ITMI970275A1 - BENZOSSAZINIL-HETEROCYCLES WITH HERBICIDE ACTIVITY - Google Patents

Description

DESCRIPTION

The present invention relates to benzoxazinyl heterocycles.

More specifically, the present invention relates to benzoxazinyl-heterocycles having high herbicidal activity, a process for their preparation and their use as herbicides for the control of weeds in agricultural crops.

Benzoxazinyl heterocycles having herbicidal activity are disclosed, among others, in US Patent Nos. 4,640,707, 4,761,174, 4,798,620, 4,877,444 and 4,902,335.

In particular, in the US patent No. 4,640,707, the compound corresponding to N- (7-fluoro-3,4-dihydro-3-oxo-4-prop-2-inyl-2H-1,4- benzoxazin-6 is described -yl) cyclohex-1-ene-1,2-dicarboximide. However, said product, when applied post-emergency, is highly phytotoxic towards all the most important agricultural crops and is therefore not usable in the aforementioned applications.

The Applicant has now found that, by suitably modifying the substituent in position 4 of the benzoxazinone ring, compounds are obtained which, in addition to having a high herbicidal activity against numerous weeds, show, at the same time, a low phytotoxicity towards a or more crops of agricultural interest even when used in post-emergency treatments. Consequently, said compounds are suitable for use as selective herbicides in both pre- and post-emergence treatments.

Consequently, the object of the present invention is benzoxazinyl-heterocycles having general formula (I):

in which:

X represents a hydrogen atom; a fluorine atom or a chlorine atom; R represents a group having general formula (II):

or a group having general formula (III):

R2 and R2, the same or different from each other, represent a hydrogen atom; or a linear or branched C1-C3 alkyl or haloalkyl group;

R3 R4 R5 R6 and R7 equal or different from each other, represent a hydrogen atom; or a linear or branched C1-C4 alkyl or haloalkyl group;

X1 and X2, the same or different from each other, represent a hydrogen atom; a linear or branched alkyl or haloalkyl group; a linear or branched C1-C4 alkoxy or haloalkoxyl group; E represents one of the following heterocyclic groups represented by the following general formulas E1E10

in which :

Rb represents a linear or branched C1 ~ C3 alkyl group;

R8 and R9, the same or different from each other, represent a linear or branched C1-C4 alkyl or haloalkyl group; R10 and R11, the same or different from each other, represent a hydrogen atom; a linear or branched C1-C6 alkyl group; a C3-C6 cycloalkyl group; a linear or branched C3-C5 alkenyl group; a linear or branched C3-C5 alkynyl group; or, R10 and R11 jointly represent a linear or branched C2-C5 alkylene or oxyalkylene chain;

r represents 1 or 2;

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

The benzoxazinyl-heterocycles having general formula (I) are endowed with a high herbicidal activity.

A further object of the present invention are the processes for the preparation of compounds having general formula (I).

Compounds having general formula (I), in which E represents an E1 group, corresponding to the following general formula (1-1):

in which X, R, R1 R2, Rb, s and r have the same meanings described above, they can be prepared by reacting an anhydride having general formula (IV):

in which Rb, s and r have the same meanings described above, with a compound having general formula (V):

where X R, R1 and Ra have the same meanings described above.

The aforementioned reaction can be carried out in the absence or in the presence of an inert organic solvent, at a temperature between room temperature and the boiling temperature of any solvent used, preferably between 60'C and 200'C, possibly in the presence of a catalyst .

Inert organic solvents useful for this purpose are, for example, benzene, toluene, xylene, chlorobenzene, acetic acid, diisopropylether, dimethoxyethane, tetrahydrofuran, dioxane.

Useful catalysts for this purpose are, for example, mixtures of nitrogenous organic bases such as, for example, triethylamine, piperidine, pyrrolidine, with aliphatic carboxylic acids such as, for example, acetic acid, propionic acid, butyric acid.

In order to facilitate the aforementioned reaction, it may also be useful to azeotropically remove the water that forms during condensation.

The anhydrides having general formula (IV) are compounds known in literature.

The aminobenzoxazinones having general formula (V) can be prepared according to known methods.

Compounds having general formula (I), in which E represents an E2 group, corresponding to the following general formula (1-2):

in which X, R, R1, R2 and R8 have the same meanings described above, they can be prepared by reacting with a cyclizing agent such as, for example, phosgene or trichloromethyl chloroformate, a hydrazide having general formula (VI):

in which X, R, R1 R2 and R8 have the same meanings described above.

The aforesaid reaction can be carried out by treating the hydrazide having general formula (VI), dissolved or suspended in a suitable inert organic solvent, with the cyclizing agent, possibly dissolved in turn in a suitable inert organic solvent, at a temperature ranging from 20'C and the boiling temperature of the reaction mixture, possibly in the presence of an inorganic or organic base.

Inert organic solvents useful for this purpose are, for example, methylene chloride, chloroform, 1,2-dichloroethane, benzene, toluene, xylene, chlorobenzene, ethyl ether, tetrahydrofuran, dioxane, ethyl acetate.

Inorganic bases useful for this purpose are, for example, sodium bicarbonate, sodium carbonate, potassium carbonate.

Organic bases useful for this purpose are, for example, triethylamine, pyridine, 4-dimethylaminopyridine.

The hydrazides having general formula (VI) can be prepared by converting the aminobenzoxazinones having general formula (V) described above into the corresponding hydrazides having general formula (VII):

in which X, R, R1 and R2 have the same meanings described above, and by making the latter react with acyl chlorides having general formula (VIII):

in which R8 has the same meanings described above, operating according to procedures known in the art.

Compounds having general formula (I) in which E represents an E3 group corresponding to the following general formula (1-3), or an E4 group corresponding to the following general formula (1-4), or an E5 group corresponding to the following general formula (1-5):

same meanings described above, can be prepared by reacting the intermediates having general formula (IX-3), (IX-4) and (IX-5), respectively:

same meanings described above, with a compound having general formula (X):

in which R 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 C1-C4 alkyl or haloalkyl group, or a phenyl group optionally substituted with linear or branched C1-C3 alkyl groups, with nitro groups, or with halogen atoms such as bromine, chlorine and fluorine.

The above reaction can be advantageously carried out in an inert organic solvent and in the presence of an inorganic base, at a temperature comprised between -10 ° C and the boiling temperature of the solvent used.

Inert organic solvents useful for this purpose are benzene, toluene, xylene, dimethoxyethane, diisopropylether, tetrahydrofuran, dioxane, acetonitrile, Ν, Ν-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone, dimethylsulfoxide.

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

The benzoxazinyl derivatives having general formula (IX-3), (IX-4) and (IX-5) and the compounds having general formula (X) can be prepared according to methods known in literature.

Compounds having general formula (I), in which E represents an E6 group, corresponding to the following general formula (1-6):

in which X, R, R1 and R2 have the same meanings described above, they can be prepared by cyclization, in the presence of a base, of a compound having general formula (XI):

wherein X, R, R1 and R2 have the same meanings described above and R "represents a linear or branched C1-C4 alkyl group.

The aforesaid reaction is preferably carried out in an inert organic solvent, in the presence of an organic or inorganic base, at a temperature comprised between room temperature and the boiling temperature of the reaction mixture.

Inert organic solvents useful for this purpose are, for example, benzene, toluene, xylene, dimethoxyethane, diisopropylether, tetrahydrofuran, dioxane, acetonitrile, Ν, Ν-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone, dimethylsulfoxide.

Organic bases useful for this purpose are, for example, triethylamine, pyridine, 4- (N, N-dimethylamino) pyridine, alkoxides of alkali metals such as, for example, sodium methoxide, sodium ethoxide, potassium t-butoxide, salts of carboxylic acids such as , for example, sodium acetate, potassium acetate. Inorganic bases useful for this purpose are, for example, sodium hydride, potassium hydride, sodium carbonate, potassium carbonate, sodium hydroxide, potassium hydroxide.

The intermediate having general formula (XI) can be prepared by reaction of an arylisocyanate having general formula (XII):

in which X, R, R1 and R2 have the same meanings described above, with a compound having general formula (XIII):

where R "has the same meaning described above.

The arylisocyanates having general formula (XII) can in turn be prepared by reaction of an aminobenzoxazinone having general formula (V) described above with phosgene or trichloromethylformate, operating according to processes known in the art.

Compounds having general formula (XIII) are known in the art.

Compounds having general formula (I), in which E represents an E7 group, corresponding to the following general formula (1-7):

in which X, R, R1, R2 and R9 have the same meanings described above, they can be prepared by reaction of an arylisothiocyanate having general formula (XIV):

in which X, R, R1 and R2 have the same meanings described above, with a compound having general formula (XV):

in which Rg has the same meanings described above, obtaining an intermediate having a general formula (XVI):

wherein X, R, R1, R2 and R9 have the same meanings described above, which is converted into the compounds having general formula (1-7) by oxidative cyclization.

The reaction between the compounds having general formula (XIV) and (XV) is carried out in the presence of an inert organic solvent, at a temperature between -50 ° C and 50 ° C, possibly in the presence of an organic or inorganic base.

Inert organic solvents useful for this purpose are, for example, ethyl ether, tetrahydrofuran, dioxane, methylene chloride, chloroform, ethyl acetate.

Organic bases useful for this purpose are, for example, triethylamine, pyridine, 4-dimethylaminopyridine.

Inorganic bases useful for this purpose are, for example, sodium bicarbonate, sodium carbonate, potassium carbonate.

The cyclization reaction of the intermediate having general formula (XVI) is carried out in the presence of an inert organic solvent, an oxidizing agent and an acid acceptor, at a temperature between -30 ° C and 30 ° C.

Inert organic solvents useful for this purpose are, for example, methylene chloride, chloroform, chlorobenzene, Ν, Ν-dimethylformamide, ethyl acetate.

Useful oxidizing agents are, for example, bromine, chlorine, sodium hypochlorite.

Acid acceptors useful for this purpose are, for example, organic bases such as, for example, triethylamine, pyridine, dimethylaniline, or inorganic bases such as, for example, sodium hydroxide, potassium carbonate, calcium carbonate.

The arylisothiocyanates having general formula (XIV) can in turn be prepared by reaction of an aminobenzoxazinone having general formula (V) described above with phosgene or trichloromethylformates, operating according to processes known in the art.

Compounds having general formula (XV) are known in the art.

Compounds having general formula (I), in which E represents an Es group, corresponding to the following general formula (1-8):

meanings described above, can be prepared by reaction with phosgene or trichloromethyl chloroformate of a compound having general formula (XVII):

The reaction is carried out by treating the compound having general formula (XVII), dissolved or suspended in a suitable inert organic solvent, with phosgene or trichloromethyl chloroformate, possibly dissolved in turn in a suitable inert organic solvent, at a temperature between 20 ° C and the boiling temperature of the reaction mixture, possibly in the presence of an organic or inorganic base.

Inert organic solvents useful for this purpose are, for example, methylene chloride, chloroform, 1,2-dichloroethane, benzene, toluene, xylene, chlorobenzene, ethyl ether, tetrahydrofuran, dioxane, ethyl acetate.

Organic bases useful for this purpose are, for example, triethylamine, pyridine, 4-dimethylaminopyridine.

Inorganic bases useful for this purpose are, for example, sodium bicarbonate, sodium carbonate, potassium carbonate.

The compounds having general formula (XVII) can in turn be prepared by reaction of an arylisothiocyanate having general formula (XIV) described above with a compound having general formula (XVIII):

in which Rb, s and r have the same meanings described above, operating according to procedures known in the art.

Compounds having general formula (I), in which E represents an E9 group, corresponding to the following general formula (1-9):

meanings described above, can be prepared by reaction with phosgene or trichloromethyl chloroformate of a compound having general formula (XIX):

The reaction is carried out by treating the compound having general formula (XIX), dissolved or suspended in a suitable inert organic solvent, with phosgene or trichloromethyl chloroformate, possibly dissolved in turn in a suitable inert organic solvent, at a temperature between 20 ° C and the boiling temperature of the reaction mixture, possibly in the presence of an organic or inorganic base.

Inert organic solvents useful for this purpose are, for example, methylene chloride, chloroform, 1,2-dichloroethane, benzene, toluene, xylene, chlorobenzene, ethyl ether, tetrahydrofuran, dioxane, ethyl acetate.

Organic bases useful for this purpose are, for example, triethylamine, pyridine, 4-dimethylaminopyridine.

Inorganic bases useful for this purpose are, for example, sodium bicarbonate, sodium carbonate, potassium carbonate.

The compounds having general formula (XIX) can in turn be prepared by reaction of an arylisocyanate having general formula (XII) described above, with a compound having general formula (XVIII) described above, operating according to processes known in the art.

Compounds having general formula (I), in which E represents an E10 group, corresponding to the following general formula (1-10):

in which X, R, R1, R2, Rb, R10 R11 s and r, have the same meanings described above, can be prepared by reaction of a compound having general formula (I-1) described above with an amine having general formula ( XX):

The reaction is carried out in an inert organic solvent, at a temperature comprised between O'C and the boiling temperature of the solvent used, possibly in the presence of an organic or inorganic base as catalyst.

Inert organic solvents useful for this purpose are, for example, methylene chloride, chloroform, carbon tetrachloride, chlorobenzene, benzene, toluene, xylene, hexane, octane, cyclohexane, ethyl ether, tetrahydrofuran, dimethoxyethane, acetone, methylethylketone, acetonitrile, ethyl acetate , dimethylformamide.

Organic bases useful for this purpose are, for example, triethylamine, pyridine.

Inorganic bases useful for this purpose are, for example, sodium carbonate, potassium carbonate ..

Specific examples of benzoxazinyl-heterocycles having general formula (I) interesting for their herbicidal activity are reported in the following Tables 1-10.

TABLE 1

Compounds having general formula (1-1):

The compounds having general formula (I), object of the present invention, have shown a high herbicidal activity which makes them suitable for use in the agricultural field in the defense of crops useful 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 or 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: Abutilon theofrasti. Amaranthus retroflexus. Caosella bursa pastoris. Chenopodium album. Convolvulus sepium. Galium aparine. Geranium dissectum. Ioomea SP .. Matricaria chamomilla, Papaver rhoaes. Phaseolus aureus. Polvgonum persicaria. Portulaca oleracea. Sida spinosa.

Solanum niarum. Stellaria average. Veronica persica.

Xanthium SP .. etc.

At the useful doses of use for agricultural applications, the above compounds did not show toxic effects towards important agricultural crops such as fOrvza satival rice, wheat (Triticum spp.), Maize and maize). soy {Glvcine maxi. etc.

A further object of the present invention is a method for the control of weeds in cultivated areas, through the application of compounds having general formula (I).

The amount of compound to be applied to obtain the desired effect can 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 its-lo, the method of application, etc.

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

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

It is possible to use compositions 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 on the 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 above 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 aforesaid 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 is between 1% and 90%, preferably between 5% and 50%.

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

EXAMPLE 1

Preparation of N- [7-fluoro-3,4-dihydro- (4-methoxybut-2-yl) -3-oxo-2H-1,4-benzoxazin-6-yl] cyclohex-1-ene-1, 2-dicarboximide (Compound No. 1).

A mixture of 6-amino-7-fluoro-4- (4-methoxybut-2-yl) -2H-1/4-benzoxazin-3 (4H) -one (0.9 g; 3.4 mmol), anhydride 3,4,5,6-tetrahydrophthalic (0.52 g; 3.4 mmoles) and acetic acid (15 ml), is heated under reflux for 2 hours. After cooling it is diluted with water and the precipitate is filtered.

The solid obtained is then purified by chromatography on silica gel eluting with hexane / ethyl acetate in a 2: 1 ratio.

0.9 g of the desired product are obtained having a melting point of 165 ° C-166'C.

EXAMPLE 2

Operating in the same way as described in example 1, the following compounds were prepared starting from 3,4,5,6-tetrahydrophthalic anhydride and the corresponding suitably substituted aminobenzoxazinones:

N- [7-fluoro-3,4-dihydro-4- (5-methoxy-3-in-2-yl) -3-OXO-2H— 1,4— benzoxazin-6-yl] cyclohex-1— ene -1, 2-dicarboximide (Compound No. 2); N- [7-fluoro-3,4-dihydro— 4— (4-methoxycarbonyl— (E) -but ~ 3-en-2-yl) -3-oxo-benzoxazin— 6— yl] cyclohex-l-ene -1,2-dicarboximide (Compound No.

3);

N- [7-fluoro-3,4-dihydro-4- (3-methoxycarbonyl-2-methoxy- (E) -prop-2-enyl) -3-oxo-2H-1,4-benzoxazine— 6— yl ] cyclohex— 1— ene— 1,2-dicarboximide (Compound No. 4).

EXAMPLE 3

Determination of the herbicidal activity in post-emergence.

The herbicidal activity of Compound No. 1 was evaluated in post-emergence treatment and compared with the herbicidal activity of N- [7-fluoro-3,4-dihydro-3-oxo-4-prop-2 -inyl-2H-1,4-benzoxazin-6-yl) cyclohex-1-ene-1,2-dicarboximide (RC) corresponding to Compound No. 20 of US Patent No. 4,640,707.

The evaluation tests of each product were carried out according to the following operating methods.

Jars (10 cm higher diameter, 10 cm high) were prepared containing sandy soil. In each of them one of the following weeds and the following crops were sown (10 pots for each species):

weeds (dicotyledons): Abutilon theofrasti (AT), Convolvulus sepium (CS), Ipomea purpurea (IP);

crops: Zea mavs (maize) Glveine max (soybeans). To each jar was added water in a suitable quantity for a good germination of the seeds. The pots were divided into two groups each containing 5 pots for each weed or crop.

Fifteen days after sowing, i.e. when the infesting seedlings, depending on the species, had a height of 10-15 cm, the first group of jars was treated with a hydroacetonic dispersion of the two products under examination (Compound No. 1 and Compound RC), acetone at 10% by volume and Tween 20 at 0.5%.

The second group was treated only with a hydroacetonic solution containing acetone at 10% by volume and Tween 20 at 0.5%, and was used as a comparison term (control).

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

temperature: 24 ° C;

relative humidity: 60%;

photoperiod: 16 hours;

light intensity: 10000 lux.

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

Fifteen days after treatment, the herbicidal activity was evaluated, expressed according to a scale of values from 0 to 100, referring to the percentage of damage detected on the treated plants compared to the untreated ones (witness). According to said scale:

0 = no herbicidal effect;

100 = death of the treated plant.

The results obtained are reported in the following Table 11.

Claims (10)

CLAIMS 1. Benzoxazinyl heterocycles having general formula (I) in which: X represents a hydrogen atom; a fluorine atom or a chlorine atom; R represents a group having general formula (II): or a group having general formula (III): R1 and R2, the same or different from each other, represent a hydrogen atom; or a linear or branched C1-C3 alkyl or haloalkyl group; R3, R4, RS, R6 and R7, the same or different from each other, represent a hydrogen atom; or a linear or branched C1-C1 alkyl or haloalkyl group; X3 and X2, the same or different from each other, represent a hydrogen atom; a linear or branched alkyl or haloalkyl group; a linear or branched C1-C4 alkoxy or haloalkoxyl group; E represents one of the following heterocyclic groups represented by the following general formulas Ε1Ε10 represent a linear or branched C1-C4 alkyl or haloalkyl group; R10 and R31, the same or different from each other, represent a hydrogen atom; a linear or branched C ^ -C8 alkyl group; a C3-C6 cycloalkyl group; a linear or branched C3-C3 alkenyl group; a linear or branched C3-C5 alkynyl group; or, R10 and R11 jointly represent a linear or branched C2-C5 alkylene or oxyalkylene chain; r represents 1 or 2; s represents an integer between 0 and 2, extremes included. 2. Herbicides consisting of benzoxazinyl-heterocycles having general formula (I): in which: X represents a hydrogen atom; a fluorine atom or a chlorine atom; R represents a group having formula R1 and R2, the same or different from each other, represent a hydrogen atom; or a linear or branched C1-C3 alkyl or haloalkyl group; R3, R4, R5 R6 and R7, the same or different from each other, represent a hydrogen atom; or a linear or branched C1-C4 alkyl or haloalkyl group; X1 and X2, the same or different from each other, represent a hydrogen atom; a linear or branched C1-C4 alkyl or haloalkyl group; a linear or branched C1-C4 alkoxy or alcoholic group; E represents one of the following heterocyclic groups represented by the following general formulas E1-E10: represent a linear or branched C1-C4 alkyl or haloalkyl group; R10 and R11, the same or different from each other, represent a hydrogen atom; a linear or branched C1-C6 alkyl group; a C3-C6 cycloalkyl group; a linear or branched C3-C5 alkenyl group; a linear or branched C3-C5 alkynyl group; or, R10 and R11 jointly represent a linear or branched C2-C5 alkylene or oxyalkylene chain; r represents 1 or 2; s represents an integer between 0 and 2, extremes included. 3. Herbicide according to claim 2, consisting of N- [7-fluoro-3,4-dihydro- (4-methoxybut-2-yl) -3-oxo-2H-1,4-benzoxazin-6-yl] cyclohex - 1-ene-1,2-dicarboximide. 4. Herbicide according to claim 2, consisting of N- [7-fluoro-3,4-dihydro-4- (5-methoxy-3-in-2-yl) -3-oxo-2H-1,4-benzoxazin -6-yl] -cyclohex-1-ene-1,2-dicarboximide. 5. Herbicide according to claim 2, consisting of N- [7-fluoro-3,4-dihydro-4- (4-methoxycarbon1- (E) -but-3-en-2-yl) -3-oxo-benzoxazin - 6-yl] cyclohex-1-ene-1,2-dicarboximide. 6. Herbicide according to claim 2, consisting of N- [7-fluoro-3,4-dihydro-4- {3-methoxycarbon1-2-methoxy- (E) -prop-2-enyl) -3-oxo— 2H - 1,4-benzoxazin-6-yl] cyclohex-1-ene - 1,2-dicarboximide. 7. Process for the preparation of benzoxazinyl-heterocycles having general formula (I) according to any one of the preceding claims, in which E represents an E ^ group corresponding to the following general formula (1-1): in which X, R, R1, R2, Rb, s and r, have the same meanings described above, which consists in the reaction of an anhydride having general formula (IV): in which Rb, s and r have the same meanings described above, with a compound having general formula (V): in which X, R, R1 and R2 have the same meanings described above, said reaction carried out in the absence or in the presence of an inert organic solvent, at a temperature between room temperature and the boiling temperature of any solvent used, possibly in presence of a catalyst. 8. Process for the preparation of benzoxazinyl-heterocycles having general formula (I) according to any one of the preceding claims, in which E represents an E2 group, corresponding to the following general formula (1-2): wherein X, R, R1 R2 and RB have the same meanings described above, which consists in the reaction of a cyclizing agent such as phosgene or trichloromethyl chloroformate, with a hydrazide having general formula (VI): in which X, R, R1, R2 and R "have the same meanings described above, said reaction carried out by treating the hydrazide having general formula (VI), dissolved or suspended in a suitable inert organic solvent, with the cyclizing agent, optionally dissolved in turn in a suitable inert organic solvent, at a temperature between 20 ° C and the boiling temperature of the reaction mixture, possibly in the presence of an inorganic or organic base. 9. Process for the preparation of benzoxazinyl-heterocycles having general formula (I) according to any one of the preceding claims, in which E represents an E3 group corresponding to the following general formula (1-3), or an E4 group corresponding to the following general formula (1-4), or a group E5 corresponding to the following general formula (1-5): same meanings described above, which consists in the reaction of the intermediates having general formula (IX-3), (IX-4) and (IX-5), respectively: in which R has the same meanings described above and X 'represents a halogen atom, or an R'SO2O group in which R' represents a linear or branched C1-C4 alkyl or haloalkyl group, or a phenyl group possibly substituted with alkyl groups Linear or branched C1-C3, with nitro groups, or with halogen atoms such as bromine, chlorine and fluorine, said reaction carried out in the presence of an inert organic solvent and in the presence of an inorganic base, at a temperature between -10 "C and the boiling temperature of the solvent used. 10. Process for the preparation of benzoxazinyl-heterocycles having general formula (I) according to any one of the preceding claims, in which E represents an E6 group, corresponding to the following general formula (1-6): in which X, R, Ri and R2 have the same meanings described above, which consists in the cyclization, in the presence of a base, of a compound having general formula (XI): in which X, R, Ri and R2 have the same meanings described above and R "represents a linear or branched C1-C4 alkyl group, said cyclization carried out in the presence of an inert organic solvent and in the presence of an organic or inorganic base, for example a temperature between room temperature and the boiling temperature of the reaction mixture. Process for the preparation of benzoxazinyl-heterocycles having general formula (I) according to any one of the preceding claims, in which E represents an E7 group, corresponding to the following general formula (1-7): in which X, R, R1 R2 and Rs have the same meanings described above, which consists of the reaction of an arylisothiocyanate having general formula (XIV): in which X, R, R1 and R2 have the same meanings described above, with a compound having general formula (XV): in which R9 has the same meanings described above, said reaction carried out in the presence of an inert organic solvent, at a temperature between -50 ° C and 50 ° C, possibly in the presence of an organic or inorganic base, obtaining an intermediate having the formula general (XVI): wherein X, R, R1, R2 and R9 have the same meanings described above, which is converted into compounds having general formula (1-7) by oxidative cyclization, in the presence of an inert organic solvent, of an oxidizing agent and of an acid acceptor, at a temperature between -30 ° C and 30'C. Process for the preparation of benzoxazinyl-heterocycles having general formula (I) according to any one of the preceding claims, in which E represents an E8 group, corresponding to the following general formula (1-8): in which X, R, R1 R2, Rb, s and r, have the same meanings described above, which consists in the reaction with phosgene or trichloromethyl chloroformate of a compound having general formula (XVII): in which X, R, R1, R2, Rb, s and r, have the same meanings described above, in which the compound having general formula (XVII), dissolved or suspended in a suitable inert organic solvent, is treated with phosgene or trichloromethyl chloroformate , optionally dissolved in turn in a suitable inert organic solvent, at a temperature between 20 ° C and the boiling temperature of the reaction mixture, possibly in the presence of an organic or inorganic base. 13. Process for the preparation of benzoxazinyl-heterocycles having general formula (I) according to any one of the preceding claims, in which E represents an E9 group, corresponding to the following general formula (1-9): in which X, R, R1, R2, Rb, s and r, have the same meanings described above, which consists in the reaction with phosgene or trichloromethyl chloroformate of a compound having general formula (XIX): in which X, R, R1 R2, Rb, s and r, have the same meanings described above, in which the compound having general formula (XIX), dissolved or suspended in suspension in a suitable inert organic solvent, is treated with phosgene or trichloromethyl chloroformate, optionally dissolved in turn in a suitable inert organic solvent, at a temperature between 20 ° C and the boiling temperature of the reaction mixture, optionally in the presence of an organic or inorganic base. 14. Process for the preparation of benzoxazinyl-heterocycles having general formula (I) according to any one of the preceding claims, in which E represents an E10 group, corresponding to the following general formula (1-10): the same meanings described above, which consists in the reaction of a compound having general formula (1-1) described above with an amine having general formula (XX): wherein R10 and R11 have the same meanings described above, said reaction carried out in an inert organic solvent, at a temperature between 0 ° C and 100 ° C, possibly in the presence of an organic or inorganic base as catalyst. 15. Compositions with herbicidal activity containing one or more benzoxazinyl-heterocycles according to any one of claims from 2 to 14, alone or in the presence of solid supports, liquid diluents, surfactants or other active ingredients. 16. Herbicidal compositions according to claim 15, wherein the concentration of active substance is between 1% and 90%. 17. Method for the control of weeds in cultivated areas which consists in applying to said areas the compositions of claims 15 and 16.