DE3902818A1 - NEW DIONE AND DERIVATIVES THEREOF - Google Patents

Abstract

Novel cyclical 1,3-dicarbonyl compounds of formula I <IMAGE> wherein Y, A2, R1, R2, R3, R4, and A3@4A are as defined in the disclosure, the use of such compounds in combatting weeds and herbicidal compositions comprising such compounds.

Description

The invention relates to novel dione compounds, the use such compounds for controlling weeds, new herbicidal compositions containing such dione compounds contained, and a method for producing such new connections.

In particular, the invention relates to novel compounds of Formula (I)

wherein

R₁, R₂, R₃ and R₄ independently represent an unsaturated aliphatic hydrocarbon group having up to 6 carbon atoms, a cycloalkyl group having up to 6 carbon atoms, a group Ar or a group (A₁) _n X, at least one of R₁, R₂, R₃ and R₄ may also be C₂-C₅ alkoxycarbonyl, at least one of R₁, R₂, R₃ and R₄ is (A₁) _n X, R₁ together with R₂ or R₃ together with R₄ may also be C₂-C₅-alkylene and R₁ together with R₂ can also form an oxo group or a C₁-C₅ alkylidene group,
Ar is an unsubstituted or substituted 5-membered or 6-membered heteroaryl group which contains 1 to 3 heteroatoms selected from O, N and S and is bonded to the ring A via a ring carbon atom,
n is 0 or 1,
X is H, OR₆, SR₇, NR₈R₉, NO₂, halogen, CN; CF₃, CHF₂, S (O) _m R₁₀, CO-NHR₁₁, CO-R₁₂, CR₁₃R₁₄-COO (C₁-C₆-alkyl) or benzyl,
A₁ is methylene or ethylene which is unsubstituted or substituted by one or more C₁-C₅ alkyl groups,
R₆ and R₇ independently represent H, a hydrocarbon group, a haloalkyl group, a heteroaryl group or a group CO-R₁₅,
R₈ is H, a hydrocarbon group, a heteroaryl group or a group CO-R₁₅,
R₉, R₁₀, R₁₃ and R₁₄ are independently H, C₁-C₆-alkyl or aryl,
R₁₁ is H or a hydrocarbon group,
R₁₂ and R₁₅ independently represent H, a hydrocarbon group or a heteroaryl group,
m stands for 1 or 2,
A₂ is a bond, CR₁₆R₁₇, CR₁₆R₁₇-CR₁₈R₁₉, O, S, NR₂₀ or CO,
R₁₆ and R₁₈ independently represent H, a hydrocarbon group or the carboxyl group in free, salt or esterified form, where R₁₆ together with R₁ on the adjacent carbon atom may also be a bond,
R₁₇ and R₁₉ are independently H, a hydrocarbon group or a group (A₁) _n X wherein A₁, n and X are as defined above, R₁₆ together with R₁₇ or R₁₈ together with R₁₉ also being a group (CH₂) _2-5 may be such that a spiro compound is formed, and / or R₁₆ together with R₁ on the adjacent carbon atom or R₁₈ together with R₃ on the adjacent carbon atom may be a group (CH₂) _1-5 , so that a bicyclic ring is formed,
R₂₀ is H, a hydrocarbyl group or a group CO-R₁₅, where R₁₅ has the above definition,
A₃ --- A₄ is C = C (ORa) (group A) or C (X₁) -C (O) (group B),
X₁ is F or Cl,
Ra is H, a salt-forming radical or, together with the oxygen atom to which this group is bonded, an ether radical or ester radical,
Y is either phenyl which is substituted by R₂₁, R₂₂ and R₂₃, or Ar ',
Ar 'is a 5-membered or 6-membered heteroaromatic group containing 1, 2 or 3 heteroatoms selected from O, S and N, said heteroaromatic group being unsubstituted or substituted and attached through a ring carbon atom to the group CO to which it is attached is
R₂₁ and R₂₂ are independently H, halogen, C₁-C₄-alkyl, C₁-C₄- alkoxy, C₁-C₄-haloalkyl, CN, NO₂, CF₃O, R ^b S (O) _p, NR ^c R ^d, C (O) - R, SO₂-NR ^c R ^d or NR ^c -C (O) -R ^d , where R₂₁ and R₂₂ together can form a methylenedioxy group,
p is 0, 1 or 2,
R ^{b is} C₁-C₄-alkyl which is optionally substituted by halogen, cyano, phenyl or benzyl,
R ^c and R ^{d are} independently H or C₁-C₄ alkyl, R is C₁-C₄ alkyl or C₁-C₄ alkoxy,
R₂₃ is halogen, NO₂, CN, C₁-C₂-alkyl, C₁-C₂-alkoxy, C₁-C₂-haloalkyl or C₁-C₄-alkyl-S (O) _q ,
q is 0, 1 or 2,

if Y is other than optionally substituted Pyrimidinyl is, then one of the radicals R₁, R₂, R₃ and R₄ also Phenyl or substituted phenyl means, with the provisos, that

• a) X is one of the radicals R₁, R₂, R₃ and R₄ only H, if at least one of the following conditions is given
  • i) CR₁R₂-A₂ is C (R₂) = C (R₁₇) or CR₁R₂-CR₁₆R₁₇-CR₁₈R₁₉,
  • ii) Y is other than optionally substituted phenyl or optionally substituted pyrimidinyl,
  • iii) R₁ and R₂ together are oxo or C₁-C₅-alkylidene,
  • iv) at least one of the other substituents R₁, R₂, R₃ and R₄ is an unsaturated aliphatic hydrocarbon group,
    a cycloalkyl group, an unsubstituted or substituted phenyl group or Ar,
  • v) at least one of the other substituents R₁, R₂, R₃, R₄, R₁₇ and R₁₇ and R₁₉ is a group (A₁) _n X, wherein X is other than H, or
  • vi) A₃ --- A₄ is C (X₁) -C (O),
• b) R₃ and R₄ are not H at the same time, if CR₁R₂-A₂ represents C (R₂) = C (R₁₇), and
• c) A₂ is not O, S, NR₂₀ or CO, if R₁ and R₂ together are oxo.

The compounds of the formula (I) are obtained by a compound of the formula (II)

wherein R₁, R₂, R₃, R₄ and A₂ are as defined above, with a compound of the formula (III)

Y-CO-Hal (III)

wherein Y is as defined above and Hal is halogen, is reacted and the resulting ester of formula (IV)  

wherein Y, R₁, R₂, R₃, R₄ and A₂ are as defined above, converted by rearrangement into compounds of formula (Ib) becomes

wherein Y, A₂, R₁, R₂, R₃ and R₄ are as defined above and M is H or a salt-forming radical,
and the compounds of the formula (Ib) thus obtained, if appropriate, by etherification, esterification or halogenation to give the corresponding 2- (Y-CO) -2-en-1-one-3-ol ethers, 2- (Y-CO) -2- En-1-one-3-ol ester or 2-X₁-2- (Y-CO) -1,3-dione compounds.

The esterification of 1-on-3-ol compounds with the halide can be done in a way as they are for making esters of an alcohol and an acid halide known per se.

The reaction is conveniently carried out in one of the reaction conditions inert solvents, such as dichloromethane,  preferably in the presence of an acid binder, such as triethylamine, carried out. A suitable reaction temperature is in the range of 0 ° C to 40 ° C and, for example, at 20 ° C.

The rearrangement of the esters of the formula (IV) thus obtained into the desired compounds of the formula (I) can be carried out under conditions known for the preparation of α- acylated β- diketones from β- ketoenol esters. For this purpose, isolation of the esters from the reaction mixture in which they are formed, is generally not necessary.

Such conversion can be carried out in the presence of a catalyst, as of 4-dimethylaminopyridine, a Lewis acid catalyst or a cyanide source, such as acetone cyanohydrin, with a medium strength Base, for example a tertiary amine base, such as Triethylamine.

Suitable Lewis acid catalysts for such rearrangement For example, aluminum chloride, zinc chloride and Tin (IV) chloride.

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

The compounds of the formula (Ib) can be prepared from the reaction mixture, in which they are formed, by workup under Application of common measures.

Depending on the reaction conditions, the compounds of Formula (Ib) in free acid form (M = H) or in salt form become.  

If the compounds of the formula (Ib) are in free acid form before, then they can occur in different tautomeric forms. Such acids can be known using per se Convert the process into the corresponding salts and vice versa.

When the compounds of formula (Ib) are in salt form (M is a salt-forming radical), then M can be an inorganic one Radical (for example, a metal equivalent of Na, Ca, Fe or Cu) or an organic radical, for example the ammonium salt radical an amine (such as 1- (methylaminomethyl) naphthalene), a sulfonium radical, a sulfoxonium radical or a phosphonium radical his. Depending on the nature of the remainder M, the salt may also be in Chelated form.

Similarly, the esters and ethers of the compounds of the Formula (I) in a conventional manner from the corresponding Compounds of formula (I) in the form of the free acids or Obtained salts.

Accordingly, the preparation of the compounds of the formula (Ia)

wherein the group OR ' _{a is} a Ether residue or an ester residue, and Y, A₂, R₁, R₂, R₃ and R₄ are as defined above, by reacting the corresponding compounds of formula (Ib) with

• a) a compound R _'a OH and a catalyst,
• b) a compound R _'a Q and a moderate base, wherein Q is a halogen atom, or
• c) a compound R₁₁NHCOCl or a functional reactive derivative thereof.

The above reaction a) is carried out in the presence of a catalyst, as concentrated sulfuric acid. The implementation is conveniently in a solvent, the also the reactant, like methanol, and at elevated temperature performed.

The above reaction b) is in the presence of a moderate Base, such as triethylamine or pyridine, and conveniently performed at room temperature or below. For the production of ether compounds, the reaction b) also under Application of a compound of formula (Ib) in the form of a silver salt be made in a conventional manner.

The above reaction c) is carried out under conditions such as they are used for the production of carbamates by implementing a optionally N-substituted carbamoyl chloride or a corresponding isocyanate with an alcohol are known. Of course, such carbamates can also on the corresponding carbonates by reaction with ammonia or obtained primary amines.

Examples of suitable ether radicals OR ' _a include hydrocarbonoxy groups such as O-C₁-C₆alkyl, O-C₂-C₆alkenyl, O-C₂-C₆alkynyl, O-benzyl, O-phenyl, O-tolyl and benzoylmethoxy.

Examples of suitable Esterreste OR _'a are acyloxy groups, such as O-COO-hydrocarbon groups, O-CO-hydrocarbon groups, and O-SO₂-hydrocarbon groups such as O-acetyl, O-mesyl, O-tosyl, O-benzoyl, O-COO- C₁-C₆alkyl (for example O-COOCH₃), O-COO-phenyl, O-CO-benzyl and O-CONHR₁₁ (for example O-CONH₂ and O-CONH-C₁-C₆-alkyl).

The compounds of formula (I) wherein Ar - A₄ is group B are prepared by chlorinating or fluorinating the compounds of formula (Ib) with a chlorinating agent or fluorinating agent.

The choice of the particular chlorinating agent or fluorinating agent depends on the respective substituents which are present on the compound of formula (Ib). To suitable Chlorinating agents include chlorine cation donors, such as Alkali metal hypochlorite (for example NaClO or KClO) or N-Cl-succinimide. To avoid chlorination of any Substituent which is present in the compound of the formula (Ib) is present, it may be appropriate to use the chlorination to carry out the compound of formula (Ib) in anion form.

Suitable fluorinating agents include fluoro cation donors such as FClO₃ or p-tosyl-N (F) CH₃. The fluorination is expediently with the compound of formula (Ib) in anion form performed.

The compounds of formula (I) are generally in the form of cis / trans mixtures, and they fall if they contain one or more chiral centers, in the form of racemic or diastereoisomeric mixtures.

Examples of preferred subgroups of compounds of Formula (I) are as follows:

• - Compound of formula (I), wherein R₁ is (A₁) _n X ', wherein X' with the exception of H corresponds to the definition of X, and A₁, n , R₂, R₃, R₄, A₂, A₃ --- A₄ and Y are as defined above [hereinafter referred to as compounds of formula (Iz)],
• Compounds of formula (I) wherein R₁ is an unsaturated aliphatic hydrocarbon group having up to 6 carbon atoms, a cycloalkyl group having up to 6 carbon atoms or a group Ar [and Ar, R₂, R₃, R₄, A₂, A₃ --- A₄ and Y are as defined above (hereinafter referred to as compounds of the formula (Iy))],
• Compounds of formula (I) wherein CR₁R₂-A₂ is C (R₂) = CR₁₇ [and R₂, R₁₇, R₁₈, R₁₉, R₃, R₄, A₃ --- A₄ and Y are as defined above (hereinafter referred to as compounds of formula (Ix))],
• Compounds of formula (I) wherein R₁ and R₂ together represent oxo or C₁-C₅ alkylidene [and A₂, A₃ --- A₄, R₃, R₄ and Y are as defined above (hereinafter referred to as compounds of formula (Iw ) designated)],
• Compounds of the formula (I) in which A₃ --- A₄ is C (X₁) -C (O) [and X₁, R₁, R₂, R₃, R₄, A₂ and Y are as defined above (hereinafter referred to as compounds of the Formula (Iv) denotes)],
• Compounds of formula (I) wherein A₂ is C (CF₃) R₁₆ or C (CF₃) R₁₆-CR₁₈R₁₉ [and R₁₆, R₁₈, R₁₉, R₁, R₂, R₃, R₄, A₃ --- A₄ and Y are as defined above are (hereinafter referred to as compounds of formula (Iu))],
• Compounds of formula (I) wherein Y is optionally substituted thienyl, pyridyl, pyrazolyl, isothiazolyl, 1,2,3-thiadiazolyl or pyrazinyl (and preferably optionally substituted thienyl, pyridyl or pyrazolyl, especially optionally substituted pyridyl or pyrazolyl all is 1-CH₃-4-NO₂-pyrazol-5-yl or 1-CH₃-4-NO₂-pyrazol-3-yl) [and R₁, R₂, R₃, R₄, A₂ and A₃ --- A₄ as defined above are (hereinafter referred to as compounds of formula (It))],
• Compounds of the formula (I) in which Y is phenyl which is substituted by R₂₁, R₂₂ and R₂₃, or an optionally substituted 5-membered or 6-membered heteroaryl group containing from 1 to 3 heteroatoms from the group O, N and S, with the exception optionally substituted pyrimidinyl, wherein said heteroaryl group is bonded via a ring carbon atom to the ring A, one of the substituents R₁, R₂, R₃ and R₄ is phenyl or substituted phenyl and the other of the substituents R₁, R₂, R₃ and R₄ is independently an unsaturated aliphatic hydrocarbon radical having up to 6 carbon atoms, a cycloalkyl group having up to 6 carbon atoms, a group Ar or a group (A₁) _n X, [wherein R₁, A₃ --- A₄, R₃ and R₄ are as defined above (hereinafter referred to as compounds of Formula (Is) denotes)],
• Compounds of the formula (I) in which CR₁-R₂-A₂ is CR₁R₂-CR₁₆R₁₇-CR₁₈R₁₉ [and R₁, R₂, R₁₆, R₁₇, R₁₈, R₁₉, R₃, R₄, A₃ --- A₄ and Y are as defined above ( hereinafter referred to as compounds of the formula (Ir))].

In the compounds of the formulas (Ir), (Iu), (Iv), (Iw), (Ix), (Iy) and (Iz), Y is preferably substituted phenyl, Pyridyl, thienyl, pyrazolyl or pyrimidinyl, more preferred substituted phenyl, pyridyl, pyrimidinyl or pyrazolyl,  most preferably substituted phenyl, pyridyl or pyrazolyl, and in particular substituted phenyl, 1-CH₃-4-NO₂- Pyrazol-5-yl or 1-CH₃-4-NO₂-pyrazol-3-yl.

In the compounds of the formula (Is), Y is preferably Phenyl substituted by R₂₁, R₂₂ and R₂₃ substituted Pyridyl, thienyl or pyrazolyl, more preferably substituted Phenyl, pyridyl or pyrazolyl, and particularly preferred substituted phenyl, 1-CH₃-4-NO₂-pyrazol-5-yl or 1-CH₃-4-NO₂-pyrazol-3-yl.

If in the compounds of the formula (Is) the substituent R₁ is phenyl or substituted phenyl, then any group (A₁) _n X is preferably H or C₁-C₄-alkyl.

Mean one or more of the substituents R₁, R₂, R₃ and R₄ is an unsaturated aliphatic hydrocarbon group with up to 6 carbon atoms, then this group contains expediently a double bond or a triple bond.

Mean one or more of the substituents R₁, R₂, R₃ and R₄ is an unsaturated aliphatic hydrocarbon group with up to 6 carbon atoms, this group preferably contains up to 4 carbon atoms, and examples of preferred Groups of this type are vinyl, allyl and propargyl.

Is any of the substituents R₁, R₂, R₃ and R₄ one Cycloalkyl group, then these are preferably to cyclopropyl.

If one of the substituents R₁, R₂, R₃ and R₄ is substituted Phenyl, then this phenyl contains expediently one, two or three substituents selected from C₁-C₄- Alkyl, C₁-C₄ alkoxy, halogen and CF₃ and is preferably  monosubstituted or disubstituted, in particular monosubstituted, wherein the substituent is especially halogen.

Is any of the substituents R₁, R₂, R₃, R₄, R₆, R₇, R₈, R₁₂ and R₁₅ for a heteroaryl group, then this is Group suitably selected from thienyl, Furyl, Pyrrolyl, isoxazolyl, isothiazolyl, pyrazolyl, 1,2,3-thiadiazolyl, Pyridyl, pyrimidinyl, pyrazinyl and pyridazinyl, these groups may be unsubstituted or substituted.

Examples of suitable substituents on such heteroaryl groups or groups Ar '(if Ar' is a substituted heteroaryl group ) are halogen (for example F, Cl or Br), C₁-C₄-alkyl which is unsubstituted or substituted by halogen is (for example F, Cl or Br), phenyl, S-C₁-C₄- Alkyl or C₁-C₄ alkoxy, NO₂, CN, C₁-C₄ alkoxy, formyl or C₂-C₄ alkanoyl and functional derivatives, such as oximes, acetals and ketals thereof (for example C (= NOC₁-C₄-alkyl) -C₁-C₃- alkyl, C (O-C₁-C₄-alkyl) ₂-C₁-C₃-alkyl, CH (O-C₁-C₄-alkyl) ₂ and the like), C₁-C₄-alkyl-S, C₁-C₄-alkyl-SO, C₁-C₄-alkyl-SO₂ and C₁-C₅ alkoxycarbonyl.

If any of the substituents R₁, R₂, R₃, R₄, R₆, R₇, R₈, R₁₂ and R₁₅ a heteroaryl group, then this is preferably Thienyl or furyl, which is unsubstituted or by Halogen, NO₂, C₁-C₄-alkyl, C₁-C₄-alkoxy or C₁-C₄-alkylthio is monosubstituted, and is preferably unsubstituted.

If any of the substituents R₁, R₂, R₃ and R₄ is optionally substituted phenyl, then this substituent preferably unsubstituted.

R₁ forms together with R₂ a C₁-C₅-alkylidene group, then contains  this group preferably 1 to 6 carbon atoms and in particular 1 or 2 carbon atoms.

Preferably, not more than one of the radicals R₁, R₂, R₃ and R₄ is a heteroaryl group or an optionally substituted phenyl group, wherein the ring A in particular is not substituted by more than one group selected is from aromatic hydrocarbon groups, araliphatic Hydrocarbon groups or heteroaryl groups.

If one or more or substituents R₆, R₇, R₈, R₁₁, R₁₂, R₁₅, R₁₆, R₁₇, R₁₈, R₁₉ and R₂₀ represent a hydrocarbon group, then, such a hydrocarbon group be aliphatic, aromatic or araliphatic and contains suitably up to 8 carbon atoms. Is it? it contains an aliphatic hydrocarbon group, then these preferably up to 5 carbon atoms and can be saturated or unsaturated. Is this one? unsaturated aliphatic hydrocarbon group, then containing this expediently a double bond or a Triple bond. If such a hydrocarbon group is aromatic or araliphatic, then it can be aromatic Ring may be substituted by one or more substituents, these substituents are suitably selected from halogen, C₁-C₄-alkoxy, C₁-C₄-alkyl and CF₃.

Is any of the substituents R₆ and R₇ is haloalkyl, then this is, for example, chloroalkyl, which preferably contains 1 to 4 carbon atoms.

Is one or more of the substituents R₉, R₁₀, R₁₃ and R₁₄ for C₁-C₆-alkyl, this is preferably to C₁-C₄alkyl, such as CH₃.  

If any of the substituents R₆ to R₂₀ is aryl, then this is preferably phenyl, which is unsubstituted is or has 1 to 3 substituents selected are halogen, C₁-C₄-alkoxy, C₁-C₄-Alykl and CF₃, in particular less than 3 substituents are present.

If any of the substituents R₆, R₇, R₈, R₁₁, R₁₂, R₁₅ to R₂₀ an araliphatic hydrocarbon group, this is preferably benzyl or α- methylbenzyl, which is unsubstituted or in the phenyl ring 1 to 3 substituents, preferably 1 or 2 substituents , which are selected from halogen, C₁-C₄-alkoxy, C₁-C₄-alkyl and CF₃.

If Ar 'is a substituted heteroaryl group, then this heteroaryl group carry 1 to 3 substituents selected are halogen, CF₃, NO₂, C₁-C₄-alkyl, C₁-C₄- Alkoxy (where two adjacent substituents together methylenedioxy can form), C₁-C₄-alkyl-S, C₁-C₄-alkyl-S-C₁-C₄- alkyl, C₁-C₄-alkyl-SO₂ and benzyl. The alkyl radicals in such Substituents preferably contain 1 or 2 carbon atoms and in particular only 1 carbon atom.

The group Ar 'is preferably a substituted heteroaryl group.

Preferred meanings for Ar 'include substituted Thienyl, pyrazolyl, isothiazolyl, 1,2,3-thiadiazolyl, pyridyl, Pyrazinyl and pyrimidinyl, more preferably substituted thienyl, Pyrazolyl, pyrimidinyl and pyridyl, and especially substituted ones Pyrazolyl, pyrimidinyl and pyridyl.

Preferably, a substituent of the group Ar 'is in o-position to the group CO, to which the group Ar 'bound  is, and / or is methylenedioxy, wherein also further substituents (1 or 2 substituents) may be present.

Suitable examples of methylenedioxy-substituted aryl groups Ar 'are 5,6-methylenedioxy-3-pyridyl, 4,5-methylenedioxy-3 pyridyl and 4,5-methylenedioxypyrimidinyl.

Preferred examples of ortho substituents of Ar 'are (besides Methylendioxy) NO₂, halogen, CN, DF₃, CH₃-SO₂ and CH₃SCH₂.

Preferred examples of other substituents are halogen and C₁-C₄ alkyl, if these substituents on a ring carbon atom and C₁-C₄alkyl, benzyl and C₁-C₄- Alkylthio-C₁-C₄-alkyl, if these substituents on a ring nitrogen atom are bound.

Particularly preferred meanings for the group Ar 'include 1-CH₃-4-NO₂-pyrazol-5-yl and 1-CH₃-4-NO₂-pyrazol-3-yl.

If Ar 'is substituted pyridyl, then this is preferred 3,5-dichloro-2-pyridyl.

A₁ is methylene or ethylene which is represented by a or a plurality of C₁-C₅-alkyl groups is substituted, then included these alkyl substituents preferably up to 4 carbon atoms and are especially methyl.

If R₂₁ is C₁-C₆-alkoxy or C₁-C₆-alkylthio, then containing these radicals suitably 1 to 4 carbon atoms, and preferably only 1 carbon atom.

Are one or more of the substituents R₂₁, R₂₂ and R₂₃ for C₁-C₆-alkylsulfonyl, then this group contains expediently 1 to 4 carbon atoms and preferably only 1 carbon atom.  

If the substituent R₂₂ is in the para position, then the substituent R₂₃ preferably in the ortho position to the carbonyl group arranged.

The substituent R₂₂ is preferably H, halogen (F, Cl, Br), C₁-C₄-alkyl-S, C₁-C₄-alkyl-SO₂ or together with the substituent R₂₁ is a methylenedioxy group. The substituent R₂₁ is preferably H, halogen or CH₃.

The substituent R₂₃ is preferably halogen (such as Cl), CF₃, NO₂, CN or CH₃-SO₂.

Examples of preferred groups CR₁R₂-A₂ are CR₁R₂, C₁R₂-CH₂, CR₁R₂-CH (CH₃), CR₁R₂-C (CH₃) ₂, CR₁R₂-CO, CR₁R₂-O, CR₁R₂-CHCF₃, CR₁R₂-CH₂-CH₂, CR₁R₂-CH (CH₃) -CH (CH₃) and C (R₂) = CH.

The substituent R₁ is preferably vinyl, allyl, propargyl, cyclopropyl, optionally substituted phenyl, furyl or thienyl, CH₂OH, CH (OH) CH₃, CH₂CH₂OH, the group (A₁) _n X ', wherein A₁ and n are as defined above and X is 'With the exception of H also as defined above, or R₁ together with R₂ is oxo, CH₂ or CH-CH₃ or together with R₁₆ for a bond. Further, R₁ is preferably C₁-C₄ alkyl, more preferably CH₃ or C₂H₅, and especially CH₃, if Y is other than optionally substituted phenyl or pyrimidinyl.

If R₁ is (A₁) X ', then A₁ is preferably CH₂ or (CH₂) ₂, optionally substituted by one or two groups CH₃ is substituted.

A₁ is methylene or ethylene which is replaced by one or two C₁-C₅ alkyl groups is substituted, then contain these Alkyl substituents preferably up to 4 carbon atoms, wherein Methyl is preferred.  

Examples of preferred groups X 'are C₁-C₄-alkylthio, Phenylthio, C₁-C₄-alkoxy, phenoxy, CHO, C₂-C₅-alkanoyl, OH and esters thereof with aliphatic carboxylic acids having 2 to 5 carbon atoms or optionally substituted Benzoic acid, C₂-C₅-carbalkoxy-CH₂, C₂-C₅-carbalkoxy-CH (CH₃), Cyano, F, Cl, CHF₂, CF₃, NO₂, CONH₂, CO-NH (C₁-C₄-alkyl), di- (C₁-C₄-alkyl) N or benzyl, and in particular C₁-C₄-alkylthio.

The group (A₁) _n X 'is preferably C₁-C₄-alkylthio.

Examples of preferred groups R₂, R₃ and R₄ are H, C₁-C₄alkyl, C₁-C₄alkoxy, C₁-C₄alkylthio, OH, C₁-C₄alkyl CO-O, C₂-C₅-carbalkoxy, thienyl and furyl, in particular H, CH₃, OCH₃, SCH₃, OH, CH₃CO-O and COOCH₃, and especially H or CH₃.

The substituent A₂ is preferably CR₁₆R₁₇ or O.

Examples of preferred meanings of the substituent R₁₆ are H, C₁-C₄-alkyl, optionally substituted phenyl or Benzyl, thienyl, furyl, COOH (in acid form, salt form or Ester form) and, as indicated above, together with R₁ a bond, especially H and CH₃, and especially H.

Examples of preferred meanings of R₁₇ are H, C₁-C₄- Alkyl, C₁-C₄-alkoxy, C₁-C₄-alkylthio, C₁-C₄-alkylthio-C₁-C₄- alkyl and CF₃, in particular H, SCH₃, CH₃ and CF₃, and before all H or CF₃:

The substituents R₁₈ and R₁₉ are preferably independently H or C₁-C₄-alkyl, in particular H or CH₃.

Particularly preferred compounds of the formula (I) have one or more of the following characteristics:

R₁ is H, CH₃, SCH₃, S (O) CH₃, SO₂CH₃, phenyl or phenyl which monosubstituted by C₁-C₄alkyl, C₁-C₄alkoxy, halogen or CF₃ is or alkenyl or alkynyl of up to 4 carbon atoms.

The substituents R₂, R₃ and R₄ are independently H or CH₃, where one of the substituents R₂, R₃ and R₄ also SCH₃, S (O) CH₃ or SO₂CH₃ can be, if only one of the substituents R₁ until R₄ is SCH₃, S (O) CH₃ or SO₂CH₃.

The substituent A₂ is CH (CF₃), CH₂ or O.

The substituent Y is 3,5-dichloro-2-pyridyl, 1-CH₃-4-NO₂-pyrazole 5-yl, 1-CH₃-4-NO₂-pyrazol-3-yl or phenyl which is replaced by R₂₁, R₂₂ and R₂₃ is substituted, these phenyl substituents the have preferred meanings given above.

Examples of such particularly preferred compounds of Formula (I) includes the following:

Compounds of formula (I) wherein R₁ is SCH₃, S (O) CH₃ or SO₂CH₃, R₂, R₃ and R₄ are independently H or CH₃, A₂ is CH₂, O or CH (CF₃), and Y is 3,5- Dichloro-2-pyridyl, 1-CH₃-4-NO₂-pyrazol-5-yl, 1-CH₃-4-NO₂-pyrazol-3-yl or phenyl which is substituted by R₂₁, R₂₂ and R₂₃.
Compounds of formula (I) wherein R₁ is SCH₃, S (O) CH₃ or SO₂CH₃, R₂, R₃ and R₄ are independently H or CH₃, A₂ is CH (CF₃) or O, and Y is phenyl represented by R₂₁ , R₂₂ and R₂₃ is substituted.
Compounds of formula (I) wherein R₁ is alkenyl or alkynyl of up to 4 carbon atoms, R₂, R₃ and R₄ are independently H, CH₃, SCH₃; S (O) CH₃ or SO₂CH₃ are, if only one of the substituents R₂ to R₄ from the group SCH₃, S (O) CH₃ and SO₂CH₃ is selected, A₂ is CH₂, O or CH (CF₃), and Y 3,5- Dichloro-2-pyridyl, 1-CH₃-4-NO₂-pyrazol-5-yl, 1-CH₃-4-NO₂-pyrazol-3-yl or phenyl which is substituted by R₂₁, R₂₂ and R₂₃.
Compounds of formula (I) wherein R₁ is phenyl or phenyl monosubstituted by C₁-C₄ alkyl, C₁-C₄ alkoxy, halogen or CF₃, R₂, R₃ and R₄ are independently H or CH₃, A₂ is CH (CF₃), CH₂ or O, and Y is 3,5-dichloro-2-pyridyl, 1-CH₃-4-NO₂-pyrazol-5-yl, 1-CH₃-4-NO₂-pyrazol-3-yl or phenyl represented by R₂₁ , R₂₂ and R₂₃ is substituted, wherein Y is in particular phenyl, which is substituted by R₂₁, R₂₂ and R₂₃.

The compounds of the formula (II), which are used as starting material be needed, can be produced in a conventional manner.

A series of compounds of the formula (IIa) which are also known in their tautomeric form of formula (IIb) may occur

wherein n , A₁, A₂, X, R₂, R₃ and R₄ are as defined above, can be conveniently obtained by gamma substitution of dianions of β- dicarbonyl compounds of the formula (V)

wherein A₂, R₂, R₃ and R₄ are as defined above, using electrophilic agents suitable for the introduction of a group (A₁) _n X.

Electrophilic agents which are suitable for the introduction of a group (A₁) _n X by gamma substitution of dianions of the β- dicarbonyl compounds of the formula (V) are known from the literature. Their type depends on the meaning of (A₁) _n X.

The following electrophilic agents are suitable for example a gamma substitution

• By Cl: Cl₃-CCl₃ or N-Cl-succinimide,
• By Br: Br₂,
• By S-hydrocarbyl: disulfides, such as alkyl-S-S-alkyl and Phenyl-S-S-phenyl,
• - by SH: sulfur,
• By OH: O₂,
• - by COOH: carbon dioxide,
• - by C (OH) RR '(for example C (OH) (phenyl) ₂): aldehydes or ketones (such as (phenyl) ₂CO) by carbonyl addition,
• - by NO₂: isopentyl nitrate,
• By aliphatic or araliphatic hydrocarbyl: the corresponding hydrocarbon halides.

If desired, the functional groups introduced in this way can be added in a conventional manner into other functional groups be transferred.  

The compounds of formula (II) wherein R₁ and R₁₆ together can form a bond by dehydrohalogenation of the corresponding halogen compounds are obtained. The thus obtained Compounds of formula (II) may also contain addition reactions with, for example, methanol, acetic acid and the like be subjected to, resulting in saturated compounds of the formula (II) obtained, for example, by methoxy, Acetoxy and the like are substituted.

A number of compounds of formula (V) can also be by cyclization using the Dieckmann condensation reaction produce:

Examples of reaction schemes involving the preparation of Compounds of formula (VI) will be apparent from the following Outline.  

The compounds of formula (II) wherein R₁ is vinyl may for example, from the corresponding compounds of the formula (I) wherein R₁ is CH₂CH₂OH by dehydration, conveniently about the tosylate, to be obtained.

Such vinyl compounds may also be in the corresponding Cyclopropyl compounds are transferred, for example according to the method of Simmon / Smith using Zn / CH₂I₂.

The compounds of formula (II) wherein R₁ and R₂ together are CH₂ can, by implementing the appropriate connection of the Formula (II) wherein R₁ and R₂ are H, in the form of dianion with ClCH₂SCH₃, S-oxidation of the compounds obtained Formula (II) wherein R₁ is CH₂SCH₃, and conversion of these Group CH₂S (O) CH₃ be obtained to the group CH₂.

The compounds of formula (II) wherein R₁ and R₂ together C₂-C₅-alkylidene can, by reaction of the corresponding A compound of formula (II) wherein R₁ and R₂ are H, in the form of dianion with an aliphatic C₂-C₅-aldehyde or C₃-C₅-ketone and by subsequent dehydration of the so produced alcohol are produced.

The choice of the most suitable reaction route and the most favorable Sequence of the reaction stages used to prepare the Of course, compounds of formula (II) are required largely on the desired combination of substituents from. However, such a selection is within the usual expert knowledge.

Unless the preparation of the starting materials is described has been known, the respective compounds are known or in the case of new compounds, preparable using methods, to the methods described herein or to Other known methods are analog.  

The compounds of formula (I) show in the form of their free Acids or in the form of their ethers, esters or agricultural acceptable salts with an interesting herbicidal activity wide range. They offer valuable alternatives to known ones Dionherbicides, for example, as they have a have interesting safety against crops and / or well received by the environment (for example as a result of optimal mobility in the soil).

The invention accordingly also relates to a method for Weed control, which is that of the individual Weed site with a herbicidally effective amount of a compound of the formula (I) in free acid form or in the form of a agriculturally acceptable salt is treated.

The pre-emergence efficacy and post-emergence efficacy may be shown by tests in the greenhouse with drug doses, which application rates of 0.33, 1.0 and 3 kg / ha correspond. The amount of each applicable compound of formula (I) depends on the respective weeds to be controlled, the each used compound, the way of applying this Compound, the condition to be treated and the like. The in each case suitable application amount can be determined by the person skilled in the art usual methods or by comparing the effectiveness of the desired Determine compound of formula (I) with standards for which the application amount is known, for example through experiments in the greenhouse. To satisfactory results In general, this is achieved by using a compound of formula (I) in an amount in the range of about 0.03 up to 3.0 kg / ha on the respective location of the plants. Various Compounds of formula (I) show within this Area an interesting selective herbicidal activity. The Compound 2.82 (later on Table A) has one excellent selectivity with soybeans and gives a very good control of broadleaf weeds, in particular  in a post-emergence application in an application set from about 1 to 2 kg / ha.

The compounds of the formula (I) can and are preferably as herbicidal compositions in combination with agricultural acceptable diluents. suitable Formulations contain 0.01 to 99% by weight of active ingredient, 0 to 20% by weight of a surfactant and 1 to 99 weight percent of a solid or liquid Diluent. Higher ratios of surface-active Agents to drug are sometimes desirable, and these can be prepared by incorporation into the formulation or by Achieve tank mixing. Corresponding forms of application A composition generally contains from 0.01 to 25 Weight percent active ingredient. Of course, it can also lower or higher levels of drug, depending on the intended application, the physical properties the particular connection and the type of application. concentrated Forms of a composition before its application to be diluted, contain 2 to 90 percent by weight and preferably 10 to 80 percent by weight of active ingredient.

Suitable formulations of the compounds of the formula (I) include dusts, granules, suspension concentrates, wettable Powder, emulsifiable concentrates, flowable preparations and the same. Such formulations can be in common Form way, for example by mixing a compound of the formula (I) with the respective diluent and if necessary with other additives.

Optionally, the compounds of formula (I) may also be used in microencapsulated form.

In the herbicidal compositions can also agricultural acceptable additives may be present, for example, the  Improve the performance of the active ingredient and a foaming, a Caking and reducing corrosion.

As used herein, surfactant is any agriculturally acceptable material intended for Emulsification, spreading, wetting, dispersing or to contributes to other surface-modifying properties. Examples of surfactants are sodium lignosulfonate and sodium lauryl sulfate.

A diluent herein is a liquid or solid agriculturally acceptable material understood that for diluting a concentrated material to a usable one or desirable strength is used. For dusts or granules may, for example, talc, kaolin or Diatomaceous earth can be used while opting for liquid concentrate forms for example, a hydrocarbon such as xylene, or an alcohol such as isopropanol, and for liquid forms of use For example, water or diesel oil in question come.

The compositions of the invention may also be other Contain compounds having biological activity, for example Compounds with similar or complementary herbicidal Efficacy or compounds with antidotischer, fungizider or insecticidal activity.

The invention will be further illustrated by the following examples. The temperature data contained therein are in ° C. The abbreviation RT is room temperature. All parts and percentages are by weight.

Herbicidal compositions example A Wettable powder

25 parts of a compound of formula (I), for example the Connection of Example 1 below will be so long with 25 parts of synthetic fine silica, 2 parts Sodium lauryl sulfate, 3 parts sodium lignosulfonate and 45 Mix finely divided kaolin and grind until the average particle size is about 5 μ.

example B emulsion concentrate

25 parts of a compound of formula (I), for example the Compound of Example 1 below, 50 parts of xylene, 15 parts of dimethylformamide and 10 parts of an emulsifier are thoroughly mixed until homogeneous Solution is obtained.

Herbicidal screening Experimental Example 1 Pre-emergence treatment

Sow pots are filled with a substrate that is sandy Clay corresponds. In each pot are seeds of abutilon theophrasti (hereinafter abbreviated as At), Amaranthus retroflexus (Ar), Sinapis alba (Sa), Solanum nigrum (Sn), Bromus tectorum (Bt), Setaria viridis (Sv), Avena fatua (AF) and Echinochloa crus-galli (Ec) are sown.

The substance to be tested of the formula (I) is then added in an amount which corresponds to 0.25, 1 and / or 4 kg of active ingredient per ha,  and with an application volume that corresponds to 1000 liters per ha, applied (whereby a spray with an aqueous Experimental liquid is carried out, which, for example, according to example B is formulated). After the treatment, the seeds covered with a thin layer (about 0.5 cm) of substrate. The pots are then left for 21 days at room temperature (20 to 24 ° C) under an exposure of 14 to 17 hours per day (daylight or similar light).

After the 21-day test period, the herbicidal action certainly. This provision includes a visual assessment the extent and quality of the damage to the various Seedlings.

The herbicidal activity is determined.

Experimental Example 2 postemergence treatment

It is a similar to Experimental Example 1 method with the Exception follows that the compounds to be tested are first applied when the plants are 2-4 petalled State have reached. The other experimental conditions (Application amount, application volume, temperature, exposure) and the assessment procedure (21 days after application) are the same as in Experimental Example 1.

The herbicidal activity is determined.

Experimental Example 3

There are similar experiments as in Experimental Examples 1 and 2, for which various compounds of the formula (I) and selected by means of various monocotyledonous and dicotyledonous weeds which are selected  are from the broad-leaved weeds Abutilon theophrasti, Capsella bursa pastoris, Cassia obtusifolia, Chenopodium album, Datura stramonium, Galium aparine, Ipomoea purpurea, Polygonum pensylvanicum, Portulaca oleracea, Senecio vulgaris, Sida spinosa, Solanum nigrum, Stellaria media and Xanthium strumarium, the grass weeds Agropyron repens, Cyperus rotundus, Alopecurus myosuroides, Apera spica-venti, Avena fatua, Brachiaria plantaginea, Bromus tectorum, Digitaria sanguinalis, Echinochloa crus-galli, Panicum dichotomiflorum, Poa annua, Setaria faberi and Sorghum halepense, as well as crops, like the broadleaf crops cotton, Soybean, sugar beet and sunflower and grassy crops Rice, corn (Zea mays) and Milo (Sorghum bicolor), with different Concentrations of the fluids to be examined applied and wherein these concentrations are selected be that the desired application rates result (viz in general application rates of 0.11, 0.33 and 1.0 kg on compound of the formula (I) per ha). The application volumes each correspond to 600 l / ha.

The assessment is made 28 days after the application. The herbicidal activity is in the scope observed from 30 to 1000 g / ha.

A particularly interesting herbicidal activity can be For example, in the following groups of compounds Watch formula (I):

Compounds of formula (Ib) wherein A₂ is CH₂, R₁ is phenyl or substituted phenyl (preferably phenyl, 2-F-phenyl or 4-F-phenyl), R₂ to R₄ are independently H or CH₃ and Y is phenyl, is substituted by radicals R₂₁, R₂₂ and R₂₃, and examples thereof are the compounds 2.82, 2.88 and 2.89 mentioned later.
Compounds of formula (Ib) wherein A₂ is CH (CF₃) and R₁ to R₄ are independently H or CH₃, for example compounds of formula (Ib) wherein A₂ is CH (CF₃), R₁ to R₄ are each H or CH₃ and Y represents phenyl substituted by R₂₁, R₂₂ and R₂₃, and examples thereof are the later-mentioned compounds having the relations 2-177, 2-192, 2-195 and 2-248.
Compounds of the formula (Ib) in which Y is substituted pyrazolyl (in particular 1-CH₃-4-NO₂-pyrazol-5-yl or 1-CH₃-4-NO₂-pyrazol-3-yl) and A₂ is CH₂ or O, and these include compounds wherein R₁ to R₄ are independently H or CH₃, and esters or salts thereof, and these include those later referred to as 2-165, 2-167, 2-169, 2-172, 2-173, 2 -174, 8-21, 9-1 and 9-2.
Compounds of formula (Ib), wherein A₃ --- A₄ is C (Cl) = C (O) and A₂ is CH₂, and these include compounds wherein Y is phenyl which is substituted by radicals R₂₁, R₂₂ and R₂₃ , and in which R₁ to R₄ are independently H or CH₃, and examples thereof are given later under the designations 10.1 and 10.2 compounds.
Compounds of formula (If) in which A₂ is CH, and include compounds wherein Y is phenyl substituted by R₂₁, R₂₂ and R₂₃, and wherein R₂ to R₄ are independently H or CH₃, and an example of one such compound is the compound later named 2-156.

Test Results 1

The experimental data presented in the following Table I show the herbicidal activity of a selection of compounds of the formula (I), which according to the experimental examples given above  1 and 2 at an application rate of each 1 kg / ha have been tested.

The evaluation of the herbicidal activity takes place after a from 1 to 10 reaching rating scale, with the rating number 1 a herbicidal efficacy of 0 to 10 percent and the rating number 10 for a herbicidal activity from 90 to 100 percent.

Table I

Test results 2

The experimental data given in the following Table II show the herbicidal activity of a solution of compounds of the formula (I) obtained by using the above experimental example 3 at the application rates listed in this table and treatment times (pre-emergence or postemergence) have been. The assessment is the same as in the table I a rating scale ranging from 1 to 10.

Table II uses the following abbreviations:

Abutilon theophrasti ABUTH Capsella bursa pastoris CAPBP Cassia obtusiflolia CASOB Chenopodium album CHEAL Datura stramonium DATST Galium aparine GALAP Ipomoea purpurea IPOMO Polygonium pensylvanicum POLPY Portulaca oleracea POROL Senecia vulgaris SENVU Sida spinosa SIDSP Solanum nigrum SOLNI Stellaria media STEMS Xanthium strumarium XANSP cotton Cotton. Soybean Sojab. sugar beet Sugar beet. sunflower Sunflower Floral. preemergence pre postemergence po Agropyron repens AGRRE Cyperus rotundus Cypro Alopecurus myosuroides ALOMY Apera spica-venti AGSSV Avena fatua AVEFA Brachiaria plantaginea BRAPL Bromus tectorum BREADS Digitaris sanguinalis DIGSA Echinochloa crus-galli ECHCG Panicum dichotomiflorum PANDI Poa annua POAAN Setaria faberi SETFA Sorghum halepense SORHA Echinochloa crus-galli wet ECHwet

Table II

Terminations Example 1 2 - [(4-chloro-2-nitro) benzoyl] -4,4,6-trimethyl-6-methylthio-1,3-CYCLOHEPTA-exandion

Dissolve 8.07 g (0.021 mol) of 3 - [(4-chloro-2-nitro) benzoyloxy] - 4,4,6-trimethyl-6-methylthio-2-cyclohexene-1-one in a warm Mixture (45 °) of 3.5 ml (0.025 mol) triethylamine, 0.4 ml Acetone cyanohydrin and 60 ml of dry acetonitrile. After 3 hours long stirring at room temperature, the reaction solution diluted with 200 ml of diethyl ether, in succession with 35 ml of 10% HCl and 150 ml of water and then over anhydrous Na₂SO₄ dried.  

The remaining after rotary evaporation of the solvent Residue is subjected to column chromatography over silica gel subjected. By elution with a 1: 1 mixture of hexane and diethyl ether gives the analytically pure title compound with a melting point of 111 to 112 ° C.

example 2

Analogous to the procedure of Example 1, the following compounds of the formula (I) (in the form of the free acid) by rearrangement the corresponding compounds (IV) prepared: Tables A, B, C and D.

Table A

(Compounds of the formula Ic)

Table B

(Compounds of formula Id)

Table C

(Compounds of the formula Ie)

Table D

(Cyclohexenedione derivatives of the formula If)

example 3 2- (2-nitrobenzoyl) -4-phenoxy-1,3-cyclohexanedione

A mixture of 4.1 g (0.02 mole) of 4-phenoxy-1,3-cyclohexanedione, 3.7 g (0.02 mol) of 2-nitrobenzoyl chloride, 2.0 g (0.02 mol) of triethylamine and 60 ml of toluene is refluxed for 1 hour touched. Then the mixture is cooled and with 200 ml Ether added. The precipitated triethylamine hydrochloride is filtered off with suction and washed with ether. The filtrate becomes the With 10 ml of 2N hydrochloric acid, 20 ml of water, Washed 10 ml of 2 N sodium hydroxide and 50 ml of water. The organic Layer is dried over MgSO₄. By evaporation of the ether under vacuum at 30 ° C results in a toluene solution of the intermediate which was used for rearrangement with 1 g (0.012 mol) Acetone cyanohydrin and 2 g (0.02 mol) triethylamine under 3 hours Stirring is added at room temperature.

The reaction mixture is dissolved in 200 ml of ether, and the solution is in turn mixed with 15 ml of 2N hydrochloric acid, 20 ml of water, 20 ml of 2N sodium hydroxide and 50 ml of water. The last two aqueous extracts are combined, washed with ether and then with 30 ml of 2N hydrochloric acid acidified with stirring. After 30 minutes, the precipitation filtered off with suction and washed with methanol, whereby one 2.8 g of a white powder having a melting point of 109 to 115 ° C receives. By recrystallization from ethanol arise 1.7 g of crystals of the title compound, which at 115 to 116 ° C. melt.

example 4

Analogous to the method of Example 3 are also in the starting from the above tables A, B, C and D. of the corresponding compounds of the formulas (II)  and (III) without isolation of the esters of formula (IV).

example 5 2- (2,4-dichlorobenzoyl) -3-methoxy-4-allyl-4,6,6-trimethyl-2-cyclo-hex n-1-one

Dissolve 3.67 g (0.01 mol) of 2 - [(2,4-dichloro) benzoyl] -4-allyl 4,6,6-trimethyl-1,3-cyclohexanedione in 10 ml of 0.1 N NaOH and treated the resulting solution of Na salt then with 1.7 g (0.01 mol) of AgNO₃ in 10 ml of water.

The precipitate of the formed Ag salt is mixed with 10 ml of water diluted, filtered off by suction and in a vacuum dried over P₂O₅. The resulting dry Ag salt is suspended in 100 ml of dry diethyl ether and with 1 ml (0.016 mol) of methyl iodide.

The reaction mixture obtained after 3 hours of refluxing is allowed to cool to ambient temperature and filtered.

The crude obtained by rotary evaporation of the filtrate Title compound in the form of a pale yellow viscous oil is chromatographically over a silica gel filled Column (eluting with a 1: 5 mixture of diethyl ether and hexane).

example 6 2 - [(2-chloro-4-methylsulfonyl) benzoyl] -3-acetoxy-4-methylthio-4,6,6-t rimethyl-2-cyclohexen-1-one

A solution of 4.87 g (0.0117 mol) of 2 - [(2-chloro-4-methylsulfonyl) benzoyl] - 4-methylthio-4,6,6-trimethyl-1,3-cyclohexanedione is added with thorough stirring at once with 0.35 g  (0.0117 moles) sodium hydride (80 percent dispersion in mineral oil) added.

After stopping the exothermic reaction (42 °), the resulting Solution of the Na salt for another hour at room temperature and then treated with 0.93 ml (0.013 mol) of acetyl chloride. After a reaction time of 18 hours at room temperature 300 ml of water are added. The precipitation of the pale yellow enol acetate formed is filtered off by suction, washed with water, thoroughly freed of water and then dried at 60 ° C.

The crude title ester obtained is chromatographed over silica gel filled column chromatographed. By elution with a 4: 1 mixture of diethyl ether and hexane gives the analytically pure title compound, which is at 126 to 128 ° C melts (Rf = 0.4 on silica gel with diethyl ether).

example 7

Analogously to the procedure of example 5, the following compounds of the formula (Ia) are prepared using the corresponding starting materials of the formula (Ib) and a compound R _a 'I:

Table E

(Compounds of the formula Ia)

example 8

Analogous to the procedure of Example 6 using the corresponding starting materials of formula (Ib) and an acyl halide R _'a Cl, the following compounds of formula (Ia) were prepared: Table F.

Table F

(Compounds of the formula Ia)

example 9 Preparation of an ammonium salt of 2 - [(2-nitro-4-chloro) benzoyl] -4-methylthio-4-methyl-1,3-cyclo hexanedione

A solution of 0.96 g (0.0056 mol) of 1- (methylaminomethyl) - naphthalene in 10 ml of methylene chloride becomes a suspension of 2.0 g (0.0056 mol) of 2 - [(2-nitro-4-chloro) benzoyl] -4-methyl thio-4-methyl-1,3-cyclohexanedione in 30 ml of methylene chloride. After 1 hour, the solvent is evaporated and the solid residue dried under reduced pressure at 40 ° C, which gives 2.95 g of the salt in the form of yellow crystals obtained a melting point of 75 to 80 ° C.

The following are analogous to the procedure of Example 9 Made connections:

• 9.1 - the triethylammonium salt of 2- (1-methyl-4-NO₂-pyrazole 5-oyl) -1,3-cyclohexanedione having a melting point of 87 to 99 ° C,
• 9.2 - the triethylammonium salt of 2- (1-methyl-4-NO₂-pyrazole- 5-oyl) -4,4,6,6-tetramethyl-1,3-cyclohexanedione with a Melting point of 144 to 145 ° C.

example 10 2-chloro-2 - [(2-nitro-4-chloro) benzoyl] -5,5-dimethyl-1,3-cyclohexanedione

A mixture of 3.25 g (0.01 mol) of 2 - [(2-nitro-4-chloro) benzoyl] - 5,5-dimethyl-1,3-cyclohexanedione and 1.3 g (0.01 mol) of N-chlorosuccinimide in 40 ml of methylene chloride is refluxed for 2 days held. Then the solvent is evaporated. The residue is treated with diethyl ether, and the undissolved Material is filtered off (0.5 g crystals of succinimide with a melting point of 123 to 125 ° C). The filtrate  is evaporated in a rotary evaporator, and the resulting Product is filled with a silica gel Chromatographed column, which with an 8: 2 mixture of Cyclohexane and ethyl acetate is eluted. The resulting obtained yellow crystals of the title compound melt at 135 up to 138 ° C.

Analogous to the procedure of Example 10 are used the desired 2-aroyl-1,3-cyclodione and N-chlorosuccinimide the following compounds are made:

• 10.1 - 2-Chloro-2- (4-chloro-2-nitrobenzoyl) -4,4,6-trimethyl-1,3- cyclohexanedione having a melting point of 77 to 78 °,
• 10.2 - 2-Chloro-2- (4-chloro-2-nitrobenzoyl) -4,4,6,6-tetramethyl- 1,3-cyclohexanedione having a melting point of 87 to 99 °.

example 11 2- (4-chloro-2-nitrobenzoyl) -1,3-cycloheptanedione

A solution of 5.95 g of cycloheptane-1,3-dione (0.472 mol) in 50 ml of CH₂Cl₂ is at once with 9.51 g of 4-chloro-2-nitrobenzoic acid (0.472 mol), followed by dropwise 6.21 g of triethylamine (1.3 equivalents) are added. The reaction mixture is stirred for 2 hours at room temperature, diluted with CH₂Cl₂ and washed with water (30 ml). By evaporation you get the nearly pure enol ester of 3- (4-chloro-2-nitrobenzoyloxy) - 2-cyclohepten-1-one.

Dissolve 14.62 g of this enol ester (0.0472 mol) in 50 ml of acetonitrile and the solution is mixed at once with 9.55 g of triethylamine.

The reaction mixture is syringed with 1.5 ml of acetone cyanohydrin and then stirred overnight at room temperature. The acetonitrile is removed under vacuum, and the  Residue is dissolved in diethyl ether. The solution is mixed with 2 n HCl, separated, dried over MgSO₄ and to a Residue evaporated, by its chromatographic purification the title compound with a melting point of 112 ° C. receives.

example 12 2 - [(2-nitro-4-chloro) benzoyl] -4-chloromethylthio-4-methyl-1,3-cyclohex-Andion

A mixture of 3.6 g (0.01 mol) of 2 - [(2-nitro-4-chloro) benzoyl] - 4-methylthio-4-methyl-1,3-cyclohexanedione and 1.3 g (0.01 mol) N-chlorosuccinimide in 50 ml of methylene chloride is allowed to rise for 5 days Reflux temperature maintained. The solvent is evaporated, and the residue is passed through a silica gel filled Column, which elutes with methylene chloride becomes. In this way the title compound is obtained in the form yellow crystals with a melting point of 143 to 144 ° C.

Intermediates (compounds of formula (IV)) example 13 3 - [(4-chloro-2-nitro) benzoyloxy] -4,4,6-trimethyl-6-methylthio-2-cyclo-hexen-1-one

A thoroughly stirred and cooled solution of 7.05 g (0.032 mol) 4-chloro-2-nitrobenzoyl chloride and 6.4 g (0.032 mol) 4-methylthio-4,6,6-trimethyl-1,3-cyclohexanedione in 70 ml dry methylene chloride is dropwise at 0 ° for 5 minutes with 6 ml (0.043 mol) of dry triethylamine.

After completion of the addition, the ice bath is removed. You leave that Keep the reaction mixture warm to ambient temperature 3 hours at this temperature and then treat it with 150 ml of water. The organic layer is separated, the  In turn with 100 ml of 2N HCl, 150 ml of water, 100 ml of 5% Washed K₂CO₃ solution and 150 ml of brine and then over dried anhydrous Na₂SO₄.

The remaining after removal of the solvent viscous Oil soon solidifies into a crystalline mass. These Mass is treated with hexane, which gives the analytical pure enol ester having a melting point of 120 to 122 °.

example 14

Analogously to the procedure of Example 13 and using the corresponding starting materials of the formulas (II) and (III), the following compounds of the formula (IVa) are prepared:

example 15

Analogous to the procedure of Example 13 using the corresponding starting materials of the formulas (II) and (III) the following compounds of the formula (IV) are prepared: Table H.  

Table H

(Compounds of formula IV)

example 16 4-methylthio-4,6,6-trimethyl-1,3-cyclohexanedione

In an atmosphere of dry nitrogen, you give 300 ml of a 1.6 M solution of n-butyllithium in hexane (0.48 mol) dropwise with stirring to 48.5 g (0.48 mol) of diisopropylamine in 420 ml of tetrahydrofuran (THF, over 4 A molecular sieves dried) at such a rate that the temperature does not rise above -68 ° C.

When the addition is complete, the reaction mixture (which Lithium diisopropylamide contains) for a further 30 minutes Stirred at -70 ° C and then at the same temperature with a Solution of 30.9 g (0.2 mol) of 4,4,6-trimethyl-1,3-cyclohexanedione treated in 200 ml of dry THF.

After addition of the entire dione, the reaction solution becomes 30 minutes kept at -70 ° C.

The solution is then added dropwise at -70 ° C for 15 minutes with 45.2 g (0.48 mol) of dimethyl disulfide in 150 ml added to dry THF.

Thereafter, the dry ice bath of solid CO₂ and Acetone removed, whereupon the reaction mixture is warmed to -9 ° and treated with 100 ml of concentrated HCl.

The obtained after rotary evaporation (30 °) of the tetrahydrofuran The residue is diluted with 200 ml of water, and the whole is extracted twice with 500 ml of diethyl ether.

The combined and dried (Na₂SO₄) ether extracts are under vacuum to about a third of its original Volumes are concentrated, and the precipitated crystals are then filtered off by suction.  

Obtained by subsequent recrystallization from isopropanol one analytically pure and named in the title Dion with a Melting point of 147 ° (Rf = 0.24 on silica gel in a 2: 1 mixture of diethyl ether and hexane).

example 17 4-Methylthio-4-methyl-1,3-cyclohexanedione

A mixture of 43 g (0.5 mol) of methyl acrylate and 59 g (0.5 mol) 3-Methylthiobutanone-2 is added with stirring for 30 minutes a solution of 100 ml of 5.4 m (0.54 mol) of methanolic Sodium methylate in 200 ml of dimethyl sulfoxide. The exothermic Reaction is kept below 40 ° C. It is about Stirred at room temperature overnight. Then the mixture becomes with pieces of ice and 60 ml of concentrated hydrochloric acid offset, and the resulting yellowish precipitate is then filtered off and dried under vacuum at 50 ° C. The product obtained melts at 120 to 122 ° C.

example 18 4-methoxy-4-carbomethoxy-1,3-cyclohexanedione

A mixture of 58 g (0.358 mol) of dimethyl methoxymalonate and 25 g (0.357 mol) of methyl vinyl ketone is added with stirring from 20 minutes to a solution of 66 ml at 5.4 m (0.356 mol) methanolic sodium methylate in 120 ml of dimethyl sulfoxide. The exothermic reaction is carried out by cooling with a Water bath maintained at 35 ° C. After 1 hour, set 200 ml Water and extracted the mixture twice with methylene chloride. The aqueous layer is with 80 ml 20prozentiger Acidified hydrochloric acid and extracted with methylene chloride. The extract is washed with water over MgSO₄ dried and evaporated under vacuum, resulting in a viscous Oil results. The obtained by treatment of this oil with ether yellow crystals melt at 122 to 124 ° C.  

example 19 4-methylthio-6,6-dimethyl-4-cyclohexene-1,3-dione

A solution of 2.8 g (0.015 mol) of 4-methylthio-6,6-dimethyl 1,3-cyclohexanedione in 50 ml of methylene chloride is used without cooling in part with 5.3 g (0.0169 mol) of m-chloroperbenzoic acid (55%).

After addition of the total peracid, the reaction mixture with 1 ml (0.0175 mol) of glacial acetic acid and 18 hours under reflux heated.

The reaction mixture will then come to ambient temperature left and then filtered.

The by rotary evaporation of the filtrate in the form of a crystalline mass obtained title compound by chromatography over silica gel (elution with a 3: 1 mixture of diethyl ether and hexane). Rf = 0.28 (over silica gel with diethyl ether). Melting point = 163 to 165 ° C.

example 20

Starting from the cyclohexane compound of Example 17 produced by addition reaction, the following further compounds:

4-methoxy-4-methylthio-6,6-dimethyl-1,3-cyclohexanedione (addition of methanol),
4-acetoxy-4-methylthio-6,6-dimethyl-1,3-cyclohexanedione (addition of acetic acid).

example 21

Analogously to the procedure of Example 17 are used corresponding methyl ketones and carboxylic acid esters as starting materials the following compounds of formula (II) are prepared: Table J.  

Table J

(Compounds of the formula II)

example 22

Analogously to the procedure of Example 16 are used corresponding starting materials of the formula (V) and electrophilic Agent (Table K) the compounds of the formula (II) prepared according to Table L.  

Table K

(Compounds of the formula V)

Table L

(Compounds of the formula II)

example 23 4,4-dimethyl-6-methylene-1,3-cyclohexanedione (a) and 4,4-dimethyl-6-methoxymethyl-1,3-cyclohexanedione (b)

A mixture of 26 g (0.2 mol) of ethyl 2-hydroxymethyl-2-propenecarboxylate and 17.2 g (0.2 mol) of 3-methyl-2-butanone is added dropwise with stirring so with a solution of 40 ml of 5.4 m methanolic sodium 02310 00070 552 001000280000000200012000285910219900040 0002003902818 00004 02191thoxid in 80 ml dry Dimethyl sulfoxide is added so that the temperature does not rise rises above 40 ° C.

When the addition is complete, the brown reaction solution becomes more Stirred for 2 hours at room temperature and then with 300 ml of water treated.

The aqueous solution is extracted twice with 100 ml CH₂Cl₂, whereupon the organic extracts are anhydrous Na₂SO₄ dried and then evaporated under vacuum. The resulting crude mixture of the two title compounds becomes by chromatography with mixtures of hexane and diethyl ether separated as the mobile phase, first with a 3: 1 mixture of hexane and ether, the substituted in position 6 dione (a) is eluted (melting point 144 to 146 °, Rf = 0.35, ether on silica gel), which is the retro-Michael Reaction product of the originally formed 6-hydroxymethyl derivative is. By continuing the elution of silica gel filled column (with a 2: 1 mixture of hexane and diethyl ether) is obtained in position 6 by methoxymethyl substituted cyclohexanedione (b) having a melting point from 108 to 110 ° (Rf = 0.24, ether on silica gel).

example 24 4-methyl-5-trifluoromethyl-1,3-cyclohexanedione

A mixture of 7.2 g (0.1 mole) of 2-butanone and 16.8 g (0.1 mole) of ethyl β- (trifluoromethyl) acrylate is added dropwise to a solution of 2.7 with stirring over 30 minutes g Na in 20 ml of methanol and 60 ml of dry xylene. The reaction mixture is refluxed for 3 hours and then evaporated to dryness. The residue is dissolved in 50 ml of water and the solution is treated with concentrated HCl. The precipitated crystals are filtered off with suction, then washed with water and diethyl ether and dried. They melt at 122 to 128 ° C.

Analogously to the procedure of Example 24, the following are further Made connections:

5-trifluoromethyl-1,3-cyclohexanedione having a melting point of 143 to 144 ° C and
4,4-dimethyl-5-trifluoromethyl-1,3-cyclohexanedione having a melting point of 122 to 128 ° C.

Claims (34)

1. Compounds of the formula (I) whereinR₁, R₂, R₃ and R₄ independently represent an unsaturated aliphatic hydrocarbon group having up to 6 carbon atoms, a cycloalkyl group having up to 6 carbon atoms, a group Ar or a group (A₁) _n X, wherein at least one of R₁, R₂, R₃ and R₄ may also be C₂-C₅ alkoxycarbonyl, at least one of R₁, R₂, R₃ and R₄ is (A₁) _n X, R₁ together with R₂ or R₃ together with R₄ may also be C₂-C₅-alkylene and R₁ together with R₂ can also form an oxo group or a C₁-C₅ alkylidene group,
Ar is an unsaturated or substituted 5-membered or 6-membered heteroaryl group which contains 1 to 3 heteroatoms selected from O, N and S and is bonded to the ring A via a ring carbon atom,
n is 0 or 1,
X is H, OR₆, SR₇, NR₈R₉, NO₂, halogen, CN; CF₃, CHF₂, S (O) _m R₁₀, CO-NHR₁₁, CO-R₁₂, CR₁₃R₁₄-COO (C₁-C₆-alkyl) or benzyl,
A₁ is methylene or ethylene which is unsubstituted or substituted by one or more C₁-C₅ alkyl groups,
R₆ and R₇ independently represent H, a hydrocarbon group, a haloalkyl group, a heteroaryl group or a group CO-R₁₅,
R₈ is H, a hydrocarbon group, a heteroaryl group or a group CO-R₁₅,
R₉, R₁₀, R₁₃ and R₁₄ are independently H, C₁-C₆-alkyl or aryl,
R₁₁ is H or a hydrocarbon group,
R₁₂ and R₁₅ independently represent H, a hydrocarbon group or a heteroaryl group,
m stands for 1 or 2,
A₂ is a bond, CR₁₆R₁₇, CR₁₆R₁₇-CR₁₈R₁₉, O, S, NR₂₀ or CO,
R₁₆ and R₁₈ independently represent H, a hydrocarbon group or the carboxyl group in free, salt or esterified form, where R₁₆ together with R₁ on the adjacent carbon atom may also be a bond,
R₁₇ and R₁₉ are independently H, a hydrocarbon group or a group (A₁) _n X, wherein A₁, n and X are as defined above, wherein R₁₆ together with R₁₇ or R₁₈ together with R₁₉ also be a group (CH₂) _2-5 may be such that a spiro compound is formed, and / or R₁₆ together with R₁ on the adjacent carbon atom or R₁₈ together with R₃ on the adjacent carbon atom may be a group (CH₂) _1-5 , so that a bicyclic ring is formed,
R₂₀ is H, a hydrocarbyl group or a group CO-R₁₅, where R₁₅ has the above definition,
A₃ --- A₄ is C = C (ORa) (group A) or C (X₁) -C (O) (group B),
X₁ is F or Cl,
Ra is H, a salt-forming radical or, together with the oxygen atom to which this group is bonded, an ether radical or ester radical,
Y is either phenyl which is substituted by R₂₁, R₂₂ and R₂₃, or Ar ',
Ar 'is a 5-membered or 6-membered heteroaromatic group containing 1, 2 or 3 heteroatoms selected from O, S and N, said heteroaromatic group being unsubstituted or substituted and attached through a ring carbon atom to the group CO to which it is attached is
R₂₁ and R₂₂ are independently H, halogen, C₁-C₄-alkyl, C₁-C₄- alkoxy, C₁-C₄-haloalkyl, CN, NO₂, CF₃O, R ^b S (O) _p, NR ^c R ^d, C (O) - R, SO₂-NR ^c R ^d or NR ^c -C (O) -R ^d , where R₂₁ and R₂₂ together can form a methylenedioxy group,
p is 0, 1 or 2,
R ^{b is} C₁-C₄-alkyl which is optionally substituted by halogen, cyano, phenyl or benzyl,
R ^c and R ^{d are} independently H or C₁-C₄ alkyl, R is C₁-C₄ alkyl or C₁-C₄ alkoxy,
R₂₃ is halogen, NO₂, CN, C₁-C₂-alkyl, C₁-C₂-alkoxy, C₁-C₂-haloalkyl or C₁-C₄-alkyl-S (O) _q ,
q is 0, 1 or 2,
wherein, if Y is other than optionally substituted pyrimidinyl, then one of R₁, R₂, R₃ and R₄ is also phenyl or substituted phenyl, with the provisos that

• a) X is one of the radicals R₁, R₂, R₃ and R₄ only H, if at least one of the following conditions is given
  • i) CR₁R₂-A₂ is C (R₂) = C (R₁₇) or CR₁R₂-CR₁₆R₁₇-CR₁₈R₁₉,
  • ii) Y is other than optionally substituted phenyl or optionally substituted pyrimidinyl,
  • iii) R₁ and R₂ together are oxo or C₁-C₅-alkylidene,
  • iv) at least one of the other substituents R₁, R₂, R₃ and R₄ is an unsaturated aliphatic hydrocarbon group, a cycloalkyl group, an unsubstituted or substituted phenyl group or Ar,
  • v) at least one of the other substituents R₁, R₂, R₃, R₄, R₁₇ and R₁₉ is a group (A₁) _n X, wherein X is other than H, or
  • vi) A₃ --- A₄ is C (X₁) -C (O),
• b) R₃ and R₄ are not H at the same time, if CR₁R₂-A₂ is C (R₂) = C (R₁₇), and
• c) A₂ does not stand for O, S, NR₂₀ or CO, if R₁ and R₂ together are oxo.

2. A compound according to claim 1, characterized in that R₁ is an unsaturated aliphatic group having up to 6 carbon atoms, a cycloalkyl group of up to 6 carbon atoms or a group Ar, wherein Ar is as defined in claim 1 is. 3. A compound according to claim 1, characterized in that CR₁R₂-A₂ is C (R₂) = CR₁₇ wherein R₂ and R₁₇ are as in claim 1 are defined. 4. A compound according to claim 1, characterized in that R₁ and R₂ together represent oxo or C₁-C₅ alkylidene. 5. A compound according to claim 1, characterized in that A₃ --- A₄ is C (X₁) -C (O) wherein X₁ is as defined in claim 1. 6. A compound according to claim 1, characterized in that R₁ is CH₃, C₂H₅, vinyl, allyl, propargyl, cyclopropyl, optionally substituted phenyl, furyl, thienyl or (A₁) _n X 'or R₁ together with R₂ oxo, CH₂ or CH -CH₃ is or R₁ together with R₁₆ is a bond, n is 0 or 1, A₁ is CH₂ or (CH₂) ₂, which is optionally substituted by one or two CH₃ groups, and X 'is C₁-C₄-alkylthio, phenylthio , C₁-C₄-alkoxy, phenoxy, CHO, C₂-C₅-alkanoyl, OH and esters thereof with aliphatic carboxylic acids having 2 to 5 carbon atoms or with optionally substituted benzoic acid, (C₂-C₅-carbalkoxy) -CH₂, (C₂-C₅- Carbalkoxy) -CH (CH₃), cyano, F, Cl, CHF₂, CF₃, NO₂, CONH₂, CONH (C₁-C₄-alkyl), di (C₁-C₄-alkyl) is N or benzyl, wherein one of the substituents R₂, R₃ and R₄ are H, C₁-C₄-alkyl, C₁-C₄-alkoxy, C₁-C₄-alkylthio, OH, C₁-C₄-alkyl-CO-O, C₂-C₅- Carbalkoxy, thienyl or furyl, and the possible residues of these substituents R₂, R₃ and R₄ are H or CH₃. 7. A compound according to claim 6, characterized in that A₂ is either a bond, CH₂, CH (CH₃), C (CH₃) ₂, CO, O, CH (CF₃), CH₂CH₂ or CH (CH₃) -CH (CH₃) mean or that A₂ together with CR₁R₂ is C (R₂) = C (R₁₇), where R₁₇ is H, SCH₃, CH₃ or CF₃ is. 8. A compound according to claim 7, characterized in that A₂ is CH₂, CH (CH₃) or C (CH₃) ₂, (A₁) _n X 'is NO₂, thienyl or furyl and Y is phenyl which is represented by R₂₁ radicals , R₂₂ and R₂₃ is substituted. 9. A compound according to claim 7, characterized in that n is 1 or 2 and Y is phenyl which is substituted by radicals R₂₁, R₂₂ and R₂₃. 10. A compound according to claim 1 to 7, characterized Y is phenyl which is substituted by radicals R₂₁, R₂₂ and R₂₃ or thienyl, pyrazolyl, isothiazolyl, pyridyl, pyrazinyl or pyrimidinyl, this heteroaromatic group by methylenedioxy, NO₂, halogen, CN, CF₃, CH₃-SO₂ or CH₃SCH₂ is ortho-substituted and optionally one or has two further substituents which are selected from halogen and C₁-C₄-alkyl, if attached to a ring carbon atom are bonded or selected from C₁-C₄-alkyl,  Benzyl and C₁-C₄-alkylthio-C₁-C₄-alkyl, if they are attached to a ring nitrogen atom are bound, R₂₂ in para position to Carbonyl group is and for H, halogen, C₁-C₄-alkyl-S or C₁-C₄-alkyl-SO₂, R₂₃ is in the ortho-position to Carbonyl group is and halogen, CF₃, NO₂, CN or CH₃SO₂ and R₂₁ is H, halogen or CH₃. 11. A compound according to claim 10, characterized in that Y is phenyl which is substituted by radicals R₂₁, R₂₂ and R₂₃ is. 12. A compound according to claim 10, characterized in that Y is substituted pyrazolyl, pyrimidinyl or pyridyl. 13. A compound according to claim 12, characterized in that Y is substituted pyrazolyl. 14. A compound according to claim 12, characterized in that Y is substituted pyridyl. 15. A compound according to claim 1, characterized in that R₁ is H, CH₃, SCH₃, S (O) CH₃, SO₂CH₃, phenyl or by C₁-C₄alkyl, C₁-C₄alkoxy, halogen or CF₃ monosubstituted Phenyl or alkenyl or alkynyl of up to 4 carbon atoms stands. 16. A compound according to claim 1 or 15, characterized that R₂, R₃ and R₄ are independently H or CH₃, wherein one of Substituents R₂, R₃ and R₄ also include SCH₃, S (O) CH₃ or SO₂ (CH₃) may be, if only one of the substituents R₂ to R₄ for SCH₃, S (O) CH₃ or SO₂CH₃ stands. 17. A compound according to claim 16, characterized in that A₂ is CH (CF₃), CH₂ or O.   18. A compound according to claim 17, characterized in that Y is 3,5-dichloro-2-pyridyl. 19. A compound according to claim 17, characterized in that Y is 1-CH₃-4-NO₂-pyrazol-5-yl or 1-CH₃-4-NO₂-pyrazol-3-yl stands. 20. A compound according to claim 17, characterized in that Y is phenyl which is substituted by radicals R₂₁, R₂₂ and R₂₃ wherein R₂₁, R₂₂ and R₂₃ as defined in claim 1 are. 21. A compound according to claim 15, characterized in that R₁ is SCH₃, S (O) CH₃ or SO₂CH₃, the substituents R₂, R₃ and R₄ are independently H or CH₃, A₂ is CH₂, O or CH (CF₃) and Y is 3,5-dichloro-2-pyridyl, 1-CH₃-4-NO₂- Pyrazol-5-yl, 1-CH₃-4-NO₂-pyrazol-3-yl or phenyl, which is substituted by radicals R₂₁, R₂₂ and R₂₃. 22. A compound according to claim 21, characterized in that A₂ is CH (CF₃) or O and Y is phenyl which is substituted by R₂₁ radicals, R₂₂ and R₂₃ is substituted. 23. A compound according to claim 15, characterized in that R₁ is alkenyl or alkynyl of up to 4 carbon atoms, the radicals R₂, R₃ and R₄ are independently H, CH₃, SCH₃, S (O) CH₃ or SO₂CH₃ are, if only one of the radicals R₂ to R₄ selected is from the group SCH₃, S (O) CH₃ and SO₂CH₃, A₂ for CH₂, O. or CH (CF₃), and Y is 3,5-dichloro-2-pyridyl, 1-CH₃-4-NO₂- Pyrazol-5-yl, 1-CH₃-4-NO₂-pyrazol-3-yl or phenyl, which is substituted by radicals R₂₁, R₂₂ and R₂₃. 24. A compound according to claim 15, characterized in that R₁ is phenyl or C₁-C₄alkyl, C₁-C₄alkoxy, halogen or  CF₃ monosubstituted phenyl, R₂, R₃ and R₄ independently H or CH₃, A₂ is CH (CF₃), CH₂ or O, and Y is 3,5-dichloro 2-pyridyl, 1-CH₃-4-NO₂-pyrazol-5-yl, 1-CH₃-4-NO₂-pyrazole 3-yl or phenyl, which is represented by radicals R₂₁, R₂₂ and R₂₃ is substituted. 25. A compound according to claim 24, characterized in that Y is phenyl which is substituted by radicals R₂₁, R₂₂ and R₂₃ is. 26. A compound according to any one of claims 1 to 25, characterized in that A₃ --- A₄ is C = C (ORa). 27. A compound according to claim 1, characterized in that this is any of the following compounds:

• a. 2- (1-methyl-4-nitro-5-pyrazolylcarbonyl) -1,3-cyclohexanedione,
• b. 2- (1-methyl-4-nitro-3-pyrazolylcarbonyl) -1,3-cyclohexanedione,
• c. 2- (1-methyl-4-nitro-3-pyrazolylcarbonyl) -5-methyl-1,3-cyclohexanedione,
• d. 2- (1-methyl-4-nitro-3-pyrazolylcarbonyl) -4,4,6-trimethyl-1,3-cyclohexanedione,
• e. 2- (1-methyl-4-nitro-3-pyrazolylcarbonyl) -4,4,6,6-tetramethyl-1,3-cyclohexanedione,
• f. 4- (1-methyl-4-nitro-3-pyrazolylcarbonyl) -2,2,6,6-tetramethyl-3,6-dihydro-2H-pyran-3-one,
• G. 2- (4-chloro-2-nitrobenzoyl) -4-phenyl-1,3-cyclohexanedione,
• H. 2- (4-chloro-2-nitrobenzoyl) -5-trifluoromethyl-1,3-cyclohexanedione,
• i. 2- (4-chloro-2-nitrobenzoyl) -4-methyl-5-trifluoromethyl-1,3-cyclohexand-ion,
• j. 2- (4-chloro-2-nitrobenzoyl) -4,4-dimethyl-5-trifluoromethyl-1,3-cyclohexanedione,
• k. 2- (4-chloro-2-nitrobenzoyl) -4- (2-fluorophenyl) -1,3-cyclohexanedione,
• l. 2- (4-chloro-2-nitrobenzoyl) -4- (4-fluorophenyl) -1,3-cyclohexanedione,
• m. 2- (2-chloro-4-methylsulfonylbenzoyl) -5-trifluoromethyl-1,3-cyclohexanedione,
• 2- (4-chloro-2-nitrobenzoyl) -4,6,6-trimethyl-4-cyclohexene-1,3-dione,
• o. 2-chloro-2- (4-chloro-2-nitrobenzoyl) -4,4,6,6-tetramethyl-1,3-cyclohexane-1,3-dione,
• p. 2-chloro-2- (4-chloro-2-nitrobenzoyl) -4,4,6-trimethyl-1,3-cyclohexane-1,3-dione or
• q. 2- (3,5-dichloro-2-pyridylcarbonyl) -1,3-cyclohexanedione.

28. A compound according to claim 26, characterized in that Ra stands for H, in free form or in the form of a salt. 29. A compound according to claim 27 in free form or in the form a salt. 30. 2- (1-Methyl-4-nitro-3-pyrazolylcarbonyl) -3- (phenoxycarbonyloxy) - 2-cyclohexen-1-one. 31. A compound according to claim 26, characterized in that Ra together with the oxygen atom to which this radical is attached is, forms an ether residue or ester residue. 32. Process for the preparation of compounds of the formula (I) according to Claim 1, characterized in that a compound of the formula (II) wherein R₁, R₂, R₃, R₄ and A₂ are as defined above, with a compound of the formula (III) Y-CO-Hal (III) wherein Y is as defined above and Hal is halogen, is reacted and the ester thus obtained the Formula (IV) wherein Y, R₁, R₂, R₃, R₄ and A₂ are as defined above, is converted by rearrangement into compounds of formula (Ib) wherein Y, A₂, R₁, R₂, R₃ and R₄ are as defined above and M is H or a salt-forming radical,
and the compounds of the formula (Ib) thus obtained, if appropriate, by etherification, esterification or halogenation to give the corresponding 2- (Y-CO) -2-en-1-one-3-ol ethers, 2- (Y-CO) -2- En-1-one-3-ol ester or 2-X₁-2- (Y-CO) -1,3-dione compounds. 33. A herbicidal composition, characterized in that a compound of formula (I) according to any of the claims 1 to 31 contains. 34. Method of controlling weeds, characterized that the weeds or the location of the weeds with a herbicidally effective amount of a compound of the formula (I) according to any one of claims 1 to 31.