CS193492A3 - Heterocyclic diones, process of their preparation and pesticidalcompositions containing said heterocyclic diones - Google Patents

Description

170649 / J‘i * JUDr. J. TRAPLOVÁ AND PARTNERSHEADER AND PATENT KANCEIÁft '71

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OJ 170 60 Prague 7, U průhonu 36

WHAT

INI (

Heterocyclic diones, a process for their preparation and pesticidal compositions containing these heterocyclic dions

Technology - - -

The present invention relates to substituted herbicidally active 3,5-dioxo-3,4,5,6-tetrahydrooxazines, a process for their preparation, intermediates necessary for their preparation, compositions containing these tetrahydrooxazines and their use as herbicides and acaricides.

U.S. Pat. No. 4,695,673 describes a large group of acylated 1,3-dicarbonyl compounds and their use as herbicidally active substances, but no mention is made of the 3,5-dioxotetrahydrooxazine ring which is characteristic of compounds of the invention.

SUMMARY OF THE INVENTION

The present invention provides compounds of formula I

(I) wherein each of R 1, and independently represents a hydrogen atom, a C 1 -C 8 alkyl group, a carboxyl group 2 an alkoxycarbonyl group having 1 to 8 carbon atoms, a phenyl group, or a phenyl group substituted with one to three groups as R 1 or R 1 and R 6 together form an alkylene bridge of 3 to 6 carbon atoms, R 4 represents a hydrogen atom, a C 1 -C 8 alkyl group, an alkylcarbonyl group having 1 to 8 carbon atoms, an alkoxycarbonyl group the alkoxy group having from 1 to 8 carbon atoms, -C (O) NR 7 R 8, (C 1 -C 8) alkylsulfonyl, P (O) - (OR 8) 2 'R 7 P (O) -OR 8, benzoyl or a cation, R is an alkyl group having 1 to 8 carbon atoms which is optionally substituted with 1 to 6 halogen atoms, an alkoxy group having 1 to 8 carbon atoms which optionally is substituted with 1 to 6 halogen atoms, alkylcarbonyl having an alkyl radical of 1 to 8 carbon atoms, an alkoxycarbonyl radical whose alkoxy radical contains 1 to 8 carbon atoms, a radical NR 1 R 2, an radical O S (O) R 11, a radical NR 1, Is a halogen atom, a cyano group or a nitro group; R6 represents an alkoxy group substituted with 1 to 6 halogen atoms;

Rg is a hydrogen atom or is selected from the group consisting of the meanings of R, each of R? and R 8 independently represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms,

R 8 represents an alkyl group having 1 to 8 carbon atoms, R iq represents an alkyl group having 1 to 8 carbon atoms which is optionally substituted with 1 to 6 halogen atoms, n represents 0 or 1, n 0, 1 or 2, subject to wherein when R 1, R 2 and R 8 are methyl, R 4 and R 8 are hydrogen and R is nitro, then R 8 is not difluoromethoxy 3

In the above meanings, halogen is suitably selected from the group consisting of chlorine, bromine and fluorine, and alkyl groups of 1 to 8 carbon atoms preferably contain 1 to 4 carbon atoms.

Preferably, each of R @ 1 and R @ 3 is hydrogen and C1 -C4 alkyl, especially hydrogen or C1 -C3 alkyl.

Suitably, the general substituent R represents an alkyl group of 1 to 4 carbon atoms which is optionally substituted with halo, - (O) n --S (O) - alkyl group whose alkyl moiety contains 1 to 4 carbon atoms, a halogen atom or a nitro group. This general substituent is preferably methyl, CF3, alkylsulfonyl, the alkyl moiety of which contains from 1 to 3 carbon atoms, alkylsulfonylcarbonyl, the alkyl moiety of which contains from 1 to 3 carbon atoms, chloro, bromo or nitro.

The general substituent R @ 1 preferably represents a fluoroalkoxy group, more preferably an OCF3 group.

The general substituent R 8 is preferably hydrogen, C 1 -C 4 alkyl, C 1 -C 4 alkoxy, bromo, chloro. More preferably, this general substituent is hydrogen, methoxy or chloro.

Suitably, R @ 1 is hydrogen, C1 -C4 alkyl, alkyl carbonyl wherein the alkyl moiety is from 4 to 8 carbon atoms, benzoyl, alkylsulfonyl, the alkyl moiety is from 1 to 4 carbon atoms, or cation. preferably the substituent is hydrogen, methyl, ethyl, tert-butylcarbonyl, isobutylcarbonyl, benzoyl or methylsulfonyl. When R 1 is a cation, 4 is preferably an alkali metal cation such as Na +, K + and Li +, or an ammonium cation. Examples of particularly preferred substituents are: each R i and

a) a hydrogen atom, an alkyl group having from 1 to 4 carbon atoms, a phenyl group or a phenyl group substituted by one or three groups R 1, b) a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a phenyl group or a phenyl group substituted by one or three groups such as R, c) hydrogen, alkyl of 1 to 3 carbon atoms, d) hydrogen to methyl, e) alkyl to 1 to 3 carbon atoms, a) alkyl of 1 b) an alkyl group having 1 to 4 carbon atoms, c) a methyl group, an ethyl group, a hydrogen atom, a) a nitro group, a chlorine atom, a trifluoromethyl group, b) a nitro group, a chlorine atom, c) a nitro group, an OCF 4 group, a hydrogen atom.

Particularly preferred are the combinations of these meanings of the various substituents.

A particularly preferred compound of the invention is 2,6,6-trimethyl-4- (4-trifluoromethoxy-2-nitrobenzyl) -2H-1,2-oxazine-3,5- (4H, 6H) -dione.

The compounds according to the invention of the formula I are novel compounds which can be prepared by processes analogous to those known for the preparation of structurally similar compounds, in particular by the processes described in the European patent application 5

application E? In particular, these compounds can be obtained by rearrangement of the enol ester of formula II

33 II) in which R, R „, Rq, R, E„ and R R are as defined above, for z nin

Of formula I wherein R 1 is an atom

VOCIKU

This rearrangement is suitably carried out by reacting a compound of formula II with a cyanide source and a mild base.

For example, this reaction may be carried out in the presence of a catalytic amount of a cyanide anion source and / or cyano-hydrogen together with a molar excess to the enol ester of the mild base. The reaction is suitably carried out in a solvent which is inert under the reaction conditions used, for example in 1,2-dichloroethane-xylene, acetonitrile, methylene chloride, ethyl acetate, dimethylformamide (DMF) and methyl isobutyl ketone (MIBK). Generally, depending on the nature of the reactants and the cyanide source, said rearrangement may be carried out at a temperature of up to about 80 ° C. In some cases, for example, when the byproduct formation is excessive, a reaction temperature of about 40 ° C should be used. Preferred cyanide sources are alkali metal cyanides such as potassium cyanide or sodium cyanide, methyl alkyl ketone cyanides having from 1 to 4 carbon atoms in the alkyl group, such as acetone or methyl isobutyl ketone cyanohydrin, cyanohydrides of benzaldehyde or aliphatic aldehydes of 2-5 carbon atoms. atoms such as acetaldehyde, propion aldehyde, etc. cyanohydrins, zinc cyanide, tri (lower alkyl) silyl cyanides, especially trimethylsilyl cyanide, and cyanogen cyanohydrin cyanide sources alone is the preferred cyanide source of acetone cyanohydrin. The cyanide source is used in an amount of up to about 50 mole percent based on the enol ester. In general, it is preferred to use about 1 to 10 mole percent cyanide source.

As used herein, the term "mild base" refers to a substance that acts as a base, the strength or potency of which as a base lies between the potency and the potency of strong bases, such as hydroxides (which could cause hydrolysis of the enol ester) and the potency and potency of the weak bases, such as hydrogen carbonates (which would not work efficiently). Suitable medium bases for use in this reaction include organic bases such as tertiary amines and inorganic bases such as alkali carbonates and phosphates. Suitable tertiary amines include trialkylamines such as triethylamine, trialkanolamines, especially triethanolamine, and pyridine. Suitable inorganic bases include potassium carbonate and sodium phosphate. The base is used in an amount of about 1 to about 4 moles per mole of enol ester, preferably in an amount of about 1.3 to 2 moles per mole of enol ester. When a cyanide alkali metal, in particular potassium cyanide, is used as the cyanide source, a phase transition catalyst may be used in the reaction. Particularly suitable phase transition catalysts are crown ethers.

Compounds of formula (I) in which R d is other than hydrogen may be prepared by reacting a compound of formula (I) wherein R is hydrogen with either a) R 6 g -OH and a catalyser; a base wherein Q is a halogen atom to form a compound of formula (I) wherein R 1g is 7 as the desired substituent. The above reaction a) is carried out in the presence of a catalyst such as concentrated sulfuric acid. The reaction is conveniently carried out in a solvent which is also a reactant such as methanol and at elevated temperature. The above reaction b) is carried out in the presence of a mild base such as triethylamine or pyridine and suitably at ambient temperature or below.

The compounds of formula I can be isolated from the reaction mixture in which they are formed by treating the reaction mixture in a conventional manner.

Compounds of formula II may be prepared by reacting a compound of formula III

(III)

with a compound of formula IV

(IV). 8

This reaction is carried out in the presence of a base such as jet triethylamine, potassium carbonate, pyridine, preferably triethiamine, and in an inert solvent such as dichloromethane, acetonitrile, toluene, tetrahydrofuran and dimethylformamide. The reaction is conveniently carried out at ambient temperature or below ambient temperature.

The remaining compounds of formula II can be prepared in an analogous manner.

The compounds of formula III are novel compounds and as such form part of the invention.

These compounds can be prepared by decarboxylating the compound of formula V (V)

wherein R 2Q is alkoxy, especially ethoxy or methoxy and R 1, and R 4 are as defined above. This reaction can be carried out at elevated temperature, for example 80 to 90 ° C, and in an inert solvent such as wet dimethyl sulfoxide.

The compounds of formula V may be prepared by ana-

9

Reaction Scheme I-NHOCCR 1 R 4 COR 2

VI ciocch2cor20

VII (a)

RjNOCÍR ^ CORJO COCH2COR2o viii (b)

Reaction a) may be dichloromethane and the aqueous solution is triethylamine or carbonic in an inert solvent, r, and in the presence of a base, bright, at ambient temperature.

Reaction b) may be carried out in an inert solvent such as toluene, benzene or tetrahydrofuran in the presence of a base such as sodium methoxide or sodium hydride.

The remaining starting materials and reactants used in the above process are known compounds and, if not known, can be prepared by methods analogous to those described herein or by known procedures for compounds VI: Kornowski et al., Bull. Soc.Chim France 1966 (2) 633 /.

2-Nioro-4-trifluoromethoxybenzoic acid is a novel compound that also forms part of the invention.

The compounds of the invention. R represents a hydrogen atom having four structural formulas: of formula I in which, as a result of tautomerism,

It goes without saying that when R5 is other than hydrogen, these may exist in forms Ib, Ic and Id or in the form of a mixture of these forms.

The novel compounds of formula (I) are useful for controlling weeds in pre-emergence and / or post-emergence applications. The compounds of formula (I) are also useful as plant growth regulators (PGRs) and ascids. These compounds can be applied in the form of powders, granules, solutions, emulsions, wettable powders, melt compositions and suspensions. Application of a compound of the invention to this herbicide is accomplished by conventional application to the weed or locus thereof using a herbicidally effective amount of a compound of the invention that is typically 0.125 to 12.5kg / ha. Application of the compound of the invention to the locus includes application to weed seeds, application to the plant (weed) of heaven on its part or application to the soil.

The application of the compound of the present invention as an acaricide is carried out by conventional application to the infestation site, employing an acaricidally effective amount of a compound of the invention, which is usually 100 g / ha to 1 kh / ha.

As used herein, the term "herbicide" refers to an active ingredient that modifies the growth of the plants in view of its phytotoxicity or growth-regulating properties such that they delay their growth or damage them to such an extent that they kill them.

The compounds of the invention exhibit a high level of herbicidal activity against broadleaf, grass and chamois weeds in post-emergence or pre-emergence applications. The thyto compounds also exhibit selective herbicidal activity in useful crops such as wheat, maize, cotton, soybean derivatives and, in some cases, rice. When using the compounds of formula (I) in order to control euphorbia and mites, the compound of formula (I) or mixtures thereof may suitably be used in the form of compositions in combination with a diluent or diluents that are acceptable for the application of weeds, mites or sites. These compositions also form part of the invention.

Methods for preparing suitable formulations that may be used in the compounds of the invention are described together with suitable liquid or solid carriers in the art, for example, in U.S. Pat. Nos. 4,192,669 and 4,163,661. readily determined by routine assays such as greenhouse tests and small school plot tests.

Suitable formulations contain from 0.01 to 99% by weight of active ingredient, from 0 to 20% by weight of surfactant and from 1 to 99.99% of solid or liquid diluent or diluents. Sometimes higher surfactant to active ingredient ratios are desired. which is achieved by incorporating the surfactant directly into the formulation or by admixing it into the tank prior to application 12

The dosage forms of the composition generally contain between 0.01 and 25% by weight of the active ingredient. However, depending on the intended use, the physical properties of the compound of the invention and the method of administration, higher or lower amounts of the active ingredient may be present in the composition. The concentrate forms of the compositions which are expected to be diluted before use generally contain between 2 and 90% by weight, preferably between 5 and 81% by weight, of the active ingredient.

Useful formulations of the compounds of formula I include dusts, granules, suspension concentrates, wettable powders, disintegrating compositions and the like. These formulations can be obtained in a conventional manner, for example by mixing the compound of formula I with a diluent or diluents and optionally other additives. Alternatively, the compounds of the general formula may be used in micro-encapsulated form.

The compounds of formula (I) may be combined with a cyclodextrin to form a cyclodextrin inclusion complex for application to weeds, mites or their sites. In herbicidal compositions, agriculturally acceptable additives may be used to improve the efficacy of the active ingredient, reduce the foaming of the composition, reduce phase elimination from the composition, reduce the corrosive effect of the composition, and the like.

As used herein, the term "surfactant" refers to an agriculturally acceptable substance which imparts the ability to form an emulsion and dispersion, to wet the surface and to spread over the surface and other surface tension modifying properties. Examples of surfactants are sodium ligninsulfonate and lauryl sulfate.

The term "diluent" as used herein means a liquid or solid agriculturally acceptable substance which is used to dilute the concentrate to a usable or desired concentration.

For dusts or granules, the diluent may be, for example, talc, kaolin or diatomaceous earth, while in the case of concentrates in liquid form, such a diluent may be, for example, hydrocarbon, especially xylene, or alcohol, especially isopropanol.

For the liquid dosage form, the diluent may be, for example, water or diesel.

The compositions of the invention may also contain other compounds having biological activity, for example compounds having similar or complementary acaricidal or herbicidal activity to a broad spectrum of weeds or compounds having antitoxic, fungicidal, insecticidal or insect-binding activity. In the following, the invention will be elucidated in more detail by means of specific examples. These examples are merely illustrative and are not intended to limit the scope of the invention which is clearly defined by the claims. All parts and percentages given in these examples are parts by weight and percentages by weight. EXAMPLE 1 Preparation of 2,6,6-Trimethyl-4- (2-nitro-4-trifluoromethoxybenzoyl) -2H-1,2-oxazine-3,5- (4H, 6H) -aion. = R 3 = CH 3, r 4 = r 6 = H, r = no 2, R 5 = OCF 3; Compound # 1 71.4 g of 2,6,6-trimethyl-5- (2-nitro-4-trifluoromethoxybenzoyloxy) -6K-1,2-oxazin-3-one is dissolved in 300 ml of acetonitrile and 49 ml of triethylamine. 3.2 ml of acetone cyanohydrin is added to this solution, cooled in an aqueous bath. The solution was stirred overnight at room temperature under a nitrogen atmosphere. The reaction mixture was concentrated to a syrupy consistency, and the collected syrup was partitioned between 400 mL of water and 150 mL of dichloromethane. The combined extracts were washed with 2N hydrochloric acid and brine, dried and evaporated to dryness to give an oil. The crude product is then crystallized from ethanol to give the desired 2,6,6-trimethyl-4- (2-nitro-4-trifluoromethoxybenzoyl) -2H-1,2-oxazine-3,5-one (411). 6H) -dione.

Melting point: 73 to 75.5 CC. . / Example 1, may be zΣ whose chemical in the following table

Using the procedure described herein, other compounds of the general structure and melting point are given in A.

Table A

Compound No. R1 R 'of R3 R4 R R. o Melting Point (° C) 1 CH3 CH3 CH-, Π KOn Z 4-OCF3 H 73-75.5 2 CH, CH3 CH3 HCl 4- EXAMPLE 2 Preparation of 2-nitro-4-trifluoromethoxybenzonitrile To a stirred solution of 64.30 g of 2-nitro-4-trifluoromethoxy-aniline (Znur. Obshchei. Khim 31, 915-24 (1961)) in 72 ml of con. concentrated hydrochloric acid and 190 ml of water cooled to 0 ° C, a solution of 20.0 g of sodium nitrite in 75 ml of water was added dropwise over 35 minutes. After stirring for 45 minutes at 0 ° C, the diazonium salt solution was added dropwise over 75 minutes to a stirred solution of 82.69 g of potassium cyanide 15 and 46.62 g of copper sulfate in 400 mL of water at 60 to 65 ° C. . The gray-green mixture was heated to 60-65 ° C with stirring for an additional 30 minutes and then allowed to cool to ambient temperature. The reaction mixture was then filtered through celite and the precipitate was washed with dichloromethane (3 x 200 mL). Dichloromethane washings are used to extract the aqueous solution. The combined extracts are washed with water and brine and dried to dryness to give an oily residue which is chromatographed on silica gel. 2-Nitro-4-trifluoromethoxybenzonitrile was obtained from the appropriate fractions. Yield: 31.44 g Example 3 Preparation of 2-nitro-4-trifluoromethoxybenzoic acid Mixed solution of 40.96 g of 2-nitro-4-trifluorobenzonitrile in 90 ml of concentrated sulfuric acid and 125 ml of water was heated to reflux 45 hours. The reaction mixture was cooled and diluted with 200 mL of cold water. The aqueous supernatant is then decanted from the brown gum. The gum-like product was dissolved in ether and extracted with 0.5 N sodium hydroxide solution. The combined basic aqueous solution was acidified with concentrated hydrochloric acid, then extracted with ether. The combined extracts were dried and evaporated to dryness to give 2-nitro-4-trifluoromethoxybenzoic acid, crystalline.

Melting point: 119 ° C. Example 4 Preparation of 2,6,6-trimethyl-5- (2-nitro-4-trifluoromethoxybenzoyl-oxy) -6H-1,2-oxazin-3-oneGeneral Formula II: R 1 = R 2 = R 3 = CH 3 'R 4 = R6 = H, R = NO2, r5 = ocf3. 16 A stirred solution of 43.98 g of 2-nitro-4-trifluoromethoxybenzoic acid in 100 ml of thionyl chloride is refluxed for 2 hours, then concentrated to dryness to give an oily 2-nitro-4-trifluoromethoxy- benzoyl chloride. To a stirred solution of 2,6,6-trimethyl-2H-1,2-oxazine-3,5- (4H, 6H) -dione (27.53 g) and triethylamine (25 ml) in dichloromethane (290 ml) cooled to ice a solution of 2-nitro-4-trifluoromethoxybenzoyl chloride in 100 ml of dichloromethane is added dropwise under a nitrogen atmosphere. After stirring at 0 ° C for 2 hours, the reaction mixture was diluted with 150 mL of dichloromethane and washed with water and brine, dried and evaporated to dryness to give 2,6,6-trimethyl-5- (2-nitro). -4-trifluoromethoxybenzoyloxy) -6-1,2-oxazin-3-one. A / CuKj 9 MUDr. Jarmila Traplová

Claims (9)

wherein each of R 1, R 2, and R 6, independently, is hydrogen, C 1 -C 8 alkyl, carboxyl, alkoxycarbonyl having 1 to 8 carbon atoms, phenyl, or phenyl substituted with one to three groups as R 1 or R 1 and R 4 together form an alkylene bridge of 3 to 6 carbon atoms, R 4 represents a hydrogen atom, a C 1 -C 8 alkyl group, an alkylcarbonyl group having 1 to 3 carbon atoms, an alkoxycarbonyl group a group having an alkoxy radical of from 1 to 8 carbon atoms, a group -C (O) NR-Ra, an alkylsulphonyl group having 1 to 8 carbon atoms, a group P (O) - (ORg) 2 <group R 7? ) -OR 8, a benzoyl group or a cation, R represents an alkyl group having 1 to 8 carbon atoms, which is optionally substituted with 1 to 6 halogen atoms, an alkoxy group having 1 to 8 carbon atoms which is optionally substituted bottom substituted with 1 to 6 halogen atoms, an alkylcarbonyl group having an alkyl radical of 1 to 8 carbon atoms, an alkoxycarbonyl radical having an alkoxy radical of 1 to 8 carbon atoms, a radical NR 1 R 8, an radical O S (O) R i, NR 2 Halogen, quano or nitro, R8 represents an alkoxy group substituted with 1 to 6 halogen atoms, R8 represents a hydrogen atom or is selected from the group consisting of R, R? and R 8 is independently hydrogen or C 1 -C 8 alkyl, R 8 is C 1 -C 8 alkyl, is C 1 -C 8 alkyl optionally substituted with 1 to 6 halogen atoms, is 0 or 1 10, 1 or 2, provided that when R 1, R 8 and R 8 are methyl, R 1 and R 8 are hydrogen and R 2 is nitro, then R 8 is not difluoromethoxy. A compound according to claim 1, wherein R 1, R 8, R 8 is independently hydrogen or C 1 -C 4 alkyl, R 2 is C 1 -C 4 alkyl optionally substituted by an atom chlorine, a bromine atom or a fluorine atom, - (O) -S (O) - - n alkyl having an alkyl radical of 1 to 4 carbon atoms, a halogen atom or a nitro group, R 8 represents a fluoroalkoxy group, R 8 represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a bromine atom or a chlorine atom, and R 4 represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkylcarbonyl group whose alkyl radical is it contains from 4 to 8 carbon atoms, a benzoyl group, an alkylsulfonyl group whose alkyl moiety contains from 1 to 4 carbon atoms or a cation. A compound according to claim 2, wherein R 1 and R 7 are each independently hydrogen or C 1 -C 3 alkyl, R 1 is hydrogen, and R is nitro, chloro or trifluoromethyl. . '· 4. A compound according to claim 3, wherein each of R, R, and R-, is methyl, R, and R5 is hydrogen, R is nitro-skuoin, and R5 is oco-ocFr- ' 5. A pesticidal composition comprising a compound of formula (I) according to claims 1 to 4 in combination with an agriculturally acceptable carrier. 6. A method for controlling weeds, applying a compound of the formula (I) to (1) to (4) to a weed or locally effective amount of a compound in which it grows. 7. A method for controlling mites, characterized by mites or habitats in which they live, is an effective amount of a compound of formula (I) according to (1) to (4). A process for preparing a compound of claim 1, wherein: a) rearrangement of the enol ester of the general formula (I) by formula (II), (II) IV wherein R 1, R 6, R 4, R 3, R 6 and R 8 are as defined in claim 1, to give a compound of formula I wherein R 1 is a hydrogen atom, and b) when R is different from hydrogen, by reacting a compound of formula (I) wherein R is hydrogen, a) R 1 -OH and a catalyst; or b) R g is a mild base wherein Q is an atom halogen, to form a compound of formula I wherein R 1 is a desired substituent. 9. 2-Nitro-4-trifluoromethoxybenzoic acid. Represented by: JUDr. Jarmile Trapjoyá