Saccharin-5-carbonyl derivatives with herbicidal effect

Details Saccharin-5-carbonyl derivatives with herbicidal effect Saccharin-5-carbonyl derivatives with herbicidal effect

2001-09-05

2002-06-25

Stockton, Laura L. (Department: 1626)

Plant protecting and regulating compositions

Plant growth regulating compositions

Organic active compound containing

C514S373000, C548S210000, C548S211000

Reexamination Certificate

active

06410485

ABSTRACT:

The present application relates to saccharin-5-carbonyl derivatives of the formula I
in which the substituents have the following meanings:
L is C
1
-C
6
-alkyl, C
1
-C
6
-alkoxy;
Z is C
1
-C
6
-alkyl, C
3
-C
8
-cycloalkyl, C
3
-C
6
-alkenyl, C
3
-C
5
-alkynyl, phenyl-C
1
-C
6
-alkyl or phenyl, where the phenyl rings can be mono- or polysubstituted by C
1
-C
6
-alkyl, C
1
-C
6
-alkoxy and halogen;
M is hydrogen, C
1
-C
6
-alkyl, C
1
-C
6
-alkoxy, halogen, cyano, nitro or halo-C
1
-C
6
-alkyl;
R
1
, R
2
, R
3
, R
4
, R
5
, R
6
, R
7
, R
8
are hydrogen, C
1
-C
6
-alkyl;
or the agriculturally utilizable salts of the compound I.
The invention further relates to crop protection compositions comprising the compounds I and processes for controlling undesired vegetation with the saccharin derivatives I and use of the compounds I for the production of crop protection compositions having herbicidal action.
WO 96/05182, WO 98/40366 and U.S. Pat. No. 5,801,120 disclose herbicidally active saccharincarbonylcyclohexanedione derivatives.
EP-A 338 992 describes herbicidal benzoyl derivatives which do not have a saccharin structure.
The use of saccharin derivatives as fungicides is furthermore known, e.g. JP Publication 72/00419 and 73/35457 and in pharmacy, e.g. EP-A 594 257.
The herbicidal properties of the known compounds and the compatibility with crop plants are, however, only of limited satisfactoriness.
The object of the present invention is to make available alternative saccharin derivatives having novel structural features. Surprisingly, it has been found that the saccharin derivatives of the formula I have improved properties in comparison with the saccharin derivatives known hitherto.
Compounds of the formula I are obtained according to Scheme 1 by acylating diones of the formula II with a saccharin-5-carbonyl chloride of the formula III and rearranging the enol esters of the formula IV obtained in the presence of a catalyst to give the active compound of the formula I.
In the above Scheme 1, the substituents R
1
to R
8
, L, M and Z have the meaning given at the outset. X is an easily removable group, such as, for example, halogen, in particular chlorine, or an anhydride group derived from an organic or inorganic acid.
The first step of the reaction sequence in Scheme 1 is carried out by addition of the acid halide III to the solution or suspension of the dione II in the presence of an auxiliary base. The reactants and the auxiliary base are Preferably employed in equimolar amounts, but a small excess of 1.2 to 1.5 molar equivalents of the auxiliary base can be advantageous. Solvents which can be used are methylene chloride, tetrahydrofuran, ethyl acetate, toluene or preferably acetonitrile. Suitable auxiliary bases are alkali metal carbonates, pyridine or tertiary alkylamines, preferably triethylamine. During the addition of the acid chloride, the reaction mixture is preferably cooled to 0 to 10° C., and then it is stirred at a temperature of 20 to 70° C., in particular 25 to 40° C., until the reaction is complete.
The enol ester IV can be isolated before the rearrangement, but the reaction is preferably carried out by adding two to four, preferably 2.5, equivalents of triethylamine to the reaction mixture and then adding 2 to 10, in particular 3, mol % of a cyano compound such as acetone cyanohydrin or preferably trimethylsilyl cyanide at 25° C. and then stirring at a temperature of 20 to 40° C., preferably at 25° C., until the enol ester IV is no longer present. Examples of the cyanide-catalyzed rearrangement of enol esters are found in EP 338 992 and EP 0 252 298.
Working-up is carried out by acidifying the reaction mixture with 5% strength by weight hydrochloric acid or sulfuric acid and then extracting with a solvent such as ethyl acetate or methylene chloride. After drying the extract over sodium sulfate or magnesium sulfate, the solvent is distilled off in vacuo and the crude product is subjected, if necessary, to purification. For purification, the reaction product can be, for example, chromatographed (silica gel, cyclohexane/ethyl acetate) or recrystallized (methanol/water or glacial acetic acid/water). A further purification method is extraction of an ethyl acetate solution of the crude product with an aqueous alkali metal carbonate solution, the final product passing into the aqueous phase. Acidification of the aqueous solution and fresh extraction yields the final product, after drying and removing the solvent, in purer form.
The diones of the formula II used as starting materials are known and can be prepared in a manner known per se [cf. EP-A 338 992; R. Gleiter, Tetrahedron 1980, 36: 655; JP 10,265441; JP 10, 265415].
The acid halides of the formula III used as starting materials are likewise known. If X=Cl, they are obtained by reaction of a suitably substituted saccharin-5-carboxylic acid with thionyl chloride. The synthesis of substituted saccharin-5-carboxylic acids is described, for example, in DE 44 27 996.
In the definition of the various radicals in formula I, the terms indicated are, either per se (such as, for example, C
1
-C
6
-“alkyl”) or as moieties or in combination with chemical groups of different composition (such as, for example, C
1
-C
6
-halo-“alkyl”, phenyl-C
1
-C
6
-“alkyl”), fundamentally a collective term for a group of compounds. In the case in which the phenyl rings can be mono- or polysubstituted, the substituents can fundamentally be identical or different.
In the definitions of the compounds I given at the beginning, collective terms were used which are generally representative of the following groups:
alkyl: straight-chain or branched alkyl groups having 1 to 6, preferably 1-4, carbon atoms, e.g. C
1
-C
4
-alkyl such as methyl, ethyl, propyl, 1-methylethyl, butyl, 1-methylpropyl, 2-methylpropyl and 1,1-dimethylethyl;
alkoxy: straight-chain or branched alkyl groups having 1 to 6, preferably 1-4, carbon atoms as mentioned above, which are bonded to the structure via an oxygen atom (—O—), e.g. C
1
-C
3
-alkoxy such as methyloxy, ethyloxy, propyloxy and 1-methylethyloxy;
cycloalkyl: monocyclic alkyl groups having 3 to 8 carbon ring members, e.g. cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl and cyclooctyl;
alkenyl: straight-chain or branched alkenyl groups having 2, preferably 3 to 6, carbon atoms and a double bond in any desired position, e.g. C
2
-C
6
-alkenyl such as ethenyl, 1-propenyl, 2-propenyl, 1-methylethenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-methyl-1-propenyl, 2-methyl-1-propenyl, 1-methyl-2-propenyl, 2-methyl-2-propenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, 1-methyl-1-butenyl, 2-methyl-1-butenyl, 3-methyl-1-butenyl, 1-methyl-2-butenyl, 2-methyl-2-butenyl, 3-methyl-2-butenyl, 1-methyl-3-butenyl, 2-methyl-3-butenyl, 3-methyl-3-butenyl, 1,1-dimethyl-2-propenyl, 1,2-dimethyl-1-propenyl, 1,2-dimethyl-2-propenyl, 1-ethyl-1-propenyl, 1-ethyl-2-propenyl, 1-hexenyl, 2-hexenyl, 3-hexenyl, 4-hexenyl, 5-hexenyl, 1-methyl-1-pentenyl, 2-methyl-1-pentenyl, 3-methyl-1-pentenyl, 4-methyl-1-pentenyl, 1-methyl-2-pentenyl, 2-methyl-2-pentenyl, 3-methyl-2-pentenyl, 4-methyl-2-pentenyl, 1-methyl-3-pentenyl, 2-methyl-3-pentenyl, 3-methyl-3-pentenyl, 4-methyl-3-pentenyl, 1-methyl-4-pentenyl, 2-methyl-4-pentenyl, 3-methyl-4-pentenyl, 4-methyl-4-pentenyl, 1,1-dimethyl-2-butenyl, 1,1-dimethyl-3-butenyl, 2,1-dimethyl-1-butenyl, 1,2-dimethyl-2-butenyl, 1,2-dimethyl-3-butenyl, 1,3-dimethyl-1-butenyl, 1,3-dimethyl-2-butenyl, 1,3-dimethyl-3-butenyl, 2,2-dimethyl-3-butenyl, 2,3-dimethyl-1-butenyl, 2,3-dimethyl-2-butenyl, 2,3-dimethyl-3-butenyl, 3,3-dimethyl-1-butenyl, 3,3-dimethyl-2-butenyl, 1-ethyl-1-butenyl, 1-ethyl-2-butenyl, 1-ethyl-3-butenyl, 2-ethyl-1-butenyl, 2-ethyl-2-butenyl, 2-ethyl-3-butenyl, 1,1,2-trimethyl-2-propenyl, 1-ethyl-1-methyl-2-propenyl, 1-ethyl-2-methyl-1-propenyl and 1-ethyl-2-methyl-2-propenyl,
alkynyl: straight-chain or branched alkynyl groups having 3 to 5 carbon atoms and a triple bond in any desired position, e.g. C
3
-C
5
-alkynyl such as 2-propynyl, 2-butynyl, 3-butynyl, 1-methyl-2-

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