ITMI960554A1 - "ARILETEROCICLI WITH HERBICIDE ACTIVITY" - Google Patents

Abstract

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Description

DESCRIPTION

The present invention relates to new arylheterocycles.

Pi? in particular, the present invention relates to arylheterocycles having high activity. herbicide, a process for their preparation and their use as herbicides for the control of weeds in agricultural crops.

Aryletherocycles having activity? herbicide are described, among others, in US Patents No.

3,835,862, 4,431,822, 4,536,209, 4,881,967 and 4,948,418. However, these products are not very selective being, in general, toxic even towards the most? important agricultural crops.

The Applicant has now found new arylheterocycles which, in addition to having a high activity? herbicide against numerous weeds show, at the same time, a low phytotoxicity? for one or more? among the crops of greatest agricultural interest and therefore suitable for use as selective herbicides.

The object of the present invention is therefore arylheterocycles having a general formula

X represents a fluorine atom or a chlorine atom;

Y represents a hydrogen atom; a halogen atom such as chlorine, fluorine, bromine or iodine; an alkyl or haloalkyl group

linear or branched; an alcos group

linear silico or haloalkoxy or ra?

mified; an alkylthio or haloal group

linear or branched kylthio; a grup?

bit cyan; a nitro group;

Z represents an oxygen atom or a group S (0) n in which n? an integer between 0 and 2 inclusive;

Q represents one of the following groups represented by the following general formulas

R and Ra, the same or different from each other, represent a hydrogen atom; a linear or branched C1-C8 alkyl or haloalkyl group; a C3-C6 cycloalkyl group; a C4-C8 cycloalkylalkyl group; an oxethanyl group or a tetrahydrofuranyl group, both optionally substituted with linear or branched C1-C4 alkyl groups; a phenyl group or a phenylalkyl group C7-C9 both optionally substituted with one or more? halogen atoms such as chlorine, fluorine, bromine or iodine or with one or more? groups selected from linear or branched C1-C4 alkyl or haloalkyl groups or between linear or branched C1-C4 alkoxyl or haloalkoxyl groups;

each independent?

mind, they represent a hydrogen atom or a linear or branched alkyl or haloalkyl group; R5 and R6, each independently, represent a hydrogen atom; a linear or branched alkyl group; or together they represent an alkylene chain or a chain

R7 and 8a, each independently, represent a linear or branched C1-C4 alkyl group; or together they represent an alkylene chain

Ar represents a phenyl group or a pyridyl group, both optionally substituted with one or more? halogen atoms such as chlorine, fluorine, bromine or iodine or with one or more? groups selected from alkyl or haloalkyl groups

linear or branched or between groups

alkoxy or haloalkoxy

neari or branched;

each independently, they represent a hydrogen atom; a halogen atom such as chlorine, fluorine, bromine or iodine; a linear or branched alkyl or haloalkyl group; a linear or branched alkoxy or haloalkoxy group;

X6 represents a halogen atom such as chlorine, fluorine, bromine or iodine; a linear or branched alkyl or haloalkyl group; a linear or branched alkoxy or haloalkoxy group; or, in the case where X represents a fluorine atom, X6 pu? also represent a hydrogen atom;

represents an atom of oxygen op?

also an atom of sulfur;

m represents an integer between 1 and 3, extremes included;

p represents 0 or 1;

q represents an integer between 0 and 3, extremes included;

E represents one of the following heterocyclic groups represented by the following general formulas

in which:

represents an alkyl group

linear or branched;

R9 and R10, each independently, represent a linear or branched alkyl or haloalkyl group;

each independently,

represent an alkyl group

linear or branched;

Ru represents a hydrogen atom; an alkoxy or haloalkoxy group

linear or branched; a group

linear or branched alkylthio or haloalkylthio;

R14 represents an OH group; a linear or branched alkoxy group; an NH2 group; an alkylamine group

linear or branched; a group

linear or branched dialkylamine; a 1-pyrrolidine group; a 1-morpholine group;

X7 represents a hydrogen atom; or a halogen atom such as chlorine, fluorine, bromine or iodine;

T represents an oxygen atom; a CH2 group; an alkylamine group or

linear haloalkylamine or branches?

ficato;

r represents 1 or 2;

s represents an integer between 0 and 2, extremes included.

The aryletherocycles having general formula (I) are endowed with a high activity? herbicide.

Specific examples of arylheterocycles having general formula (I) interesting for their activity? herbicide are:

a process for the preparation of compounds having general formula (I).

Compounds having general formula (I), in which Z represents an oxygen atom or a sulfur atom, can be obtained by a process which comprises the reaction of a phenol or a thiophenol having general formula (II):

in which X, Y and E have the same meaning described above and Z 'represents an oxygen atom or a sulfur atom, with a compound having general formula (III):

in which Q has the same meanings described above and X 'represents a halogen atom, preferably chlorine or bromine, or an R'S020 group in which R' represents a linear or branched C ^ -C, alkyl or haloalkyl group or a phenyl group also optionally substituted with linear or branched alkyl groups, nitro groups, halogen atoms such as chlorine, fluorine or bromine.

The above procedure can? advantageously be carried out in the presence of an inert organic solvent and in the presence of an inorganic or organic base, at a temperature between -10 ° C and the boiling temperature of the solvent used, preferably between 0 ° C and 100 ° C.

Inert organic solvents useful for this purpose are, for example, benzene, toluene, xylene, acetone, methylethylketone, methylpropylketone, ethyl acetate, dimethoxyethane, diisopropyl ether, tetrahydrofuran, dioxane, acetonitrile, N, N-dimethylformamide,?,? - dimethylacetamide, -methylpyrrolidone, fossid dimethylsol.

Inorganic bases useful for this purpose are, for example, sodium, potassium and calcium hydroxides and carbonates.

Organic bases useful for this purpose are, for example, triethylamine, pyridine, 4-dimethylaminopyridine, diazabicyclooctane (DABCO), diazabicicloundecene (DBU).

The above procedure can? be also advantageously conducted in a biphasic system under phase transfer conditions as, for example, described by Dehmlow and Dehmlow in "Phase Transfer Catalysis" (1983), Verlag Chemie Ed.

The compounds having general formula (I) in which Z represents a SO or S02 group, can be obtained by oxidation of the corresponding compounds having general formula (I) in which Z represents a sulfur atom, in the presence of hydrogen peroxide or peracids such as, for example, peracetic acid, meta-chloroperbenzoic acid and the like. Said oxidation reaction is preferably carried out in the presence of an inert organic solvent such as, for example, acetone, glacial acetic acid, methylene chloride, chloroform, at a temperature between -20 ° C and 100 ° C, preferably between 0 ? C and 50? C.

In case you want to prepare a compound having general formula (I) in which Z represents a SO group,? It is advisable to use an oxidizing agent / substrate molar ratio between 1 and 1.2.

In the case in which it is desired to prepare a compound having general formula (I) in which Z represents an S02 group,? It is advisable to use an oxidizing agent / substrate molar ratio of between 2 and 5.

The phenols or thiophenols having general formula (II) and the compounds having general formula (III), are commercially available products or in any case easily prepared according to methods known in the practice of organic chemistry.

In some cases, the compounds having general formula (I), can be obtained in the form of two or more? optical and / or geometric isomers. It therefore falls within the spirit of the present invention to consider both the compounds having general formula (I) isomerically pure, and mixtures thereof, possibly obtained during the preparation of the compounds having general formula (I) or deriving from an incomplete separation of the isomers themselves, in any proportion.

The compounds having general formula (I), object of the present invention, have shown a high activity. herbicide that makes them suitable for use in the agricultural field in the defense of useful crops from weeds.

In particular, the compounds having general formula (I) are effective in the control, both in pre-emergence and in post-emergence, of numerous monocotyledonous and dicotyledonous weeds. At the same time, said compounds, show compatibility? o absence of toxic effects towards useful crops, both in pre-emergence and post-emergence treatments.

Examples of weeds which can be effectively controlled using the compounds having general formula (I) object of the present invention are: Sorahum halepense. Echinocloa crusaalli. Avena fatua. Amni maius, Abutilon theofrasti. Stellaria average. Convolvulus sepium, Amaranthus retroflexus, Chenopodium album, Galium aparine. Senecio vulaaris. Alopecurus myosuroides. Cvperus SPP .. etc.

At the useful doses of use for agricultural applications, the above compounds did not show toxic effects towards important agricultural crops such as rice (Orvza satival. Wheat fTriticum SPP.), Corn (Zea mais1. Soy (Glvcine maxi, etc.)

Further object of the present invention? a method for the control of weeds in cultivated areas, by applying the compounds having general formula (I).

The quantity of compound to be applied to obtain the desired effect pu? vary according to various factors such as, for example, the compound used, the crop to be preserved, the weeds to be affected, the degree of infestation, the climatic conditions, the characteristics of the soil, the method of application, etc.

Compost doses ranging from 1g to 1000g per hectare generally provide sufficient control.

For practical uses in agriculture? it is often advantageous to use activity compositions? herbicide containing, as an active substance, one or more? compounds having general formula (I), optionally also as a mixture of isomers.

It is possible to use compositions which are in the form of dry powders, wettable powders, emulsifiable concentrates, microemulsions, pastes, granulates, solutions, suspensions, etc: the choice of the type of composition will depend. from specific use.

The compositions are prepared according to known methods, for example by diluting or dissolving the active substance with a solvent medium and / or a solid diluent, optionally in the presence of surfactants.

Kaolin, alumina, silica, talc, bentonite, gypsum, quartz, dolomite, attapulgite, montmorillonite, diatomaceous earth, cellulose, starch, etc. can be used as solid inert diluents or supports.

As liquid inert diluents, in addition of course to water, organic solvents such as aromatic hydrocarbons (xylols, mixtures of alkylbenzols, etc.), aliphatic hydrocarbons (hexane, cyclohexane, etc.), halogenated aromatic hydrocarbons (chlorobenzol, etc.), alcohols ( methanol, propanol, butanol, octanol, etc.), esters (isobutyl acetate, etc.), ketones (acetone, cyclohexanone, acetophenone, isophorone, ethylamyl ketone, etc.), or vegetable or mineral oils or their mixtures, etc.

Non-ionic wetting and emulsifying agents can be used as surfactants (polyethoxylated alkylphenols, polyethoxylated fatty alcohols, etc.), anionic (alkylbenzenesulphonates, alkylsulfonates, etc.), cationic (quaternary alkylammonium salts, etc.).

Furthermore, dispersants (for example lignin and its salts, cellulose derivatives, alginates, etc.), stabilizers (for example antioxidants, absorbers of ultraviolet rays, etc.) can also be added.

To broaden the spectrum of action of the aforementioned compositions,? It is possible to add to them other active ingredients such as, for example, other herbicides, fungicides, insecticides or acaricides, fertilizers.

The concentration of active substance in the above compositions can? vary within a wide range, depending on the active compound, the applications for which they are intended, the environmental conditions and the type of formulation adopted.

In general the concentration of active substance? between 1% and 90%, preferably between 5% and 50%.

The examples reported below are for illustrative and not limitative purposes of the present invention.

To a solution of 1 g (3.38 mmol) of N- (4-chloro-2-fluoro-5-hydroxy phenyl]? 3,4,5,6-tetrahydro? Phthalimide in 10 ml of?,? - dimethylformamide 170 mg (3.39 mmoles) of potassium carbonate are added The reaction mixture is kept under stirring, at room temperature, for 30 minutes.

Subsequently, a solution of 630 mg (3.54 mmoles) of 4-methoxy-2-butynyl methanesulfonate in 5 ml of N, N-dimethylformamide is added dropwise and the mixture is heated at 60 ° C for 4 hours.

The obtained mixture is poured into water (150 ml) and extracted with ethyl ether (3 x 50 ml). The organic phase is washed to neutrality. with a saturated solution of sodium chloride, anhydrified with sodium sulphate and concentrated by rotovapor. The crude obtained is purified by chromatography on silica gel eluting with hexane / ethyl acetate in the ratio 65:35.

600 mg of a thick oil corresponding to Compound No. 1 are obtained.

EXAMPLE 2

Determination of the activity? herbicide.

The activity Compound No. 1 herbicide? was evaluated against both monocotyledonous and dicotyledonous weeds, in post-emergence treatment.

The evaluation tests were performed according to the following modalities? operational.

Jars (10 cm higher diameter, 10 cm high) were prepared containing sandy soil. In each of them? one of the following weeds was sown:

To each jar? was added water in quantity? suitable for good seed germination. The pots were divided into two groups each containing at least 5 pots for each weed.

The first group is not? been treated with herbicide and? was used as a term of comparison (witness).

The second group of jars? been treated after fifteen days from sowing, when what? the weed seedlings, depending on the species, had a height of 10-15 cm, to evaluate the activity? herbicide in post-emergence, with a hydroacetonic dispersion at 20% by volume of acetone of the product under examination (Compound No. 1).

All the jars were kept under observation in a conditioned environment under the following environmental conditions:

temperature: 15? C-26'C;

humidity relative: 60%;

photoperiod: 12 hours;

intensity bright: 5000 lux.

Every two days the jars were watered evenly in order to ensure a degree of humidity. sufficient for good plant development.

After twenty-one days from the treatment? was the activity evaluated? herbicide based on the following scale of values referring to the percentage of damage detected on treated plants compared to untreated ones (witness):

0 = 0% -20% damage;

1 = 21% -40% damage;

2 = 41% -60% damage;

3 = 61% -80% damage;

4 = 81% -95% damage;

5 = death of the treated plant.

The results obtained are reported in the following Table 1.

Claims (1)

CLAIMS 1. Arylheterocycles having general formula (I): X represents a fluorine atom or a chlorine atom; Y represents a hydrogen atom; a halogen atom such as chlorine, fluorine, bromine or iodine; a linear or branched alkyl or haloalkyl group; an alcos group linear silico or haloalkoxy or ra? mified; an alkylthio or haloal group linear or branched kylthio; a grup? bit cyan; a nitro group; Z represents an oxygen atom or a group S (0) n in which n? an integer between 0 and 2 inclusive; Q represents one of the following groups represented by the following general formulas where: the same or different from each other rap? they have a hydrogen atom; an alkyl or haloalkyl group linear or branched; a cycloalkyl group a cycloalkylalkyl group an oxethanyl group or a tetrahydrofuranyl group, both optionally substituted with linear or branched alkyl groups; a phenyl group or a phenylalkyl group both optionally substituted with one or more? halogen atoms such as chlorine, fluorine, bromine or iodine or with one or more? groups selected from linear or branched alkyl or haloalkyl groups or between alkoxy or haloalkoxyl groups they represent a hydrogen atom or a linear or branched alkyl or haloalkyl group; each independently, represent a hydrogen atom; a linear or branched alkyl group; or together they represent an alkylene chain or a chain R7 and RB, each independently, represent an alkyl group linear or branched; or together they represent an alkylene chain Ar represents a phenyl group or a pyridyl group, both optionally substituted with one or more? halogen atoms such as chlorine, fluorine, bromine or iodine or with one or more? groups selected from alkyl or haloalkyl groups linear or branched or between groups linear or branched alkoxy or haloalkoxy; each indepen? dently, they represent a hydrogen atom; a halogen atom such as chlorine, fluorine, bromine or iodine; a linear or branched alkyl or haloalkyl group; a linear or branched alkoxy or haloalkoxy group; X6 represents a halogen atom such as chlorine, fluorine, bromine or iodine; a linear or branched alkyl or haloalkyl group; a linear or branched alkoxy or haloalkoxy group; or, in the case where X represents a fluorine atom, X6 pu? also represent a hydrogen atom; Zx represents an oxygen atom or a sulfur atom; m represents an integer between 1 and 3, extremes included; p represents 0 or 1; q represents an integer between 0 and 3, extremes included; E represents one of the following heterocycle groups represented by the following general formulas in which: Rb represents an alkyl group linear or branched; R9 and R10, each independently, represent a linear or branched alkyl or haloalkyl group; each independently, represent an alkyl group linear or branched; R13 represents a hydrogen atom; a linear or branched alkoxy or haloalkoxy group; a group linear or branched alkylthio or haloalkylthio; R14 represents an OH group; a linear or branched alkoxy group; an NH2 group; a linear or branched alkylamine group; a group linear or branched dialkylamine; a 1-pyrrolidine group; a 1-morpholine group; X7 represents a hydrogen atom; or a halogen atom such as chlorine, fluorine, bromine or iodine; T represents an oxygen atom; a X represents a fluorine atom or a chlorine atom; Y represents a hydrogen atom; a halogen atom such as chlorine, fluorine, bromine or iodine; a linear or branched alkyl or haloalkyl group; an alcos group linear silico or haloalkoxy or ra? mified; an alkylthio or haloal group linear or branched kylthio; a grup? bit cyan; a nitro group; Z represents an oxygen atom or a group S (0) n in which n? an integer between 0 and 2 inclusive; Q represents one of the following groups represented by the following general formulas in which : R and Ra, the same or different from each other, represent a hydrogen atom; an alkyl or haloalkyl group linear or branched; a cycloalkyl group a cycloalkylalkyl group an oxethanyl group or a tetrahydrofuranyl group, both optionally substituted with linear or branched alkyl groups; a phenyl group or a phenylalkyl group both optionally substituted with one or more? halogen atoms such as chlorine, fluorine, bromine or iodine or with one or more? groups selected from linear or branched alkyl or haloalkyl groups or between linear or branched alkoxyl or haloalkoxyl groups; each independent <?> mind, they represent a hydrogen atom or a linear or branched alkyl or haloalkyl group; each independently, represent a hydrogen atom; a linear or branched alkyl group; or together they represent an alkylene chain or a chain R7 and RB, each independently, represent an alkyl group linear or branched; or together they represent an alkylene chain Ar represents a phenyl group or a pyridyl group, both optionally substituted with one or more? halogen atoms such as chlorine, fluorine, bromine or iodine or with one or more? groups selected from alkyl or haloalkyl groups linear or branched or between groups alkoxy or haloalkoxy neari or branched; each independently, they represent a hydrogen atom; a halogen atom such as chlorine, fluorine, bromine or iodine; a linear or branched alkyl or haloalkyl group; a linear or branched alkoxy or haloalkoxy group; XE represents a halogen atom such as chlorine, fluorine, bromine or iodine; a linear or branched alkyl or haloalkyl group; a linear or branched alkoxy or haloalkoxy group; or, in the case where X represents a fluorine atom, X6 pu? also represent a hydrogen atom; Z1 represents an oxygen atom or a sulfur atom; m represents an integer between 1 and 3, extremes included; p represents 0 or 1; q represents an integer between 0 and 3, extremes included; E represents one of the following heterocycle groups represented by the following general formulas in which Rb represents a linear or branched C1-C3 alkyl group; each independently, represent a linear or branched alkyl or haloalkyl group; each independently, represent an alkyl group linear or branched; represents a hydrogen atom; a linear or branched alkoxy or haloalkoxy group; a group linear or branched alkylthio or haloalkylthio; R14 represents an OH group; a linear or branched alkoxy group; an NH2 group; a linear or branched alkylamino group; a group linear or branched dialkylamine; a 1-pyrrolidine group; a 1-morpholine group; X7 represents a hydrogen atom; or a halogen atom such as chlorine, fluorine, bromine or iodine; T represents an oxygen atom; a CH2 group; a linear or branched C1-C6 alkylamino or haloalkylamino group; r represents 1 or 2; s represents an integer between 0 and 2, extremes included. 3. Herbicide according to claim 2, consisting of N- [4-chloro-2-fluoro-5- (4-methoxy-2-butynyloxy) -phenyl] -3,4,5,6-tetrahydrophthalimide. 4. Process for the preparation of the aryl heterocycles having general formula (I) according to any one of the preceding claims, which comprises the reaction of a phenol or a thiophenol having general formula (II): in which X, Y and E have the same meaning described above and Z 'represents an oxygen atom or a sulfur atom, with a compound having general formula (III): in which Q has the same meanings described above and X 'represents a halogen atom, or an R'S020 group in which R <'> represents a C1-C4 alkyl or haloalkyl group, linear or branched, or a phenyl group also possibly substituted with linear or branched C1-C3 alkyl groups, nitro groups, halogen atoms, in the presence of an inert organic solvent and an inorganic or organic base, at a temperature between -10 ° C and the boiling temperature of the solvent used. 5. Process according to claim 4, wherein the temperature? between 0? C and 100? C. 6. Process according to claim 4, wherein the organic solvent is inert? chosen from benzene, toluene, xylene, acetone, methylethyl ketone, methylpropyl ketone, ethyl acetate, dimethoxyethane, diisopropyl ether, tetrahydrofuran, dioxane, acetonitrile, N, N-dimethylformamide,?,? - dimethylacetylside, N-methylpyrrolidone. 7. Process according to claim 4, wherein the inorganic base? choice between sodium, potassium and calcium hydroxides and carbonates. 8. Process according to claim 4, wherein the organic base? choice between triethylamine, pyridine, 4-dimethylaminopyridine, diazabicyclooctane (DABCO) diazabicicloundecene (DBU). 9. Process for the preparation of compounds having general formula (I) according to claim 1 or 2, in which Z represents a SO group, which consists in the oxidation of the corresponding compounds having general formula (I) in which Z represents an atom of sulfur, in the presence of hydrogen peroxide or peracids and of an inert organic solvent, at a temperature between -20 ° C and 100 ° C, operating with an oxidizing agent / substrate molar ratio between 1 and 1.2. 10. Process for the preparation of compounds having general formula (I) according to claim 1 or 2, wherein Z represents an S02 group, which consists in the oxidation of the corresponding compounds having general formula (I) in which Z represents a sulfur atom , in the presence of hydrogen peroxide or peracids and an inert organic solvent, at a temperature between -20 ° C and 100 ° C, operating with an oxidizing agent / substrate molar ratio between 2 and 5. 11. Process according to claim 9 or 10, wherein the peracid? selected from peracetic acid, meta-chloroperbenzoic acid. 12. Process according to claim 9 or 10, wherein the organic solvent is inert? chosen from acetone, glacial acetic acid, methylene chloride, chloroform. 13. Activity compositions herbicide containing one or more? aryletherocycles according to any one of claims from 2 to 12, alone or in the presence of solid supports, liquid diluents, surfactants or other active ingredients. 14. Activity compositions herbicide according to claim 13, wherein the concentration of active substance? between 1% and 90%. 15. Method for the control of weeds in cultivated areas which consists in applying to said areas the compositions of claims 13 and 14.