CA1293513C - Cyclohexenone derivatives, their preparation and their use for controlling undesirable plant growth - Google Patents
Cyclohexenone derivatives, their preparation and their use for controlling undesirable plant growthInfo
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- CA1293513C CA1293513C CA000520008A CA520008A CA1293513C CA 1293513 C CA1293513 C CA 1293513C CA 000520008 A CA000520008 A CA 000520008A CA 520008 A CA520008 A CA 520008A CA 1293513 C CA1293513 C CA 1293513C
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/24—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with substituted hydrocarbon radicals attached to ring carbon atoms
- C07D213/44—Radicals substituted by doubly-bound oxygen, sulfur, or nitrogen atoms, or by two such atoms singly-bound to the same carbon atom
- C07D213/53—Nitrogen atoms
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/02—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms
- A01N43/04—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom
- A01N43/06—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom five-membered rings
- A01N43/08—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom five-membered rings with oxygen as the ring hetero atom
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/02—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms
- A01N43/04—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom
- A01N43/14—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom six-membered rings
- A01N43/16—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom six-membered rings with oxygen as the ring hetero atom
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/02—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms
- A01N43/04—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom
- A01N43/14—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom six-membered rings
- A01N43/18—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom six-membered rings with sulfur as the ring hetero atom
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/02—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms
- A01N43/24—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with two or more hetero atoms
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/34—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom
- A01N43/40—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom six-membered rings
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/90—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having two or more relevant hetero rings, condensed among themselves or with a common carbocyclic ring system
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
- C07D307/04—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having no double bonds between ring members or between ring members and non-ring members
- C07D307/10—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having no double bonds between ring members or between ring members and non-ring members with substituted hydrocarbon radicals attached to ring carbon atoms
- C07D307/14—Radicals substituted by nitrogen atoms not forming part of a nitro radical
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D309/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings
- C07D309/02—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings having no double bonds between ring members or between ring members and non-ring members
- C07D309/04—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings having no double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
- C07D309/06—Radicals substituted by oxygen atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D321/00—Heterocyclic compounds containing rings having two oxygen atoms as the only ring hetero atoms, not provided for by groups C07D317/00 - C07D319/00
- C07D321/02—Seven-membered rings
- C07D321/04—Seven-membered rings not condensed with other rings
- C07D321/06—1,3-Dioxepines; Hydrogenated 1,3-dioxepines
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D335/00—Heterocyclic compounds containing six-membered rings having one sulfur atom as the only ring hetero atom
- C07D335/02—Heterocyclic compounds containing six-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D493/00—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system
- C07D493/02—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system in which the condensed system contains two hetero rings
- C07D493/04—Ortho-condensed systems
Abstract
Abstract of the disclosure: Cyclohexenone derivatives of the formula
Description
The present invention relates to novel cyclohexe-none derivatives, a process for their preparation, herbi-cides which contain these compounds as active ingredients,and a method of controlling undes;rable plant growth.
DE-A-2 439 104 discloses that cyclohexenone deri-vatives can be used for controlling undesirable grasses ;n broad-leavèd crops. Furthermore, DE-A-3 121 355, DE-A-3 123 312 and DE-A-3 239 071 descr;be derivatives substi-tuted by heterocyclic structures.
We have found nove~ cyclohexenone derivatives of the formula I
oR4 / N_~R1 R3 ~ C~ R2 ~I) Q
~here R1 is 2-fluoroethyl, 2-chloroethyl, but-2-en-1-yl, methoxymethyl or methoxyethyl, R2 is C1-C4-alkyl, pre-ferably C2- or C3-alkyl, R3 is 2-isopropyl-1,3-di-oxepan-S-yl, tetrahydrothiopyran-3-yl~ tetrahydropyran-3-yl, tetrahydropyran-4-yl, 3-methyltetrahydropyran-4-yl, pyrid-3-yl, tetrahydrofuran-3-yl or 4a, 7,8,8a-tetrahydro-2H, SH-pyrano~4,3-b]pyran-3-yl, and R4 is hydrogen, C1-C20-alkylcarbonyl, C2-C20-alkenylcarbonyl, which preferably has one C-C double bond, or benzoyl which is unsubstitu-ted or substituted by C1-Cg-alkyl, or is C1-C4-tr;alkyl-s;lyl, C1-C4-alkylsulfonyl, phenylsulfonyl which is unsubstituted or substituted by C1-C4-alkyl, or Cl-C4-dialkylphosphono or C1-C4-dialkylthiophosphono, and salts of these compounds.
,;, 5~
- la -In particular, the invention provides such a derivative where R4 is hydrogen and provides for use of this compount in a process for the control of unwanted plants.
The novel cyclohexenone derivatives have a good herbicidal action, preferably against species from the grass family (Gramineae).
The compounds of the formula I can occur in a plurality of tautomeric fonms, all of which are embraced .' /
/
/
.. . . . . ..
3~ 3 - 2 - o.Z. 0050/38036 the claim. Far example, the compounds in which R4 is hyd-rogen can occur, inter alia, in the following tautomeric forms:
lORl ~XoRl ~ o 1 The compound in which R1 is but-2-en-1-yl is understood as meaning both the E and the Z isomer~
In formuLa I, R2 is, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, ;sobutyl or tert-butyl, and R4 ;s, for example, hydrogen, acetyl, pro-pionyl, acryloyl, butyryl, isobutyryl, p;valoyl, valeryl, caproyl, capronyl, lauroyl, palmitoyl, stearoyl, oleoyl, benzoyl, 4-methylben20yl, 4-he~ylbenzoyl, tr;methyls;lyl, tr;ethyls;lyl, methylsulfonyl, ethylsulfonyl, benzoyl-sulfonyl, 4-methylphenylsulfonyl, diethylphosphono or di-ethylth;ophosphono.
Su;table salts of the compounds of the formula Iare those which can be used in agriculture, for example the alkali metal salts, in particu~ar the potassium or sodium salts, alkaline earth metal salts, in particular calcium and magnesium salts, manganese, copper, zinc or iron salts and ammonium, sulfonium and phosphonium salts.
The novel compounds of the formula I can be ob-tained by first reacting a tricarbonyl compound of the for-mula II
o R2 where R2 and R3 have the above meanings, with an ammonium compound of the formula R10-NH3Y, where R1 has the above meanings and Y is an anion, for example a halide such as fluoride, chloride, bromide or iodide, carbonate or sulfate, i ~313 .
DE-A-2 439 104 discloses that cyclohexenone deri-vatives can be used for controlling undesirable grasses ;n broad-leavèd crops. Furthermore, DE-A-3 121 355, DE-A-3 123 312 and DE-A-3 239 071 descr;be derivatives substi-tuted by heterocyclic structures.
We have found nove~ cyclohexenone derivatives of the formula I
oR4 / N_~R1 R3 ~ C~ R2 ~I) Q
~here R1 is 2-fluoroethyl, 2-chloroethyl, but-2-en-1-yl, methoxymethyl or methoxyethyl, R2 is C1-C4-alkyl, pre-ferably C2- or C3-alkyl, R3 is 2-isopropyl-1,3-di-oxepan-S-yl, tetrahydrothiopyran-3-yl~ tetrahydropyran-3-yl, tetrahydropyran-4-yl, 3-methyltetrahydropyran-4-yl, pyrid-3-yl, tetrahydrofuran-3-yl or 4a, 7,8,8a-tetrahydro-2H, SH-pyrano~4,3-b]pyran-3-yl, and R4 is hydrogen, C1-C20-alkylcarbonyl, C2-C20-alkenylcarbonyl, which preferably has one C-C double bond, or benzoyl which is unsubstitu-ted or substituted by C1-Cg-alkyl, or is C1-C4-tr;alkyl-s;lyl, C1-C4-alkylsulfonyl, phenylsulfonyl which is unsubstituted or substituted by C1-C4-alkyl, or Cl-C4-dialkylphosphono or C1-C4-dialkylthiophosphono, and salts of these compounds.
,;, 5~
- la -In particular, the invention provides such a derivative where R4 is hydrogen and provides for use of this compount in a process for the control of unwanted plants.
The novel cyclohexenone derivatives have a good herbicidal action, preferably against species from the grass family (Gramineae).
The compounds of the formula I can occur in a plurality of tautomeric fonms, all of which are embraced .' /
/
/
.. . . . . ..
3~ 3 - 2 - o.Z. 0050/38036 the claim. Far example, the compounds in which R4 is hyd-rogen can occur, inter alia, in the following tautomeric forms:
lORl ~XoRl ~ o 1 The compound in which R1 is but-2-en-1-yl is understood as meaning both the E and the Z isomer~
In formuLa I, R2 is, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, ;sobutyl or tert-butyl, and R4 ;s, for example, hydrogen, acetyl, pro-pionyl, acryloyl, butyryl, isobutyryl, p;valoyl, valeryl, caproyl, capronyl, lauroyl, palmitoyl, stearoyl, oleoyl, benzoyl, 4-methylben20yl, 4-he~ylbenzoyl, tr;methyls;lyl, tr;ethyls;lyl, methylsulfonyl, ethylsulfonyl, benzoyl-sulfonyl, 4-methylphenylsulfonyl, diethylphosphono or di-ethylth;ophosphono.
Su;table salts of the compounds of the formula Iare those which can be used in agriculture, for example the alkali metal salts, in particu~ar the potassium or sodium salts, alkaline earth metal salts, in particular calcium and magnesium salts, manganese, copper, zinc or iron salts and ammonium, sulfonium and phosphonium salts.
The novel compounds of the formula I can be ob-tained by first reacting a tricarbonyl compound of the for-mula II
o R2 where R2 and R3 have the above meanings, with an ammonium compound of the formula R10-NH3Y, where R1 has the above meanings and Y is an anion, for example a halide such as fluoride, chloride, bromide or iodide, carbonate or sulfate, i ~313 .
- 3 - O.Z. 0053/38036 and then, where R4 is not hydrogen, reacting the product with a compound R4X in which R4 has the above meanings, with the exception of hydrogen, and X is a leaving group, in the presence or absence of an inert soLvent.
The reaction with the ammonium compound is advan-tageously carried out in the heterogeneous phase in an inert diluent at from O to 80C or from 0C to the boil-ing point of the reaction mixture in the presence of a base. Examples of suitable bases are the carbonates, bi-carbonates, acetates, alkanolates, hydroxides and oxides of alkali metals and alkaline earth metals, in particular of sodium, potassium, magnesium and calcium. Organic bases, such as pyridine or tertiary amines, may also be used.
Examples of suitable ;nert diluents for th;s reac-tion step are dimethyl sulfoxide, alcohols, such as ~etha-nol, ethanol or isopropanol, benzene, hydrocarbons and chlorohydrocarbons, such as chloroform, d;chloroethane, hexane or cyclohexane, carboxylates, such as ethyl acetate, and ethers, such as dioxane or tetrahydrofuran.
The reaction is complete after a few hours. The product can then be isolated by evaporating down the mix-ture, adding water and extracting with a nonpolar solvent, such as methylene chloride, and then distilling off the solvent under reduced pressure.
Instead of an ammonium compound, the tricarbonyl compounds of the formula II can first be reacted with a hydroxylamine of the formula R10-NH2, in which R1 has the above meanings, in an inert diluent at from 0C to the boil;ng point of the reaction mixture, in particular from 15 to 70C. If desired, the hydroxylamine can be employed in the form of an aqueous solution.
Examples of suitable solvents for this reaction are alcohols, such as methanol, ethanol, isopropanol or cyclohexanol, hydrocarbons and chlorohydrocarbons, such as hexane, cyclohexane, methylene chloride, toluene or dichloroethane, carboxylates, such as ethyl acetate, i3 - 4 - O.Z. 0050/38036 nitriles, such as acetonitrile, and cyclic ethers, such as tetrahydrofuran.
Where R4 in formula I is hydrogen, the end prod-uct is already obtained after the reaction with the ammon-ium compound or with the hydroxylamine.
However, where R4 in formula I is other thanhydrogen, the above reaction is foLLowed by a further re-action with a compound of the formula R4X in which R4 has the above meanings with the exception of hydrogen, and X
is a leaving group (eg. chlorine, bromine or hydroxyl).
This reaction step is a conventionaL esterifica-tion or silylation reaction. Such reactions are gene-ralLy carried out at from 0 to 150C, in the presence or absence of an inert solvent (eg~ toluene or chlorobenzene) and of an auxiliary base (eg. potassium carbonate).
The above alkali metal salts of the cyclohexenone derivatives of the formula I can be obtained by treating these compounds with sodium hydroxide or potassium hyd-roxide in aqueous solution or in an organic solvent, such as methanol, ethanol or acetone. Sodium alkanolates and potassium alkanolates may also be used as bases.
The other metal salts, for example the manganese, copper, zinc, iron, calcium and magnesium salts, can be prepared from the sodium salts by reaction with the app-ropriate metal chloride in aqueous solution. The ammonium, sulfonium and phosphonium salts can be prepared by reac-ting the novel compounds of the formula I with ammonium or phosphonium hydroxides, if necessary in aqueous solu-tion.
The tricarbonyl compounds of the formula II can be prepared from cyclohexenones of the formula III, which may occur in the tautomeric form IIIa (I~I) (IlIi~
1~3S~l~
The reaction with the ammonium compound is advan-tageously carried out in the heterogeneous phase in an inert diluent at from O to 80C or from 0C to the boil-ing point of the reaction mixture in the presence of a base. Examples of suitable bases are the carbonates, bi-carbonates, acetates, alkanolates, hydroxides and oxides of alkali metals and alkaline earth metals, in particular of sodium, potassium, magnesium and calcium. Organic bases, such as pyridine or tertiary amines, may also be used.
Examples of suitable ;nert diluents for th;s reac-tion step are dimethyl sulfoxide, alcohols, such as ~etha-nol, ethanol or isopropanol, benzene, hydrocarbons and chlorohydrocarbons, such as chloroform, d;chloroethane, hexane or cyclohexane, carboxylates, such as ethyl acetate, and ethers, such as dioxane or tetrahydrofuran.
The reaction is complete after a few hours. The product can then be isolated by evaporating down the mix-ture, adding water and extracting with a nonpolar solvent, such as methylene chloride, and then distilling off the solvent under reduced pressure.
Instead of an ammonium compound, the tricarbonyl compounds of the formula II can first be reacted with a hydroxylamine of the formula R10-NH2, in which R1 has the above meanings, in an inert diluent at from 0C to the boil;ng point of the reaction mixture, in particular from 15 to 70C. If desired, the hydroxylamine can be employed in the form of an aqueous solution.
Examples of suitable solvents for this reaction are alcohols, such as methanol, ethanol, isopropanol or cyclohexanol, hydrocarbons and chlorohydrocarbons, such as hexane, cyclohexane, methylene chloride, toluene or dichloroethane, carboxylates, such as ethyl acetate, i3 - 4 - O.Z. 0050/38036 nitriles, such as acetonitrile, and cyclic ethers, such as tetrahydrofuran.
Where R4 in formula I is hydrogen, the end prod-uct is already obtained after the reaction with the ammon-ium compound or with the hydroxylamine.
However, where R4 in formula I is other thanhydrogen, the above reaction is foLLowed by a further re-action with a compound of the formula R4X in which R4 has the above meanings with the exception of hydrogen, and X
is a leaving group (eg. chlorine, bromine or hydroxyl).
This reaction step is a conventionaL esterifica-tion or silylation reaction. Such reactions are gene-ralLy carried out at from 0 to 150C, in the presence or absence of an inert solvent (eg~ toluene or chlorobenzene) and of an auxiliary base (eg. potassium carbonate).
The above alkali metal salts of the cyclohexenone derivatives of the formula I can be obtained by treating these compounds with sodium hydroxide or potassium hyd-roxide in aqueous solution or in an organic solvent, such as methanol, ethanol or acetone. Sodium alkanolates and potassium alkanolates may also be used as bases.
The other metal salts, for example the manganese, copper, zinc, iron, calcium and magnesium salts, can be prepared from the sodium salts by reaction with the app-ropriate metal chloride in aqueous solution. The ammonium, sulfonium and phosphonium salts can be prepared by reac-ting the novel compounds of the formula I with ammonium or phosphonium hydroxides, if necessary in aqueous solu-tion.
The tricarbonyl compounds of the formula II can be prepared from cyclohexenones of the formula III, which may occur in the tautomeric form IIIa (I~I) (IlIi~
1~3S~l~
- 5 - O.Z. 0050/38036 by reaction with carboxylic anhydrides by a conventional method (Tetrahedron Lett. 29 (1975), 2491).
It is also possible to prepare the tricarbonyl compounds of the formula II via the enol ester inter-S mediates. These are obtained in the reaction of the cyclo-hexenones of the formula III (possibly as isomer mixtures) and can be subjected to a rearrangement reaction in the presence of an imidazole or pyridine derivative (JP-A-36052/1979).
The compounds of the formula III are likewise ob-tained by methods known from the literature, as shown ;n the scheme below:
3~l3 - 6 - O. Z . 0050/38036 R 3-CHo \
o / \ CR2tt:oo8)2 -C-~H3 / \ Pyrid~i~e ~ase O O
R3--CH~CH-C-CH3 R3~ ~C~-c--OH
\ C~2(C00~1~3~2 ~ C83-O~
\ Cl~3OI~4 ,-R3-CII-C~I-COOCH3 /H3 C CH2 COOCH3/~H3ODs ~ .' r~ ' ~13COOC
1 ) KOI~
~ 2 ) ~ICl R3~
~~0 3~; l3 - 7 - O.Z. 0050/38036 The aldehydes of the general formula R3-CHo which are shown in the above scheme are obtainable by conven-tional methods, for example by oxidation of the correspond-ing alcohols, reduction of carbo%ylic acid derivatives or S hydroformylation of olefins.
The Examples which follow illustrate the prepara-tion of the novel cyclohexenone derivatives. Parts by weight bear the same relation to parts by volume as that of the kilogram to the liter.
The 1H NMR spectra were recorded in deuterochloro-form as solvent, with tetramethyls;lane as the internal nal standard. The 1H chemical shifts are stated as ~ppm]
in each case. The following abbreviations are used to describe the signal structure:
s ~ s;nglet, d - doublet, t = tr;plet, q = quartet, m =
multiplet ~strongest s;gnal).
In the Examples, but-2-en-l-yl ;s abbreviated to 2-butenyl. The ;somer form ;s spec;f;ed ;n each case.
7.3 parts by we;ght of 2-acetyl-5-(3-tetrahydro-th;opyranyl)-cyclohexane-1,3-d;one, 3.6 parts by weight of 2-butenyloxyammon;um chloride and 2.4 parts by weight of sodium bicarbonate in 100 parts by volume of methanol were st;rred for 16 hours at room temperature. The sol-vent was evaporated off under reduced pressure, the resi-due was stirred with a mixture of 50 parts by volume of water and 50 parts by volume of d;chloromethane, and the aqueous phase was extracted once with 50 parts by valume of dichloromethane. The combined organic phases were washed with water and dr;ed over sod;um sulfate, and the solvent was d;st;lled off under reduced pressure. 2-~1-(2-butenyloxyimino)-ethyl]-3-hydroxy-5-(3-tetrahydrothio-pyranyl)-cyclohex-2-en-1-one was obtained as a solid of melt;ng point 65C (compound No. 2).
86 parts by weight of 2-butyryl-5-(3-tetrahydro-thiopyranyl)-cyclohexane-1,3-dione and Z.6 parts by weight .
l~r`~S:l~
It is also possible to prepare the tricarbonyl compounds of the formula II via the enol ester inter-S mediates. These are obtained in the reaction of the cyclo-hexenones of the formula III (possibly as isomer mixtures) and can be subjected to a rearrangement reaction in the presence of an imidazole or pyridine derivative (JP-A-36052/1979).
The compounds of the formula III are likewise ob-tained by methods known from the literature, as shown ;n the scheme below:
3~l3 - 6 - O. Z . 0050/38036 R 3-CHo \
o / \ CR2tt:oo8)2 -C-~H3 / \ Pyrid~i~e ~ase O O
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~~0 3~; l3 - 7 - O.Z. 0050/38036 The aldehydes of the general formula R3-CHo which are shown in the above scheme are obtainable by conven-tional methods, for example by oxidation of the correspond-ing alcohols, reduction of carbo%ylic acid derivatives or S hydroformylation of olefins.
The Examples which follow illustrate the prepara-tion of the novel cyclohexenone derivatives. Parts by weight bear the same relation to parts by volume as that of the kilogram to the liter.
The 1H NMR spectra were recorded in deuterochloro-form as solvent, with tetramethyls;lane as the internal nal standard. The 1H chemical shifts are stated as ~ppm]
in each case. The following abbreviations are used to describe the signal structure:
s ~ s;nglet, d - doublet, t = tr;plet, q = quartet, m =
multiplet ~strongest s;gnal).
In the Examples, but-2-en-l-yl ;s abbreviated to 2-butenyl. The ;somer form ;s spec;f;ed ;n each case.
7.3 parts by we;ght of 2-acetyl-5-(3-tetrahydro-th;opyranyl)-cyclohexane-1,3-d;one, 3.6 parts by weight of 2-butenyloxyammon;um chloride and 2.4 parts by weight of sodium bicarbonate in 100 parts by volume of methanol were st;rred for 16 hours at room temperature. The sol-vent was evaporated off under reduced pressure, the resi-due was stirred with a mixture of 50 parts by volume of water and 50 parts by volume of d;chloromethane, and the aqueous phase was extracted once with 50 parts by valume of dichloromethane. The combined organic phases were washed with water and dr;ed over sod;um sulfate, and the solvent was d;st;lled off under reduced pressure. 2-~1-(2-butenyloxyimino)-ethyl]-3-hydroxy-5-(3-tetrahydrothio-pyranyl)-cyclohex-2-en-1-one was obtained as a solid of melt;ng point 65C (compound No. 2).
86 parts by weight of 2-butyryl-5-(3-tetrahydro-thiopyranyl)-cyclohexane-1,3-dione and Z.6 parts by weight .
l~r`~S:l~
- 8 - O.Z. 0050/38036 of 2-butenyloxyamine in dichloromethane were stirred for 16 hours at room temperature. The solution was washed with 5% strength by weight hydrochloric acid and water and dried over sodium sulfate, and the solvent was dis-tilled off under reduced pressure. 2-[1-(2-3utenyloxy-imino)-butyl]-3-hydroxy-5-(3-tetrahydrothiopyranyL)-cyclo-hex-2-en-1-one was obtained in the form of an oil (com-pound No. 14).
S parts by weight of 2-butyryl-5-(tetrahydrothio-pyran-3-yl)-cyclohexane-1,3-dione, 2.31 parts by weight of 2-fluoroethoxyammonium chloride and 1.68 parts by weight of sodium bicarbonate in 100 parts by volume of methanol were stirred for 16 hours at room temperature.
The solvent was distilled off under reduced pressure, the residue was taken up with dichloromethane, and water was added to the solution in a ratio of 1:1. The aqueous phase was separated off and extracted with d;chloromethane.
The combined organic phases were dried over sodium sul-fate and concentrated under reduced pressure. 5.3 parts(85%) of 2-~1-(2-fluoroethoximino)-butyl]-3-hydroxy-5-(tetrahydrothiopyran-3-yl)-cyclohex-2-en-1-one were ob-tained as a pale yellow oil (compound No. 13).
Other cyclohexenone derivatives are listed in Tables 1 and 2 and are prepared in a similar manner.
In Table 1, R4 is hydrogen.
S parts by weight of 2-butyryl-5-(tetrahydrothio-pyran-3-yl)-cyclohexane-1,3-dione, 2.31 parts by weight of 2-fluoroethoxyammonium chloride and 1.68 parts by weight of sodium bicarbonate in 100 parts by volume of methanol were stirred for 16 hours at room temperature.
The solvent was distilled off under reduced pressure, the residue was taken up with dichloromethane, and water was added to the solution in a ratio of 1:1. The aqueous phase was separated off and extracted with d;chloromethane.
The combined organic phases were dried over sodium sul-fate and concentrated under reduced pressure. 5.3 parts(85%) of 2-~1-(2-fluoroethoximino)-butyl]-3-hydroxy-5-(tetrahydrothiopyran-3-yl)-cyclohex-2-en-1-one were ob-tained as a pale yellow oil (compound No. 13).
Other cyclohexenone derivatives are listed in Tables 1 and 2 and are prepared in a similar manner.
In Table 1, R4 is hydrogen.
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.13 - 17 - O.Z. 0~50/38036 The cyclohexenone derivatlves of the formula I may be applied for instance in the form of directly sprayable solutions, powders, suspensions (including high-percentage aqueous, oily or other suspensions), dispersions, emulsions, 05 oil dispersions, pastes, dusts, broadcasting agents, or granules by spraying, atomizing, dusting, broadcasting or watering. The forms of application depend entirely on the purpose for which the agents are being used, but they must ensure as fine a distribution of the active ingredients according to the invention as possible.
For the preparation of solutions, emulsions, pastes and oil dispersions to be sprayed direck, mineral oil frac-tions of medium to high boiling point, such as kerosene or diesel oil, further coal-tar oils, and oils of vegetable or lS animal origin, aliphatic, cyclic and aromatic hydrocarbons such as benzene, toluene, xylene, paraffin, tetrahydro-naphthalene, alkylated naphthalenes and their derivatives such as methanol, ethanol, propanol, butanol, chloroform, carbon tetrachloride, cyclohexanol, cyclohexanone, chloro-benzene, isophorone, etc., and strongly polar solvents suchas dimethylformamide, dimethyl sulfoxide, N-methyl-pyrrolidone, water, etc. are suitable.
Aqueous formulations may be prepared from emulsion con-centrates, pastes, oil dispersions, wettable powders or water-dispersible granules by adding water. To prepare emulsions, pastes and oil dispersions the ingredients as such or dissolved in an oil or solvent may be homogenized in water by means of wetting or dispersing agents, adherents or emulsifiers. Concentrates which are suitable for dilution with water may be prepared from active in-gredient, wetting agent, adherent, emulsifying or dispersing agent and possibly solvent or oil.
Examples of surfactants are: alkali metal, alkaline earth metal and ammonium salts of ligninsulfonic acid, naphthalenesulfonic acids, phenolsulfonic acids, alkylaryl sulfonates, alkyl sulfates, and alkyl sulfonates, alkali ?3S:~3 - 18 - O.Z. 0050/38036 metal and alkaline earth metal salts of dibutylnaphthalene-sulfonic acid, lauryl ether sulfate, fatty alcohol sul-fates, alkali metal and alkaline earth metal salts of fatty acids, salts of sulfated hexadecanols, heptadecanols, and 05 octadecanols, salts of sulfated fatty alcohol glycol ethers, condensation products of sulfonated naphthalene and naphthalene derivatives with formaldehyde, condensation products of naphthalene or naphthalenesulfonic acids with phenol and formaldehyde, polyoxyethylene octylphenol ethers, ethoxylated isooctylphenol, ethoxylated octylphenol and ethoxylated nonylphenol, alkylphenol polyglycol ethers, tributylphenyl polyglycol ethers, alkylaryl polyether alcohols, isotridecyl alcohol, fatty alcohol ethylene oxide condensates, ethoxylated castor oil, polyoxyethylene alkyl ethers, ethoxylated polyoxypropylene, lauryl alcohol poly-glycol ether acetal, sorbitol esters, lignin, sulEite waste li~uors and methyl cellulose.
Powders, dusts and broadcasting agents may be prepared by mixing or grinding the active ingredients with a solid carrier.
Granules, e.g., coated, impregnated or homogeneous gra-nules, may be prepared by bonding the active ingredients to solid carriers. Examples o~ solid carriers are mineral earths such as 9ilicic acid, silica gels, silicates, talc, kaolin, attapulgus clay, limestone, lime, chalk, bole, loess, clay, dolomite, diatomaceous earth, calcium sulfate, magnesium sulfate, magnesium oxide, ground plastics, fertilizers such as ammonium sulfate, ammonium phosphate, ammonium nitrate, and ureas, and vegetable products such as grain flours, bark meal, wood meal, and nutshell meal, cellulosic powders, etc.
The formulations contain from O.l to 9S, and prefer-ably 0.5 to 9O, ~; by weight of active ingredient.
~t~ ,13 - 19 - O.Z. 0050/38036 Examples of formulations are given below.
I. 90 parts by weight of compound no. 134 is mixed with 10 parts by weight of N-methyl-alpha-pyrrolidone. A
05 mixture is obtained which is suitable for application in the form of very fine drops.
II. 20 parts by weight of compound no. 50 is dis-solved in a mixture consisting of 80 parts by weight of xylene, 10 parts by weight of the adduct of 8 to 10 moles of ethylene oxide and 1 mole of oleic acid-N-monoethanol-amide, 5 parts by weight of the calcium salt of dodecyl-benzenesulfonic acid, and 5 parts by weight of the adduct of 40 moles of ethylene oxide and 1 mole of castor oi:L. By pouring the solution into 100,000 parts by weight of water and uniormly distributing it therein, an aqueou~ disper-sion i~ obtained containing 0.02% by weight oE the active ingredient.
III. 20 parts by weight of compound no. 2 is dis-solved in a mixture consisting of 40 parts by weight of cyclohexanone, 30 parts by weight of isobutanol, 20 parts by weight of the adduct of 7 moles of ethylene oxide and 1 mole of isooctylphenol, and 10 parts by weight of the adduct of 40 moles of ethylene oxide and 1 mole of castor oil. By pouring the solution into 100,000 parts by weight of water and finely distributing it therein, an aqueous dispersion is obtained containing 0.02~ by weight of the active ingredient.
IV. 20 parts by weight of compound no. 104 is dis-solved in a mixture consisting of 25 parts by weight of cyclohexanone, 65 parts by weight of a mineral oil fraction having a boiling point between 210 and 280C, and 10 parts by weight of the adduct of 40 moles of ethylene oxide and 1 mole of castor oil. By pouring the solution into 100,000 parts by weight of water and uniformly distributing it therein, an aqueous dispersion is obtained containing 0.02~; by weight of the active ingredient.
- 20 - o.z. 0050/38036 V. 20 parts by weight of compound no. 14 is well mixed with 3 parts by weight of the sodium salt of diiso-butylnaphthalene-alpha-sulfonic acid, 17 parts by weight of the sodium salt of a lignin-sulfonic acid obtained from a 05 sulfite waste liquor, and 60 parts by weight of powdered silica gel, and triturated in a hammer mill. By uniformly distributing the mixture in 20,000 parts by weight of water, a spray liquor is obtained containing O.l~i by weight of the active ingredient.
VI. 3 parts by weight of compound no. 122 is intimately mixed with 97 parts by weight of particulate kaolin. ~ dust is obtained containing 3~, by weight of the active ingredient.
VII. 30 parts by weight of compound no. 2 is intimately mixed with a mixture consisting of 92 parts by weight of powdered silica gel and 8 parts by weight oE
par~fin oil which has been sprayed onto the surface o~
this silica gel. A Eormulation of the active ingredient is obtained having good adherence.
VIII. 20 parts by weight of compound no. 50 is intimately mixed with 2 parts by weight of the calcium salt of dodecylbenzenesulfonic acid, 8 parts by weight of a fatty alcohol polyglycol ether, 2 parts by weight of the sodium salt of a phenolsulfonic acid-urea-formaldehyde condensate and 68 parts by weight of a paraffinic mineral oil. A stable oily dispersion is obtained.
IX. 40 parts by weight of compound no. 2 is dissolved in 60 parts by weight of a mixture consisting of 93 wt~. of xylene and 7 wt~ of the adduct of 8 moles of ethylene oxide and 1 mole of nonyl phenol. A solution is obtained contain-ing 40 wt~ of active ingredient.
The novel herbicides exhibit a good herbicidal action especially on Gramineae species. They are tolerated by, and are thus selective in, broadleaved crops and monocotyledons not belonging to the Gramineae family. Some of the novel compounds also have a herbicidal action on broadleaved plants, and some are suitable for non-selective control or suppression of unwanted vegetation.
3~:13 - 21 - O.Z. 0050/38036 The active ingredients may be applied pre- or post-emergence. If certain crop plants tolerate the active ingredients less well, application techniques may be used in which the herbicidal agents are sprayed from suitable 05 equipment in such a manner that the leaves of sensitive crop plants are if possible not touched, and the agents reach the soil or the unwanted plants growing beneath the crop plants (post-directed, lay-by treatment).
The amount of active ingredient applied depends on the time of the year, the plants to be combated and their growth stage, and varies from 0.015 to 3 kg/ha, but is preferably from 0.05 to 0.5 kg/ha.
The action of the cyclohexenone derivatives of the formula I on plant growth is demonstrated in greenhouse experiment~.
The vessels emplo~ed were plastic Elowerpots having a volume o 300 cm3, and which were filled with a sandy loam containing about 1.5~ humus. The seeds of the test plants were sown shallow, and separately, according to species.
For the preemergence treatment, the active ingredients were applied to the surface of the soil immediately after the seeds had been sown. The compounds were emulsified or sus-pended in water as vehicle, and sprayed through finely distributing nozzles. The application rate was 3.0 kg of active ingredient per hectare.
After the agents had been applied, the vessels were lightly sprinkler-irrigated to induce germination and growth. Transparent plastic covers were then placed on the vessels until the plants had taken root. The cover ensured uniform germination of the plants, insofar as this was not impaired by the active ingredients.
For the postemergence treatment, the plants were first grown in the vessels to a height of from 3 to 15 cm, depend-ing on growth form, before being treated. The soybean plants were grown in a peat-enriched substrate. For this treatment, either plants which had been sown directly in the pots and grown there were selected, or plants which had - 22 - o.Z. 0050/38036 been grown from seedlings and were transplanted to the pots a few days before treatment. The application rates for postemergence treatment were 0.015 to 3 kg of active ingre-dients per hectare. No covers were placed on the vessels in 05 this method.
The pots were set up in the greenhouse - species from warmer areas at from 20 to 35C, and species from moder-ate climates at lO to 25C. The experiments were run for 2 to 4 weeks. During this period, the plants were tended and their reactions to the various treatments assessed. The scale used for assessment was O to lOO, O denoting no damage or normal emergence, and lOO denoting nonemergence or complete destruction of at least the visible plant parts.
The plants used in the e~periments were Alepecurus myosuroides, Avena fatua, ~eta vulgaris, Centaurea cyanus, Digitaria sanguinalis, Echinochloa crus-galli, Gl~cine max., Hordium vulgare, Ipomoea spp., Mercurialis annua, Oryza sativa, Setaria italica, Sinapis alba, Sorghum bicolor, Triticum aestivum and Zea mays.
The herbicidal action of active ingredients nos. 134, 122, 50 and 104 selected by way of example on common grassy weeds and volunteer plants is far superior to that of closely related chemical derivatives. For comparison pur-poses, herbicides were used which contained active ingre-dients disclosed in DE-A-3,34~,265, DE-A-3,239,071, DE-A-3,123,312 and DE-A-3,121,355.
For example compounds nos. 2 and 14, applied at a rate of 3 kg/ha, are suitable for combatting unwanted grassy vegetation in boradleaved crops such as soybeans and sugar-beets, without appreciably influencing them. They have a greater herbicidal action than comparable prior art com-pounds disclosed in DE-A-3,121,355.
Compound no. 2 selected by way of example demonstrates the possibility of using the novel compounds for suppressing unwanted broadleaved vegetation. A far better herbicidal action is achieved both pre- and postemergence than with prior art active ingredients.
, - 23 - O.Z. 0~50/38036 Compared with prior art compounds known from British 2,137,200 and EP-125,094, for instance compound no. 49 has, at a low application rate, a far greater herbicidal action on unwanted grasses and volunteer wheat, 05 and is excellently tolerated by soybeans.
Compounds nos. 8, 26 and 62 are suitable even at low application rates for combatting a broad spectrum of unwanted grassy plants without damaging soybeans.
In view of the number of weeds which can be combatted, the tolerance of the novel compounds by crop plants or the desired influcence on growth, and in view of the numerous application methods possible, the compounds according to the invention may be used in a large number of crops example are given below:
15 Botanical name Common name Allium cepa onions Ananas comosus pineapples Arachis hypogaea peanuts (groundnuts) 20 Asparagus officinalis asparagus Beta vulgaris spp. altissima sugarbeets Beta vulgaris spp. rapa fodder beets Beta vulgaris spp. esculenta table beets, red beets Brassica napus var. napus rapeseed 25 Brassica napus var. napobrassica swedes Brassica napus var. rapa turnips Brassica rapa var. silvestris Camellia sinensis tea plants Carthamus tinctorius safflower 30 Carya illinoinensis pecan trees Citrus limon lemons Citrus maxima grapefruits Citrus reticulata mandarins Citrus sinensis orange trees 35 Coffea arabica (Coffea canephora, Coffea liberica) coffee plants Cucumis melo melons Cucumis sativus cucumbers 3~13 - 24 - O.Z. 0050/38036 Botanical name Common name Cynodon dactylon Bermudagrass Daucus carota carrots 05 Elais guineensis oil palms Fragaria vesca strawberries Glycine max soybeans Gossypium hirsutum (Gossypium arboreum cotton lO Gossypium herbaceum Gossypium vitifolium) Helianthus annuus sunflowers Helianthus tuberosus Jerusalem artichoke Hevea brasiliensis rubber plants 15 Humulus lupulus hops Ipomoea batatas sweet potatoes Juglans regia walnut trees Lactuca sativa lettuce Lens culinaris lentils 20 Linum usitatissimum flax Lycopersicon lycopersicum tomatoes Malus spp. apple trees Manihot esculenta cassava Medicago sativa alfalfa (lucerne) 25 Mentha piperita peppermint Musa spp. banana plants Nicothiana tabacum tobacco (N. rustica) Olea europaea olive trees 30 Phaseolus lunatus limabeans Phaseolus mungo mungbeans Phaseolus vulgar~s snapbeans, green beans, dry beans Petroselinum crispum parsley spp. tuberosum Picea abies Norway spruce Abies alba fir trees Pinus spp. pine trees - 25 - O.Z. 0050/38036 Botanical name Common name Pisum sativum English peas Prunus avium cherxy trees OS Prunus domestica plum trees Prunus dulcis almond trees Prunus persica peach trees Pyrus communis pear trees Ribes sylvestre redcurrants ~O Ribes uva-crispa gooseberries Ricinus communis castor-oil plants Saccharum officinarum sugar cane Secale cereale rye Sesamum indicum sesame 15 Solanum tuberosum Irish potatoes Spinacia oleracea spinach Theobroma cacao cacao plants Trifolium pratense red clover Triticum aestivum wheat 20 Vaccinium corymbosum blueberries Vaccinium vitis-idaea cranberries Vicia faba tick beans Vigna sinensis (V. unguiculata) cow peas Vitis vinifera grapes 25 Zea mays Indian corn, sweet corn, maize _ To increase the spectrum of action and to achieve synergistic effects, the cyclohexenone derivatives of the formula I may be mixed and applied together with numerous representatives of other herbicidal or growth-regulating active ingredient groups. Examples of suitable mixture components are diazines, 4H-3,1-benzoxazine derivatives, benzothiadiazinones, 2,6-dinitroanilines, N-phenyl-carbamates, thiolcarbamates, halocarboxylic acids, triazines, amides, ureas, triazinones, uracils, benzofuran derivatives, quinolinecarboxylic acids, etc.
S~3 - 26 - O.Z. 0050/38036 It may also be useful to apply the compounds of the formula I, either alone or in combination with other herbicldes, in admixture with other crop protection agents, e.g., agents for combatting pests or phytopathogenic fungi 05 or bacteria. The compounds may also be mixed with solutions of mineral salts used to remedy nutritional or trace element deficiencies. Non-phytotoxic oils and oil concentrates may also be added.
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.13 - 17 - O.Z. 0~50/38036 The cyclohexenone derivatlves of the formula I may be applied for instance in the form of directly sprayable solutions, powders, suspensions (including high-percentage aqueous, oily or other suspensions), dispersions, emulsions, 05 oil dispersions, pastes, dusts, broadcasting agents, or granules by spraying, atomizing, dusting, broadcasting or watering. The forms of application depend entirely on the purpose for which the agents are being used, but they must ensure as fine a distribution of the active ingredients according to the invention as possible.
For the preparation of solutions, emulsions, pastes and oil dispersions to be sprayed direck, mineral oil frac-tions of medium to high boiling point, such as kerosene or diesel oil, further coal-tar oils, and oils of vegetable or lS animal origin, aliphatic, cyclic and aromatic hydrocarbons such as benzene, toluene, xylene, paraffin, tetrahydro-naphthalene, alkylated naphthalenes and their derivatives such as methanol, ethanol, propanol, butanol, chloroform, carbon tetrachloride, cyclohexanol, cyclohexanone, chloro-benzene, isophorone, etc., and strongly polar solvents suchas dimethylformamide, dimethyl sulfoxide, N-methyl-pyrrolidone, water, etc. are suitable.
Aqueous formulations may be prepared from emulsion con-centrates, pastes, oil dispersions, wettable powders or water-dispersible granules by adding water. To prepare emulsions, pastes and oil dispersions the ingredients as such or dissolved in an oil or solvent may be homogenized in water by means of wetting or dispersing agents, adherents or emulsifiers. Concentrates which are suitable for dilution with water may be prepared from active in-gredient, wetting agent, adherent, emulsifying or dispersing agent and possibly solvent or oil.
Examples of surfactants are: alkali metal, alkaline earth metal and ammonium salts of ligninsulfonic acid, naphthalenesulfonic acids, phenolsulfonic acids, alkylaryl sulfonates, alkyl sulfates, and alkyl sulfonates, alkali ?3S:~3 - 18 - O.Z. 0050/38036 metal and alkaline earth metal salts of dibutylnaphthalene-sulfonic acid, lauryl ether sulfate, fatty alcohol sul-fates, alkali metal and alkaline earth metal salts of fatty acids, salts of sulfated hexadecanols, heptadecanols, and 05 octadecanols, salts of sulfated fatty alcohol glycol ethers, condensation products of sulfonated naphthalene and naphthalene derivatives with formaldehyde, condensation products of naphthalene or naphthalenesulfonic acids with phenol and formaldehyde, polyoxyethylene octylphenol ethers, ethoxylated isooctylphenol, ethoxylated octylphenol and ethoxylated nonylphenol, alkylphenol polyglycol ethers, tributylphenyl polyglycol ethers, alkylaryl polyether alcohols, isotridecyl alcohol, fatty alcohol ethylene oxide condensates, ethoxylated castor oil, polyoxyethylene alkyl ethers, ethoxylated polyoxypropylene, lauryl alcohol poly-glycol ether acetal, sorbitol esters, lignin, sulEite waste li~uors and methyl cellulose.
Powders, dusts and broadcasting agents may be prepared by mixing or grinding the active ingredients with a solid carrier.
Granules, e.g., coated, impregnated or homogeneous gra-nules, may be prepared by bonding the active ingredients to solid carriers. Examples o~ solid carriers are mineral earths such as 9ilicic acid, silica gels, silicates, talc, kaolin, attapulgus clay, limestone, lime, chalk, bole, loess, clay, dolomite, diatomaceous earth, calcium sulfate, magnesium sulfate, magnesium oxide, ground plastics, fertilizers such as ammonium sulfate, ammonium phosphate, ammonium nitrate, and ureas, and vegetable products such as grain flours, bark meal, wood meal, and nutshell meal, cellulosic powders, etc.
The formulations contain from O.l to 9S, and prefer-ably 0.5 to 9O, ~; by weight of active ingredient.
~t~ ,13 - 19 - O.Z. 0050/38036 Examples of formulations are given below.
I. 90 parts by weight of compound no. 134 is mixed with 10 parts by weight of N-methyl-alpha-pyrrolidone. A
05 mixture is obtained which is suitable for application in the form of very fine drops.
II. 20 parts by weight of compound no. 50 is dis-solved in a mixture consisting of 80 parts by weight of xylene, 10 parts by weight of the adduct of 8 to 10 moles of ethylene oxide and 1 mole of oleic acid-N-monoethanol-amide, 5 parts by weight of the calcium salt of dodecyl-benzenesulfonic acid, and 5 parts by weight of the adduct of 40 moles of ethylene oxide and 1 mole of castor oi:L. By pouring the solution into 100,000 parts by weight of water and uniormly distributing it therein, an aqueou~ disper-sion i~ obtained containing 0.02% by weight oE the active ingredient.
III. 20 parts by weight of compound no. 2 is dis-solved in a mixture consisting of 40 parts by weight of cyclohexanone, 30 parts by weight of isobutanol, 20 parts by weight of the adduct of 7 moles of ethylene oxide and 1 mole of isooctylphenol, and 10 parts by weight of the adduct of 40 moles of ethylene oxide and 1 mole of castor oil. By pouring the solution into 100,000 parts by weight of water and finely distributing it therein, an aqueous dispersion is obtained containing 0.02~ by weight of the active ingredient.
IV. 20 parts by weight of compound no. 104 is dis-solved in a mixture consisting of 25 parts by weight of cyclohexanone, 65 parts by weight of a mineral oil fraction having a boiling point between 210 and 280C, and 10 parts by weight of the adduct of 40 moles of ethylene oxide and 1 mole of castor oil. By pouring the solution into 100,000 parts by weight of water and uniformly distributing it therein, an aqueous dispersion is obtained containing 0.02~; by weight of the active ingredient.
- 20 - o.z. 0050/38036 V. 20 parts by weight of compound no. 14 is well mixed with 3 parts by weight of the sodium salt of diiso-butylnaphthalene-alpha-sulfonic acid, 17 parts by weight of the sodium salt of a lignin-sulfonic acid obtained from a 05 sulfite waste liquor, and 60 parts by weight of powdered silica gel, and triturated in a hammer mill. By uniformly distributing the mixture in 20,000 parts by weight of water, a spray liquor is obtained containing O.l~i by weight of the active ingredient.
VI. 3 parts by weight of compound no. 122 is intimately mixed with 97 parts by weight of particulate kaolin. ~ dust is obtained containing 3~, by weight of the active ingredient.
VII. 30 parts by weight of compound no. 2 is intimately mixed with a mixture consisting of 92 parts by weight of powdered silica gel and 8 parts by weight oE
par~fin oil which has been sprayed onto the surface o~
this silica gel. A Eormulation of the active ingredient is obtained having good adherence.
VIII. 20 parts by weight of compound no. 50 is intimately mixed with 2 parts by weight of the calcium salt of dodecylbenzenesulfonic acid, 8 parts by weight of a fatty alcohol polyglycol ether, 2 parts by weight of the sodium salt of a phenolsulfonic acid-urea-formaldehyde condensate and 68 parts by weight of a paraffinic mineral oil. A stable oily dispersion is obtained.
IX. 40 parts by weight of compound no. 2 is dissolved in 60 parts by weight of a mixture consisting of 93 wt~. of xylene and 7 wt~ of the adduct of 8 moles of ethylene oxide and 1 mole of nonyl phenol. A solution is obtained contain-ing 40 wt~ of active ingredient.
The novel herbicides exhibit a good herbicidal action especially on Gramineae species. They are tolerated by, and are thus selective in, broadleaved crops and monocotyledons not belonging to the Gramineae family. Some of the novel compounds also have a herbicidal action on broadleaved plants, and some are suitable for non-selective control or suppression of unwanted vegetation.
3~:13 - 21 - O.Z. 0050/38036 The active ingredients may be applied pre- or post-emergence. If certain crop plants tolerate the active ingredients less well, application techniques may be used in which the herbicidal agents are sprayed from suitable 05 equipment in such a manner that the leaves of sensitive crop plants are if possible not touched, and the agents reach the soil or the unwanted plants growing beneath the crop plants (post-directed, lay-by treatment).
The amount of active ingredient applied depends on the time of the year, the plants to be combated and their growth stage, and varies from 0.015 to 3 kg/ha, but is preferably from 0.05 to 0.5 kg/ha.
The action of the cyclohexenone derivatives of the formula I on plant growth is demonstrated in greenhouse experiment~.
The vessels emplo~ed were plastic Elowerpots having a volume o 300 cm3, and which were filled with a sandy loam containing about 1.5~ humus. The seeds of the test plants were sown shallow, and separately, according to species.
For the preemergence treatment, the active ingredients were applied to the surface of the soil immediately after the seeds had been sown. The compounds were emulsified or sus-pended in water as vehicle, and sprayed through finely distributing nozzles. The application rate was 3.0 kg of active ingredient per hectare.
After the agents had been applied, the vessels were lightly sprinkler-irrigated to induce germination and growth. Transparent plastic covers were then placed on the vessels until the plants had taken root. The cover ensured uniform germination of the plants, insofar as this was not impaired by the active ingredients.
For the postemergence treatment, the plants were first grown in the vessels to a height of from 3 to 15 cm, depend-ing on growth form, before being treated. The soybean plants were grown in a peat-enriched substrate. For this treatment, either plants which had been sown directly in the pots and grown there were selected, or plants which had - 22 - o.Z. 0050/38036 been grown from seedlings and were transplanted to the pots a few days before treatment. The application rates for postemergence treatment were 0.015 to 3 kg of active ingre-dients per hectare. No covers were placed on the vessels in 05 this method.
The pots were set up in the greenhouse - species from warmer areas at from 20 to 35C, and species from moder-ate climates at lO to 25C. The experiments were run for 2 to 4 weeks. During this period, the plants were tended and their reactions to the various treatments assessed. The scale used for assessment was O to lOO, O denoting no damage or normal emergence, and lOO denoting nonemergence or complete destruction of at least the visible plant parts.
The plants used in the e~periments were Alepecurus myosuroides, Avena fatua, ~eta vulgaris, Centaurea cyanus, Digitaria sanguinalis, Echinochloa crus-galli, Gl~cine max., Hordium vulgare, Ipomoea spp., Mercurialis annua, Oryza sativa, Setaria italica, Sinapis alba, Sorghum bicolor, Triticum aestivum and Zea mays.
The herbicidal action of active ingredients nos. 134, 122, 50 and 104 selected by way of example on common grassy weeds and volunteer plants is far superior to that of closely related chemical derivatives. For comparison pur-poses, herbicides were used which contained active ingre-dients disclosed in DE-A-3,34~,265, DE-A-3,239,071, DE-A-3,123,312 and DE-A-3,121,355.
For example compounds nos. 2 and 14, applied at a rate of 3 kg/ha, are suitable for combatting unwanted grassy vegetation in boradleaved crops such as soybeans and sugar-beets, without appreciably influencing them. They have a greater herbicidal action than comparable prior art com-pounds disclosed in DE-A-3,121,355.
Compound no. 2 selected by way of example demonstrates the possibility of using the novel compounds for suppressing unwanted broadleaved vegetation. A far better herbicidal action is achieved both pre- and postemergence than with prior art active ingredients.
, - 23 - O.Z. 0~50/38036 Compared with prior art compounds known from British 2,137,200 and EP-125,094, for instance compound no. 49 has, at a low application rate, a far greater herbicidal action on unwanted grasses and volunteer wheat, 05 and is excellently tolerated by soybeans.
Compounds nos. 8, 26 and 62 are suitable even at low application rates for combatting a broad spectrum of unwanted grassy plants without damaging soybeans.
In view of the number of weeds which can be combatted, the tolerance of the novel compounds by crop plants or the desired influcence on growth, and in view of the numerous application methods possible, the compounds according to the invention may be used in a large number of crops example are given below:
15 Botanical name Common name Allium cepa onions Ananas comosus pineapples Arachis hypogaea peanuts (groundnuts) 20 Asparagus officinalis asparagus Beta vulgaris spp. altissima sugarbeets Beta vulgaris spp. rapa fodder beets Beta vulgaris spp. esculenta table beets, red beets Brassica napus var. napus rapeseed 25 Brassica napus var. napobrassica swedes Brassica napus var. rapa turnips Brassica rapa var. silvestris Camellia sinensis tea plants Carthamus tinctorius safflower 30 Carya illinoinensis pecan trees Citrus limon lemons Citrus maxima grapefruits Citrus reticulata mandarins Citrus sinensis orange trees 35 Coffea arabica (Coffea canephora, Coffea liberica) coffee plants Cucumis melo melons Cucumis sativus cucumbers 3~13 - 24 - O.Z. 0050/38036 Botanical name Common name Cynodon dactylon Bermudagrass Daucus carota carrots 05 Elais guineensis oil palms Fragaria vesca strawberries Glycine max soybeans Gossypium hirsutum (Gossypium arboreum cotton lO Gossypium herbaceum Gossypium vitifolium) Helianthus annuus sunflowers Helianthus tuberosus Jerusalem artichoke Hevea brasiliensis rubber plants 15 Humulus lupulus hops Ipomoea batatas sweet potatoes Juglans regia walnut trees Lactuca sativa lettuce Lens culinaris lentils 20 Linum usitatissimum flax Lycopersicon lycopersicum tomatoes Malus spp. apple trees Manihot esculenta cassava Medicago sativa alfalfa (lucerne) 25 Mentha piperita peppermint Musa spp. banana plants Nicothiana tabacum tobacco (N. rustica) Olea europaea olive trees 30 Phaseolus lunatus limabeans Phaseolus mungo mungbeans Phaseolus vulgar~s snapbeans, green beans, dry beans Petroselinum crispum parsley spp. tuberosum Picea abies Norway spruce Abies alba fir trees Pinus spp. pine trees - 25 - O.Z. 0050/38036 Botanical name Common name Pisum sativum English peas Prunus avium cherxy trees OS Prunus domestica plum trees Prunus dulcis almond trees Prunus persica peach trees Pyrus communis pear trees Ribes sylvestre redcurrants ~O Ribes uva-crispa gooseberries Ricinus communis castor-oil plants Saccharum officinarum sugar cane Secale cereale rye Sesamum indicum sesame 15 Solanum tuberosum Irish potatoes Spinacia oleracea spinach Theobroma cacao cacao plants Trifolium pratense red clover Triticum aestivum wheat 20 Vaccinium corymbosum blueberries Vaccinium vitis-idaea cranberries Vicia faba tick beans Vigna sinensis (V. unguiculata) cow peas Vitis vinifera grapes 25 Zea mays Indian corn, sweet corn, maize _ To increase the spectrum of action and to achieve synergistic effects, the cyclohexenone derivatives of the formula I may be mixed and applied together with numerous representatives of other herbicidal or growth-regulating active ingredient groups. Examples of suitable mixture components are diazines, 4H-3,1-benzoxazine derivatives, benzothiadiazinones, 2,6-dinitroanilines, N-phenyl-carbamates, thiolcarbamates, halocarboxylic acids, triazines, amides, ureas, triazinones, uracils, benzofuran derivatives, quinolinecarboxylic acids, etc.
S~3 - 26 - O.Z. 0050/38036 It may also be useful to apply the compounds of the formula I, either alone or in combination with other herbicldes, in admixture with other crop protection agents, e.g., agents for combatting pests or phytopathogenic fungi 05 or bacteria. The compounds may also be mixed with solutions of mineral salts used to remedy nutritional or trace element deficiencies. Non-phytotoxic oils and oil concentrates may also be added.
Claims (7)
1. A cyclohexenone derivative of the formula I:
(I), where R1 is 2-fluoroethyl, 2-chloroethyl, but-2-en-yl, methoxymethyl or methoxyethyl, R2 is C1-C4-alkyl, R3 is 2-isopropyl-1,3-dioxepan-5-yl, tetrahydrothiopyran-3-yl, tetrahydropyran-3-yl, tetrahydro-pyran-4-yl, 3-methyltetra-hydropyran-4-yl, pyrid-3-yl, tetrahydrofuran-3-yl or 4a, 7,8,8a-tetrahydro-2H,5H-pyrano-[4,3-b]pyran-3-yl.
(I), where R1 is 2-fluoroethyl, 2-chloroethyl, but-2-en-yl, methoxymethyl or methoxyethyl, R2 is C1-C4-alkyl, R3 is 2-isopropyl-1,3-dioxepan-5-yl, tetrahydrothiopyran-3-yl, tetrahydropyran-3-yl, tetrahydro-pyran-4-yl, 3-methyltetra-hydropyran-4-yl, pyrid-3-yl, tetrahydrofuran-3-yl or 4a, 7,8,8a-tetrahydro-2H,5H-pyrano-[4,3-b]pyran-3-yl.
2. A process for the control of unwanted plants, wherein the unwanted plants or the area to be kept free of unwanted plants are treated with a herbicidally active amount of a cyclohexenone derivative of the formula I:
(I), where R1 is 2-fluoroethyl, 2-chloroethyl, but-2-en-yl, methoxymethyl or methoxyethyl, R2 is C1-C4-alkyl, R3 is 2-isopropyl-1,3-dioxepan-5-yl, tetrahydrothiopyran-3-yl, tetrahydropyran-3-yl, tetrahydropyran-4-yl, 3-methyltetra-hydroppyran-4-yl, pyrid-3-yl, tetrahydrofuran-3-yl or 4a,7,8,8a-tetrahydro-2H,5H-pyrano-[4,3-b]pyran-3-yl.
(I), where R1 is 2-fluoroethyl, 2-chloroethyl, but-2-en-yl, methoxymethyl or methoxyethyl, R2 is C1-C4-alkyl, R3 is 2-isopropyl-1,3-dioxepan-5-yl, tetrahydrothiopyran-3-yl, tetrahydropyran-3-yl, tetrahydropyran-4-yl, 3-methyltetra-hydroppyran-4-yl, pyrid-3-yl, tetrahydrofuran-3-yl or 4a,7,8,8a-tetrahydro-2H,5H-pyrano-[4,3-b]pyran-3-yl.
3. A cyclohexenone derivative of the formula I as defined in claim 1, wherein R1 is but-2-en-1-yl, R2 is methyl, ethyl or propyl and R3 has the meanings specified in claim 1.
4. A cyclohexenone derivative of the formula I as defined in claim 1, wherein R2 is C2- or C3-alkyl.
5. 2-[1-(2-butenyloxyimino)-ethyl]-3-hydroxy-5-(3-tetrahydrothiopyranyl)-cyclohex-2-en-1-one.
6. A composition for use to control undesirable plant growth, comprising a herbicidically active amount of a cyclohexenone derivative of the formula I as defined in claim 1, 3 or 4, in admixture with an agriculturally acceptable carrier.
7. A composition for use to control undesirable plant growth, comprising a herbicidally active amount of the derivative of claim 5 in admixture with an agriculturally acceptable carrier.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19853536117 DE3536117A1 (en) | 1985-10-10 | 1985-10-10 | CYCLOHEXENON DERIVATIVES, METHOD FOR THE PRODUCTION THEREOF AND THEIR USE FOR CONTROLLING UNWANTED PLANT GROWTH |
| DEP3536117.4 | 1985-10-10 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1293513C true CA1293513C (en) | 1991-12-24 |
Family
ID=6283222
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000520008A Expired - Lifetime CA1293513C (en) | 1985-10-10 | 1986-10-07 | Cyclohexenone derivatives, their preparation and their use for controlling undesirable plant growth |
Country Status (7)
| Country | Link |
|---|---|
| EP (1) | EP0218233B1 (en) |
| AT (1) | ATE51226T1 (en) |
| BR (1) | BR8604910A (en) |
| CA (1) | CA1293513C (en) |
| CS (1) | CS255000B2 (en) |
| DE (2) | DE3536117A1 (en) |
| HU (1) | HU201646B (en) |
Families Citing this family (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3600642A1 (en) * | 1986-01-11 | 1987-07-16 | Basf Ag | CYCLOHEXENON DERIVATIVES, METHOD FOR THE PRODUCTION THEREOF AND THEIR USE AS AN HERBICIDE AGENT |
| GB8711525D0 (en) * | 1987-05-15 | 1987-06-17 | Shell Int Research | Oximino ether compounds |
| GB8722838D0 (en) * | 1987-09-29 | 1987-11-04 | Shell Int Research | Oximino ether compounds |
| DE4014983A1 (en) * | 1990-05-09 | 1991-11-14 | Basf Ag | CYCLOHEXENONOXIMETHER, METHOD AND INTERMEDIATE PRODUCTS FOR THEIR PREPARATION AND THEIR USE AS HERBICIDES |
| EP0456112B1 (en) * | 1990-05-09 | 1994-08-31 | BASF Aktiengesellschaft | Cyclohexenone oxime ethers, process for their preparation and their use as herbicides |
| US5364833A (en) * | 1990-05-09 | 1994-11-15 | Basf Aktiengesellschaft | Cyclohexenone oxime ethers, their preparation and their use as herbicides |
| DE4014984A1 (en) * | 1990-05-09 | 1991-11-14 | Basf Ag | CYCLOHEXENONOXIMETHER, METHOD AND INTERMEDIATE PRODUCTS FOR THEIR PREPARATION AND THEIR USE AS HERBICIDES |
| DE4014987A1 (en) * | 1990-05-09 | 1991-11-14 | Basf Ag | CYCLOHEXENONOXIMETHER, METHOD AND INTERMEDIATE PRODUCTS FOR THEIR PREPARATION AND THEIR USE AS HERBICIDES |
| DE4031723A1 (en) * | 1990-10-06 | 1992-04-09 | Basf Ag | METHOD FOR PRODUCING (ALPHA), (BETA) -UNATURED CARBONYL COMPOUNDS |
| EP0481354B1 (en) * | 1990-10-19 | 1994-08-03 | BASF Aktiengesellschaft | Unsaturated cyclohexenonoximethers |
| EP2501229A4 (en) * | 2009-11-17 | 2014-08-06 | Univ Rochester | Compounds and methods for altering lifespan of eukaryotic organisms |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3121355A1 (en) * | 1981-05-29 | 1982-12-16 | Basf Ag, 6700 Ludwigshafen | CYCLOHEXANDION DERIVATIVES, METHOD FOR THE PRODUCTION THEREOF AND HERBICIDES CONTAINING THEM |
| DE3340265A1 (en) * | 1983-11-08 | 1985-05-15 | Basf Ag, 6700 Ludwigshafen | CYCLOHEXAN-1,3-DIONE DERIVATIVES, METHOD FOR THE PRODUCTION THEREOF AND THEIR USE FOR COMBATING UNWANTED PLANT GROWTH |
| NZ205525A (en) * | 1982-09-29 | 1985-12-13 | Ici Australia Ltd | 5-(pyridyl)-cyclohexene-1,3-dione derivatives and herbicidal compositions |
| DE3239071A1 (en) * | 1982-10-22 | 1984-04-26 | Basf Ag, 6700 Ludwigshafen | CYCLOHEXAN-1,3-DIONE DERIVATIVES, METHOD FOR THE PRODUCTION THEREOF AND THEIR USE FOR COMBATING UNWANTED PLANT GROWTH |
| DE3412794A1 (en) * | 1983-09-30 | 1985-04-18 | Basf Ag, 6700 Ludwigshafen | CYCLOHEXENON DERIVATIVES, METHOD FOR THE PRODUCTION THEREOF AND THEIR USE FOR CONTROLLING UNWANTED PLANT GROWTH |
| EP0136702B1 (en) * | 1983-10-05 | 1990-05-09 | BASF Aktiengesellschaft | Cyclohexenol derivatives, process for their preparation and their use in combating undesirable plant growth |
-
1985
- 1985-10-10 DE DE19853536117 patent/DE3536117A1/en not_active Withdrawn
-
1986
- 1986-10-07 EP EP86113873A patent/EP0218233B1/en not_active Expired - Lifetime
- 1986-10-07 AT AT86113873T patent/ATE51226T1/en not_active IP Right Cessation
- 1986-10-07 DE DE8686113873T patent/DE3669718D1/en not_active Expired - Lifetime
- 1986-10-07 CA CA000520008A patent/CA1293513C/en not_active Expired - Lifetime
- 1986-10-08 BR BR8604910A patent/BR8604910A/en unknown
- 1986-10-09 HU HU864236A patent/HU201646B/en not_active IP Right Cessation
- 1986-10-09 CS CS867296A patent/CS255000B2/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| HUT42259A (en) | 1987-07-28 |
| DE3669718D1 (en) | 1990-04-26 |
| BR8604910A (en) | 1987-07-07 |
| CS255000B2 (en) | 1988-02-15 |
| EP0218233A3 (en) | 1988-01-27 |
| ATE51226T1 (en) | 1990-04-15 |
| EP0218233A2 (en) | 1987-04-15 |
| EP0218233B1 (en) | 1990-03-21 |
| DE3536117A1 (en) | 1987-04-16 |
| HU201646B (en) | 1990-12-28 |
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