GB2167062A - N-Substituted phenyl imidazolidinones - Google Patents

Abstract

N-substituted phenyl imidazolidinone derivatives having the formula I:- <IMAGE> wherein A represents a hydrogen or halogen atom or an alkyl, alkoxy, phenoxy, or nitro group; one of X and Y represents a carbonyl group and the other represents the alkylidene group <IMAGE> R1 represents an alkyl or cycloalkyl group; R2 represents an alkyl, haloalkyl, cycloalkyl, alkenyl, phenyl, halophenyl or benzyl group; or R1 and R2, together with the interjacent carbon atom, jointly represent a cycloalkyl group; R3 represents a hydrogen atom or a salt forming cation, or an optionally halogenated alkyl, alkenyl, alkynyl, alkoxyalkyl, cycloalkyl, phenyl, furyl, or benzyl group; and Ac represents a group derived from an organic acid by the removal of an -OH group e.g. -COR4 or SO2R4 wherein R4 represents H, alkyl, haloalkyl, cycloalkyl, alkoxy, alkoxyalkyl, alkylthio, alkylamino or phenylamino or a possibly substituted phenyl or furyl group, and, except where R3 is a salt-forming cation, the acid addition salts thereof, have herbicidal use.

Description

SPECIFICATION Imidazolidinone herbicides This invention relates to certain N-acyl phenyl imidazolidinone derivatives, the preparation of such compounds, herbicidal compositions containing them, and to their use in controlling undesired plant growth.

US Patent No. 4188487 describes certain imidazolinyl benzoic acids, their esters and salts, and their use as herbicides. It has now been found that useful herbicidal activity is present in imidazolidinone derivatives which bear an acyl sybstituent on a ring nitrogen atom.

Accordingly, the present invention provides N-acyl phenyl imidazolidinone derivatives having the general formula I:

wherein A represents a hydrogen or halogen atom or an alkyl, alkoxy, phenoxy or nitro group; one of X and Y represents a carbonyl group and the other represents the alkylidene group

R1 represents an alkyl or cycloalkyl group; R2 represents an alkyl, haloalkyl, cycloalkyl, alkenyl, phenyl, halophenyl or benzyl group; or R1 and R2, together with the interjacent carbon atom, jointly represent a cycloalkyl group; R3 represents a hydrogen atom or a salt forming cation, or an optionally halogenated alkyl, alkenyl, alkynyl, alkoxyalkyl, cycloalkyl, phenyl, furyl, or benzyl group; and Ac represents an acyl group.

The term "acyl" is used herein to denote the radical derived from an organic acid by the removal of a hydroxyl group; the organic acid may be a carboxylic acid (including carbamic acid derivatives) or a so phonic acid, examples of suitable acyl groups being groups of the formula -COR4 or -SO2R4 wherein R4 represents a hydrogen atom or an alkyl, haloalkyl, cycloalkyl, alkoxyalkyl, alkoxy, alkylthio, alkylamino, or phenylamino group, or a phenyl or furyl group optionally substituted by a halogen atom or an alkyl, haloalkyl or nitro group.

When any of the above substituents contains an alkyl, alkenyl or alkynyl substituent group, this may be linear or branched and may contain up to 10, preferably up to 6, carbon atoms, suitable examples being methyl, ethyl and propyl, and in the case of an alkyl group may also be substituted by a halogen, especially chlorine, atom or an alkoxy group such as a methoxy group. When they contain a cycloalkyl substituent group this may contain from 3 to 10, preferably 3 to 8, carbon atoms, and is suitably cyclopropyl. When they contain a haloalkyl substituent group this suitably contains up to 6, preferably up to 4, carbon atoms and the halogen atom is stably fluorine or chlorine, trifluoromethyl being particularly preferred.

When R3 represents a salt-forming cation, this may be derived from any suitable base; convenient cation species including alkali metal atoms and ammonium or alkylammonium.

Preferred compounds are those wherein A represents a hydrogen atom or an alkyl group of 1 to 6 carbon atoms, especially methyl; R1, R2 and R3 each represents an alkyl group of 1 to 6 carbon atoms especially those wherein R1 represents a methyl group, R2 represents an isopropyl group and R3 represents a methyl or ethyl group. Representative examples of individual acyl substituents which may be present as group Ac include carbonyl groups of formula -COR4wherein R4 denotes a hydrogen atom or a methyl, ethyl, propyl, cyclopropyl, chloromethyl, methoxymethyl, ethoxy, ethylthio, methylamino, phenylamino, furyl, or phenyl optionally substituted by a chlorine atom or a trifluoromethyl or nitro group, or a sulphonyl group of formula -SO2R5 wherein R5 denotes a methyl group.

The invention also provides a process for the preparation of N-acyl imidazolidinones as defined above, which comprises reacting an acyl halide of formula Ac-Hal with a phenyl imidazolidinone of general formula ll:-

The substituents A, X, Y, R1, R2, R3 and Ac have the meanings defined above and Hal denotes a halogen, conveniently chlorine, atom. Where the acid from which the acyl group is derived can form a conveniently manipulated anhydride (as, for example, in the case of lower alkanoic acids, such as acetic), then such an anhydride may be used as acylating reactant in place of the acyl halide.The reaction is conveniently carried out in an inert, organic solvent such as benzene or tetrahydrofuran, though it may sometimes be convenient to use an excess of the acylating agent as solvent (e.g. acetic anhydride), and preferably in the presence of a base such as triethylamine.

The imidazolidinones of formula II above can, of course, exist in alternative tautomeric forms, and can therefore undergo chemical reaction via either tautomer, subject to the particular reaction conditions and reagents involved. When the reaction involves substitution onto one of the nitrogen atoms of the imidazolidinone ring, the different tautomers will yield isomerically different final products. Thus, in the case of the acylation process defined above, one tautomer will yield the product wherein Xis the carbonyl group and the other tautomer will yield the product wherein Y is the carbonyl group. Under conventional acylation conditions, it has been found that a mixture of both isomers is obtained, the predominent isomer being that wherein Y is the carbonyl group.

The compounds of general formula I have been found to show interesting activity as herbicides.

Accordingly, the invention further provides a herbicidal composition comprising a compound of formula I as defined above in association with at least one carrier, and a method of making such a composition which comprises bringing a compound of formula I into association with at least one carrier.

The invention also provides the use of such a compound or composition according to the invention as a herbicide. Further, in accordance with the invention there is provided a method of combating undesired plant growth at a locus by treating the locus with a compound or composition according to the invention.

Application to the locus may be pre-emergence or post-emergence.The dosage of active ingredient used may, for example, be from 0.05 to 4kg/ha. A carrier in a composition according to the invention is any material with which the active ingredient is formulated to facilitate application to the locus to be treated, which may for example be a plant, seed or soil, orto facilitate storage, transport or handling. A carrier may be a solid or a liquid, including a material which is normally gaseous but which has been compressed to form a liquid, and any of the carriers normally used in formulating herbicidal compositions may be used.

Preferably compositions according to the invention contain 0.5 to 95% by weight of active ingredient.

Suitable solid carriers include natural and synthetic clays and silicates, for example natural silicas such as diatomaceous earths; magnesium silicates, for example talcs; magnesium aluminium silicates, for example attapulgites and vermiculites; aluminium silicates, for example kaolinites, montomorillonites and micas; calcium carbonate; calcium sulphate; ammonium sulphate; synthetic hydrated silicon oxides and synthetic calcium or aluminium silicates; elements, for example carbon and sulphur; natural and synthetic resins, for example coumarone resins, polyvinyl chloride, and styrene polymers and copolymers; solid polychlorophenols; bitumen; waxes; and solid fertilisers, for example superphosphates.

Suitable liquid carriers include water; alcohols, for example isopropanol and glycols; ketones, for example acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone; ethers, aromatic or araliphatic hydrocarbons, for example benzene, toluene and xylene; petroleum fractions, for example kerosine and light mineral oils; chlorinated hydrocarbons, for example carbon tetrachloride, perchloroethylene and trichloroethane. Mixtures of different liquids are often suitable.

Agricultural compositions are often formulated and transported in a concentrated form which is subsequently diluted by the user before application. The presence of small amounts of a carrier which is a surface-active agent facilitates this process of dilution. Thus preferably at least one carrier in a composition according to the invention is a surface-active agent. For example the composition may contain at least two carriers, at least one of which is a surface-active agent.

A surface-active agent may be an emulsifying agent, a dispersing agent or a wetting agent; it may be nonionic or ionic. Examples of suitable surface-active agents include the sodium or calcium salts of polyacrylic acids and lignin so phonic acids; the condensation 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 glycerol, sorbitan, sucrose or pentaerythritol; condensates of these with ethylene oxide and/or propylene oxide; condensation products of fatty alcohol or alkyl phenols, for examplep-octyiphenol or p-octylcresoi, with ethylene oxide and/or propylene oxide; sulphates or sulphonates of these condensation products; alkali or alkaline earth metal salts, preferably sodium salts, of sulphuric or sulphonic acid esters containing at least 10 carbon atoms in the molecule, for example sodium lauryl sulphate, sodium secondary alkyl sulphates, sodium salts of sulphonated castor oil, and sodium alkylaryl suiphonates such as dodecylbenzene sulphonate; and polymers of ethylene oxide and copolymers of ethylene oxide and propylene oxide.

The compositions of the invention may for example be formulated as wettable powders, dusts, granules, solutions, emulsifiable concentrates, emulsions, suspension concentrates and aerosols. Wettable powders usually contain 25, 50 or 75% w of active ingredient and usually contain in addition to solid inert carrier, 3-10% w of a dispersing agent and, where necessary, 0-10% w of stabiliser(s) and/or other additives such as penetrants or stickers. Dusts are usually formulated as a dust concentrate having a similar composition to that of a wettable powder but without a dispersant, and are diluted in the field with further solid carrier to give a composition usually containing 1/2-10% w of active ingredient.Granules are usually prepared to have a size between 10 and 100 BS mesh (1.676 - 0.152 mm), and may be manufactured by agglomeration or impregnation techniques. Generally, granules will contain 1/2-75% w active ingredient and 0-10% w of additives such as stabilisers, surfactants, slow release modifiers and binding agents. The so-called "dry flowable powders" consist of relatively small granules having a relatively high concentration of active ingredient.Emulsifiable concentrates usually contain, in addition to a solvent and, when necessary, co-solvent, 10-50% w/v active ingredient, 2-20% w/v emulsifiers and 0-20% w/v of other additives such as stabilisers, penetrants and corrosion inhibitors. suspension conentrates are usually compounded so as to obtain a stable, non-sedimenting flowable product and usually contain 10-75% w active ingredient, 0.5-15% w of dispersing agents, 0.1-10% w of suspending agents such as protective colloids and thixotropic agents, 0-10% w of other additives such as defoamers, corrosion inhibitors, stabilisers, penetrants and stickers, and water or an organic liquid in which the active ingredient is substantially insoluble; certain organic solids or inorganic salts may be present dissolved in the formulation to assist in preventing sedimentation or as antifreeze agents for water.

Aqueous dispersions and emulsions, for example compositions obtained by diluting a wettable powder or a concentrate according to the invention with water, also lie within the scope of the invention. The said emulsions may be of the water-in-oil or of the oil-in-water type, and may have a thick 'mayonnaise'-like consistency.

The composition of the invention may also contain other ingredients, for example other compounds possessing herbicidal, insecticidal or fungicidal properties.

The invention is illustrated in the following Examples.

EXAMPLE 1 Ethyl 2-(1-propionyl-4-isopropyl-4-methyl-5-oxo-2-imidazolin-2-yl)benzoate Ethyl 2-(5-isopropyl-5-methyl-4-oxo-2-imidazolin-2-yl) benzoate 119; prepared according to procedures described in US Patents 4017510 and 4188487) was dissolved in dry benzene (15ml), and triethylamine (0.359) added. The mixture was cooled to 0-5oC, and a solution of propionyl chloride (0.329) in dry benzene (5ml) added with stirring. After stirring at room temperature for 3 hours, the mixture was filtered to obtain the desired, title product, which was chromatographically purified to yield a colourless solid, m.pt. 123-5 C.

Analysis Calculated C 66.3; H7.0; N8.1% Found C 64.8; H 7.2; N 7.7% EXAMPLE 2 Preparation of Methyl 2-(l-formyl-5isoprop y/-5-m eth y/-4-oxo-24midazo/in-2-y/) benzoate (2B) and the isomeric form methyl 2-(1-formy-4-isopropyl-4-methyl-5-oxo-2-imidazolin-2-yl) benzoate (2A) Methyl 2-(5-isopropyl-5-methyl-4-oxo-2-imidazolin-2-yl) benzoate (19) was dissolved in dry benzene (20ml) at room temperature under nitrogen. To this solution was added a solution of formic-acetic anhydride (0.329) in dry benzene (3ml) dropwise, with stirring, over ten minutes.The reaction mixture was then stirred for two hours at 40-45"C. Thin layer chromatography revealed 2 products : Rf 0.33 Rf 0.53 (S.M.-Rf 0.16) The reaction mixture was concentrated to give a crude oil which was purified by flash chromatography (silica gel/40-601l) /ethyl acetate/hexane 1:1.

Two products were obtained: 2A (major product) Rf=0.53, a colourless solid, m.p. 62-64"C.

C H N Calc: 63.6 5.9 9.3 Found: 58.8 5.8 8.0

and 2B (minor product), Rf=0.33, a colourless oil C H N Calc: 63.6 5.9 9.3 Found: 60.9 6.0 8.2

EXAMPLE 3-24 Following procedures similar to those described in Example 1 and 2, but substituting different acyl halides/anhydrides, further examples of compounds of the invention were prepared whose physical characteristics and elemental analyses are set out in Table 1 below. In all cases the identity of the product was confirmed by n.m.r. analysis. In the Table, the compounds are identified by reference to the substituents Ac, Rs and A in the formula:

TABLE 1 Ex. Ac R3 A M.Pt. Analysis No. "C Calc. Found C H N C H N 3 COCH3 C2H5 H 74-6 65.4 6.7 8.5 64.6 7.2 8.5 4 COC3H7 C2H5 H 73-75 67.0 7.3 7.8 66.2 7.1 7.6 5 CO C2H5 H 86-9 67.4 6.7 7.9 66.6 6.9 7.3 6 COm C2H5 H 64-5 68.1 7.0 7.6 66.3 8.2 8.5 7 COCH2CI C2H H oil 59.6 5.8 7.7 57.8 5.3 6.5 8 COOC2H5 C2H5 H oil 63.7 6.7 7.8 64.3 7.2 7.6 9 COSC2H5 C2H5 H oil 60.6 6.4 7.5 60.4 6.7 7.1 10 COH C2H5 H 84-5 64.6 6.3 8.9 63.1 6.3 8.7 11 COPh C2H5 H oil 70.4 6.1 7.2 68.8 6.3 6.4 12 CO-Ph- C2H5 H oil 62.9 5.0 6.1 63.0 5.0 6.0 mCF3 13 CO-Ph- C2H H 88-90 63.1 5.3 9.6 62.3 5.3 9.2 mNO2 14 CO-Ph- C2H5 H 124-6 59.8 4.8 6.1 59.4 4.8 5.9 3,4C12 15 CO-Furyl C2H5 H 94-7 66.0 5.8 7.3 66.0 5.4 7.3 16 COCH2- C2H H oil 63.3 6.7 7.8 63.0 6.8 7.7 OCH3 17 SO2CH3 C2H H oil 55.7 6.0 7.7 53.8 5.9 6.9 18 CONHCH3 C2H5 H 78-80 62.6 6.7 12.2 61.7 7.0 11.7 19 CONHPh C2H5 H oil 67.8 6.1 10.3 66.9 5.5 9.1 20 COCH3 CH3 H 80-84 64.7 6.1 8.9 64.8 6.5 8.9 21 COCH3 CH3 CH3 oil 65.4 6.7 8.4 66.1 7.4 7.7 22 COC2H5 CH3 CH3 oil 66.3 7.0 8.1 65.7 7.4 7.5 23 COCH2CI CH3 CH3 oil 59.2 5.8 7.7 59.4 5.9 6.7 24 CO-Ph- CH3 CH3 64-66 62.6 5.0 6.1 61.2 5.1 5.0 mCF3 EXAMPLE 25 Herbicidal activity To evaluate their herbicidal activity, compounds according to the invention were tested using as representative range of plants: maize, Zea mays (Mz); rice, Oryza sativa (R); barnyard grass, Echinochloa crusgalli (BG); oat, Avena sativa (0); linseed, Linum usitatissisum (L); mustard, Sinapsis alba (M); sugar beet, Beta vulgaris (SB) and soya bean, Glycine max (S).

The tests fall into two categories, pre-emergence and post-emergence. The pre-emergence tests involved spraying a liquid formulation of the compound onto the soil in which the seeds of the plant specied mentioned above had recently been sown. The post-emergence tests involved two types of test, viz., soil drench and foliar spray tests. In the soil drench tests the soil in which the seedling plants of the above species were growing was drenched with a liquid formulation containing a compound of the invention, and in the foliar spray tests the seedling plants were sprayed with such a formulation.

The soil used in the tests was a prepared horticultural loam.

The formulations used in the tests were prepared from solutions of the test compounds in acetone containing 0.4% by weight of an alkylphenol/ethylene oxide condensate available under the trade mark TRITON X-155. These acetone solutions were diluted with water and the resulting formulations applied at dosage levels corresponding to 5 kg or 1 kg of active material per hectare in a volume equivalent to 600 litres per hectare in the soil spray and foliar spray test, and at a dosage of level equivalent to 10 kilograms of active material per hectare in a volume equivalent to approximately 3,000 litres per hectare in the soil drench tests.

In the pre-emergence tests untreated sown soil and in the post-emergence tests untreated soil bearing seedling plants were used as controls.

The herbicidal effects of the test compounds were assessed visually twelve days after spraying the foliage and the soil, and thirteen days after drenching the soil and were recorded on a 0-9 scale. A rating 0 indicates growthvas untreated control, a rating 9 indicates death. An increase of 1 unit on the linear scale approximates to a 10% increase in the level of effect.

The results of the tests are set out in Table 2.

Compound TABLE 2 of Soil drench 10/kg/ha Dosage Foliar spray Pre-emergence Ex. No. Mz R BG O L M SB S kg/ha Mz R BG O L M SB S Mz R BG O L M SB S 1 4 6 3 7 4 8 3 5 5 3 4 5 7 5 8 7 7 3 3 2 7 3 7 8 1 1 2 0 2 6 2 5 6 5 0 0 0 7 0 3 5 0 3 6 6 6 6 4 5 6 6 5 6 5 6 6 5 7 7 6 5 0 4 7 0 7 6 6 1 4 0 2 4 2 5 5 4 0 0 1 6 0 5 5 2 5 6 5 7 7 6 7 8 7 5 6 0 0 6 4 6 6 6 5 0 0 6 3 6 8 4 1 7 5 5 3 8 4 8 8 5 5 6 2 2 7 5 8 8 7 3 4 0 8 5 7 8 5 1 2 0 0 7 3 6 5 3 0 0 0 7 0 5 6 0 8 6 6 3 7 2 8 7 5 5 6 2 5 7 5 8 7 6 3 3 2 8 5 7 8 6 1 2 0 2 7 3 6 6 4 1 0 0 7 0 7 6 0 9 5 4 4 6 1 6 6 5 5 6 0 4 7 6 8 7 4 5 0 2 7 0 6 7 5 1 4 0 2 6 2 5 6 4 2 0 1 4 0 4 6 5 11 4 5 2 7 2 7 7 3 5 1 0 0 5 2 6 4 5 0 0 0 5 0 3 0 0 1 12 6 6 7 7 4 7 8 6 5 7 6 7 7 7 8 8 7 5 0 4 7 4 8 8 7 1 5 4 4 7 4 6 8 6 5 0 2 7 2 8 8 6 13 5 5 6 6 3 6 4 7 5 5 5 6 4 5 7 7 6 6 0 0 6 0 5 4 0 1 2 0 2 0 0 6 6 6 0 0 0 2 0 4 2 0 TABLE 2 continued...

Compound Soil drench 10/kg/ha Dosage Foliar spray Pre-emergence Ex. No. Mz R BG O L M SB S kg/ha Mz R BG O L M SB S Mz R BG O L M SB S 14 3 3 2 6 2 5 7 4 5 4 3 4 7 5 7 7 6 2 2 0 7 2 4 8 0 1 0 0 1 5 2 5 5 4 0 0 0 4 0 4 2 0 20 6 5 7 6 5 7 8 7 5 6 4 7 6 6 8 7 7 6 8 8 7 7 7 8 7 1 5 2 5 5 4 6 7 7 4 3 7 6 4 6 8 4 19 4 2 3 6 0 6 8 5 5 3 0 3 6 4 7 8 5 3 2 3 7 5 6 8 5 1 1 0 0 5 1 5 6 4 0 0 0 6 0 5 6 0 6 6 2 4 6 4 7 7 7 5 7 0 6 7 6 7 7 7 6 0 4 7 4 6 7 6 1 5 0 4 5 5 6 6 6 4 0 0 7 0 5 7 5 21 5 5 6 7 6 6 8 8 6 5 8 8 7 8 7 7 2 1 2 5 4 5 5 7 7 4 2 4 7 6 4 6 7 1

Claims (14)

1. N-acyl phenyl imidazolidinone derivatives having the general formula I:

wherein A represents a hydrogen or halogen atom or an alkyl, alkoxy, phenoxy, or nitro group; one of X and Y represents a carbonyl group and the other represents the alkylidene group

R1 represents an alkyl orcycloalkyl group; R2 represents an alkyl, haloalkyl, cycloalky, alkenyl, phenyl, halophenyl or benzyl group; or R1 and R2, together with the interjacent carbon atom, jointly represent a cycloalkyl group; R3 represents a hydrogen atom or a salt forming cation, or an optionally halogenated alkyl, alkenyl, alkynyl, alkoxyalkyl, cycloalkyl, phenyl, furyl, or benzyl group; and Ac represents an acyl group; and, except where R3 is a salt-forming cation, the acid addition salts thereof.

2. Imidazolidinone derivatives as claimed in claim 1 wherein A represents a hydrogen atom or an alkyl group of 1 to 6 carbon atoms; R1, R2 and R3 each represents an alkyl group of 1 to 6 carbon atoms; and Ac represents an acyl group of formula -COR4 or -SO2R wherein R4 represents a hydrogen atom or an alkyl, haloalkyl, cycloalkyl, alkoxyalkyl, alkoxy, alkylthio, alkylamino or phenyiamino group, or a phenyl or furyl group optionally substituted by a halogen atom or an alkyl, haloalkyl, or nitro group and the acid addition salts thereof.

3. Imidazolidinone derivatives as claimed in claim 2 wherein A represents a hydrogen atom or a methyl group; R1 represents a methyl group; R2 represents an isopropyl group; and R3 represents a methyl or ethyl group.

4. Imidazolidinone derivatives as claimed in claim 2 or 3 wherein Ac represents the group -COR4 wherein R4 represents a hydrogen atom or a methyl, ethyl, propyl, cyclopropyl, chloromethyl, methoxymethyl, ethoxy, ethylthio, methylamino, phenylamino, furyl, or phenyl optionally substituted by a chlorine atom or a trifluoromethyl or nitro group, or the group -SO2R5wherein R5 represents a methyl group.

5. Compounds as claimed in claim 1 and specifically named in any one of Examples 1-24 herein.

6. Process for the preparation of a compound of the general formula I as defined in claim 1, which comprises reacting an acyl halide offormula Ac-Hal with a phenyl imidazolidinone of general formula ll:-

wherein A, X, Y, R1, R2, R3 and Ac are as defined in claim 1 and Hal represents a halogen atom.

7. Process as claimed in claim 6 wherein the reaction is carried out in an inert organic solvent and in the presence of a base.

8. Process as claimed in claim 7 wherein the solvent is benzene ortetrahydrofuran and the base is triethylamine.

9. Process as claimed in claim 6 carried out substantially as hereinbefore described with particular reference to Example 1 or 2.

10. A compound as defined in claim 1, whenever prepared by a process as claimed in any one of claims 6-9.

11. Herbicidal composition, which comprises a compound as claimed in any of claims 1 to 5 and 10, together with a carrier.

12. A composition as claimed in claim 11, which comprises at least two carriers, at least one of which is a surface-active agent.

13. Method of combating undesired plant growth at a locus, which comprises treating the locus with a compound as claimed in any one of claims 1 to 5 and 10, or a composition as claimed in either of claims 11 to 12.

14. The use of a compound as claimed in any one of claims 1 to 5 and 10 as a herbicide.