide is added thereto,

  to pH 10. The solution is extracted with dichloromethane.

  The extracts are dried (MgSO4) and evaporated. 2-methyl-6-acetylaniline (49.3 g) is obtained under the

  form of a solid substance of tan color.

  B. 25 g of 2-methyl-6-acetylaniline and 26.5 g of pyridine are cooled in one liter of methylene chloride in an ice-acetate bath. A solution of 37.9 g of chloroacetyl chloride in 100 ml of

  Methylene chloride is slowly dripped.

  The solution is stirred at room temperature for 2 hours, washed with 10% HCl, 10% NaOH, dried over MgSO 4 and evaporated. The title product is obtained as a white solid

melting at 88-89 C.

EXAMPLE 2

  Preparation of 2,4-dimethyl-2- (3'-methyl-2'-chloroacetamido

  phenyl) dioxolane 4.51 g of N-chloroacetyl-2-methyl-6-acetylaniline (from Example 1), 3.7 ml of 1,2-propanediol, and a small amount of toluenesulphonic acid are combined

  in 50 ml of toluene and heated under reflux. Water dis-

  by-product is collected in a Dean-Stark separator. When the water has stopped distilling, methylene chloride is added and the mixture is extracted successively with a solution of bicarbonate

  and water, then dehydrated (MgSO4) and evaporated to give

  3.3 g of a brown oil. The oil is purified on a column of silica gel (eluent hexane: ethyl acetate) to give the title product (compound N 2

of Table A).

EXAMPLE 3

  Preparation of 2,4,4,5-tetramethyl-2- (3'-methyl-2'-chloro)

  acetamidophenyl) dioxolane The procedure of Example 2 is used

  by replacing 1,2-propanediol with 2-methyl-butane

2,3-diol.

  The product is purified on a column of silica gel giving the product indicated in the title

(compound N 3 of Table A).

EXAMPLE 4

  Preparation of 2-methyl-4-ethyl-2- (3'-methyl-2'-chloro)

  acetamidophenyl) dioxolane The procedure of Example 2 is used, replacing 1,2-propanediol with 1,2-butanediol. The product is purified on a column of silica gel and the product indicated in the title is obtained.

(compound N i of Table A).

TABLE A

Compounds of formula: CH3 o

NH - C CH2C1

R2 R3

Mp

R4 C

C

CAL. TR.

H analysis

CAL. TR.

NOT

CAL. TR.

61t4 57r93 601rl 67.3

618 7.5 4.7

6.39 6.58 4; 94

  7t1 7t2 4t5 774 8t0 413 6177 6r63 4r7

- -1311 *

* Chlorine.

  No. R1 C2115 CH3 Cf! 3 C2115 C113 II Il IIt H H CH3 CI3 H C13 H Il C2I15 Il il Oil il w Il -57 Oil t5 59,26 61t6, 50 4 5 4,5 4 58

11.7 *

you% O tn r '

TABLE I

  HERBICIDE ACTIVITY AT 27.5 gg / cm2 C / 0/0/0 M / 0/0/0 Inhibition%, pre / post

A D P

/ 0 - / 10 100/65

/ 0 100/20 100/35

/ 0 100/0 100/0

  Av. / 0/10/0 Lamb's-quarters (Chenopodium album) Mustard (Brassica arvensis) Amaranth (Amaranthus retroflexus) Digitaria (Digitaria sanguinalis) Panic-foot (Echinochloa crusgalli) = Wild oats (Avenua fatua) N 1 C = M = A = D = P = Av.

TABLE II

PRE-EVENT HERBICIDE ACTIVITY

PHYTOTOXICITY%

i 0 plg / cm2

1, 4.4

1.8X7

2 4X4

1T8

3,414

1.8 0.7 SOJA o0 o RICE C M A D P Av

62 20 53 0 100 98 68

7 0 0 0 88 95 7

0 0 0 0 37 70 0

0.

47 73

0 53

0 0

85

53 10

0 0

100

0 100

0 70

0 100

0 94

0 33

o

47,100

0 96

0 52

0 0

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

Ni NO tA A rua 4t4 1t8 0; 28 i

TABLE III

  INHIBITION OF GROWTH OF GRASS

A TURF

  Destruction% ppm Iv. o F o o Pa o o D o o Iv = Ivy F = Fescue Pa = Paturin D = Digitaria No

Claims (12)

  1. Compound characterized in that it meets the formula: R6 R 1 0 R1 - R R7 N-CCH2X   Wherein X is halogeno; n and m are individually 0 or 1; R1 and R3 individually represent hydrogen or an alkyl group having 1 to 4 carbon atoms or R1 and R3 together form a carbocyclic ring containing 10 carbon atoms; R2 and R4 are each hydrogen, an alkyl group having 1 to 4 atoms   carbon, the phenyl group or a substituted phenyl group   killed with 1 to 4 halo, alkyl of 1 to 4 carbon atoms, alkoxy of 1 to 4 carbon atoms or nitro; R5 and R6 individually represent hydrogen, an alkyl group having 1 to 4 carbon atoms or an alkoxyalkyl group having 2 to 6 carbon atoms; R7 is hydrogen, halo, nitro, alkylthio having 1 to 4 carbon atoms, alkoxy having 1 to 4 carbon atoms or alkyl having 1 to 4 carbon atoms; and Y is oxygen or NR8, wherein R8 is hydrogen or an alkyl group having 1 to 4 carbon atoms provided that when R6 is H or an alkyl group and n is 0, R5 is a group R1 2 3 4   alkyl and Y represents oxygen, (1) R1, R, R3 and R are not all hydrogen and (2) if one of R and R2 is hydrogen and the other is an alkyl group and one of R3 and R4 is hydrogen, the other is not the same alkyl group.   2. A compound according to claim 1 in which m and n are 0.   The compound of claim 2 wherein R 7 is an alkyl group having 1 to 4 carbon atoms and Y is oxygen. The compound according to claim 3, wherein R 1 is an alkyl group having 1 to 4 carbon atoms and R 2, R 3 and R 4 individually represent hydrogen or an alkyl group having 1 to 4 carbon atoms. carbon.   5. Compound according to claim 4, characterized in that X is the chloro radical, R7 is a methyl group R5 is an alkyl group having 1 to 4 carbon atoms and R6 is hydrogen.   The compound of claim 5 wherein R5 is methyl, R1 is ethyl   and R2, R3 and R4 are hydrogen.   The compound of claim 5 wherein R5 and R1 are methyl and R 2, R3 and R4. are hydrogen.   The compound of claim 5 wherein R5, R1, R2 and R3 are methyl and R4 is hydrogen.   9. A herbicidal composition, characterized in that it comprises a biologically inert carrier and a herbicidally effective amount of a compound according to claim 1.   10. A method of destroying vegetation, characterized   in that it consists in applying to said vegetation or its growth medium an effective amount of   herbicide point of view of a compound according to the claim 1.   11. Process for delaying the growth of plants, characterized in that it consists in applying to the plants or to their growth medium a retarding quantity   plant growth of a compound of formula claim 1.   12. Process for retarding the growth of fescue, bluegrass and digitaria, characterized in that it consists in applying to said plants or to their growth medium a retarding amount of the growth of the plants of a compound of formula according to claim 1. -