CA1334593C - Cyclohexenone derivatives - Google Patents
Cyclohexenone derivativesInfo
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- CA1334593C CA1334593C CA000611625A CA611625A CA1334593C CA 1334593 C CA1334593 C CA 1334593C CA 000611625 A CA000611625 A CA 000611625A CA 611625 A CA611625 A CA 611625A CA 1334593 C CA1334593 C CA 1334593C
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- alkylthio
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D271/00—Heterocyclic compounds containing five-membered rings having two nitrogen atoms and one oxygen atom as the only ring hetero atoms
- C07D271/02—Heterocyclic compounds containing five-membered rings having two nitrogen atoms and one oxygen atom as the only ring hetero atoms not condensed with other rings
- C07D271/06—1,2,4-Oxadiazoles; Hydrogenated 1,2,4-oxadiazoles
-
- 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
- A01N43/10—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 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
- A01N43/04—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
-
- 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
- A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
- A01N43/50—1,3-Diazoles; Hydrogenated 1,3-diazoles
-
- 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
- A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
- A01N43/74—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms five-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,3
-
- 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
- A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
- A01N43/80—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms five-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,2
-
- 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
- A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
- A01N43/82—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms five-membered rings with three ring hetero atoms
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D261/00—Heterocyclic compounds containing 1,2-oxazole or hydrogenated 1,2-oxazole rings
- C07D261/02—Heterocyclic compounds containing 1,2-oxazole or hydrogenated 1,2-oxazole rings not condensed with other rings
- C07D261/04—Heterocyclic compounds containing 1,2-oxazole or hydrogenated 1,2-oxazole rings not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D261/00—Heterocyclic compounds containing 1,2-oxazole or hydrogenated 1,2-oxazole rings
- C07D261/02—Heterocyclic compounds containing 1,2-oxazole or hydrogenated 1,2-oxazole rings not condensed with other rings
- C07D261/06—Heterocyclic compounds containing 1,2-oxazole or hydrogenated 1,2-oxazole rings not condensed with other rings having two or more double bonds between ring members or between ring members and non-ring members
- C07D261/08—Heterocyclic compounds containing 1,2-oxazole or hydrogenated 1,2-oxazole rings not condensed with other rings having two or more 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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D271/00—Heterocyclic compounds containing five-membered rings having two nitrogen atoms and one oxygen atom as the only ring hetero atoms
- C07D271/02—Heterocyclic compounds containing five-membered rings having two nitrogen atoms and one oxygen atom as the only ring hetero atoms not condensed with other rings
- C07D271/10—1,3,4-Oxadiazoles; Hydrogenated 1,3,4-oxadiazoles
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
- C07D333/02—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings
- C07D333/04—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom
- C07D333/06—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to the ring carbon atoms
- C07D333/22—Radicals substituted by doubly bound hetero atoms, or by two hetero atoms other than halogen singly bound to the same carbon atom
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D413/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms
- C07D413/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings
- C07D413/04—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings directly linked by a ring-member-to-ring-member bond
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Wood Science & Technology (AREA)
- Environmental Sciences (AREA)
- Plant Pathology (AREA)
- Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- Dentistry (AREA)
- General Health & Medical Sciences (AREA)
- Agronomy & Crop Science (AREA)
- Zoology (AREA)
- Pest Control & Pesticides (AREA)
- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Nitrogen And Oxygen As The Only Ring Hetero Atoms (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Plural Heterocyclic Compounds (AREA)
- Pyrrole Compounds (AREA)
- Heterocyclic Compounds Containing Sulfur Atoms (AREA)
- Thiazole And Isothizaole Compounds (AREA)
- Nitrogen- Or Sulfur-Containing Heterocyclic Ring Compounds With Rings Of Six Or More Members (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Cyclohexenone derivatives of the general formula I
I
where the substituents have the following meanings:
R1 substituted or unsubstituted C1-C6-alkyl, C3-C6-alkenyl or C3-C6-alkynyl, phenyl, benzyl or thenyl;
R2 substituted or unsubstituted C1-C6-alkyl, C3-C6-alkenyl, C3-C6-alkynyl or phenyl;
R3 hydrogen, C1-C6-alkyl, C1-C10-alkylcarbonyl, C1-C6-alkylsulfonyl, C1-C4-trialkylsilyl, C1-C4-dialkylphosphonyl, C1-C4-dialkylthio-phosphonyl, C3-C6-alkenyl, C3-C6-alkenylcarbonyl, C3-C6-alkynyl or substituted or unsubstituted benzoyl- or phenylsulfonyl;
R4 hydrogen, cyano, halogen, C1-C6-alkyl or C1-C6-alkoxycarbonyl;
A a substituted or unsubstituted C1-C4-alkylene chain in which a methylene group may be replaced by an oxygen or sulfur atom;
m 0 or 1;
B a 5-membered mono- or diunsaturated heterocycle containing up to 2 nitrogen atoms and/or up to one oxygen or sulfur atom;
substituted or unsubstituted C1-C6-alkyl, C2-C6-alkenyl or C2-C6-alkynyl;
C1-C4-alkoxy, C1-C4-alkylthio, C3-C6-alkenyloxy or C3-C6-alkynyloxy;
n 1, 2 or 3;
Y not denoting hydrogen when m is 0, B is isoxazol-5-yl and X is 3-(C3-C6-cycloalkyl), and environmentally acceptable salts thereof, processes for their manufacture, and their use as herbicidal agents.
I
where the substituents have the following meanings:
R1 substituted or unsubstituted C1-C6-alkyl, C3-C6-alkenyl or C3-C6-alkynyl, phenyl, benzyl or thenyl;
R2 substituted or unsubstituted C1-C6-alkyl, C3-C6-alkenyl, C3-C6-alkynyl or phenyl;
R3 hydrogen, C1-C6-alkyl, C1-C10-alkylcarbonyl, C1-C6-alkylsulfonyl, C1-C4-trialkylsilyl, C1-C4-dialkylphosphonyl, C1-C4-dialkylthio-phosphonyl, C3-C6-alkenyl, C3-C6-alkenylcarbonyl, C3-C6-alkynyl or substituted or unsubstituted benzoyl- or phenylsulfonyl;
R4 hydrogen, cyano, halogen, C1-C6-alkyl or C1-C6-alkoxycarbonyl;
A a substituted or unsubstituted C1-C4-alkylene chain in which a methylene group may be replaced by an oxygen or sulfur atom;
m 0 or 1;
B a 5-membered mono- or diunsaturated heterocycle containing up to 2 nitrogen atoms and/or up to one oxygen or sulfur atom;
substituted or unsubstituted C1-C6-alkyl, C2-C6-alkenyl or C2-C6-alkynyl;
C1-C4-alkoxy, C1-C4-alkylthio, C3-C6-alkenyloxy or C3-C6-alkynyloxy;
n 1, 2 or 3;
Y not denoting hydrogen when m is 0, B is isoxazol-5-yl and X is 3-(C3-C6-cycloalkyl), and environmentally acceptable salts thereof, processes for their manufacture, and their use as herbicidal agents.
Description
133~593 O.Z. OOS0/40230 Cyclohexenone derivatives The present invention relates to novel cyclo-heYenone derivatives of the general formula I
x oR3 /(8)--(A)m~ORI I
Yn R4 where Rl i8 Cl-C6-alkyl, C3-C6-alkenyl or C3-C6-alkynyl and these groups may carry from one to three of the following radicals: halogen, C1-C4-alkoxy, C1-C4-alkylthio and/or phenyl, and the phenyl group in turn may be monosub-stituted to trisubstituted by halogen, C1-C4-alkyl, C1-C4-alkoxy, C1-C4-alkylthio, C1-C~-haloalkyl and/or cyano;
phenyl, benzyl or thenyl, where the aromatic nuclei may carry from one to three of the following radicals: halo-gen, Cl-C4-alkyl, Cl-C4-alkoxy, Cl-C4-alkylthio, Cl-C4-halo-alkyl, nitro and/or cyano;
R2 i8 C1-C6-alkyl, C3-C6-alkenyl, C3-C6-alkynyl or phenyl, and these groups may carry from one to three of the following radicals: halogen, C1-C4-alkoxy, C1-C4-alkylthio and/or cyano;
R3 is hydrogen, C1-C6-alkyl, C1-C10-alkylcarbonyl, C1-C6-alkylsulfonyl, Cl-C~-trialkylsilyl, Cl-C4-dialkylphosphon-yl, Cl-C"-dialkylthiophosphonyl, C3-C6-alkenyl, C3-C6-alkenylcarbonyl or C3-C6-alkynyl or a benzoyl or phenylsulfonyl group which may be monosub-stituted to trisubstituted by halogen, nitro, cyano, C1-C4-alkyl, C1-C~-haloalkyl, C1-C4-alkoxy and/or C1-C4-alkyl-thio;
R4 i8 hydrogen, cyano, halogen, C1-C6-alkyl or C1-C6-alkoxycarbonyl;
A is a C1-C4-alkylene chain in which a methylene group may be replaced by an oxygen or sulfur atom and which may carry one or two of the following substituents: C1-C4-alkyl, Cl-C4-alkoxy, C1-C4-alkylthio and/or halogen;
~.
133~93 m is 0 or 1, B is a 5-membered monounsaturated or diunsaturated heterocyclic radical having not more than 2 nitrogen atoms and/or not more than one oxygen or sulfur atom, X is a 3-membered to 7-membered cycloalkyl radical or a 5-membered to 7-membered cycloalkenyl radical, wherein a methylene group in these ring systems may be replaced by an oxygen or sulfur atom;
a 5-membered or 6-membered heteroaromatic radical containing up to three atoms selected amongst nitrogen, oxygen and sulfur, where the ring may carry from one to three of the following groups:
C1-C4-alkyl, C1-C4-alkoxy, C1-C4-alkylthio, C1-C4-haloalkyl, halogen, cyano and/or nitro, or if B is isoxazolinyl, is also hydrogen;
Y is hydrogen, halogen, cyano or nitro;
C1-C6-alkyl, Cz-C6-alkenyl or C2-C6-alkynyl, and these groups may carry from one to three of the following radicals: phenyl, halogen, C1-C4-alkoxy and/or C1-C4-alkylthio, C1-C4-alkoxy, C1-C4-alkylthio, C3-C6-alkenyloxy or C3-C6-alkynyloxy;
n is 1, 2 or 3 with the proviso that Y does not, or all the Y's when n is greather than 1, denote hydrogen when m is 0, B is isoxazol-5-yl and X is 3-(C3-C6-cycloalkyl), and their environmentally compatible salts.
The present invention furthermore relates to the preparation of the compounds I, their use as herbicides and mixtures for controlling undesirable plant growth which contain the compounds of the formula (I).
1~3~593 - 2a -The compounds of the formula (I) may occur in a plurality of tautomeric forms, all of which are embraced by ~bo claim and, ~hcle ~ ~
- 133~593 - 3 - O. Z . 0050/40230 OH ~ R~NH-OR 1 R~2 ~ ~ORl In this scheme, as in all the equations below, the radical x ~(B)--(A)m--Yn is denoted by R for greater clarity.
The herbicidal action of 3-hydroxy-2-cyclohexen-l-one oxime ether derivatives which carry a 5-membered heterocyclic radical in the 5-position is disclosed in EP-A 125 094, EP-A 162 224 and EP-A 238 021.
It is an ob~ect of the present invention to pro-vide compounds which can be used at lower application rates, are better tolerated by crop plants (greater selectivity) and have a good action against weeds.
We have found that this ob~ect is achieved by the cycloheYPnone~ I defined at the outset.
These novel cyclohexenone derivatives have a good lS herbicidal action preferably against species from the family of the grasses (Gramineae). They are tolerated and therefore have selective action in broad-leaved crops and in monocotyledons which do not belong to the Gramineae. They furthermore include compounds which also 2 0 have a selective action in graminaceous crops such as wheat, barley and rice and at the same time control un-desirable grasses. The novel cyclohexenone derivatives of formula I also have a growth-regulating action against species from the family of the grasses.
- 4 - O.Z. 0050/40230 The compounds I are prepared in four reaction steps according to the following scheme:
8ase RCHO ~ Ph3P=CH-COCH3 III VI
Base RCHO ~ (CH3)2CO [ St~p Al III ~ R-CH=CH-COCH 3 3ase V
RCHO ~ CH 3CO-CH2CO2CH3 III
RCH2Cl ~ Ph3P 8ase IV
OH
V ~ R~_~CO2CH3 8as~ R
VIII
OH
VIII ~ RlCOCl 8asa Bas-~Rlo~H~ e R~ R~
I (R3 = H) I (R3 ~ H) The required intermediates are obt~ hle by many methods which have been described in a large number of patent publications, for example EP-A 125 094, EP-A 150 433 or EP-A 238. 021.
A) Step A comprises the preparation of the vinyl ketones of formula V.
Alternatively, for example, the following processes are possible:
An aldehyde of the formula III i~ reacted with acetone in the presence of a base or with a Wittig 133~593 5 - O.Z. 0050/40230 reagent of the formula VI or with ethyl acetoacetate in the presence of a base to give the vinyl ketone of the formula V.
Halomethyl compounds of the formula IV may also be used, these compounds first being converted into the phosphonium salts and then being reacted with methyl-glyoxal to give the desired vinyl ketones of the formula R-CH2Ct Ph3P R-CH2-P$Ph3Cle OHC-COCH3 R-CH=CH-COCH3 IV Base B) Step B relates to the synthesis of the 3-hydroxy-2-cyclohexen-1-one~ of the formula VIII. For this pur-pose, the vinyl ketones of the formula V are reacted with, for example, an e~ter derivative of the formula VII
in the presence of a base, the desired compounds of the formula VIII being formed.
R4~_-CO2CH3 OH
R-CH=CH-COCH3 ~ R
V 3ase R4 VIII
C) Step C gives the 2-acyl-3-hydroxy-2-cyclohexen-1-ones of the formula II. For this purpose, the deriva-tives of the formula VIII are reacted with an acyl chlor-ide of the formula IX in the presence of a base to give O-acylated derivatives of the formula X, which are then sub~ected to a rearrangement reaction in the presence of a Lewis acid or of a base, such as imidazole, pyridine or 4-N,N-dimethylaminopyridine, to give the C-acylated com-pound of the formula II.
R ~ 8ase ~ or Lewis ~2 D) Step D relates to the preparation of the com-pounds of the formula I, which are ob~A i n~ from the 2-acyl-3-hydroxy-2-cyclohexen-1-ones II by reaction with an - 6 - O.Z. OOSO/40230 alkoxyammonium salt of the formula RlONH~.HQ, where Q is a suitable leaving group, such as chloride. Alternative-ly, it is also possible to use the free alkoxyamine R10NH2.
Compounds which contain a substituent R3 which is not hydrogen are obtAinAhle from compounds of the formula I where R3 is H in a conventional manner as described below.
In the case of the ethers, esters and sulfones, the compounds of the formula I where R3 is H are reacted with a corresponding alkylating, acylating or sulfonating agent.
Other suitable starting materials for this pur-pose are the alkali metal salts of the compounds of the formula I, which are obtA i n~ by reaction with an alkali metal hydroxide, an alkali metal alcoholate or an alkali metal hydride.
If, in formula I, R3 is another inorganic or or-ganic cation, these compounds are obt~inAhle from the alkali metal salts using transition metal salts or or-ganic bases. Examples of these are manganese chloride, copper chloride, zinc chloride and iron chloride and the corresponding sulfates, as well as magnesium methylate, magnesium ethylate, calcium methylate and calcium ethylate.
The ma~ority of the heterocyclic aldehydes III
and chloromethyl compounds IV required as starting mater-ials are novel but can be prepared by conventional pro-cesses.
The isoxazoles are prepared, for example, under the conditions described in DE-A 2 754 832. They are ob-tAi~Ahle from aldoximes by 1,3-dipolar cycloaddition with propargyl alcohols or propargyl halides. The 5-hydroxy-methyl-substituted isoxazoles can be converted into the 5-formyl derivative by conventional oxidation processes.
The regioisomers which are bonded in the 3- or 4-position can be prepared, inter alia, according to Baraldi et al., 1334~93 - 7 - O.Z. 0050/40230 J. Het. Chem. 19 (1982), 557 and Bertini et al., J. Chem.
Soc. Perkin Trans I 1976, 570.
Syntheses of 1,3-oxazoles are described in The Chemistry of Penicillins.
1,3-Thiazoles which are bonded in the 4- or 5-position are obtAinAhle, for example, by processes described by A. Beuko et al., Liebigs Ann. Chem. 717 (1968), 148-153.
Syntheses of 1,2,4-oxadiazole~ are described in, for example, Chem. Ber. 17 (1889), 1685 and Tetrahedron Lett. (1961), 587-589.
With regard to the use of the compounds I in accordance with regulations, the radicals below are pre-ferred substituents.
Alkyl groups Rl are methyl, ethyl, propyl, 1-methylethyl, butyl, l-methylpropyl, 2-methylpropyl, 1,1-dimethylethyl, pentyl, l-methylbutyl, 2-methylbutyl, 3-methylbutyl, l,l-dimethylpropyl, 1,2-dimethylpropyl,2,2-dimethylpropyl, 1-ethylpropyl, hexyl, l-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, l,l-dimeth-ylbutyl, 1,2-dimethylbutyl, 1,3-dimethylbutyl, 2,2-dimethylbutyl, 2,3-dimethylbutyl, 3,3-dimethylbutyl, 1-ethylbutyl, 2-ethylbutyl, 1,1,2-trimethylpropyl, 1,2,2-trimethylpropyl, l-ethyl-l-methylpropyl and l-ethyl-2-methylpropyl, ethyl and propyl being preferred.
Al kenyl groups in thi~ position are 2-propenyl, 2-butenyl, 3-butenyl, 1-methyl-2-propenyl, 2-methyl-2-plo~el.yl~ 2-pentenyl, 3-pentenyl, 4-pentenyl, l-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-2-propenyl, 1-ethyl-2-propenyl, 2-hexenyl, 3-hexenyl, 4-hexenyl, 5-hexenyl, l-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-4-pentenyl, 1-methyl-4-pentenyl, 2-methyl-4-pentenyl, 3-methyl-4-pentenyl, 3-methyl-4-pentenyl, 4-133~5~3 _ - 8 - O.Z. 0050/40230 methyl-4-pentenyl, 1,1-dimethyl-2-butenyl, l,l-dimethyl-3-butenyl, 1,2-dimethyl-2-butenyl, 1,2-dimethyl-3-buten-yl, 1,3-dimethyl-2-butenyl, 1,3-dimethyl-3-butenyl, 2,2-dimethyl-3-butenyl,2,3-dimethyl-2-butenyl,2,3-dimethyl-3-butenyl, 1-ethyl-2-butenyl, 2-ethyl-2-butenyl, l-ethyl-3-butenyl,2-ethyl-3-butenyl,1,1,2-trimethyl-2-propenyl, l-ethyl-l-methyl-2-propenyl and 1-ethyl-2-methyl-2-propenyl, in particular 2-propenyl and 2-butenyl.
Preferred alkynyl radicals R1 are 2-plo~yllyl~ 2-butynyl, 3-butynyl, 1-methyl-2-pLo~ylLyl~ 2-pentynyl, 3-pentynyl, 4-pentynyl, 1-methyl-2-butynyl, 1-methyl-3-butynyl, 2-methyl-3-butynyl, 1,l-dimethyl-2-pLo~yl~yl~ 1-ethyl-2-p opyllyl~ 2-hexynyl, 3-hexynyl, 4-hexynyl, 5-hexynyl, l-methyl-2-pentynyl, 4-methyl-2-pentynyl, 1-methyl-3-pentynyl, 2-methyl-3-pentynyl, 1-methyl-4-pentynyl, 2-methyl-4-pentynyl, 3-methyl-4-pentynyl, 1,1-dimethyl-2-butynyl,l,l-dimethyl-3-butynyl,1,2-dimethyl-3-butynyl, 2,2-dimethyl-3-butynyl, 1-ethyl-2-butynyl, 1-ethyl-3-butynyl, 2-ethyl-3-butynyl and l-ethyl-l-methyl-2-p o~yl~yl~ in particular 2-PLO~Y1~Y1 and 2-butynyl.
These alkyl, alkenyl and alkynyl groups may be substituted by from one to three of the following groups:
halogen atom~, such as bromine and iodine, preferably however from one to three fluorine and/or chlorine atoms, (E)-3-chloroprop-2-enyl being particularly preferred;
alkoxy, such as methoxy, ethoxy, propoxy, l-methylethoxy, butoxy, l-methylpropoxy, 2-methylpropoxy and l,l-dimeth-ylethoxy, in particular one or two methoxy or ethoxy groups;
Alkylthio, such as methylthio, ethylthio, propyl-thio, l-methylethylthio, butylthio, l-methylpropylthio, 2-methylpropylthio and l,1-dimethylethylthio, one or two ethylthio groups being preferred, and/or a phenyl ring which, in addition to the abovementioned halogen atoms, alkyl groups, alkoxy groups and alkylthio groups, may also carry cyano and haloalkyl, such as fluoromethyl, difluoromethyl, trifluoromethyl, chloromethyl, dichloro-133~593 - - - 9 - O.Z. 0050/40230 methyl, trichloromethyl, difluorochloromethyl, l-fluoro-ethyl, 2-fluoroethyl, l,l-difluoroethyl, 1,1,2-trifluoro-ethyl, 1,2,2-trifluoroethyl and 2,2,2-trifluoroethyl; in particular, the phenyl ring is unsubstituted or substituted in the 4-position by fluorine, chlorine, methyl, trifluoromethyl, or l,l-dimethylethyl and/or in the 2-position by chlorine or methoxy.
R1 may furthermore be phenyl, thenyl or benzyl, and the aromatic nuclei may also be substituted by nitro, cyano and/or alkyl groups, such as methyl, ethyl, propyl, l-methylethyl, butyl, l-methylpropyl, 2-methylpropyl and l,l-dimethylethyl, in addition to the abovementioned halogen atoms, alkoxy groups, alkylthio groups and haloalkyl groups. The 5-chlorothenyl radical is parti-cularly preferred.
The alkyl, alkenyl and alkynyl groups R2 and thephenyl radical R2 and its substituents have the same general and particular me~ni~gs as R1.
Suitable radicals R3 in addition to the above-mentioned alkyl, alkenyl and alkynyl groups are radicalsof saturated and unsaturated carboxylic acids, such as acetyl, propionyl, butyryl and pivaloyl, in particular acetyl and butyryl;
and alkylsulfonyl, alkylsilyl, alkylphosphonyl or alkyl-thiophosphonyl groups, the alkyl radicals preferably being methyl~ ethyl, l-methylethyl and l,l-dimethylethyl, and benzoyl and phenylsulfonyl. The last-mentioned aromatic radicals may be monosubstituted to trisub-stituted. The possible substituents correspond to the substituents stated under Rl.
Suitable radicals R4 in addition to hydrogen and cyano are the halogen atoms and alkyl groups already mentioned for Rl and alkoxycarbonyl groups, such as meth-oxycarbonyl, ethoxycarbonyl, propoxycarbonyl, l-methyl-ethoxycarbonyl, butoxycarbonyl, l-methylpropylcarbonyl, 2-methylpropylcarbonyl and l,l-dimethylethoxycarbonyl, but in particular methoxycarbonyl and ethoxycarbonyl.
133459~
10 - O.Z. 0050/40230 Preferred radicals R4 are hydrogen, cyano and methoxycarbonyl.
A is an alkylene, alkyleneoxyalkylene or alkylenethioalkylene chain having up to four members.
Examples of these are methylene, ethylene, propylene, butylene, methyleneoxymethylene, methyleneoxyethylene, methylenethiomethylene,methylenethioethylene,propylene-oxy, propylenethio, ethyleneoxy, ethylenethio, methylene-oxy, methylenethio, oxy and thio bridges.
The compounds of the formula I preferably contain no bridge A or a l-membered or 2-membered bridge A.
The 5-membered heterocyclic radicals B are rings such as dihydrofuranyl, dihydrothienyl, pyrrolinyl, pyrazolinyl, imidazolinyl, isoxazolinyl, oxazolinyl, iso-thiazolinyl, thiazolinyl, furanyl, thienyl, pyrrolyl,pyrazolyl, isoxazolyl, oxazolyl, isothiazolyl, thiazolyl, oY~ zolyl and thi~ 701yl -Particularly preferred compounds of the formulaI are those in which a 4,5-dihydroisoxazolyl ring is bonded at its 4- or 5-position by one of the above-mentioned bridges to the cycloheY~none system, and those in which one of the listed heteroaromatic rings is bonded directly to the cycloheYenone ring.
Sui~able g ou~ X are the following:
cycloalkyl, such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl and cycloheptyl, preferably cyclopropyl and cyclohexyl;
cycloAl~enyl, for example cyclopentenyl, cyclohexenyl and cycloheptenyl, preferably cyclopentenyl and cyclohexenyl;
heterocyclic aliphatic radicals, for example epoxyethyl, oxetanyl, tetrahydrofuranyl, tetrahydropyranyl, thietan-yl, tetrahydrothienyl and tetrahydrothiopyranyl, preferably 3-tetrahydropyranyl, tetrahydrothiopyranyl and 1,3-dioxan-2-yl;
heterocyclic alkenyl rings, including the dihydrofuranyl, dihydrothienyl, dihyd~o~ylanyl and dihydrothiopyranyl radical, but in particular the dihydropyranyl and the di-133~5g3 - 11 - o.Z. 0050/40230 hydrothiopyranyl radical;
heteroaromatic groups, for example pyrrolyl, pyrazolyl, imidazolyl, triazolyl, pyridyl, pyrimidyl, pyrazinyl, pyridazinyl, quinolyl or isoquinolyl, furanyl, thienyl, isoxazolyl, oxazolyl, oxathiazolyl, isothiazolyl and thiA7olyl, preferably 2-pyridyl and 2-furyl, and hydrogen, if 8 is isoxazolinyl.
Heteroaromatic rings may carry up to three ~ub-stituents. In addition to cyano and nitro groups, the abovementioned halogen atoms, alkyl groups, haloalkyl ~oup~, alkoxy y oups and alkylthio groups are suitable for this purpose.
Yn are from one to three identical or different rA~icAls from amongst the abovementioned alkyl, alkenyl lS or alkynyl groups, as well as hydrogen, halogen, cyano and nitro. In psrticular, alkenyl may also be vinyl or alkynyl here, especially ethynyl.
These compounds do not include those in which Y
is hydrogen when B is ;~OXA~O1-5-Y1~ m is O and X i~ 3-(c3-c~-cycloalkyl).
13~4593 12 O.Z. 0050/40230 In detail, the invention embraces preferably the following structures:
a) Pyrroles of the formula Y op3 pO2R 1 I . 01 x oR3 ~ OR1 I.02 b) Furans and thiophenes of the formula Yn oR3 X ~ 02Rl I 04 E=S
X Yn OR3 ~ 2 I 05 E-O
c) Pyrazoles of the formula x Y oP3 ~ OR1 I.07 x oR3 2R1 I.08 X ~ O2R1 I.09 - 1~3~593 13 O.Z. 0050/40230 d) Isoxazoles and isothiazoles of the formula E-N ~ ,NOR1 I.10 E=O
~ ~-4R2 I.11 E=S
X Yn R4 x oR3 E ~ O2R1 I }3 E-S
Yn R4 Yn OR3 X ~ OR1 I }4 E-O
R ~ O
e) Oxazoles and thiazoles of the formula Yn oR3 ~N ,-~ ~NORl I.16 E=O
X- -E ~ R2 I.17 E=S
oR3 E ~ O2R1 I }9 E-S
Yn R4 X ~ O2R1 I 21 E-S
f) 1,2,3-Oxadiazoles and 1,2,3-thiadiazoles of the formula oR3 E ~ O2R1 I 23 E-S
x oR3 N ~ OR1 I 24 E-O
1~3~593 14 O.Z. 0050/40230 9) 1,2,4-Oxadiazoles and 1,2,4-thiadiazoles of the formula L N~ ~ OR1 I 27 E_O
X R ~ O
x oR3 ~ ~ ~ oR1 I 29 E-S
~0 R
h) 1,3,4-Oxadiazoles and 1,3,4-thiadiazoles of the formula oR3 N-N ~ O2R1 I 30 E-O
5 i) 4,5-Dihydroisoxazolines of the formula X ~ I.32 ,~OR 1 X
The cyclohexenone derivatives I, and herbicidal agents containing them, may be applied for instance in the form of directly sprayable solutions, powders, suspensions (including high-percentage aqueous, oily or other lO suspensions), dispersions, emulsions, oil dispersions, pastes, dusts, broadcasting agents, or granules by spraying, atomizing, dusting, broad-casting 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 15 possible.
For the preparation of solutions, emulsions, pastes and oil dispersions to be sprayed direct, mineral oil fractions of medium to high boiling point, such as kerosene or diesel oil, further coal-tar oils, and oils of 20 vegetable or animal origin, aliphatic, cyclic and aromatic hydrocarbons such as toluene, xylene, paraffin, tetrahydronaphthalene, alkylated naphthalenes and their derivatives such as methanol, ethanol, propanol, butanol, cyclohexanol, cyclohexanone, chlorobenzene, isophorone, etc., O.Z. 0050/40230 and strongly polar solvents such as N,N-dimethylformamide, dimethyl sulfoxide, N-methylpyrrolidone, water, etc. are suitable.
Aqueous formulations may be prepared from emulsion concentrates, pastes, 5 oil dispersions or wettable powders 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 ingredient, wetting agent, 10 adherent, emulsifying or dispersing agent and possibly solvent or oil.
Examples of surfactants are: alkali metal, alkaline earth metal and ammonium salts of aromatic sulfonic acids, e.g., ligninsulfonic acid, phenolsulfonic acid, naphthalenesulfonic acid and dibutylnaphthalene-15 sulfonic acid, and of fatty acids, alkyl and alkylaryl sulfonates, andalkyl, lauryl ether and fatty alcohol sulfates, alkali metal and alkaline earth metal salts of dibutylnaphthalenesulfonic acid, lauryl ether sul-fate, fatty alcohol sulfates, and salts of sulfated hexadecanols, hepta-decanols, and octadecanols, salts of fatty alcohol glycol ethers, conden-20 sation products of sulfonated naphthalene and naphthalene derivatives withformaldehyde, condensation products of naphthalene or naphthalenesulfonic acids with phenol and formaldehyde, polyoxyethylene octylphenol ethers, ethoxylated isooctylphenol, ethoxylated octylphenol and ethoxylated nonyl-phenol, alkylphenol polyglycol ethers, tributylphenyl polyglycol ethers, 25 alkylaryl polyether alcohols, isotridecyl alcohol, fatty alcohol ethylene oxide condensates, ethoxylated castor oil, polyoxyethylene alkyl ethers, ethoxylated polyoxypropylene, lauryl alcohol polyglycol ether acetal, sorbitol esters, lignin-sulfite waste liquors and methyl cellulose.
30 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 granules, may be prepared by bonding the active ingredients to solid carriers. Examples of 35 solid carriers are mineral earths such as silicic 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 40 products such as grain meals, bark meal, wood meal, and nutshell meal, cellulosic powders, etc.
- 13345~3 16 O.Z. 0050/40230 The formulations contain from O.l to 95, and preferably 0.5 to 90, % by weight of active ingredient.
The agents may be applied pre- or postemergence. If certain crop plants5 tolerate the active ingredients less well, application techniques may be used in which the herbicidal agents are sprayed from suitable 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 application rates depend on the objective to be achieved, the time of the year, the plants to be combated and their growth stage, and are from O.Ol to 3.0, preferably 0.05 to l.0, kg of active ingredient per hectare.
l5 In view of the spectrum of weeds that can be combated, the tolerance by crop plants and the desired influence on plant growth, and in view of the number of application methods possible, the compounds according to the invention may be used in a further large number of crops for removing unwanted plants. The following crops are given by way of example:
Botanical name Common name Allium cepa onions Ananas comosus pineapples Arachis hypogaea peanuts (groundnuts) 25 Asparagus officinalis asparagus Avena sativa oats Beta vulgaris spp. altissima sugarbeets Beta vulgaris spp. rapa fodder beets Beta vulgaris spp. esculenta table beets, red beets 30 Brassica napus var. napus rapeseed Brassica napus var. napobrassica swedes Brassica napus var. rapa turnips Brassica rapa var. silvestris Camellia sinensis tea plants 35 Carthamus tinctorius safflower Carya illinoinensis pecan trees Citrus limon lemons Citrus maxima grapefruits Citrus reticulata mandarins 40 Citrus sinensis orange trees Coffea arabica (Coffea canephora, Coffea liberica) coffee plants Cucumis melo melons Cucumis sativus cucumbers 133~593 17 O.Z. 0050/40230 Botanical name Common name Cynodon dactylon Bermudagrass Daucus carota carrots Elais guineensis oil palms 5 Fragaria vesca strawberries Glycine max soybeans Gossypium hirsutum (Gossypium arboreum, Gossypium herbaceum, Gossypium vitifolium) cotton Helianthus annuus sunflowers IO Helianthus tuberosus Jerusalem artichoke Hevea brasiliensis rubber plants Hordeum vulgare barley Humulus lupulus hops Ipomoea batatas sweet potatoes lS Juglans regia walnut trees Lactuca sativa lettuce Lens culinaris lentils Linum usitatissimum flax Lycopersicon Iycopersicum tomatoes 20 Malus spp. apple trees Manihot esculenta cassava Medicago sativa alfalfa (lucerne) Mentha piperita peppermint Musa spp. banana plants 25 Nicotiana tabacum (N. rustica) tobacco Olea europaea olive trees Oryza sativa rice Panicum miliaceum millet Phaseolus lunatus limabeans 30 Phaseolus mungo mungbeans Phaseolus vulgaris snapbeans, green beans, dry beans Pennisetum glaucum pearl millet Petroselinum crispum spp. tuberosum parsley 35 Picea abies Norway spruce Abies alba fir trees Pinus spp. pine trees Pisum sativum English peas Prunus avium cherry trees 40 Prunus domestica plum trees Prunus dulcis almond trees Prunus persica peach trees Pyrus communis pear trees Ribes sylvestre redcurrants 1~34593 18 O.Z. 0050/40230 Botanical name Common name Ribes uva-crispa gooseberries Ricinus communis castor-oil plants Saccharum officinarum sugar cane 5 Secale cereale rye Sesamum indicum sesame Solanum tuberosum Irish potatoes Sorghum bicolor (s. vulgare) sorghum Sorghum dochna sorgo 10 Spinacia oleracea spinach Theobroma cacao cacao plants Trifolium pratense red clover Triticum aestivum wheat Triticum durum durum wheat 15 Vaccinium corymbosum blueberries Vaccinium vitis-idaea cranberries Vicia faba tick beans Vigna sinensis (V. unguiculata) cow peas Vitis vinifera grapes 20 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 25 together with numerous representatives of other herbicidal or growth-regulating active ingredient groups. Examples of suitable components are diazines, 4H-3,1-benzoxazine derivatives, benzothiadiazinones, 2,6-dinitroanilines, N-phenylcarbamates, thiolcarbamates, halocarboxylic acids, triazines, amides, ureas, diphenyl ethers, triazinones, uracils, 30 benzofuran derivatives, quinolinecarboxylic acids, cyclohexenones, aryloxy- or heteroaryloxy-phenoxypropionic acids and salts, esters and amides thereof, etc.
It may also be useful to apply the cyclohexenone compounds of the 35 formula I, either alone or in combination with other herbicides, in admixture with other crop protection agents, e.g., agents for combating pests or phytopathogenic fungi 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 40 added.
1~34~9~
19 O.Z. 0050/40230 In the synthesis methods below, the individual steps of the synthQsis are described with reference to some specific examples.
1. Preparation of the hete~o~i~clic chloromethyl compounds a) 5-Chloromethyl-3-pyrid-2-ylisoxazole 774 g of a 14% strength sodium hypochlorite solu-tion were added to a mixture of 122 g of 2-pyridylaldox-ime, 1.5 1 of water, 500 ml of dichloromethane, 15 g of ~odium dih~d o~en phosphate dihydrate, 18 g of ~odium hy~o~en phosphate dihydrate and 150 g of propargyl chloride at 20-25C. Stirring was carried out for 10 hour~ at 25C, the phases were separated and the aqueous phase was e~tracted with twice 150 ml of dichloromethane.
The combined organic phase~ were dried over sodium sulfate and evaporated down. 170 g of a brown ~olid were obt~ine-l. The product was reacted without further purification.
b) 5-Chloromethyl-3-cyclopentyl-1,2,4-oxadiazole 100 g of hydroxylamine hydrochloride were dis-solved in 360 ml of water, and 122 g of sodium bicarbon-ate were added a little at a time at 25C. Thereafter, 138 g of cyclopentanecarbonitrile, dissolved in 400 ml of ethanol, were added dropwise. The reaction mixture was refluxed for 10 hour~ at 80C, cooled and then evaporated down. The residue was taken up in a 1: 1 mixture of ethyl acetate and water and stirred. The organic pha~e was separated off, the aqueous pha~e was extracted twice with ethyl acetate and the combined organic phases were dried and ev~porated down. 166 g of a white solid were 3 0 obtA i n~-l . This solid was added a little at a time to a mixture of 99.4 g of chloroacetyl chloride, 600 ml of toluene and 0.5 g of p-toluenesulfonic acid, which mix-ture had been brought to the reflux temperature for a short time. After the end of the addition, the mixture was refluxed again and the water of reaction wa~ removed.
After water no longer ~eparated off, 250 ml of water were - added. The m$xture was neutralized with 10% strength 133~593 O.Z. 0050/40230 , .
sodium hydroxide ~olution, after which the organic phase was separated off, the aqueous phase was extracted three times with toluene and the combined organic pha~es were dried and evaporated down. The dark brown liquid ob-5 tA i n~ was sub~ected to fractional distillation.Yields 100 g of a colorle~s liquid.
Bp. 85-87C/0.1 mbar.
c) 3-Tert-butyl-5-hydroxymethyl-5-methylisoxazoline 1596 g (3.0 moles) of a 14% strength ~odium hypo-chlorite solution were added to a mixture of 303.0 g (3.0 moles) of pivalinaldoxime, 216.0 g (3.0 moles) of 2-methylallyl alcohol, 500 ml of dichloromethane, 800 ml of water, 80.1 g ~0.45 mole) of a 15 mol % disodium hydrogen phosphate solution and 23.4 g (0.15 mole) of a 5 mol %
~odium dihydrogen phosphate ~olution at 20-25C and the mixture wa~ stirred overnight at this temperature. The organic phase was separated off and the aqueous phase wa~
extracted twice with dichloromethane. The combined or-ganic pha~es were dried over ~odium sulfate and evaporated down. The resulting colorless liquid was ~ub-~ected to fractional distillation under reduced pre~ure.
Yield: 401 g of a colorles~ oil which cry~tallizes on stAn~in~.
Bp. 80-84C/0.01 mbar.
d) 3-Tert-butyl-5-formyl-5-methyli~oxAzoline A ~olution of 117.0 g (1.5 moles) of dimethyl-sulfoxide in 300 ml of dichloromethane was added dropwise to a solution of 83.8 g (0.66 mole) of oxalyl chloride in 750 ml of dichloromethane at -60C. The reaction mixture was stirred for 15 minute~ at this temperature, after which 102.6 g (0.6 mole) of 3-tert-butyl-5-hydroxymethyl-5-methylisoxazoline were added and stirring was continued for a further 15 minutes. After the dropwise addition of 303.6 g (3.0 moles) of triethylamine, the mixture was stirred for a further 10 minute~ and was heated to 25C
and 1.8 1 of water were added. After 10 minutes, the organic phase wa~ separated off, the aqueous phase wa~
133~593 21 O.Z. 0050/40230 extracted with twice 600 ml of dichloromethsne and the combined organic phasQs were washed with three times 450 ml of a 1 N hydrochloric acid and once with 450 ml of a saturated sodium carbonate solution, dried and evaporated down. 100 g of a yellow liquid were obtAi~e~, this liquid being sub~ected to fractional distillation under 0.2 mbar.
Yields 77.4 g of a colorless liquid.
Bp. 58-62C/0.4-0.2 mbar.
2. Preparation of the vinyl ketones V
a) 4-~3-Pyrid-2-ylisoxazol-5-yl]-3-buten-2-one 100 g of 5-chloromethyl-3-pyrid-2-ylisoxazole and 175 g of triphenylphosphane were dissolved in 300 ml of chloroform and the solution was refluxed for 2 days.
After the reaction mixture had been cooled and evaporated down, the residue was ~tirred with tert-butyl methyl ether and the brown ~olid was separated off and dried.
210 g of phosphonium ~alt were obt~insA, to which 113 g of a 40% strength methylglyoxal solution in water, 250 ml of water and 250 ml of dichloromethane were added. 46 g of ~odium bicarbonate were added a little at a time at 25C, after which the mixture was stirred for 1 hour, the organic phase wa8 separated off and the aqueous phase was extracted twice with dichloromethane. The combined or-ganic phases were evaporated down and the residue wa~
stirred with tert-butyl methyl ether to give 100 g of a pale brown solid, which was reacted without further purification.
b) 4-t3-Tetrahyd o~ an-2-ylisoxazol-5-yl]-3-buten-2-one 47 g of 1-triphenylphosphoranylidene-2-propanone were dissolved in 50 ml of dichloromethane, and 27 g of 5-formyl-3-tetrahydropyran-2-ylisoxazole were added. The reaction mixture wa8 stirred for 1 day at room tempera-ture and then evaporated down, the residue being stirred in methyl tert-butyl ether. After the triphenylphosphine oxide had been ~eparated off, 43 g of a yellow oil remained.
22 O.Z. 0050/40230 c) 4-[3-Tert-butyl-S-methyli~oY~zolin-5-yl]-3-buten-2-one 35.0 g (0.21 mole) of 3-tert-butyl-5-formyl-5-methylisoxazoline were added dropwise to a solution of 79 g (0.25 mole) of 1-triphenylphosphoranylidene-2-propanone in 200 ml of dichloromethane. The reaction mixture was kept at 40C for 8 hours and then stirred with tert-butyl methyl ether. The residue was filtered off under suction and the filtrate was evaporated down to give 43 g of a yellow oil which slowly crystallized.
3. Preparation of the 3-hydroxy-2-cyclohexen-1-ones VIII
a) 3-Hydroxy-5-t3-tetrahydrofur-3-ylisoxazol-5-yl]-2-cyclohexen-l-one 10.6 g of dimethyl malonate in 300 ml of methanol were initially taken, and 14.4 g of a 30% strength sodium ethylate solution in methanol were added at room tempera-ture. Thereafter, 16.0 g of 4-ttetrahydrofur-3-yl-isoxazol-5-yl]-3-buten-2-one were added and the mixture was stirred for 1 day at 25C. The residue which remain-ed after the ~olvent had been removed was taken up in 10%
strength sodium hydroxide solution and stirred for 24 hours at 25C. The sodium hydroxide pha~e was washed with methyl tert-butyl ether, acidified to pH 2 with con-centrated hydrochloric acid and then heated at 85C for 2 hour~. The solid formed was filtered off, wa~hed with water and dried. 12.3 g of a beige solid of melting point 142-144C were obt~ine~.
b) 5-t3-sec-Butyl-5-methylisoxazolin-5-yl]-3-hydroxy-2-cyclohexen-l-one 31.7 g (0.24 mole) of dimethyl malonate were dissolved in 300 ml of methanol, and 43.2 g (0.24 mole) of 30% strength sodium methylate solution in methanol were added at < 30C. Thereafter, a solution of 50.2 g (0.24 mole) of 4-t3-sec-butyl-5-methylisoxazolin-5-yl]-3-buten-2-one in 50 ml of methanol was added. After 24 hours at 25C, the solvent was removed under reduced pressure .
The residue was taken up in 400 ml of 10%
1~34593 23 O.Z. 0050/40230 ~trength ~odium hydroxide solution and the ~olution was ~tirred for 1 day at 25C. The sodium hydroxide phase was extracted twice with tert-butyl methyl ether and acidified to pH 5 at 50C with concentrated hydrochloric acid. Stirring was then cont~nue~ for 2 hours at 85C
and the pH was brought to 3. The aqueous phase was ex-tracted with dichloromethane, and the extract was washed with water, dried over sodium sulfate and evaporated down. 56 g of a red oil were obtAineA.
x oR3 /(8)--(A)m~ORI I
Yn R4 where Rl i8 Cl-C6-alkyl, C3-C6-alkenyl or C3-C6-alkynyl and these groups may carry from one to three of the following radicals: halogen, C1-C4-alkoxy, C1-C4-alkylthio and/or phenyl, and the phenyl group in turn may be monosub-stituted to trisubstituted by halogen, C1-C4-alkyl, C1-C4-alkoxy, C1-C4-alkylthio, C1-C~-haloalkyl and/or cyano;
phenyl, benzyl or thenyl, where the aromatic nuclei may carry from one to three of the following radicals: halo-gen, Cl-C4-alkyl, Cl-C4-alkoxy, Cl-C4-alkylthio, Cl-C4-halo-alkyl, nitro and/or cyano;
R2 i8 C1-C6-alkyl, C3-C6-alkenyl, C3-C6-alkynyl or phenyl, and these groups may carry from one to three of the following radicals: halogen, C1-C4-alkoxy, C1-C4-alkylthio and/or cyano;
R3 is hydrogen, C1-C6-alkyl, C1-C10-alkylcarbonyl, C1-C6-alkylsulfonyl, Cl-C~-trialkylsilyl, Cl-C4-dialkylphosphon-yl, Cl-C"-dialkylthiophosphonyl, C3-C6-alkenyl, C3-C6-alkenylcarbonyl or C3-C6-alkynyl or a benzoyl or phenylsulfonyl group which may be monosub-stituted to trisubstituted by halogen, nitro, cyano, C1-C4-alkyl, C1-C~-haloalkyl, C1-C4-alkoxy and/or C1-C4-alkyl-thio;
R4 i8 hydrogen, cyano, halogen, C1-C6-alkyl or C1-C6-alkoxycarbonyl;
A is a C1-C4-alkylene chain in which a methylene group may be replaced by an oxygen or sulfur atom and which may carry one or two of the following substituents: C1-C4-alkyl, Cl-C4-alkoxy, C1-C4-alkylthio and/or halogen;
~.
133~93 m is 0 or 1, B is a 5-membered monounsaturated or diunsaturated heterocyclic radical having not more than 2 nitrogen atoms and/or not more than one oxygen or sulfur atom, X is a 3-membered to 7-membered cycloalkyl radical or a 5-membered to 7-membered cycloalkenyl radical, wherein a methylene group in these ring systems may be replaced by an oxygen or sulfur atom;
a 5-membered or 6-membered heteroaromatic radical containing up to three atoms selected amongst nitrogen, oxygen and sulfur, where the ring may carry from one to three of the following groups:
C1-C4-alkyl, C1-C4-alkoxy, C1-C4-alkylthio, C1-C4-haloalkyl, halogen, cyano and/or nitro, or if B is isoxazolinyl, is also hydrogen;
Y is hydrogen, halogen, cyano or nitro;
C1-C6-alkyl, Cz-C6-alkenyl or C2-C6-alkynyl, and these groups may carry from one to three of the following radicals: phenyl, halogen, C1-C4-alkoxy and/or C1-C4-alkylthio, C1-C4-alkoxy, C1-C4-alkylthio, C3-C6-alkenyloxy or C3-C6-alkynyloxy;
n is 1, 2 or 3 with the proviso that Y does not, or all the Y's when n is greather than 1, denote hydrogen when m is 0, B is isoxazol-5-yl and X is 3-(C3-C6-cycloalkyl), and their environmentally compatible salts.
The present invention furthermore relates to the preparation of the compounds I, their use as herbicides and mixtures for controlling undesirable plant growth which contain the compounds of the formula (I).
1~3~593 - 2a -The compounds of the formula (I) may occur in a plurality of tautomeric forms, all of which are embraced by ~bo claim and, ~hcle ~ ~
- 133~593 - 3 - O. Z . 0050/40230 OH ~ R~NH-OR 1 R~2 ~ ~ORl In this scheme, as in all the equations below, the radical x ~(B)--(A)m--Yn is denoted by R for greater clarity.
The herbicidal action of 3-hydroxy-2-cyclohexen-l-one oxime ether derivatives which carry a 5-membered heterocyclic radical in the 5-position is disclosed in EP-A 125 094, EP-A 162 224 and EP-A 238 021.
It is an ob~ect of the present invention to pro-vide compounds which can be used at lower application rates, are better tolerated by crop plants (greater selectivity) and have a good action against weeds.
We have found that this ob~ect is achieved by the cycloheYPnone~ I defined at the outset.
These novel cyclohexenone derivatives have a good lS herbicidal action preferably against species from the family of the grasses (Gramineae). They are tolerated and therefore have selective action in broad-leaved crops and in monocotyledons which do not belong to the Gramineae. They furthermore include compounds which also 2 0 have a selective action in graminaceous crops such as wheat, barley and rice and at the same time control un-desirable grasses. The novel cyclohexenone derivatives of formula I also have a growth-regulating action against species from the family of the grasses.
- 4 - O.Z. 0050/40230 The compounds I are prepared in four reaction steps according to the following scheme:
8ase RCHO ~ Ph3P=CH-COCH3 III VI
Base RCHO ~ (CH3)2CO [ St~p Al III ~ R-CH=CH-COCH 3 3ase V
RCHO ~ CH 3CO-CH2CO2CH3 III
RCH2Cl ~ Ph3P 8ase IV
OH
V ~ R~_~CO2CH3 8as~ R
VIII
OH
VIII ~ RlCOCl 8asa Bas-~Rlo~H~ e R~ R~
I (R3 = H) I (R3 ~ H) The required intermediates are obt~ hle by many methods which have been described in a large number of patent publications, for example EP-A 125 094, EP-A 150 433 or EP-A 238. 021.
A) Step A comprises the preparation of the vinyl ketones of formula V.
Alternatively, for example, the following processes are possible:
An aldehyde of the formula III i~ reacted with acetone in the presence of a base or with a Wittig 133~593 5 - O.Z. 0050/40230 reagent of the formula VI or with ethyl acetoacetate in the presence of a base to give the vinyl ketone of the formula V.
Halomethyl compounds of the formula IV may also be used, these compounds first being converted into the phosphonium salts and then being reacted with methyl-glyoxal to give the desired vinyl ketones of the formula R-CH2Ct Ph3P R-CH2-P$Ph3Cle OHC-COCH3 R-CH=CH-COCH3 IV Base B) Step B relates to the synthesis of the 3-hydroxy-2-cyclohexen-1-one~ of the formula VIII. For this pur-pose, the vinyl ketones of the formula V are reacted with, for example, an e~ter derivative of the formula VII
in the presence of a base, the desired compounds of the formula VIII being formed.
R4~_-CO2CH3 OH
R-CH=CH-COCH3 ~ R
V 3ase R4 VIII
C) Step C gives the 2-acyl-3-hydroxy-2-cyclohexen-1-ones of the formula II. For this purpose, the deriva-tives of the formula VIII are reacted with an acyl chlor-ide of the formula IX in the presence of a base to give O-acylated derivatives of the formula X, which are then sub~ected to a rearrangement reaction in the presence of a Lewis acid or of a base, such as imidazole, pyridine or 4-N,N-dimethylaminopyridine, to give the C-acylated com-pound of the formula II.
R ~ 8ase ~ or Lewis ~2 D) Step D relates to the preparation of the com-pounds of the formula I, which are ob~A i n~ from the 2-acyl-3-hydroxy-2-cyclohexen-1-ones II by reaction with an - 6 - O.Z. OOSO/40230 alkoxyammonium salt of the formula RlONH~.HQ, where Q is a suitable leaving group, such as chloride. Alternative-ly, it is also possible to use the free alkoxyamine R10NH2.
Compounds which contain a substituent R3 which is not hydrogen are obtAinAhle from compounds of the formula I where R3 is H in a conventional manner as described below.
In the case of the ethers, esters and sulfones, the compounds of the formula I where R3 is H are reacted with a corresponding alkylating, acylating or sulfonating agent.
Other suitable starting materials for this pur-pose are the alkali metal salts of the compounds of the formula I, which are obtA i n~ by reaction with an alkali metal hydroxide, an alkali metal alcoholate or an alkali metal hydride.
If, in formula I, R3 is another inorganic or or-ganic cation, these compounds are obt~inAhle from the alkali metal salts using transition metal salts or or-ganic bases. Examples of these are manganese chloride, copper chloride, zinc chloride and iron chloride and the corresponding sulfates, as well as magnesium methylate, magnesium ethylate, calcium methylate and calcium ethylate.
The ma~ority of the heterocyclic aldehydes III
and chloromethyl compounds IV required as starting mater-ials are novel but can be prepared by conventional pro-cesses.
The isoxazoles are prepared, for example, under the conditions described in DE-A 2 754 832. They are ob-tAi~Ahle from aldoximes by 1,3-dipolar cycloaddition with propargyl alcohols or propargyl halides. The 5-hydroxy-methyl-substituted isoxazoles can be converted into the 5-formyl derivative by conventional oxidation processes.
The regioisomers which are bonded in the 3- or 4-position can be prepared, inter alia, according to Baraldi et al., 1334~93 - 7 - O.Z. 0050/40230 J. Het. Chem. 19 (1982), 557 and Bertini et al., J. Chem.
Soc. Perkin Trans I 1976, 570.
Syntheses of 1,3-oxazoles are described in The Chemistry of Penicillins.
1,3-Thiazoles which are bonded in the 4- or 5-position are obtAinAhle, for example, by processes described by A. Beuko et al., Liebigs Ann. Chem. 717 (1968), 148-153.
Syntheses of 1,2,4-oxadiazole~ are described in, for example, Chem. Ber. 17 (1889), 1685 and Tetrahedron Lett. (1961), 587-589.
With regard to the use of the compounds I in accordance with regulations, the radicals below are pre-ferred substituents.
Alkyl groups Rl are methyl, ethyl, propyl, 1-methylethyl, butyl, l-methylpropyl, 2-methylpropyl, 1,1-dimethylethyl, pentyl, l-methylbutyl, 2-methylbutyl, 3-methylbutyl, l,l-dimethylpropyl, 1,2-dimethylpropyl,2,2-dimethylpropyl, 1-ethylpropyl, hexyl, l-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, l,l-dimeth-ylbutyl, 1,2-dimethylbutyl, 1,3-dimethylbutyl, 2,2-dimethylbutyl, 2,3-dimethylbutyl, 3,3-dimethylbutyl, 1-ethylbutyl, 2-ethylbutyl, 1,1,2-trimethylpropyl, 1,2,2-trimethylpropyl, l-ethyl-l-methylpropyl and l-ethyl-2-methylpropyl, ethyl and propyl being preferred.
Al kenyl groups in thi~ position are 2-propenyl, 2-butenyl, 3-butenyl, 1-methyl-2-propenyl, 2-methyl-2-plo~el.yl~ 2-pentenyl, 3-pentenyl, 4-pentenyl, l-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-2-propenyl, 1-ethyl-2-propenyl, 2-hexenyl, 3-hexenyl, 4-hexenyl, 5-hexenyl, l-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-4-pentenyl, 1-methyl-4-pentenyl, 2-methyl-4-pentenyl, 3-methyl-4-pentenyl, 3-methyl-4-pentenyl, 4-133~5~3 _ - 8 - O.Z. 0050/40230 methyl-4-pentenyl, 1,1-dimethyl-2-butenyl, l,l-dimethyl-3-butenyl, 1,2-dimethyl-2-butenyl, 1,2-dimethyl-3-buten-yl, 1,3-dimethyl-2-butenyl, 1,3-dimethyl-3-butenyl, 2,2-dimethyl-3-butenyl,2,3-dimethyl-2-butenyl,2,3-dimethyl-3-butenyl, 1-ethyl-2-butenyl, 2-ethyl-2-butenyl, l-ethyl-3-butenyl,2-ethyl-3-butenyl,1,1,2-trimethyl-2-propenyl, l-ethyl-l-methyl-2-propenyl and 1-ethyl-2-methyl-2-propenyl, in particular 2-propenyl and 2-butenyl.
Preferred alkynyl radicals R1 are 2-plo~yllyl~ 2-butynyl, 3-butynyl, 1-methyl-2-pLo~ylLyl~ 2-pentynyl, 3-pentynyl, 4-pentynyl, 1-methyl-2-butynyl, 1-methyl-3-butynyl, 2-methyl-3-butynyl, 1,l-dimethyl-2-pLo~yl~yl~ 1-ethyl-2-p opyllyl~ 2-hexynyl, 3-hexynyl, 4-hexynyl, 5-hexynyl, l-methyl-2-pentynyl, 4-methyl-2-pentynyl, 1-methyl-3-pentynyl, 2-methyl-3-pentynyl, 1-methyl-4-pentynyl, 2-methyl-4-pentynyl, 3-methyl-4-pentynyl, 1,1-dimethyl-2-butynyl,l,l-dimethyl-3-butynyl,1,2-dimethyl-3-butynyl, 2,2-dimethyl-3-butynyl, 1-ethyl-2-butynyl, 1-ethyl-3-butynyl, 2-ethyl-3-butynyl and l-ethyl-l-methyl-2-p o~yl~yl~ in particular 2-PLO~Y1~Y1 and 2-butynyl.
These alkyl, alkenyl and alkynyl groups may be substituted by from one to three of the following groups:
halogen atom~, such as bromine and iodine, preferably however from one to three fluorine and/or chlorine atoms, (E)-3-chloroprop-2-enyl being particularly preferred;
alkoxy, such as methoxy, ethoxy, propoxy, l-methylethoxy, butoxy, l-methylpropoxy, 2-methylpropoxy and l,l-dimeth-ylethoxy, in particular one or two methoxy or ethoxy groups;
Alkylthio, such as methylthio, ethylthio, propyl-thio, l-methylethylthio, butylthio, l-methylpropylthio, 2-methylpropylthio and l,1-dimethylethylthio, one or two ethylthio groups being preferred, and/or a phenyl ring which, in addition to the abovementioned halogen atoms, alkyl groups, alkoxy groups and alkylthio groups, may also carry cyano and haloalkyl, such as fluoromethyl, difluoromethyl, trifluoromethyl, chloromethyl, dichloro-133~593 - - - 9 - O.Z. 0050/40230 methyl, trichloromethyl, difluorochloromethyl, l-fluoro-ethyl, 2-fluoroethyl, l,l-difluoroethyl, 1,1,2-trifluoro-ethyl, 1,2,2-trifluoroethyl and 2,2,2-trifluoroethyl; in particular, the phenyl ring is unsubstituted or substituted in the 4-position by fluorine, chlorine, methyl, trifluoromethyl, or l,l-dimethylethyl and/or in the 2-position by chlorine or methoxy.
R1 may furthermore be phenyl, thenyl or benzyl, and the aromatic nuclei may also be substituted by nitro, cyano and/or alkyl groups, such as methyl, ethyl, propyl, l-methylethyl, butyl, l-methylpropyl, 2-methylpropyl and l,l-dimethylethyl, in addition to the abovementioned halogen atoms, alkoxy groups, alkylthio groups and haloalkyl groups. The 5-chlorothenyl radical is parti-cularly preferred.
The alkyl, alkenyl and alkynyl groups R2 and thephenyl radical R2 and its substituents have the same general and particular me~ni~gs as R1.
Suitable radicals R3 in addition to the above-mentioned alkyl, alkenyl and alkynyl groups are radicalsof saturated and unsaturated carboxylic acids, such as acetyl, propionyl, butyryl and pivaloyl, in particular acetyl and butyryl;
and alkylsulfonyl, alkylsilyl, alkylphosphonyl or alkyl-thiophosphonyl groups, the alkyl radicals preferably being methyl~ ethyl, l-methylethyl and l,l-dimethylethyl, and benzoyl and phenylsulfonyl. The last-mentioned aromatic radicals may be monosubstituted to trisub-stituted. The possible substituents correspond to the substituents stated under Rl.
Suitable radicals R4 in addition to hydrogen and cyano are the halogen atoms and alkyl groups already mentioned for Rl and alkoxycarbonyl groups, such as meth-oxycarbonyl, ethoxycarbonyl, propoxycarbonyl, l-methyl-ethoxycarbonyl, butoxycarbonyl, l-methylpropylcarbonyl, 2-methylpropylcarbonyl and l,l-dimethylethoxycarbonyl, but in particular methoxycarbonyl and ethoxycarbonyl.
133459~
10 - O.Z. 0050/40230 Preferred radicals R4 are hydrogen, cyano and methoxycarbonyl.
A is an alkylene, alkyleneoxyalkylene or alkylenethioalkylene chain having up to four members.
Examples of these are methylene, ethylene, propylene, butylene, methyleneoxymethylene, methyleneoxyethylene, methylenethiomethylene,methylenethioethylene,propylene-oxy, propylenethio, ethyleneoxy, ethylenethio, methylene-oxy, methylenethio, oxy and thio bridges.
The compounds of the formula I preferably contain no bridge A or a l-membered or 2-membered bridge A.
The 5-membered heterocyclic radicals B are rings such as dihydrofuranyl, dihydrothienyl, pyrrolinyl, pyrazolinyl, imidazolinyl, isoxazolinyl, oxazolinyl, iso-thiazolinyl, thiazolinyl, furanyl, thienyl, pyrrolyl,pyrazolyl, isoxazolyl, oxazolyl, isothiazolyl, thiazolyl, oY~ zolyl and thi~ 701yl -Particularly preferred compounds of the formulaI are those in which a 4,5-dihydroisoxazolyl ring is bonded at its 4- or 5-position by one of the above-mentioned bridges to the cycloheY~none system, and those in which one of the listed heteroaromatic rings is bonded directly to the cycloheYenone ring.
Sui~able g ou~ X are the following:
cycloalkyl, such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl and cycloheptyl, preferably cyclopropyl and cyclohexyl;
cycloAl~enyl, for example cyclopentenyl, cyclohexenyl and cycloheptenyl, preferably cyclopentenyl and cyclohexenyl;
heterocyclic aliphatic radicals, for example epoxyethyl, oxetanyl, tetrahydrofuranyl, tetrahydropyranyl, thietan-yl, tetrahydrothienyl and tetrahydrothiopyranyl, preferably 3-tetrahydropyranyl, tetrahydrothiopyranyl and 1,3-dioxan-2-yl;
heterocyclic alkenyl rings, including the dihydrofuranyl, dihydrothienyl, dihyd~o~ylanyl and dihydrothiopyranyl radical, but in particular the dihydropyranyl and the di-133~5g3 - 11 - o.Z. 0050/40230 hydrothiopyranyl radical;
heteroaromatic groups, for example pyrrolyl, pyrazolyl, imidazolyl, triazolyl, pyridyl, pyrimidyl, pyrazinyl, pyridazinyl, quinolyl or isoquinolyl, furanyl, thienyl, isoxazolyl, oxazolyl, oxathiazolyl, isothiazolyl and thiA7olyl, preferably 2-pyridyl and 2-furyl, and hydrogen, if 8 is isoxazolinyl.
Heteroaromatic rings may carry up to three ~ub-stituents. In addition to cyano and nitro groups, the abovementioned halogen atoms, alkyl groups, haloalkyl ~oup~, alkoxy y oups and alkylthio groups are suitable for this purpose.
Yn are from one to three identical or different rA~icAls from amongst the abovementioned alkyl, alkenyl lS or alkynyl groups, as well as hydrogen, halogen, cyano and nitro. In psrticular, alkenyl may also be vinyl or alkynyl here, especially ethynyl.
These compounds do not include those in which Y
is hydrogen when B is ;~OXA~O1-5-Y1~ m is O and X i~ 3-(c3-c~-cycloalkyl).
13~4593 12 O.Z. 0050/40230 In detail, the invention embraces preferably the following structures:
a) Pyrroles of the formula Y op3 pO2R 1 I . 01 x oR3 ~ OR1 I.02 b) Furans and thiophenes of the formula Yn oR3 X ~ 02Rl I 04 E=S
X Yn OR3 ~ 2 I 05 E-O
c) Pyrazoles of the formula x Y oP3 ~ OR1 I.07 x oR3 2R1 I.08 X ~ O2R1 I.09 - 1~3~593 13 O.Z. 0050/40230 d) Isoxazoles and isothiazoles of the formula E-N ~ ,NOR1 I.10 E=O
~ ~-4R2 I.11 E=S
X Yn R4 x oR3 E ~ O2R1 I }3 E-S
Yn R4 Yn OR3 X ~ OR1 I }4 E-O
R ~ O
e) Oxazoles and thiazoles of the formula Yn oR3 ~N ,-~ ~NORl I.16 E=O
X- -E ~ R2 I.17 E=S
oR3 E ~ O2R1 I }9 E-S
Yn R4 X ~ O2R1 I 21 E-S
f) 1,2,3-Oxadiazoles and 1,2,3-thiadiazoles of the formula oR3 E ~ O2R1 I 23 E-S
x oR3 N ~ OR1 I 24 E-O
1~3~593 14 O.Z. 0050/40230 9) 1,2,4-Oxadiazoles and 1,2,4-thiadiazoles of the formula L N~ ~ OR1 I 27 E_O
X R ~ O
x oR3 ~ ~ ~ oR1 I 29 E-S
~0 R
h) 1,3,4-Oxadiazoles and 1,3,4-thiadiazoles of the formula oR3 N-N ~ O2R1 I 30 E-O
5 i) 4,5-Dihydroisoxazolines of the formula X ~ I.32 ,~OR 1 X
The cyclohexenone derivatives I, and herbicidal agents containing them, may be applied for instance in the form of directly sprayable solutions, powders, suspensions (including high-percentage aqueous, oily or other lO suspensions), dispersions, emulsions, oil dispersions, pastes, dusts, broadcasting agents, or granules by spraying, atomizing, dusting, broad-casting 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 15 possible.
For the preparation of solutions, emulsions, pastes and oil dispersions to be sprayed direct, mineral oil fractions of medium to high boiling point, such as kerosene or diesel oil, further coal-tar oils, and oils of 20 vegetable or animal origin, aliphatic, cyclic and aromatic hydrocarbons such as toluene, xylene, paraffin, tetrahydronaphthalene, alkylated naphthalenes and their derivatives such as methanol, ethanol, propanol, butanol, cyclohexanol, cyclohexanone, chlorobenzene, isophorone, etc., O.Z. 0050/40230 and strongly polar solvents such as N,N-dimethylformamide, dimethyl sulfoxide, N-methylpyrrolidone, water, etc. are suitable.
Aqueous formulations may be prepared from emulsion concentrates, pastes, 5 oil dispersions or wettable powders 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 ingredient, wetting agent, 10 adherent, emulsifying or dispersing agent and possibly solvent or oil.
Examples of surfactants are: alkali metal, alkaline earth metal and ammonium salts of aromatic sulfonic acids, e.g., ligninsulfonic acid, phenolsulfonic acid, naphthalenesulfonic acid and dibutylnaphthalene-15 sulfonic acid, and of fatty acids, alkyl and alkylaryl sulfonates, andalkyl, lauryl ether and fatty alcohol sulfates, alkali metal and alkaline earth metal salts of dibutylnaphthalenesulfonic acid, lauryl ether sul-fate, fatty alcohol sulfates, and salts of sulfated hexadecanols, hepta-decanols, and octadecanols, salts of fatty alcohol glycol ethers, conden-20 sation products of sulfonated naphthalene and naphthalene derivatives withformaldehyde, condensation products of naphthalene or naphthalenesulfonic acids with phenol and formaldehyde, polyoxyethylene octylphenol ethers, ethoxylated isooctylphenol, ethoxylated octylphenol and ethoxylated nonyl-phenol, alkylphenol polyglycol ethers, tributylphenyl polyglycol ethers, 25 alkylaryl polyether alcohols, isotridecyl alcohol, fatty alcohol ethylene oxide condensates, ethoxylated castor oil, polyoxyethylene alkyl ethers, ethoxylated polyoxypropylene, lauryl alcohol polyglycol ether acetal, sorbitol esters, lignin-sulfite waste liquors and methyl cellulose.
30 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 granules, may be prepared by bonding the active ingredients to solid carriers. Examples of 35 solid carriers are mineral earths such as silicic 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 40 products such as grain meals, bark meal, wood meal, and nutshell meal, cellulosic powders, etc.
- 13345~3 16 O.Z. 0050/40230 The formulations contain from O.l to 95, and preferably 0.5 to 90, % by weight of active ingredient.
The agents may be applied pre- or postemergence. If certain crop plants5 tolerate the active ingredients less well, application techniques may be used in which the herbicidal agents are sprayed from suitable 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 application rates depend on the objective to be achieved, the time of the year, the plants to be combated and their growth stage, and are from O.Ol to 3.0, preferably 0.05 to l.0, kg of active ingredient per hectare.
l5 In view of the spectrum of weeds that can be combated, the tolerance by crop plants and the desired influence on plant growth, and in view of the number of application methods possible, the compounds according to the invention may be used in a further large number of crops for removing unwanted plants. The following crops are given by way of example:
Botanical name Common name Allium cepa onions Ananas comosus pineapples Arachis hypogaea peanuts (groundnuts) 25 Asparagus officinalis asparagus Avena sativa oats Beta vulgaris spp. altissima sugarbeets Beta vulgaris spp. rapa fodder beets Beta vulgaris spp. esculenta table beets, red beets 30 Brassica napus var. napus rapeseed Brassica napus var. napobrassica swedes Brassica napus var. rapa turnips Brassica rapa var. silvestris Camellia sinensis tea plants 35 Carthamus tinctorius safflower Carya illinoinensis pecan trees Citrus limon lemons Citrus maxima grapefruits Citrus reticulata mandarins 40 Citrus sinensis orange trees Coffea arabica (Coffea canephora, Coffea liberica) coffee plants Cucumis melo melons Cucumis sativus cucumbers 133~593 17 O.Z. 0050/40230 Botanical name Common name Cynodon dactylon Bermudagrass Daucus carota carrots Elais guineensis oil palms 5 Fragaria vesca strawberries Glycine max soybeans Gossypium hirsutum (Gossypium arboreum, Gossypium herbaceum, Gossypium vitifolium) cotton Helianthus annuus sunflowers IO Helianthus tuberosus Jerusalem artichoke Hevea brasiliensis rubber plants Hordeum vulgare barley Humulus lupulus hops Ipomoea batatas sweet potatoes lS Juglans regia walnut trees Lactuca sativa lettuce Lens culinaris lentils Linum usitatissimum flax Lycopersicon Iycopersicum tomatoes 20 Malus spp. apple trees Manihot esculenta cassava Medicago sativa alfalfa (lucerne) Mentha piperita peppermint Musa spp. banana plants 25 Nicotiana tabacum (N. rustica) tobacco Olea europaea olive trees Oryza sativa rice Panicum miliaceum millet Phaseolus lunatus limabeans 30 Phaseolus mungo mungbeans Phaseolus vulgaris snapbeans, green beans, dry beans Pennisetum glaucum pearl millet Petroselinum crispum spp. tuberosum parsley 35 Picea abies Norway spruce Abies alba fir trees Pinus spp. pine trees Pisum sativum English peas Prunus avium cherry trees 40 Prunus domestica plum trees Prunus dulcis almond trees Prunus persica peach trees Pyrus communis pear trees Ribes sylvestre redcurrants 1~34593 18 O.Z. 0050/40230 Botanical name Common name Ribes uva-crispa gooseberries Ricinus communis castor-oil plants Saccharum officinarum sugar cane 5 Secale cereale rye Sesamum indicum sesame Solanum tuberosum Irish potatoes Sorghum bicolor (s. vulgare) sorghum Sorghum dochna sorgo 10 Spinacia oleracea spinach Theobroma cacao cacao plants Trifolium pratense red clover Triticum aestivum wheat Triticum durum durum wheat 15 Vaccinium corymbosum blueberries Vaccinium vitis-idaea cranberries Vicia faba tick beans Vigna sinensis (V. unguiculata) cow peas Vitis vinifera grapes 20 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 25 together with numerous representatives of other herbicidal or growth-regulating active ingredient groups. Examples of suitable components are diazines, 4H-3,1-benzoxazine derivatives, benzothiadiazinones, 2,6-dinitroanilines, N-phenylcarbamates, thiolcarbamates, halocarboxylic acids, triazines, amides, ureas, diphenyl ethers, triazinones, uracils, 30 benzofuran derivatives, quinolinecarboxylic acids, cyclohexenones, aryloxy- or heteroaryloxy-phenoxypropionic acids and salts, esters and amides thereof, etc.
It may also be useful to apply the cyclohexenone compounds of the 35 formula I, either alone or in combination with other herbicides, in admixture with other crop protection agents, e.g., agents for combating pests or phytopathogenic fungi 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 40 added.
1~34~9~
19 O.Z. 0050/40230 In the synthesis methods below, the individual steps of the synthQsis are described with reference to some specific examples.
1. Preparation of the hete~o~i~clic chloromethyl compounds a) 5-Chloromethyl-3-pyrid-2-ylisoxazole 774 g of a 14% strength sodium hypochlorite solu-tion were added to a mixture of 122 g of 2-pyridylaldox-ime, 1.5 1 of water, 500 ml of dichloromethane, 15 g of ~odium dih~d o~en phosphate dihydrate, 18 g of ~odium hy~o~en phosphate dihydrate and 150 g of propargyl chloride at 20-25C. Stirring was carried out for 10 hour~ at 25C, the phases were separated and the aqueous phase was e~tracted with twice 150 ml of dichloromethane.
The combined organic phase~ were dried over sodium sulfate and evaporated down. 170 g of a brown ~olid were obt~ine-l. The product was reacted without further purification.
b) 5-Chloromethyl-3-cyclopentyl-1,2,4-oxadiazole 100 g of hydroxylamine hydrochloride were dis-solved in 360 ml of water, and 122 g of sodium bicarbon-ate were added a little at a time at 25C. Thereafter, 138 g of cyclopentanecarbonitrile, dissolved in 400 ml of ethanol, were added dropwise. The reaction mixture was refluxed for 10 hour~ at 80C, cooled and then evaporated down. The residue was taken up in a 1: 1 mixture of ethyl acetate and water and stirred. The organic pha~e was separated off, the aqueous pha~e was extracted twice with ethyl acetate and the combined organic phases were dried and ev~porated down. 166 g of a white solid were 3 0 obtA i n~-l . This solid was added a little at a time to a mixture of 99.4 g of chloroacetyl chloride, 600 ml of toluene and 0.5 g of p-toluenesulfonic acid, which mix-ture had been brought to the reflux temperature for a short time. After the end of the addition, the mixture was refluxed again and the water of reaction wa~ removed.
After water no longer ~eparated off, 250 ml of water were - added. The m$xture was neutralized with 10% strength 133~593 O.Z. 0050/40230 , .
sodium hydroxide ~olution, after which the organic phase was separated off, the aqueous phase was extracted three times with toluene and the combined organic pha~es were dried and evaporated down. The dark brown liquid ob-5 tA i n~ was sub~ected to fractional distillation.Yields 100 g of a colorle~s liquid.
Bp. 85-87C/0.1 mbar.
c) 3-Tert-butyl-5-hydroxymethyl-5-methylisoxazoline 1596 g (3.0 moles) of a 14% strength ~odium hypo-chlorite solution were added to a mixture of 303.0 g (3.0 moles) of pivalinaldoxime, 216.0 g (3.0 moles) of 2-methylallyl alcohol, 500 ml of dichloromethane, 800 ml of water, 80.1 g ~0.45 mole) of a 15 mol % disodium hydrogen phosphate solution and 23.4 g (0.15 mole) of a 5 mol %
~odium dihydrogen phosphate ~olution at 20-25C and the mixture wa~ stirred overnight at this temperature. The organic phase was separated off and the aqueous phase wa~
extracted twice with dichloromethane. The combined or-ganic pha~es were dried over ~odium sulfate and evaporated down. The resulting colorless liquid was ~ub-~ected to fractional distillation under reduced pre~ure.
Yield: 401 g of a colorles~ oil which cry~tallizes on stAn~in~.
Bp. 80-84C/0.01 mbar.
d) 3-Tert-butyl-5-formyl-5-methyli~oxAzoline A ~olution of 117.0 g (1.5 moles) of dimethyl-sulfoxide in 300 ml of dichloromethane was added dropwise to a solution of 83.8 g (0.66 mole) of oxalyl chloride in 750 ml of dichloromethane at -60C. The reaction mixture was stirred for 15 minute~ at this temperature, after which 102.6 g (0.6 mole) of 3-tert-butyl-5-hydroxymethyl-5-methylisoxazoline were added and stirring was continued for a further 15 minutes. After the dropwise addition of 303.6 g (3.0 moles) of triethylamine, the mixture was stirred for a further 10 minute~ and was heated to 25C
and 1.8 1 of water were added. After 10 minutes, the organic phase wa~ separated off, the aqueous phase wa~
133~593 21 O.Z. 0050/40230 extracted with twice 600 ml of dichloromethsne and the combined organic phasQs were washed with three times 450 ml of a 1 N hydrochloric acid and once with 450 ml of a saturated sodium carbonate solution, dried and evaporated down. 100 g of a yellow liquid were obtAi~e~, this liquid being sub~ected to fractional distillation under 0.2 mbar.
Yields 77.4 g of a colorless liquid.
Bp. 58-62C/0.4-0.2 mbar.
2. Preparation of the vinyl ketones V
a) 4-~3-Pyrid-2-ylisoxazol-5-yl]-3-buten-2-one 100 g of 5-chloromethyl-3-pyrid-2-ylisoxazole and 175 g of triphenylphosphane were dissolved in 300 ml of chloroform and the solution was refluxed for 2 days.
After the reaction mixture had been cooled and evaporated down, the residue was ~tirred with tert-butyl methyl ether and the brown ~olid was separated off and dried.
210 g of phosphonium ~alt were obt~insA, to which 113 g of a 40% strength methylglyoxal solution in water, 250 ml of water and 250 ml of dichloromethane were added. 46 g of ~odium bicarbonate were added a little at a time at 25C, after which the mixture was stirred for 1 hour, the organic phase wa8 separated off and the aqueous phase was extracted twice with dichloromethane. The combined or-ganic phases were evaporated down and the residue wa~
stirred with tert-butyl methyl ether to give 100 g of a pale brown solid, which was reacted without further purification.
b) 4-t3-Tetrahyd o~ an-2-ylisoxazol-5-yl]-3-buten-2-one 47 g of 1-triphenylphosphoranylidene-2-propanone were dissolved in 50 ml of dichloromethane, and 27 g of 5-formyl-3-tetrahydropyran-2-ylisoxazole were added. The reaction mixture wa8 stirred for 1 day at room tempera-ture and then evaporated down, the residue being stirred in methyl tert-butyl ether. After the triphenylphosphine oxide had been ~eparated off, 43 g of a yellow oil remained.
22 O.Z. 0050/40230 c) 4-[3-Tert-butyl-S-methyli~oY~zolin-5-yl]-3-buten-2-one 35.0 g (0.21 mole) of 3-tert-butyl-5-formyl-5-methylisoxazoline were added dropwise to a solution of 79 g (0.25 mole) of 1-triphenylphosphoranylidene-2-propanone in 200 ml of dichloromethane. The reaction mixture was kept at 40C for 8 hours and then stirred with tert-butyl methyl ether. The residue was filtered off under suction and the filtrate was evaporated down to give 43 g of a yellow oil which slowly crystallized.
3. Preparation of the 3-hydroxy-2-cyclohexen-1-ones VIII
a) 3-Hydroxy-5-t3-tetrahydrofur-3-ylisoxazol-5-yl]-2-cyclohexen-l-one 10.6 g of dimethyl malonate in 300 ml of methanol were initially taken, and 14.4 g of a 30% strength sodium ethylate solution in methanol were added at room tempera-ture. Thereafter, 16.0 g of 4-ttetrahydrofur-3-yl-isoxazol-5-yl]-3-buten-2-one were added and the mixture was stirred for 1 day at 25C. The residue which remain-ed after the ~olvent had been removed was taken up in 10%
strength sodium hydroxide solution and stirred for 24 hours at 25C. The sodium hydroxide pha~e was washed with methyl tert-butyl ether, acidified to pH 2 with con-centrated hydrochloric acid and then heated at 85C for 2 hour~. The solid formed was filtered off, wa~hed with water and dried. 12.3 g of a beige solid of melting point 142-144C were obt~ine~.
b) 5-t3-sec-Butyl-5-methylisoxazolin-5-yl]-3-hydroxy-2-cyclohexen-l-one 31.7 g (0.24 mole) of dimethyl malonate were dissolved in 300 ml of methanol, and 43.2 g (0.24 mole) of 30% strength sodium methylate solution in methanol were added at < 30C. Thereafter, a solution of 50.2 g (0.24 mole) of 4-t3-sec-butyl-5-methylisoxazolin-5-yl]-3-buten-2-one in 50 ml of methanol was added. After 24 hours at 25C, the solvent was removed under reduced pressure .
The residue was taken up in 400 ml of 10%
1~34593 23 O.Z. 0050/40230 ~trength ~odium hydroxide solution and the ~olution was ~tirred for 1 day at 25C. The sodium hydroxide phase was extracted twice with tert-butyl methyl ether and acidified to pH 5 at 50C with concentrated hydrochloric acid. Stirring was then cont~nue~ for 2 hours at 85C
and the pH was brought to 3. The aqueous phase was ex-tracted with dichloromethane, and the extract was washed with water, dried over sodium sulfate and evaporated down. 56 g of a red oil were obtAineA.
4. Prepsration of the 2-acyl-3-hydroxy-2-cyclohexen-1-ones II
a) 2-Butyryl-3-hydroxy-5-t3-(tetrahydrofuryl)isoxazol-5-yl]-2-cyclohexen-1-one 12.0 g of the diketone from 3a) were dissolved in 300 ml of tetrahydrofuran, and 5.4 g of triethylamine and then 5.6 g of butyryl chloride were added. The reaction mixture was stirred for 24 hours at 25C, after which water was added and the mixture was extracted with di-chloromethane. The organic phase was washed once with water, dried and evaporated down. 15.2 g of an orange oil remained; thi~ oil was taken up in 150 ml of di-chloromethane, and 3.0 g of 4-N,N-dimethylaminopyridine were added. After 3 days, the mixture was ~tirred into 10% strength hydrochloric acid. The organic phase was ~eparated off, washed once with water, dried and evapora-ted down. 14.1 g of a yellow solid of melting point 102-104C were ObtA ~ ngA .
b) S-(sec-Butyl-S-methylisoxazolin-5-yl)-2-butyryl-3-hydroxy-2-cyclohexen-1-one 28.0 g (0.11 mole) of the diketone according to 3b) were dissolved in 300 ml of tetrahydrofuran, and 13.1 g (0.13 mole) of triethylamine and 13.8 g (0.13 mole) of butyryl chloride were added. 10.2 g of a yellow ~olid of melting point 53-55C were obtAlne~ by a procedure ~imi-lar to the working-up steps described under 4a).
a) 2-Butyryl-3-hydroxy-5-t3-(tetrahydrofuryl)isoxazol-5-yl]-2-cyclohexen-1-one 12.0 g of the diketone from 3a) were dissolved in 300 ml of tetrahydrofuran, and 5.4 g of triethylamine and then 5.6 g of butyryl chloride were added. The reaction mixture was stirred for 24 hours at 25C, after which water was added and the mixture was extracted with di-chloromethane. The organic phase was washed once with water, dried and evaporated down. 15.2 g of an orange oil remained; thi~ oil was taken up in 150 ml of di-chloromethane, and 3.0 g of 4-N,N-dimethylaminopyridine were added. After 3 days, the mixture was ~tirred into 10% strength hydrochloric acid. The organic phase was ~eparated off, washed once with water, dried and evapora-ted down. 14.1 g of a yellow solid of melting point 102-104C were ObtA ~ ngA .
b) S-(sec-Butyl-S-methylisoxazolin-5-yl)-2-butyryl-3-hydroxy-2-cyclohexen-1-one 28.0 g (0.11 mole) of the diketone according to 3b) were dissolved in 300 ml of tetrahydrofuran, and 13.1 g (0.13 mole) of triethylamine and 13.8 g (0.13 mole) of butyryl chloride were added. 10.2 g of a yellow ~olid of melting point 53-55C were obtAlne~ by a procedure ~imi-lar to the working-up steps described under 4a).
5. Preparation of the cycloheYenone oxime ether deriva-tives of the formula I
24 O.Z. 0050/40230 a) 2~ Ethoxyiminobutyl)-3-hydroxy-5-[3-tetrahydrofur-3-yliRox_zol-5-yl]-2-cyclohexen-1-one A mixture of 3.0 g of the acyl compound according to 4a), 0.9 g of ~odium bicarbonate, 1.1 g of ethoxyamine hydrochloride and 100 ml of methanol was ~tirred for 24 hour~ at 25C, and then evaporated down, the residue was taken up in ethyl acetate and the ~olution was purified by chromatography.
2.5 g of a yellow solid of melting point 58-60C
were obtAir~e~ (compound 3.9).
b) 2-(1-Ethoxyimino-n-butyl)-3-hydroxy-5-(3-i~opropyl-5-methyli~oxA7olin-5-yl)-2-cyclohe~sn-l-one A mixture of 3.5 g (11 millimoles) of the acyl compound according to 4b), 1.0 g (12 millimoles) of ~odium bicArho~Ate, 1.2 g (12 millimoles) of ethoxyamine hyd~ochloride and 100 ml of methanol was stirred for 24 hours at room temperature. The reaction mixture wa~
evaporated down, the re~idue was taken up in 50 ml of 10%
~trength ~odium hydroxide solution and the ~olution was washed with dichloromethane. The aqueous pha~e wa~
acidified with concentrated hydrochloric acid, the pre-cipitated ~olid was separated off and the filtrate wa~
extracted twice with dichloromethane. The organic phase was dried over sodium sulfate and evaporated down. 3.3 g of a yellow solid of melting point 85C were obtAi nq-l (compound 8.17).
The compounds of the formula I which are li~ted in the Table and characterized by their melting point (mp.) can be prepared in a ~imilar manner. Tables 7 and 12 list the compound~ which could not be i~olated as a solid. Compounds for which no physical data are given can be obtAirleA in a similar manner.
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v~ c O ~ <~I ~) co 0 OD CO 0 0~ a) co ~o 0 - 13345 ~3 47 O.z. 0050/40230 The herbicidal action of the cyclohexenone derivatives of the formula I is demonstrated by the following greenhouse experiments:
The vessels employed were plastic flowerpots having a volume of 300 cm3 5 and filled with a sandy loam containing about 3.0% humus. The seeds of the test plants were sown separately, according to species.
For the preemergence treatment, the formulated active ingredients were applied to the surface of the soil immediately after the seeds had been 10 sown. The compounds were emulsified or suspended in water as vehicle, and sprayed through finely distributing nozzles. The application rate was 0.5 kg/ha.
After the agents had been applied, the vessels were lightly sprinkler-15 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.
20 For the postemergence treatment, the plants were grown, depending on growth form, to a height of 3 to 15 cm before being treated. In this treatment method, either plants which had been sown in the pots and grown there were selected, or they were cultivated separately as seedlings and transplanted to the pots a few days before being treated. The application 25 rates for postemergence treatment were 0.125 and 0.25 kg/ha. No covers were placed on the vessels in this method.
The pots were set up in the greenhouse, species from warmer climates in warmer areas (20 to 35C) and species from moderate climates at 10 to 30 25C. The experiments were run for from 2 to 4 weeks. During this time the plants were tended and their reactions to the various treatments assessed.
The assessment scale was 0 to 100, 100 denoting nonemergence or complete destruction of at least the visible plant parts, and 0 denoting no damage or normal growth.
The plants employed for the experiments were Avena fatua, Digitaria sanguinalis, Echinochloa crus-galli, Lolium multiflorum, Medicago sativa, Setaria viridis, Sinapis alba, Triticum aestivum and Zea mays.
40 On preemergence application of 0.5 kg/ha, active ingredients 8.20 and 8.16 had a strong herbicidal action on grassy plants; mustard as an example of a broadleaved species remained undamaged.
133~593 48 O.Z. 0050/40230 For combating grassy vegetation, compounds 3.23 and 3.24 were suitable at a postemergence rate of 0.25 kg/ha, and compounds 8.75 and 8.77 at a post-emergence rate of 0.125 kg/ha. Broadleaved crops - as illustrated by alfalfa - remained undamaged. The novel active ingredients have a selec-5 tive herbicidal action.
Active ingredients 3.22 and 3.21 may be used postemergence at a rate of 0.125 kg/ha for combating unwanted grassy species in wheat. The crop plants suffer no damage.
24 O.Z. 0050/40230 a) 2~ Ethoxyiminobutyl)-3-hydroxy-5-[3-tetrahydrofur-3-yliRox_zol-5-yl]-2-cyclohexen-1-one A mixture of 3.0 g of the acyl compound according to 4a), 0.9 g of ~odium bicarbonate, 1.1 g of ethoxyamine hydrochloride and 100 ml of methanol was ~tirred for 24 hour~ at 25C, and then evaporated down, the residue was taken up in ethyl acetate and the ~olution was purified by chromatography.
2.5 g of a yellow solid of melting point 58-60C
were obtAir~e~ (compound 3.9).
b) 2-(1-Ethoxyimino-n-butyl)-3-hydroxy-5-(3-i~opropyl-5-methyli~oxA7olin-5-yl)-2-cyclohe~sn-l-one A mixture of 3.5 g (11 millimoles) of the acyl compound according to 4b), 1.0 g (12 millimoles) of ~odium bicArho~Ate, 1.2 g (12 millimoles) of ethoxyamine hyd~ochloride and 100 ml of methanol was stirred for 24 hours at room temperature. The reaction mixture wa~
evaporated down, the re~idue was taken up in 50 ml of 10%
~trength ~odium hydroxide solution and the ~olution was washed with dichloromethane. The aqueous pha~e wa~
acidified with concentrated hydrochloric acid, the pre-cipitated ~olid was separated off and the filtrate wa~
extracted twice with dichloromethane. The organic phase was dried over sodium sulfate and evaporated down. 3.3 g of a yellow solid of melting point 85C were obtAi nq-l (compound 8.17).
The compounds of the formula I which are li~ted in the Table and characterized by their melting point (mp.) can be prepared in a ~imilar manner. Tables 7 and 12 list the compound~ which could not be i~olated as a solid. Compounds for which no physical data are given can be obtAirleA in a similar manner.
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v~ c O ~ <~I ~) co 0 OD CO 0 0~ a) co ~o 0 - 13345 ~3 47 O.z. 0050/40230 The herbicidal action of the cyclohexenone derivatives of the formula I is demonstrated by the following greenhouse experiments:
The vessels employed were plastic flowerpots having a volume of 300 cm3 5 and filled with a sandy loam containing about 3.0% humus. The seeds of the test plants were sown separately, according to species.
For the preemergence treatment, the formulated active ingredients were applied to the surface of the soil immediately after the seeds had been 10 sown. The compounds were emulsified or suspended in water as vehicle, and sprayed through finely distributing nozzles. The application rate was 0.5 kg/ha.
After the agents had been applied, the vessels were lightly sprinkler-15 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.
20 For the postemergence treatment, the plants were grown, depending on growth form, to a height of 3 to 15 cm before being treated. In this treatment method, either plants which had been sown in the pots and grown there were selected, or they were cultivated separately as seedlings and transplanted to the pots a few days before being treated. The application 25 rates for postemergence treatment were 0.125 and 0.25 kg/ha. No covers were placed on the vessels in this method.
The pots were set up in the greenhouse, species from warmer climates in warmer areas (20 to 35C) and species from moderate climates at 10 to 30 25C. The experiments were run for from 2 to 4 weeks. During this time the plants were tended and their reactions to the various treatments assessed.
The assessment scale was 0 to 100, 100 denoting nonemergence or complete destruction of at least the visible plant parts, and 0 denoting no damage or normal growth.
The plants employed for the experiments were Avena fatua, Digitaria sanguinalis, Echinochloa crus-galli, Lolium multiflorum, Medicago sativa, Setaria viridis, Sinapis alba, Triticum aestivum and Zea mays.
40 On preemergence application of 0.5 kg/ha, active ingredients 8.20 and 8.16 had a strong herbicidal action on grassy plants; mustard as an example of a broadleaved species remained undamaged.
133~593 48 O.Z. 0050/40230 For combating grassy vegetation, compounds 3.23 and 3.24 were suitable at a postemergence rate of 0.25 kg/ha, and compounds 8.75 and 8.77 at a post-emergence rate of 0.125 kg/ha. Broadleaved crops - as illustrated by alfalfa - remained undamaged. The novel active ingredients have a selec-5 tive herbicidal action.
Active ingredients 3.22 and 3.21 may be used postemergence at a rate of 0.125 kg/ha for combating unwanted grassy species in wheat. The crop plants suffer no damage.
Claims (6)
1. A cyclohexenone derivative of the formula (I):
(I) where the substituents have the following meanings:
R1 C1-C6-alkyl, C3-C6-alkenyl or C3-C6-alkynyl, each of these groups being unsubstituted or carrying from one to three radicals selected from the group consisting of halogen, C1-C4-alkoxy, C1-C4-alkylthio and phenyl, said phenyl radical in turn being unsubstituted or carrying one to three substituents selected from the group consisting halogen, C1-C4-alkyl, C1-C4-alkoxy, C1-C4-alkylthio, C1-C4-haloalkyl and cyano;
phenyl, benzyl or thenyl, the aromatic nuclei of which are unsubstituted or carry from one to three radicals selected from the group consisting of halogen, C1-C4-alkyl, C1-C4-alkoxy, C1-C4-alkylthio, C1-C4-haloalkyl, nitro and cyano;
R2 is C1-C6-alkyl, C3-C6-alkenyl, C3-C6-alkynyl or phenyl, each of these groups being unsubstituted or carrying from one to three radicals selected from the group consisting of halogen, C1-C4-alkoxy, C1-C4-alkylthio and cyano;
R3 is hydrogen, C1-C6-alkyl, C1-C10-alkylcarbonyl, C1-C6-alkylsulfonyl, C1-C4-trialkylsilyl, C1-C4-dialkylphos-phonyl, C1-C4-dialkylthiophosphonyl, C3-C6-alkenyl, C3-C6-alkenylcarbonyl, C3-C6-alkynyl or benzoyl- or phenylsulfonyl, each of which is unsubsti-tuted or carrying from one to three radicals selected from the group consisting of halogen, nitro, cyano, C1-C4-alkyl, C1-C4-haloalkyl, C1-C4-alkoxy and C1-C4-alkylthio;
R4 is hydrogen, cyano, halogen, C1-C6-alkyl or C1-C6-alkoxycarbonyl;
A is a C1-C4-alkylene chain in which a methylene group is replaced or not by an oxygen or sulfur atom and which is unsubstituted or carries one or two radicals selected from the group consisting of C1-C4-alkyl, C1-C4-alkoxy, C1-C4-alkylthio and halogen;
m is 0 or 1;
B is a 5-membered mono- or diunsaturated heterocycle containing up to 2 nitrogen atoms and/or up to one oxygen or sulfur atom;
X is a 3 - 7-membered cycloalkyl radical or a 5 -7-membered cycloalkenyl radical, a methylene group in these ring systems being replaced or not by an oxygen or a sulfur atom;
a 5 - 6-membered heteroaromatic ring containing up to three atoms selected from the group consisting of nitrogen, oxygen and sulfur, this ring being unsubsti-tuted or carrying from one to three radicals selected from the group consisting of C1-C4-alkyl, C1-C4-alkoxy, C1-C4-alkylthio, C1-C4-haloalkyl, halogen, cyano and nitro or, when B is isoxazolinyl, X is also hydrogen;
Y is hydrogen, halogen, cyano or nitro;
C1-C6-alkyl, C2-C6-alkenyl or C2-C6-alkynyl, these groups being unsubstituted or carrying from one to three radicals selected from the group consisting of phenyl, halogen, C1-C4-alkoxy and C1-C4-alkylthio, C1-C4-alkoxy, C1-C4-alkylthio, C3-C6-alkenyloxy or C3-C6-alkynyloxy; and n is 1, 2 or 3;
with the proviso that Y does not, or not all the Y's when n is greater than 1, denote hydrogen when m is 0, B is isoxazol-5-yl and X is 3-(C3-C6-cycloalkyl), and environmentally acceptable salts thereof.
(I) where the substituents have the following meanings:
R1 C1-C6-alkyl, C3-C6-alkenyl or C3-C6-alkynyl, each of these groups being unsubstituted or carrying from one to three radicals selected from the group consisting of halogen, C1-C4-alkoxy, C1-C4-alkylthio and phenyl, said phenyl radical in turn being unsubstituted or carrying one to three substituents selected from the group consisting halogen, C1-C4-alkyl, C1-C4-alkoxy, C1-C4-alkylthio, C1-C4-haloalkyl and cyano;
phenyl, benzyl or thenyl, the aromatic nuclei of which are unsubstituted or carry from one to three radicals selected from the group consisting of halogen, C1-C4-alkyl, C1-C4-alkoxy, C1-C4-alkylthio, C1-C4-haloalkyl, nitro and cyano;
R2 is C1-C6-alkyl, C3-C6-alkenyl, C3-C6-alkynyl or phenyl, each of these groups being unsubstituted or carrying from one to three radicals selected from the group consisting of halogen, C1-C4-alkoxy, C1-C4-alkylthio and cyano;
R3 is hydrogen, C1-C6-alkyl, C1-C10-alkylcarbonyl, C1-C6-alkylsulfonyl, C1-C4-trialkylsilyl, C1-C4-dialkylphos-phonyl, C1-C4-dialkylthiophosphonyl, C3-C6-alkenyl, C3-C6-alkenylcarbonyl, C3-C6-alkynyl or benzoyl- or phenylsulfonyl, each of which is unsubsti-tuted or carrying from one to three radicals selected from the group consisting of halogen, nitro, cyano, C1-C4-alkyl, C1-C4-haloalkyl, C1-C4-alkoxy and C1-C4-alkylthio;
R4 is hydrogen, cyano, halogen, C1-C6-alkyl or C1-C6-alkoxycarbonyl;
A is a C1-C4-alkylene chain in which a methylene group is replaced or not by an oxygen or sulfur atom and which is unsubstituted or carries one or two radicals selected from the group consisting of C1-C4-alkyl, C1-C4-alkoxy, C1-C4-alkylthio and halogen;
m is 0 or 1;
B is a 5-membered mono- or diunsaturated heterocycle containing up to 2 nitrogen atoms and/or up to one oxygen or sulfur atom;
X is a 3 - 7-membered cycloalkyl radical or a 5 -7-membered cycloalkenyl radical, a methylene group in these ring systems being replaced or not by an oxygen or a sulfur atom;
a 5 - 6-membered heteroaromatic ring containing up to three atoms selected from the group consisting of nitrogen, oxygen and sulfur, this ring being unsubsti-tuted or carrying from one to three radicals selected from the group consisting of C1-C4-alkyl, C1-C4-alkoxy, C1-C4-alkylthio, C1-C4-haloalkyl, halogen, cyano and nitro or, when B is isoxazolinyl, X is also hydrogen;
Y is hydrogen, halogen, cyano or nitro;
C1-C6-alkyl, C2-C6-alkenyl or C2-C6-alkynyl, these groups being unsubstituted or carrying from one to three radicals selected from the group consisting of phenyl, halogen, C1-C4-alkoxy and C1-C4-alkylthio, C1-C4-alkoxy, C1-C4-alkylthio, C3-C6-alkenyloxy or C3-C6-alkynyloxy; and n is 1, 2 or 3;
with the proviso that Y does not, or not all the Y's when n is greater than 1, denote hydrogen when m is 0, B is isoxazol-5-yl and X is 3-(C3-C6-cycloalkyl), and environmentally acceptable salts thereof.
2. A process for the manufacture of a compound of the formula (I) as set forth in claim 1, wherein a compound of the formula (II):
(II) where R2, R3, R4, A, B, X, Y m and n are defined as in claim 1 is reacted with:
a) a hydroxylamine derivative of the formula [R1 ONH3]?Q ?, where R1 is defined as in claim 1 and Q ? is any anion, in an inert solvent at from 0 to 80° C, in the presence or absence of an auxiliary base, or b) a hydroxylamine of the formula R1ONH2 where R1 is defined as in claim 1, in an inert solvent at from 0 to 90°C.
(II) where R2, R3, R4, A, B, X, Y m and n are defined as in claim 1 is reacted with:
a) a hydroxylamine derivative of the formula [R1 ONH3]?Q ?, where R1 is defined as in claim 1 and Q ? is any anion, in an inert solvent at from 0 to 80° C, in the presence or absence of an auxiliary base, or b) a hydroxylamine of the formula R1ONH2 where R1 is defined as in claim 1, in an inert solvent at from 0 to 90°C.
3. A herbicidal composition containing an effective amount of cyclohexenone derivative of the formula (I) as set forth in claim 1, in admixture with at least one inert additive.
4. A herbicidal composition as set forth in claim 3, containing at least one further active compound.
5. A process for combating the growth of unwanted plants, wherein the unwanted plants and/or their habitat are treated with a herbicidally effective amount of a cyclohexenone derivative of the formula (I) as set forth in claim 1.
6. The use of a cyclohexenone derivative of the formula (I) as set forth in claim 1 as a herbicide.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE3833264A DE3833264A1 (en) | 1988-09-30 | 1988-09-30 | cyclohexenone |
| DEP3833264.7 | 1988-09-30 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1334593C true CA1334593C (en) | 1995-02-28 |
Family
ID=6364090
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000611625A Expired - Fee Related CA1334593C (en) | 1988-09-30 | 1989-09-15 | Cyclohexenone derivatives |
Country Status (6)
| Country | Link |
|---|---|
| EP (1) | EP0365833B1 (en) |
| JP (1) | JP2848642B2 (en) |
| KR (1) | KR0150439B1 (en) |
| CA (1) | CA1334593C (en) |
| DE (2) | DE3833264A1 (en) |
| HU (1) | HU206099B (en) |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3230087A1 (en) * | 1982-08-13 | 1984-02-16 | Basf Ag, 6700 Ludwigshafen | CYCLOHEXAN-1,3-DION DERIVATIVES, METHOD FOR THE PRODUCTION THEREOF AND THEIR USE FOR CONTROLLING UNWANTED PLANT GROWTH |
| NZ207964A (en) * | 1983-05-06 | 1987-03-31 | Ici Australia Ltd | 5-heteroaryl-cyclohexane-1,3-dione derivatives |
| IL73152A0 (en) * | 1983-10-05 | 1985-01-31 | Basf Ag | Cyclohexenol derivatives and their use as herbicides |
| DE3430229A1 (en) * | 1984-03-29 | 1985-10-10 | Basf Ag, 6700 Ludwigshafen | CYCLOHEXENON DERIVATIVES, METHOD FOR THE PRODUCTION THEREOF AND THEIR USE FOR CONTROLLING UNWANTED PLANT GROWTH |
| DE3437238A1 (en) * | 1984-10-11 | 1986-04-17 | Basf Ag, 6700 Ludwigshafen | NEW COMPOUNDS, METHOD FOR THEIR PRODUCTION AND THEIR USE FOR CONTROLLING UNWANTED PLANT GROWTH |
| DE3601066A1 (en) * | 1986-01-16 | 1987-07-23 | Basf Ag | CYCLOHEXENON DERIVATIVES, A METHOD FOR THE PRODUCTION THEREOF AND THEIR USE AS HERBICIDES AND REGULATIVE AGENTS FOR REGULATING THE PLANT |
| DE3609181A1 (en) * | 1986-03-19 | 1987-09-24 | Basf Ag | CYCLOHEXENON DERIVATIVES, METHOD FOR THE PRODUCTION THEREOF AND THEIR USE FOR CONTROLLING UNWANTED PLANT GROWTH |
-
1988
- 1988-09-30 DE DE3833264A patent/DE3833264A1/en not_active Withdrawn
-
1989
- 1989-09-15 CA CA000611625A patent/CA1334593C/en not_active Expired - Fee Related
- 1989-09-22 EP EP89117556A patent/EP0365833B1/en not_active Expired - Lifetime
- 1989-09-22 DE DE58908003T patent/DE58908003D1/en not_active Expired - Lifetime
- 1989-09-27 JP JP1249404A patent/JP2848642B2/en not_active Expired - Lifetime
- 1989-09-29 HU HU895130A patent/HU206099B/en not_active IP Right Cessation
- 1989-09-30 KR KR1019890014100A patent/KR0150439B1/en not_active IP Right Cessation
Also Published As
| Publication number | Publication date |
|---|---|
| KR0150439B1 (en) | 1998-10-15 |
| DE3833264A1 (en) | 1990-04-05 |
| JP2848642B2 (en) | 1999-01-20 |
| EP0365833B1 (en) | 1994-07-06 |
| JPH02149557A (en) | 1990-06-08 |
| EP0365833A3 (en) | 1990-09-26 |
| DE58908003D1 (en) | 1994-08-11 |
| HU206099B (en) | 1992-08-28 |
| KR900004682A (en) | 1990-04-12 |
| EP0365833A2 (en) | 1990-05-02 |
| HUT52076A (en) | 1990-06-28 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| MKLA | Lapsed |