2-benzoylcyclohexane-1,3-dione as herbicides

Details 2-benzoylcyclohexane-1,3-dione as herbicides 2-benzoylcyclohexane-1,3-dione as herbicides

2000-02-07

2002-08-13

Raymond, Richard L. (Department: 1624)

Plant protecting and regulating compositions

Plant growth regulating compositions

Organic active compound containing

C504S282000, C504S287000, C548S366100, C548S374100, C548S564000, C548S363100

Reexamination Certificate

active

06432881

ABSTRACT:

The present invention relates to substituted 2-benzoylcyclohexane-1,3-diones of the formula I:
where:
R
1
and R
2
are each hydrogen, mercapto, nitro, halogen, cyano, thiocyanato, C
1
-C
6
-alkyl, C
1
-C
6
-haloalkyl, C
1
-C
6
-alkoxy, C
2
-C
6
-alkenyl, C
2
-C
6
-alkynyl, —OR
3
, —OCOR
3
, —OSO
2
R
3
, —S(O)
n
R
3
, —SO
2
OR
3
, —SO
2
N(R
3
)
2
, —NR
3
SO
2
R
3
or —NR
3
COR
3
;
R
3
is hydrogen, C
1
-C
6
-alkyl, C
1
-C
6
-haloalkyl, C
2
-C
6
-alkenyl, C
2
-C
6
-alkynyl, phenyl or phenyl-C
1
-C
6
-alkyl; where the abovementioned alkyl radicals may be partially or fully halogenated and/or may carry one to three of the following groups:
hydroxyl, mercapto, amino, cyano, R
3
, —OR
3
, —SR
3
, —N (R
3
)
2
, ═NOR
3
, —OCOR
3
, —SCOR
3
, —NR
3
COR
3
, —CO
2
R
3
, —COSR
3
, —CON(R
3
)
2
, C
1
-C
4
-alkyliminooxy, C
1
-C
4
-alkoxyamino, C
1
-C
4
-alkylcarbonyl, C
1
-C
4
-alkoxy-C
2
-C
6
-alkoxycarbonyl, C
1
-C
4
-alkylsulfonyl, heterocyclyl, heterocyclyloxy, phenyl, benzyl, hetaryl, phenoxy, benzyloxy and hetaryloxy, where the eight last mentioned radicals may in turn be substituted;
n is 0, 1 or 2;
Q is a cyclohexane-1,3-dione ring with or without substitution which is attached in position 2;
X
1
is a straight-chain or branched C
1
-C
6
-alkylene, a C
2
-C
6
-alkenylene or a C
2
-C
6
-alkynylene chain which is interrupted by a hetero atom selected from the group consisting of:
oxygen or sulfur,
where the abovementioned alkyl, alkenyl or alkynyl radicals may be partially halogenated and/or may carry one to three of the following groups:
—OR
4
, —OCOR
4
, —OCONHR
4
or —OSO
2
R
4
;
is hydrogen, C
1
-C
6
-alkyl, C
2
-C
6
-alkenyl, C
2
-C
6
-alkynyl, phenyl, phenyl-C
1
-C
6
-alkyl, where the abovementioned alkyl, alkenyl or alkynyl radicals may be partially or fully halogenated and/or may be substituted by one or more of the following radicals:
hydroxyl, mercapto, amino, cyano, nitro, formyl, C
1
-C
4
-alkylamino, C
1
-C
4
-dialkylamino, C
1
-C
4
-alkoxycarbonyl, C
1
-C
4
-alkylcarbonyl, C
1
-C
4
-alkylcarbonyloxy, C
1
-C
4
-alkyl, C
1
-C
4
-haloalkyl, C
1
-C
4
-alkylthio, C
l
-C
4
-haloalkylthio, C
1
-C
4
-alkoxy, C
1
-C
4
-haloalkoxy;
Het is a three- to six-membered partially or fully saturated heterocyclic group or a three- to six-membered heteroaromatic group having up to three hetero atoms selected from the following three groups:
nitrogen,
oxygen in combination with at least one nitrogen or
sulfur in combination with at least one nitrogen,
where the abovementioned heterocyclic or heteroaromatic group may be partially or fully halogenated and/or may be substituted by R
5
;
R
5
is hydrogen, hydroxyl, mercapto, amino, cyano, nitro, formyl, C
1
-C
4
-alkylamino, C
1
-C
4
-dialkylamino, C
l
-C
4
-alkoxycarbonyl, C
1
-C
4
-alkylcarbonyl, C
1
-C
4
-alkylcarbonyloxy, C
1
-C
4
-alkyl, C
1
-C
4
-haloalkyl, C
1
-C
4
-alkylthio, C
1
-C
4
-haloalkylthio, C
1
-C
4
-alkoxy, C
1
-C
4
-haloalkoxy, where the alkyl radicals may in each case be substituted by in each case one or more of the following radicals:
cyano, formyl, C
l
-
4
-alkylamino, C
1
-C
4
-dialkylamino, C
1
-C
4
-alkoxycarbonyl, C
1
-C
4
-alkylcarbonyl, C
l
-
4
-alkylcarbonyloxy, C
1
-C
4
-alkyl, C
1
-C
4
-haloalkyl, C
1
-C
4
-alkylthio, C
1
-C
4
-haloalkylthio, C
1
-C
4
-alkoxy, C
1
-C
4
-haloalkoxy;
and agriculturally useful salts thereof.
In addition, the invention relates to processes and intermediates for preparing compounds of the formula I, to compositions comprising them and to the use of the compounds of the formula I and to compositions comprising them for controlling harmful plants.
2-Benzoylcyclohexane-1,3-diones are disclosed in the literature, for example in EP-A 278 742, EP-A 298 680, EP-A 320 864 and WO 96/14285.
However, the herbicidal properties of the prior art compounds and their crop plant safety are not entirely satisfactory.
It is an object of the present invention to provide novel, in particular herbicidally active, compounds having improved properties.
We have found that this object is achieved by the 2-benzoylcyclohexane-1,3-diones of the formula I and their herbicidal activity.
Furthermore, we have found herbicidal compositions which comprise the compounds I and have very good herbicidal activity. Moreover, we have found processes for preparing these compositions and methods for controlling unwanted vegetation using the compounds I.
The present invention also provides stereoisomers of the compounds of the formula I. Pure stereoisomers and also mixtures thereof are included.
Depending on the substitution pattern, the compounds of the formula I may contain one or more chiral centers and, if this is the case, are present as mixtures of enantiomers or diastereomers. The invention provides the pure enantiomers or diastereomers and also mixtures thereof.
The compounds of the formula I may also be present in the form of their agriculturally useful salts, the kind of salt generally not being important. The salts of those cations or the acid addition salts of those acids whose cations or anions, respectively, do not adversely affect the herbicidal activity of the compounds I are generally suitable.
Suitable cations are in particular ions of the alkali metals, preferably lithium, sodium and potassium, of the alkaline earth metals, preferably calcium and magnesium, and of the transition metals, preferably manganese, copper, zinc and iron, and ammonium, where, if desired, one to four hydrogen atoms may be replaced by C
1
-C
4
-alkyl or hydroxy-C
1
-C
4
-alkyl and/or one phenyl or benzyl, preferably diisopropylammonium, tetramethylammonium, tetrabutylammonium, trimethylbenzylammonium, furthermore phosphonium ions, sulfonium ions, preferably tri(C
1
-C
4
-alkyl)sulfonium, and sulfoxonium ions, preferably tri(C
1
-C
4
-alkyl)sulfoxonium.
Anions of usable acid addition salts are primarily chloride, bromide, fluoride, hydrogen sulfate, sulfate, dihydrogen phosphate, hydrogen phosphate, nitrate, hydrogen carbonate, carbonate, hexafluorosilicate, hexafluorophosphate, benzoate and the anions of C
1
-C
4
-alkanoic acids, preferably formate, acetate, propionate and butyrate.
Emphasis is given to the compounds of the formula I according to the invention where the variable Q is a cyclohexane-1,3-dione ring of the formula II
which is attached in position 2, where II may also represent the tautomeric formulae II′ and II″,
where
R
6
, R
7
, R
9
and R
11
are each hydrogen or C
1
-C
4
-alkyl;
R
8
is hydrogen, C
1
-C
4
-alkyl or C
3
-C
4
-cycloalkyl, where the two last mentioned groups may carry one to three of the following substituents:
halogen, C
1
-C
4
-alkylthio or C
1
-C
4
-alkoxy; or
is tetrahydropyran-2-yl, tetrahydropyran-3-yl, tetrahydropyran-4-yl, tetrahydrothiopyran-2-yl, tetrahydrothiopyran-3-yl, tetrahydrothiopyran-4-yl, 1,3-dioxolan-2-yl, 1,3-dioxan-2-yl, 1,3-oxathiolan-2-yl, 1,3-oxathian-2-yl, 1,3-dithiolan-2-yl or 1,3-dithian-2-yl, where the 6 last mentioned radicals may be substituted by one to three C
l
-C
4
-alkyl radicals;
R
10
is hydrogen, C
l
-C
4
-alkyl or C
1
-C
6
-alkoxycarbonyl; or
R
8
and R
11
together form a &pgr; bond or a three- to six-membered carbocyclic ring; or
the CR
8
R
9
unit may be replaced by C═O.
Process A
Reactions of the cyclohexane-1,3-dione of the formula II with an activated carboxylic acid IIIa or a carboxylic acid IIIb, which is preferably activated in situ, to give the acylation product IV, and subsequent rearrangement to the compounds of the formula I according to the invention.
L
1
is a nucleophilically replaceable leaving group such as halogen, for example bromine or chlorine, hetaryl, for example imidazolyl or pyridyl, or carboxylate, for example acetate, trifluoroacetate, etc.
The activated carboxylic acid can be employed directly, as in the case of acyl halides, or be generated in situ, for example by using dicyclohexylcarbodiimide, triphenylphosphine/azodicarboxylic esters, 2-pyridine disulfid/triphenylphosphine, carbonyldiimidazole, etc.
It may be advantageous to carry out the acylation reaction in the presence of a base. Starting materials and

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