FR2563830A1 - DIOXACYCLOHEXYLANILIDES, PROCESS FOR PREPARING THEM AND THEIR APPLICATIONS AS HERBICIDES - Google Patents

Abstract

DIOXACYCLOHEXYLANILIDES WITH HERBICIDAL ACTIVITY RESPONDING TO GENERAL FORMULA I: (CF DRAWING IN BOPI) IN WHICH R AND R, WHICH MAY BE IDENTICAL OR DIFFERENT, EACH INDEPENDENTLY REPRESENT AN ALKYL GROUP OR HALOGENO, ALKYL OR HALOGENE, OR ALKYL-FORMULA, OR HALOGENENTLE, OR ALKYLENE GROUP, OR HALOGENENT SO WITH THE INTERMEDIATE CARBON ATOM A CYCLOALKYLIDENE GROUP; R REPRESENTS AN ALKYL, HALOGENOALKYL OR CYCLOALKYL GROUP; AND X REPRESENTS A HYDROGEN OR HALOGEN ATOM OR AN ALKYL GROUP. PREPARATION OF THESE COMPOUNDS, OF HERBICIDE COMPOSITIONS CONTAINING THEM AND THEIR USE AS HERBICIDES.

Description

This invention relates to certain herbicides based on

  dioxacyclohexylanilides, the preparation of these compounds,

  the herbicidal compositions containing them and their use

  in the fight against the growth of inde-

so rables.

  Certain substituted phenylurea derivatives are known to be effective herbicides, for example as described in U.S. Patent Nos. 2,655,444 to 2,655,447. The dioxacyclohexyl-phenylureas are described as herbicides in Applicant's Patent Application No. 0097980. It has now been discovered that

  useful herbicidal activity is present in dioxacyclo-

  hexylanilides. Accordingly, the present invention relates to dioxacyclohexylanilides having the general formula I: R 0

/ \ NHCOR3

X

  wherein R1 and R2, which may be the same or different, each independently represent a group

  alkyl or haloalkyl, or R1 and R2 represent

  seems an alkylene group, thus forming with the atom of

  intermediate carbon cycloalkylidene group; R3

  has an alkyl, haloalkyl or cycloalkyl group and X represents a hydrogen or halogen atom or a

alkyl group.

  When any of the substituents R1, R2

  R3 or X represents an alkyl, cycloalkyl or halogen group;

  noalkyl, it advantageously contains up to 6, of

  preferably up to 4 carbon atoms, being preferably

  cation, methyl, ethyl, cyclopropyl or methyl

  1-cyclopropyl, and the halogen atom of the halogen group

  genoalkyl is preferably fluorine or chlorine, fluoromethyl, trifluoromethyl and chloromethyl being preferred. When R 1 and R 2 together represent an alkylene group, it preferably has 4 or carbon atoms and is preferably unbranched, thereby forming with the intermediate carbon atom a cyclopentyl or cyclohexyl ring system. Substituent X

  is preferably located in meta of the amide group (i.e.

  say in ortho of the dioxane ring) and is advantageously a

  chlorine atom or a methyl group.

  The subject of the invention is also a method for

  preparation of anilides as described above, which

  takes the reaction of an aniline of formula II:

(II)

  with an acyl halide of formula R3COHal, in the

  which Hal represents a halogen atom, preferably chlorine, or an acyl anhydride derived from the same acyl group

  R3CO-. The reaction is advantageously carried out in

  a base for eliminating hydrogen halide,

  such as triethylamine, and is advantageously

  killed in an organic solvent such as toluene.

  The starting aniline of formula II can be prepared by

  by adapting appropriately the methods of

  established, advantageously from a 2-phenyl-1,3-

diol of formula III

2O (III)

HO X

  R1 R2 HO by reaction with a halogenocyte of formula IV R2

  followed by a reduction of the dioxacyclohexylnitrobenzene re-

  sultant. The diol-ketone reaction is advantageously carried out

  in the presence of p-toluenesulfonic acid and in an organic solvent such as benzene, and the reduction of the product is advantageously carried out by reaction with hydrogen gas in the presence of a platinum catalyst

  in an organic solvent such as an alcohol.

  The compounds of the general formula I have proved

  present an interesting activity of herbicides. As a result

  Furthermore, the subject of the invention is a composition

  herbicide comprising a compound of formula I as defined

  finished above, in association with at least one vehicle,

  and a method of manufacturing this composition which

  takes the combination of a compound of formula I with at least

a vehicle.

  The subject of the invention is also the use of such a compound or of such a composition according to the invention as a herbicide. In addition, according to the invention, it is described

  a method for combating the growth of undesirable plants

  in one place by treating the place with a compound or composition according to the invention. The application instead can be pre-emergence or post-emergence. The dose of active substance used may be, for example, from 0.05 to 4 kg / ha. A vehicle in a composition according to the invention

  is any material with which the substance is formulated

  tive to facilitate the application to the place to be treated which may be, for example, a plant, a seed or the soil,

  or to facilitate the storage, transport or handling of

  tion. A vehicle may be a solid or a liquid and

  takes a material that is normally gaseous but has been compressed to form a liquid and one can be used

  any of the vehicles normally used in the

  mulation of herbicidal compositions. Preferably, the compositions according to the invention contain 0.5 to 95% by weight.

weight of active substance.

  Suitable solid vehicles include

  natural and synthetic clays and silicates, for example

  natural silicas such as diatomites; Silicas

  magnesium cates, for example talcs; Alumino

  magnesium silicates, for example attapulgites and vermiculites; aluminum silicates, for example-the

  kaolinites, montmorillonites and micas; the carbona

  calcium, calcium sulphate; Ammonium sulfate

  minium; synthetic hydrated silicon oxides and

  synthetic calcium or aluminum silicates; the ele-

  such as carbon and sulfur; the resins

  natural and synthetic, for example the resins of cou-

  marone, polyvinyl chloride and polymers and co-

  styrene polymers; solid polychlorophenols; bitumen; waxes; and solid fertilizers, for example

superphosphates.

  Suitable liquid vehicles include

  the water; alcohols, for example isopropanol and glycan

  collars; ketones, for example acetone, methylethyl-

  ketone, methyl isobutyl ketone and cyclohexanone; the ethers; aromatic or arylaliphatic hydrocarbons,

  for example benzene, toluene and xylene; the frac-

  oil, for example, kerosene and

  light minerals; chlorinated hydrocarbons, for example the

  carbon tetrachloride, perchlorethylene and tri-

  chloroethane. Mixtures of different liquids

often.

  Agricultural compositions are often formulated

  and transported in concentrated form which are then

  read by the user before the application. The presence of

  small amounts of a vehicle that is a surfactant

  active facilitates this dilution process. Thus, preferably

  at least one vehicle in a composition according to

  the invention is a surfactant. For example, the

  position may contain at least two vehicles, one of which

less is a surfactant.

  A surfactant may be an emulsifying agent

  a dispersing agent or a wetting agent; it can be nonionic or ionic. Examples of suitable surfactants are the sodium or

  calcium from polyacrylic acids and lignin

  sulfonic; condensation of fatty acids or amines or

  of aliphatic amides containing at least 12 carbon atoms

  bone in the molecule with ethylene oxide and / or propylene oxide; esters of fatty acid and glycerol,

  sorbitan, sucrose or pentaerythritol; professionals-

  condensates of these with ethylene oxide and / or propylene oxide; condensation products

  fatty alcohol or alkylphenols, for example p-octyl-

  phenol or p-octylcresol, with ethylene oxide and / or propylene oxide; sulphates or sulphonates of these condensation products; alkali metal or alkaline earth metal salts, preferably sodium salts, or esters of sulfuric or sulfonic acids containing at least 10 carbon atoms in the molecule, for example sodium lauryl sulphate, secondary alkyl sulphates of sodium, sodium salts of sulfonated castor oil and

  sodium alkylarylsulfonates such as dodecylbenzoate;

  zènesulfonate; and polymers of ethylene oxide and

  copolymers of ethylene oxide and propylene oxide

pylene.

  The compositions of the invention may be formulated

  for example, in the form of wettable powders,

  dust, granules, solutions, emulsion concentrates,

  sifiables, emulsions, concentrated suspensions and

  rosols. The wettable powders usually contain 25, 50 or 75% by weight of active substance and usually contain, in addition to the inert solid carrier, 3 to 10% by weight of a dispersing agent and, if necessary, 0 to 10% by weight of stabilizer (s) and / or other adjuvants

  penetration adjuvants or adhesive agents.

  Dusts are usually formulated in concentrate of

  dust having a composition similar to that of a

  wettable, but without dispersant, and are diluted in

  the field with an additional quantity of

  to give a composition usually containing Yt to

  % by weight of active substance. The granules are usually

  have been prepared to have a size between 1.676 to 0.152 mm (between 10 and

  British standard) and may be manufactured by

  agglomeration or impregnation. In general, the granules will contain from 75% by weight of active substance and from 0 to 10% by weight of additives such as stabilizers, surfactants, release retarders and binding agents. The so-called "dry flowable powders" consist of relatively small granules having a relatively high concentration of active substance. Emulsifiable concentrates usually contain, besides a solvent and, optionally, a cosolvent, 10 to 50% w / v of active substance, 2 to 20% w / v

  emulsifiers and 0 to 20% w / v of other additives

  such as stabilizers, penetration adjuvants,

  and corrosion inhibitors. Suspensions

  centered are usually developed to give

  a stable castable product that does not redeposit and

  usually 10 to 75% by weight of active substance

  ve, 0.5 to 15% by weight of dispersing agents, 0.1 to 10% by weight of suspending agents such as protective colloids and thixotropic agents, 0 to 10% by weight of other additives such as suds suppressors, corrosion inhibitors, stabilizers, penetration aids and adhesives, and water or

  organic liquid in which the active substance is sen-

  insoluble; some organic solids or mineral salts may be present dissolved in the formulation to help prevent sedimentation or as agents

anti-freezes for water.

  Aqueous dispersions and emulsions, for example

  compositions obtained by diluting a wettable powder

  lable or a concentrate according to the invention with water are also part of the scope of the invention. The said emulsions may be of the water-in-oil or oil-in-water type and may have the thick consistency of a mayonnaise. The composition of the invention may also contain

  other ingredients, for example other compounds with

  with herbicidal, insecticidal or fungicidal properties.

  The invention is illustrated in the following examples:

solvents.

  Example 1 Preparation of 4- (2-methyl-2-chloromethyl)

  1,3-dioxacyclohex-5-yl) -3-methyl-1 '- methyl

cyclopropanilide

  A) Dissolve 3-methyl-4- (1,3-dihydroxy-prop-2-yl) -

  nitrobenzene (5 g) in benzene (100 ml) is added chloroacetone (2.4 g) and p-toluenesulfonic acid

  (0.5 g) and the reaction mixture is refluxed

  one night. The solvent is removed, diluted with methylene chloride, the product washed with sodium bicarbonate solution, dried, purified by

  chromatography and recrystallized to obtain 4-

  (2-methyl-2-chloromethyl-1,3-dioxacyclohex-5-yl) -3-methyl-

  nitrobenzene, melting point 105-106C.

  B) The product of A) (4.0 g) is dissolved in ethanol,

  5% platinum / charcoal is added and the mixture is

  hydrogen under 3 atmospheres. After 2 hours,

  the aniline product by chromatography and use

  get straight into the final stage.

  C) The product of B) (0.9 g) was dissolved in toluene and triethylamine (0.35 g) was added followed by 1-methyl-cyclopropanoyl chloride (0.42 g). The reaction mixture is stirred at room temperature for 1 hour, the toluene is removed and the product is made by dilution with methylene chloride, washing, drying and chromatographic separation on silica (2G0-450 mesh) to obtain the product of the desired title of

melting point 125 + 0.4 C.

  Analysis Calculated C 64.0; H, 7.1; N 4.1%

Found C 63.6; H, 7.1; N 4.1%.

  Examples 2 to 11 Following similar procedures to those described in the preceding example, additional examples of compounds of the invention are prepared, the melting points and chemical analyzes are set forth in Table I below. In this table, the compounds are identified by reference to an identity of the substituents in the following formula:

<NHICOR3

R2 0 "X

TABLE 1

  EK. No R R R X Melting Point R2 Analysis

2

  2 C 2 H 5 C H 5 CH 3 CH 3 97-9875 Calc. C 72t5; H 8, 8; N 4; 2 Found C 72] 4; H 9; 3; N 4t 2 3 - (Ci 2) 4 148 Calc. C 7219; H, 8.2; N 4 3

2 4 7

  Found C 6713; H 811; N 570 4 CH CHF 128 Calc. C 6713; H, 7.5; N 4! 4

3 2 C

  Found C 66, 8; H, 716; N, 419 CH3 C25-11275-113r5 Calc C 71; 9; H 8 5; N 474 Found C 72; 2; H 8; 3; N 4 14 6 CH2 CHH C2H2H5; 76-77 Calc C 70.8; ## STR2 ## wherein ## STR2 ## wherein ## STR1 ## wherein ## STR2 ## 4.4 8 CF3 120-121 Calc C 51.2, H 48, N 4 O Found C 5175, H 510, N 3.7 9- "C1 90-92 Calc. C 45; 2; H 3.8; N 3.8 N Found C 45.4; H 4; 0; N 37 CO TABLE 1 (continued) Ex. M R1 R2 R X Melting point Analysis CH3 CH2Cl> CH3 Ci 99.5-100.5 Calc. C 57 0; H 519; N 319 Found C 5672; H 579; N 3 8 11 C 2 H 5 C 97.5-98.5 Calc. C 54f2; H, 5f7; N, 2 Found C 54r3; H, 5r8; EXAMPLE 12 Herbicidal Activity In order to evaluate their herbicidal activity, the compounds according to the invention were tested using a representative range of plants: maize, Zea mays (Ms); rice, Oryza sativa (R), Japanese millet, Echinochloa crusgal-

  li (MJ); oats, Avena sativa (A); Linen, Linum unit

  tissue (L); mustard, Sinapsis alba (M); the better

  sugar, Beta vulgaris (BS) and soybean, Glycine

do not max (S).

  The tests fall into two categories, pre-emer-

  and post-emergence. Pre-emergence tests consist

  attempt to vaporize a liquid formulation of the compound on the soil in which the seeds of

  plant species mentioned above. Post-tests

  emergence consist of two types of tests, namely soil spraying and leaf spraying. In soil sprinkling tests, the soil in

  which the plants of the above species grow is asper-

  of a liquid formulation containing a compound of the invention

  and, in the spray tests on the sheets,

  the, we spray on the plants this formulation.

  The soil used in the trials is a vegetated soil

horticultural tale prepared.

  The formulations used in the tests are pre-

  prepared from solutions of the test compounds in

  acetone containing 0.4% by weight of a condensate product

  alkylphenol / ethylene oxide available under the trademark "Triton X-155". These solutions are diluted with water in acetone and the resulting formulations are applied at dosage levels corresponding to 5 kg or 1 kg of active ingredient per hectare in a volume equivalent to 600 liters per hectare, for the soil spray test and

  the spraying test on the leaves, and in an equiva-

  10 kilograms of active ingredient per hectare in a volume equivalent to approximately 3 000 liters per hectare in

soil sprinkling tests.

  We use as controls, in the pre-emer-

  seeded untreated soil and, in post-harvest tests,

  untreated soil with plants.

  The herbicidal effects of test compounds are visually assessed twelve days after spraying

  on leaves and soil and thirteen days after having

  perge the soil and are recorded on a scale of 0 to 9.

  A score of 0 indicates growth similar to the untreated control and a score of 9 indicates death. An increase of 1 unit on the linear scale represents approximately one

  10% increase in the level of the effect.

  The results of the tests are shown on the ta--

Bleau II below.

TABLE 2

  Cajosed soil sprinkler. 10 / kg / ha Rate Spray on leaves Pre-emergence Ex. No. Ms R MJ A L M BS S kg / ha Ms R MJ A L M BS S Ms R MJ A L M BS S

  1 2 4 6 2 7 9 9 4 5 4 6 8 7 9 9 9 8 0 3 8 3 3 9 9 3

1 2 0 7 5 9 9 9 3 0 0 0 0 0 8 9 0

  2 0 0 4 0 6 9 9 5 5 2 2 9 7 9 9 9 9 0 0 3 3 5 9 9 0

1 00 6 2 8 9 9 8 0 0 0 0 0 0 8 0

3 0 0 0 0 2 3 0 2 5 O 0 6 5 7 9 8 4

1 O 0 6 '3 6 8 7 3

  4 2 7 8 6 8 9 9 8 5 3 2 9 7 9 9 9 6 0 0 8 2 5 8 8 1

1 0 O0 7 6 8 9 9 4 O 0 2 0 0 7 8 0

  0 2 7 4 8 9 9 6 5 3 2 8 8 9 9 9 6 0 0 0 0 3 7 8 0

1 2 1 7 6 8 9 9 6 0 0 0 0 0 5 8 0 N

  no LAN CD TABLE 2 (cont'd) Soil spraying 10 / kg / ha Dose Pulverisotion on leaves Pre-emergence Ex. No. Ms R MJ ALM BS S kg / ha Ms R MJ ALM BS S Ms R MJ ALM BS S

  6 0 8 0 4 3 9 9 6 5 3 3 8 7 8 9 9 7 0 0 4 2 3 8 8 0

1 1 1 7 5 6 9 9 5 0 0 0 0 2 0 8 0

  7 5 4 8 6 3 9 9 5 5 4 3 9 8 8 9 9 9 3 0 5 3 0 9 9 4

1 0 2 8 7 6 9 9 5 0 0 0 0 0 7 8 0

  8 0 0 4 0 0 9 9 0 5 3 3 8 6 6 9 9 2 0 0 0 0 0 0 8 0

1 1 1 2 5 4 9 8 0 0 0 0 0 0 0 7 0

  9 0 2 3 0 0 9 5 6 5 3 3 7 4 4 9 9 6 0 0 0 0 0 0 0 0

1 1 1 2 1 2 8 7 2 0 0 0 0 0 0 0 0

  0 1 4 0 3 9 9 2 5 4 4 8 6 8 9 9 2 0 0 0 0 4 8 8 0

1 2 2 4 4 7 9 9 0 0 0 0 0 0 7 0 0

  o LN CD TABLE 2 (cont.) Compound of soil spraying 10 / kg / ha Rate Spray on leaves Pre-emergence Ex. No. Ms R MJ ALM BS S kg / ha Ms R MJ ALM BS S Ms R MJ ALM BS S

  11 0 0 0 0 0 9 9 6 5 3 3 8 6 7 9 9 6 0 0 0 0 0 8 8 0

1 2 2 5 4 6 9 9 2 0 0 0 0 0 3 3 0

Ln r> LY1 {J co n4 o

Claims (11)

  1. Dioxacyclohexylanilides characterized in that   they correspond to the general formula I: R <O a (I) in which R1 and R2, which may be the same or different, each independently represent a group   alkyl or haloalkyl, or R1 and R2 represent   seems an alkylene group, thus forming with the atom of   intermediate carbon cycloalkylidene group; R3   has an alkyl, haloalkyl or cycloalkyl group; and X represents a hydrogen or halogen atom or a alkyl group.   2. Compounds according to claim 1, characterized in that R1 and R2 each represent, independently, a   alkyl group containing up to 6 carbon atoms,   optionally carrying a fluorine or chlorine substituent, or   R1 and R2 together represent an alkylene group containing   4 or 5 carbon atoms; R3 represents a group   alkyl, haloalkyl or cycloalkyl having up to 6 atoms   carbon mon; and X represents a halogen atom or a   alkyl group having up to 4 carbon atoms.   3. Compounds according to claim 2, characterized in that R1 and R2 each independently represent a methyl or ethyl group, optionally comprising a fluorine or chlorine substituent, or R1 and R2 represent   together a tetramethylene group; R3 represents a group   eg methyl, ethyl, trifluoromethyl. cyclopropyl or   1-thylcyclopropyl; and X represents a chlorine atom or   a methyl group located in meta of the amide group.   4. Process for the preparation of a compound of general formula   Neral I according to Claim 1, characterized in that it comprises the reaction of an aniline of formula II O} <N H 2 (II) R2 X   with an acyl halide of formula R3COHal, in the   which Hal represents a halogen atom, or an anhydride derived from the acyl group R3CO-.   5. Process according to claim 4, characterized in that the reaction is carried out in an organic solvent in presence of a base.   6. Process according to claim 4, characterized in that   that the aniline of formula II is prepared by reaction of diol of formula III (III) HO X   with a haloketone of formula IV R1 C = 0 R2 followed by a reduction of the product.   7. Process according to claim 6, characterized in that   that the diol-ketone reaction is carried out in the presence of   cool tosylic and in an organic solvent and in that the   reduction is carried out with hydrogen gas in pre- the presence of a platinum catalyst.   8. Compound according to claim 1, characterized in that it is prepared by a process according to any one of Claims 4 to 7.   9. A herbicidal composition, characterized in that   comprises a compound according to any one of the claims   1 to 4 and 8 and a vehicle.   10. Process for combating the growth of plants   desirable in one place, characterized in that it comprises the treatment of the place with a compound according to any one   Claims 1 to 4 and 8 or with a composition according to claim 9.   11. Use of a compound according to any one of   claim 4 to 8 as herbicide.