DE3820538A1 - SUBSTITUTED 3- (PYRIDYLCARBONYL-AZA, -OXA- AND THIACYCLOHEX-5-EN-2,4-DIONE, YOUR BENZO (B) - OR 5,6-DIHYDRO DERIVATIVES, PRODUCTION AND USE THEREOF AS HERBICIDE - Google Patents

Abstract

Heterocyclic aza-, oxa- or thia-5-cyclohexene-2,4-dione compounds and benzo [b] fused or 5,6-dihydro derivatives thereof, which compounds are substituted in the 3-position by an ortho substituted pyridoyl group and may bear further substituents in the 5- and 6- positions where the heteroring is monocyclic, and in the 1-position where the heteroatom is nitrogen, the process of preparing such compounds, their use in combatting weeds and herbicidal compositions comprising them.

Description

The invention relates to new heterocyclic aza, oxa and Thia-5-cyclohexene-2,4-dione compounds and benzo [b] derivatives or 5,6-dihydro derivatives thereof, the use of these ver weed control, new herbicidal agents compositions containing such dione compounds and a process for making these new compounds.

In particular, the invention relates to new heterocyc Aza, oxa and thia-5-cyclohexene-2,4-dione compounds and benzo [b] derivatives or 5,6-dihydro derivatives thereof described in Position 3 by an ortho-substituted pyridoyl group sub are in positions 5 and 6 if the Heteroring is monocyclic, and in position 1 if that Hetero atom is nitrogen, contain further substituents can. (These connections are referred to below as the verb of the formula (A)).

The term ortho-substituted pyridoyl as used herein refers to any aryl-CO group wherein aryl is a 2-, 3- or 4-pyridyl group substituted ortho to the CO group. Examples of suitable ortho substituents are halogen, NO₂, C₁-C₄-alkyl, C₁-C₄-alkyl-S (O) _n , where n is 0, 1 or 2, or C₁-C₄-haloalkyl and C₂-C₅- Alkenyl. The pyridyl group can carry one or two further substituents. In games for such additional substituents on the aryl group are halogen, C₁-C₄-alkyl, C₁-C₄-alkoxy, NO₂, C₁-C₄-haloalkyl, cyano, R _a R _b N (SO₂) _m , in which R _a and R _b independently of one another are hydrogen or C₁-C₄-alkyl and m is 0 or 1, and hydrocarbyl-S (O) _{n ′} , in which hydrocarbyl is understood to mean an aliphatic, aromatic or araliphatic group, such as C₁-C₄- Alkyl, phenyl or benzyl, which can be substituted, for example, by halogen or cyano, and n 'represents 0, 1 or 2. Any substituent present on the pyridyl radical in addition to the ortho substituent is preferably not in the ortho'-position to the group CO. The pyridoyl group is preferably monosubstituted, disubstituted or trisubstituted.

Examples of suitable substituents in position 5 of the Aza, oxa or thia-5-cyclohexene-2,4-dione rings and the Benzo [b] derivatives or the 5,6-dihydro derivatives of this ring (This is referred to below as the hetero basic ring net) are halogen and C₁-C₄-alkyl.

Examples of suitable substituents in position 6 of the hetero rings are hydrogen and aliphatic or aromatic Hydrocarbyl, such as C₁-C₄-alkyl, C₃-C₆-cycloalkyl or Phenyl. This phenyl group can be unsubstituted or substituted ized, for example monosubstituted or disubstituted, be. Examples of suitable substituents on this phenyl group are C₁-C₄ alkyl and halogen.

If the hetero ring is 5,6-dihydrated, this ring can also be in position 5 and / or 6 disubstituted. Is the stel lung 5 and / or 6 disubstituted, then it is this substitution, for example, by di-C₁-C₄-alkyl.

If the hetero ring contains nitrogen as a hetero atom, then can this ring nitrogen atom is unsubstituted or substituted be. Examples of suitable N substituents are Hydrocarbyl groups such as C₁-C₄ alkyl, phenyl or phenyl alkyl, or unsubstituted or substituted amino, such as for example C₁-C₄ alkylamino.

The compounds of formula (A) are acidic compounds You can in free form or in salt form, for example  wise in the form of alkali metal salts or alkaline earth metal salts, such as the sodium salts, or in the form of additions salt, for example with amines, such as trialkylamines come.

A preferred subset of compounds of formula (A) which are in the herbicidal composition according to the invention can be used are the compounds of formula (I) and (Ia)

wherein

X represents O, S or NR, R₁ is pyridyl which is ortho-substituted by halogen, C₁-C₄-alkoxy, NO₂, C₁-C₄-alkyl, C₁-C₄-alkyl-S (O) _n or C₁-C₄-haloalkyl or C₂-C₅ alkenyl and which optionally has one or two further substituents which are selected from halogen, C₁-C₄-alkyl, C₁-C₄-alkoxy, NO₂, C₁-C₄-haloalkyl, C₁-C₄-haloalkoxy, CN , R _a R _b N (SO₂) _m , C₁-C₄-alkyl-S (O) _{n ′} , C₁-C₄-alkyl-CO or C₁-C₄-alkoxy-CO, n and n ′ independently 0, 1 or 2 are, m is 0 or 1, R _a and R _{b are} independently H or C₁-C₄-alkyl, A and _{B are} independently H or C₁-C₄-alkyl or together form a bond, R₂ is H, halogen or C₁-C₄- Is alkyl, R₃ is H, C₁-C₄-alkyl or phenyl, which may be unsubstituted, monosubstituted or disubstituted, the substituents being selected from halogen or C₁-C₄-alkyl and where, if A and B together represent a bond, R₂ and R₃ together can form the group -CH = CH-CH = CH-, and R for H, C₁-C₄-alkyl, phenyl or C₁-C₄- Alkylphenyl stands.

As shown above, the compounds of formula (I) in their tautomeric forms which correspond to the formula (Ia) correspond. There is of course a similar tautomerism for the other compounds of formula (A).

The heteroatom X is preferably oxygen.

The new compounds of the formulas (A) and (I) can be manufacture by esterification of the corresponding, in position 3 unsubstituted aza-, oxa- or thia-3,5-cyclohexadiene 2-one-4-ole or aza-, oxa- or thia-3-cyclohexen-2-one-4-ole with the desired pyridoyl halide and subsequent Umla the resulting 4-pyridyloxy compound.

The invention therefore also includes a method of manufacture of compounds of formula (I), characterized in that is that a compound of formula (II)

wherein

X, R₂, R₃, A and B are as defined above,

With a compound of formula (III)

R₁-CO-Hal (III)

wherein

R 1 is as defined above and Stands for halogen,

is reacted and the ester of formula (VI) thus obtained

wherein

X, R₁, R₂, R₃, A and B are as defined above,

undergoes a rearrangement.

The esterification of the 2-one-4-ol compounds with a pyrido yl halide can be carried out in a manner as it is for the production of esters from an alcohol and a Acid halide is known.

The reaction is advantageously carried out in a solvent, which is inert under the reaction conditions, such as dichloro methane, and preferably in the presence of an acid binder means such as triethylamine. The implementation tem temperature is advantageously in the range of 0 ° C and 40 ° C, for example at about 20 ° C.

The rearrangement of the esters to the desired compounds of formula (A) can be carried out under conditions known for the preparation of α- acylated β- diketones from β- keto enol esters.

Such rearrangement can occur in the presence of a Lewis acid Catalyst or a cyanide source such as acetone cyanohydrin, carried out together with a tertiary amine as the base the.

Lewis acid suitable for such a rearrangement reaction Examples of catalysts are aluminum chloride or zinc chloride.

Examples of suitable solvents are methylene chloride, Acetonitrile or toluene. The reaction temperature is moving expediently between 0 ° C and reflux temperature, wherein working at room temperature (about 20 ° C) is preferred.

The compounds of the formula (A) can be obtained from the reaction mixture mix in which they are formed by working up Application of known methods can be obtained.

Depending on the reaction conditions used, the ver Compounds of formula (A) in the form of their free acids or of their salts.

The salts of the compounds of formula (A) can be obtained from the free acid by using methods known per se and received vice versa.

The output to be used in the process described above materials and reagents are either known or can if new, made using methods as to the methods described herein or known methods are analogous.

The compounds of formula (A) defined above are both in free acid form as well as in agricultural form acceptable salts interesting broad spectrum herbicides, and this applies in particular to the compounds of the formula (I).  

The invention therefore also includes a control method of weeds, which is that the location of the Un herbs with a herbicidally effective amount of a compound of formula (A) in free acid form or in the form of a land economically acceptable salt is treated.

The effectiveness of these compounds as pre-emergence herbicides and post-emergence herbicides can be found in the greenhouse using Experiments using test doses show which Application amounts of 0.33, 1.0 and 3 kg / ha are equivalent. The one to be used by each compound of formula (A) The amount depends on the weeds to be controlled tern, the connection used in each case, the type of their connection application, treatment conditions and the like. The ever Weil suitable amount of use can be in the specialist in determine in the usual way or it can by comparing the Effectiveness of the desired compound of formula (A) with the Effectiveness of standards, the amount of which is known, be determined, for example, by experiments in the blowing can be done at home. Satisfactory results are obtained generally when the respective compound of the formula (A) in an amount in the range of about 0.03 to 3.0 kg / ha of the respective plant location is applied.

The compounds of formula (A) can together as herbicidal measures in connection with agriculturally acceptable Diluents are used, and such applications manure is also preferred. Suitable formulations of this type contain 0.01 to 99 wt .-% active ingredient, 0 to 20% of an upper surfactant and 1 to 99.99% of a solid or liquid diluent. Sometimes higher ver ratios of surfactant to active ingredient wishes, and such relationships can be worked through in the respective formulation or by mixing tanks to reach. The use forms of a composition contain  generally between 0.01 and 25 percent by weight of active ingredient material. Depending on the intended application, the physi properties of the connection and the type of application higher or lower amounts of active ingredient may also be present be. Concentrated forms of a composition before their use should generally be diluted NEN 2 to 90 weight percent, preferably 10 to 80 Ge weight percent active ingredient.

Suitable formulations for compounds of the formula (A) include dusts, granules, suspension concentrates, wettable Powders, emulsifiable concentrates, flowable preparations and the same. Such formulations can be found in obtained conventionally, for example by mixing a compound of formula (A) with diluents and other additives if necessary.

Alternatively, the compounds of formula (A) can also be in the form of microcapsules.

The herbicidal compositions can also be used by farmers socially acceptable additives are used to make up the To improve performance of the active ingredient and, for example, a Foaming to reduce caking or corrosion gene.

In the present case, a surface active agent is a understood agriculturally acceptable material, the emul yawing, spreading, wetting, dispersing or other gives surface-modifying properties. At Suitable surfactants are sodium lignin sulfonate and sodium lauryl sulfate.

A diluent is herein a liquid or solid agricultural acceptable material understood,  that for diluting a concentrated material to a usable or desired starch. For dusts or Granules can, for example, talc, kaolin or diatoms earth can be used while going for liquid concentrates for example hydrocarbons, such as xylene or alcohols, such as isopropanol, and for liquid application forms For example, water or diesel oil can be used.

The compositions of the invention can also be others Contain compounds with biological activity for example, connections with similar or complementary herbicidal activity or compounds with antidotic, fungicidal or insecticidal activity.

The following examples further illustrate the invention purifies. All temperatures are in ° C. The Abbreviation RT means room temperature. All information in parts and percentages are by weight.

Herbicidal compositions Example A Wettable powder

25 parts of a compound of the formula (A) are mixed in for example the connection of the example given later 1, in a grinder with 25 parts synthetic, fine grain according to silicon dioxide, 2 parts of sodium lauryl sulfate, 3 parts Sodium lignin sulfonate and 45 parts of finely ground kaolin until an average particle size of about 5 microns is reached.

Example B Emulsion concentrate

25 parts of a compound of the formula (A) are mixed in for example the connection of the example given later 1.50 parts xylene, 15 parts dimethylformamide and 10 parts  Emulsifier thoroughly until you have a homogeneous solution Has.

Herbicidal studies Experimental example 1 Pre-emergence treatment

Seed pots are filled with a substrate that a sandi is comparable to clay. Grains are placed in each pot from Abutilon theophrasti, Amaranthus retroflexus, Sinapis alba, Solanum nigrum, Bromus tectorum, Setaria viridis, Avena Fatua and Echinochloa crus-galli sown.

Then the test substance of formula (A) in one Amount corresponding to 1 kg and 4 kg of active ingredient per hectare, applied, the application volume 100 l per hectare corresponds. The application takes place by spraying one aqueous test liquid, the formulation of which, for example example B corresponds to the above. After treatment the seeds with a thin layer (about 0.5 cm) Sub strat covered. The pots are kept at room temperature for 21 days (20 to 24 ° C) with daily exposure to light 14 to 17 hours (daylight or comparable Light source).

The herbicidal activity is reduced after the 21-day trial duration determined. This determination is a visual one Assessment of the extent and quality of the damage ver different seed plants.

The herbicidal activity is observed.

Experimental example 2 Post-emergence treatment

The procedure is similar to that of Experimental Example 1 with the exception that the test connections are only  be applied when the plants are already 2 to 4 Have leaves. The other test conditions (application quantity, application volume, temperature, light) and the appraisal division procedure (21 days after application of the active substance) are the same as in experimental example 1.

The herbicidal activity is observed.

Experimental example 3

Experiments similar to experimental examples 1 and 2 are made with different monocotyledonous and double-germ leafy weeds using different cones concentrations of the liquids to be examined leads, the respective concentrations selected so are that the desired application amounts result. The Application volume corresponds to 600 l per ha.

The test evaluation is carried out 28 days after the application of the Active ingredient carried out.

The herbicidal activity becomes effective with application amounts of 30 up to 1000 g per ha observed.

End connections Example 1 3- (3,5-dichloro-2-pyridoyl) -4-hydroxy-6-methyl-2-pyrone

A suspension of 4.00 g of 3,5-dichloro-2-pyridoyl chloride and 2.40 g of 4-hydroxy-6-methyl-2-pyrone in 80 ml of CH₂Cl₂ dropwise with 1.8 ml of triethylamine at room temperature puts. After the exothermic reaction subsides, the Ge mix stirred for 6 hours at room temperature. Thereupon first 2.8 ml of triethylamine and then 0.7 ml of acetone cyano hydrin and stir the solution obtained overnight.  

The reaction mixture is extracted with 1 molar NaOH. Man washes the aqueous extract with CH₂Cl₂, acidifies with 1 molar HCl to pH 3 and extracted with three parts of CH₂Cl₂. The combined CH₂Cl₂ extracts are washed with water, dried over MgSO₄, filtered and evaporated in vacuo, resulting in a raw solid. This solid is recrystallized from CH₂Cl₂ and diethyl ether, whereby to 1.28 g of white crystals with a melting point of 166 to 168 ° C reached, and these white crystals correspond Chen based on a 1 H NMR spectrum of the desired structure.

Elemental analysis:
Calculated: C 48.0%, H 2.4%, N 4.7%, Cl 23.6%; Found: C 47.9%, H 2.3%, N 4.7%, Cl 24.2%.

Example 2

Analogous to the procedure of Example 1, are used the corresponding starting materials of formulas (II) and (III) the following compounds of formula (I) are prepared:

Table I

Compounds of formula (I) in which R₁ is 3,5-dichloro-2-pyridoyl and X is O.

Intermediates

Starting from 2,3,5-trichloropyridine (compound (V)) 3,5-dichloro-2-pyridoyl chloride by the following procedure produced.  

Example 3 2- [CH (COOC₂H₅) ₂] -3,5-dichloropyridine (compound (VI))

A suspension of 10.4 g 80% NaH (in mineral oil) in 500 ml of N, N-dimethylformamide is made under a nitrogen atmosphere dropwise at room temperature with a solution of 45.0 g Diethyl malonate in 100 ml of N, N-dimethylformamide. To When the addition is complete, the mixture obtained is first 15 minutes at room temperature and then stirred at 50 ° C for 30 minutes. The The mixture is then mixed with a solution of 45.7 g of 2,3,5-trichlor pyridine in 100 ml of N, N-dimethylformamide and over Stirred at 50 ° C overnight.

The solvent is evaporated off under vacuum, taken up in CH₂Cl₂, washed with 4 parts of water, dried over MgSO₄, filtered and evaporated under vacuum. The liquid obtained is chromatographed on silica gel eluting with a 9: 1 mixture of hexane and ethyl acetate. The fractions containing the desired product are contaminated with diethyl malonate, whereupon the whole is distilled under reduced pressure and 25.2 g of a pure product are obtained which have a boiling point of 103 ° C. at 0.024 mbar (n = 1.5068) . Due to its 1 H NMR spectrum, this liquid corresponds to the desired material.

Example 4 3,5-dichloro-2-methylpyridine (compound (VII))

A suspension of 70.0 g of compound (VI) is 17 hours heated to 110 ° C in 2 molar H₂SO₄. The mixture obtained is cooled and extracted exhaustively with CH₂Cl₂. The CH₂Cl₂ extracts are dried over magnesium sulfate, fil trated and evaporated in vacuo to give 37.0 g a solid with a melting point of 43 to 44 ° C er holds. Due to a 1 H NMR Spectrum of the desired product.  

Example 5 3,5-dichloropyridine-2-carboxylic acid (compound (VIII))

A solution of 1.25 ml tricaprylmethylammonium chloride (Aliquat 336) in 175 ml water is first mixed with 4.00 g 3.5- Dichloro-2-methylpyridine and then mixed with 19.8% KMnO₄. The mixture obtained is stirred at 95 ° C. for 90 minutes. To The aqueous layer is cooled to room temperature CH₂Cl₂ washed with concentrated H₂SO₄ to a pH acidified by 5 and under vacuum to a third of their ur of the original volume. The solution then continues acidified to pH 1, and the white precipitate obtained is collected by filtration. This gives 0.95 g a material with a melting point of 152 ° C. This Material corresponds to the ge based on a 1 H NMR analysis wanted product.

Example 6 3,5-dichloro-2-pyridoyl chloride

A suspension of 14.3 g of 3,5-dichloropyridine-2-carboxylic acid in 60 ml of thionyl chloride is refluxed for 5 hours heated, forming a solution. The cooled one Solution is evaporated in vacuo to give 15.7 g of a white solid with a melting point of 58 to 60 ° C. This solid corresponds due to a 1 H NMR analysis of the desired structure.

Claims (6)

1. Heterocyclic aza, oxa and thia-5-cyclohexene-2,4-dione compounds and benzo [b] derivatives or 5,6-dihydro derivatives of these, which are in position 3 by an ortho-substituted one Pyridoyl group are substituted and in positions 5 and 6 if the hetero ring is monocyclic, and in the Position 1, if the heteroatom is nitrogen, further May contain substituents. 2. Compounds according to claim 1 of the formula (I) and (Ia) whereinX is O, S or NR, R₁ is pyridyl which is ortho-substituted by halogen, C₁-C₄-alkoxy, NO₂, C₁-C₄-alkyl, C₁-C₄-alkyl-S (O) _n or C₁-C₄-haloalkyl or C₂-C₅ alkenyl and which optionally has one or two further substituents which are selected from halogen, C₁-C₄-alkyl, C₁-C₄-alkoxy, NO₂, C₁-C₄-haloalkyl, C₁-C₄-haloalkoxy, CN , R _a R _b N (SO₂) _m , C₁-C₄-alkyl-S (O) _{n ′} , C₁-C₄-alkyl-CO or C₁-C₄-alkoxy-CO, n and n ′ independently 0, 1 or 2 are, m is 0 or 1, R _a and R _{b are} independently H or C₁-C₄-alkyl, A and _{B are} independently H or C₁-C₄-alkyl or together form a bond, R₂ is H, halogen or C₁-C₄- Alkyl is R₃ is H, C₁-C₄-alkyl or phenyl, which may be unsubstituted, monosubstituted or disubstituted, the substituents being selected from halogen or C₁-C₄-alkyl and wherein, if A and B together mean a bond ten, R₂ and R₃ together can form the group -CH = CH-CH = CH-, and R for H, C₁-C₄-alkyl, phenyl or C₁-C₄ alkylphenyl. 3. Process for the preparation of the dione compounds according to An saying 1, characterized in that aza, oxa or Thia-5-cyclohexene-2,4-dione compounds and benzo [b] deri vate or 5,6-dihydro derivatives thereof, which are in the Stellun gene 5 and 6 if the cyclodione is monocyclic, and in position 1 if the heteroatom is nitrogen, May contain substituents with an ortho-substit ized pyridoyl halide and be implemented here by rearrangement obtained 4-pyridoyloxy compound is subjected. 4. The method according to claim 3 for the preparation of compounds of formula (I) according to claim 2, characterized in that a compound of formula (II) whereinX, R₂, R₃, A and B are as defined in claim 2, with a compound of the formula (III) R₁-CO-Hal (III) whereinR₁ as defined in claim 2 and Hal is halogen, and the resulting 4 Pyridoyl esters of the formula (VI) whereinX, R₁, R₂, R₃, A and B as defined in claim 2 is subjected to a rearrangement. 5. Herbicidal agent, characterized in that it is a Contains compound according to claim 1 or 2 as an active ingredient. 6. Weed control method, characterized thereby records that the location of the weeds with a herbi Zid effective amount of a compound according to claim 1 or 2 is treated.