CA2041793A1 - Cyclohexenone oxime ethers, their preparation and their use as herbicides - Google Patents
Cyclohexenone oxime ethers, their preparation and their use as herbicidesInfo
- Publication number
- CA2041793A1 CA2041793A1 CA002041793A CA2041793A CA2041793A1 CA 2041793 A1 CA2041793 A1 CA 2041793A1 CA 002041793 A CA002041793 A CA 002041793A CA 2041793 A CA2041793 A CA 2041793A CA 2041793 A1 CA2041793 A1 CA 2041793A1
- Authority
- CA
- Canada
- Prior art keywords
- alkyl
- alkoxy
- group
- alkylthio
- halogen
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Abandoned
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/24—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with substituted hydrocarbon radicals attached to ring carbon atoms
- C07D213/44—Radicals substituted by doubly-bound oxygen, sulfur, or nitrogen atoms, or by two such atoms singly-bound to the same carbon atom
- C07D213/53—Nitrogen atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D309/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings
-
- 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
- A01N35/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having two bonds to hetero atoms with at the most one bond to halogen, e.g. aldehyde radical
- A01N35/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having two bonds to hetero atoms with at the most one bond to halogen, e.g. aldehyde radical at least one of the bonds to hetero atoms is to nitrogen
- A01N35/10—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having two bonds to hetero atoms with at the most one bond to halogen, e.g. aldehyde radical at least one of the bonds to hetero atoms is to nitrogen containing a carbon-to-nitrogen double bond
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C251/00—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton
- C07C251/32—Oximes
- C07C251/50—Oximes having oxygen atoms of oxyimino groups bound to carbon atoms of substituted hydrocarbon radicals
- C07C251/52—Oximes having oxygen atoms of oxyimino groups bound to carbon atoms of substituted hydrocarbon radicals of hydrocarbon radicals substituted by halogen atoms or by nitro or nitroso groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C323/00—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups
- C07C323/23—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and nitrogen atoms, not being part of nitro or nitroso groups, bound to the same carbon skeleton
- C07C323/24—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and nitrogen atoms, not being part of nitro or nitroso groups, bound to the same carbon skeleton having the sulfur atoms of the thio groups bound to acyclic carbon atoms of the carbon skeleton
- C07C323/29—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and nitrogen atoms, not being part of nitro or nitroso groups, bound to the same carbon skeleton having the sulfur atoms of the thio groups bound to acyclic carbon atoms of the carbon skeleton the carbon skeleton containing six-membered aromatic rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
- C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D307/38—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with substituted hydrocarbon radicals attached to ring carbon atoms
- C07D307/52—Radicals substituted by nitrogen atoms not forming part of a nitro radical
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D309/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings
- C07D309/02—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings having no double bonds between ring members or between ring members and non-ring members
- C07D309/04—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings having no double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
- C07D309/06—Radicals substituted by oxygen atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D317/00—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms
- C07D317/08—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3
- C07D317/10—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings
- C07D317/14—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings with substituted hydrocarbon radicals attached to ring carbon atoms
- C07D317/28—Radicals substituted by nitrogen atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D335/00—Heterocyclic compounds containing six-membered rings having one sulfur atom as the only ring hetero atom
- C07D335/02—Heterocyclic compounds containing six-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
- C07C2601/14—The ring being saturated
Landscapes
- 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)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Pyridine Compounds (AREA)
- Pyrane Compounds (AREA)
- Heterocyclic Compounds Containing Sulfur Atoms (AREA)
- Furan Compounds (AREA)
- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Nitrogen And Oxygen As The Only Ring Hetero Atoms (AREA)
Abstract
O.Z. 0050/41598 Abstract of the Disclosure: Cyclohexenone oxime ethers of the formula I
Description
! O.Z. 0050/41598 Cyclohexenone oxime ether~, their pre~ara~ion and thei.r use a~ herbicides The present invention relates to novel herbicidal cyclohexenone oxime ethers of the formula I
~ ,-o-(cH2)4 ~ xn (I) whe~e Rl i5 Cl-C6-X is halogen, n is from 1 to 5, R2 is Cl~C~-alkoxy-Cl-C6-alkyl or Cl-C4 alkyl~hio-Cl-C~-alkyl, C3-C7-cycloalkyl or C5-C7-cycloalkenyl, and these groups may additionally carry from one to three radicAls selected from the group con~isting of Cl-C~-alkyl, Cl-C4~
alkoxy, Cl-C4-alkylthio, Cl-C4-haloalkyl, hydroxyl and halogen, a 5-membered saturated heterocyclic structure which contains one sr two hetero atoms ~elected from the group consisting of oxygen and sulfur and may additionally carry from one to three radicals selected from the group consisting C1-C4-alkyl, Cl-C4-alkoxy, Cl-C4-alkylthio and Cl-C4-haloalkyl, a 6-membered or 7-me~bered saturated or mono- or diunsaturated hoterocyclic structure containing one or two~.hetero atom~ selected from the group con~isting of oxygen and sulfur, and the heterocyclic ~tructure may additionally carry ~rom one to three radicals selected from the group con~i~tinq of hydroxyl, halogen, C~-C4-alkyl, Cl-C4-alkoxy, C~-C4-al~ylthio and C1-C4-haloalkyl, 30 a 5-membered heteroaromatic ~tructure containing one to three hetero atoms selected from the group consisting of two nitrogen atom~ and one oxygen or ~ulfur atom, and this ring may additionally carry from one to three radicals ~elected from the group consi~ting of halogen, cyano, Cl-C4-alkyl, Cl-C4-alkoxy, Cl-C4-alkylthio, : .
`` 2~79~3 - 2 - O. Z . 0~50/41598 Cl-C4-haloalkyl, C2-C6-alkenyl, C2-Ca-aIkenyloxy, CZ-C6-haloalkenyl and Cl-C4-alkoxy- C1-C4-alkyl, phenyl or pyridyl ~ and the~e group~ may additionally carry from one to three radicals selected from the group consisting of halogen, nitro, cyano, Cl-C4-alkyl, Cl-C4-alkoxy, Cl-C4-alkylthio, Cl-C4-haloalkyl, C3-C6 alkenyloxy, C3-C6-alXynyloxy and -NR3R4, where R3 is hydrogen, C1-C4-alkyl, C3-C6-alk~nyl or C3-C6-alkynyl and R4 is hydrogen, C1 C4-alkyl, C3-C6-alkenyl, C3-C6-alkynyl, C1 C6-acyl or benzoyl, and ~he aromatic ring may addition-ally carry from one to three radical~ selected from the group consisting of nitro, cyano, halogen, Cl-C4-alkyl, Cl-Cb-alkoxy, Cl-C4-alkylthio and C1-C4-haloalkyl, and ~heir agriculturally usable salts and esters of Cl-C1O-carboxylic acid and inorganic acid~.
The present invention furthermora relates to a process for their preparation and their use as crop protection a~ents.
The novel cyclohexenone~ I obviously have acidic character, ie. they can form simple reaction products, such a~ salts of alkali metal or alkaline earth metal compounds or enol e~ters.
Tha compounds of the formula I may occur in a plurality of tautomeric forms, all of ~hich are embraced by the claim.
DE-A 38 38 309 describes herbicidal cyclohexenone oxi~ne ethers whoRe general formula cover~ the axyl-butyleneoximinocyclohexanediones I defined at tha outset.
Compound of the formula I' X
2~4 ~ I' o R
where X is p-trifluoromethyl or p-tert-butyl, n i 0 or 1 and R1 and R2 have the meanings stated under I, are 2 ~ 3 I - 3 - O.Z. 0050/41598 mentioned in particular.
It i~ an object of the present invention to synthesize cyclohexenon~ oxime ether~ which have high sel~ctivity compared with the known members of thi~ class of substances in controlling weeds in gramineous crop~, such as rice.
We have found that thi~ object is achieved by the novel cyclohexenone oxime ether of the formula I which are defined at the outset and which have a good herbicid-al action, preferably against specie~ from the gra sfamily (Gramineae). They are tolerated and hence selec-tive in broad-leaved crops and in monocotyledon culture~
which do not belong to the Gramineae. They also include compounds which exhibit selectivity also in gramineous crops and at ~he same time centrol undesirable gras~e~.
The cyclohexenone~ of the formula I can be prepared in a conventional manner from derivatives of the formula II (EP-A 80 301, EP-A-125 094, EP-A-142 741, US-A 4 249 937, EP-A 137 174 a~d EP-A 177 913) and the corresponding hydro~ylamines of the formula III (EP-A 169 521).
R2 ~ ~ ~ H2NO(CH2)4 ~ ~ R2 ~ ~o(CH2)4 ~ xn II III I
The reaction is advantageously carried out in the heterogeneou~ pha~a in a solvent, at an adequate tempera-ture below about 80C, in the pre~ence of a base, and the hydroxylamine III i~ used in the form of it~ ammonium salt.
Examples of ~uitabla ba~es are carbonates, bicarbonates, acetat0~, alcoholates or oxide~ of alkali or alkaline ear~h metals, in particular ~odium hydroxide, potas~ium hydroxide, magnesium oxide and calcium oxide.
Organic ba~es, ~uch a~ pyridine or tertiary amine~, can . ,: , . , . ,:
,. . . , :
2~1 7~3 I ~ 4 - U.Z. 0050/41598 also be used~ The ba~e i~ added, for example, in an amount of from 0.5 to 2 mole equivalents, based on the ammonium compound.
Examples of suitable solv2nt~ are dLmethyl S sulfoxide, alcohol~, such a methanol, ethanol and isopropanol, aromatic hydrocarbons, such as benzene and toluene, chlorohydrocarbons, ~uch as chloroform and dichloroethane, aliphatic hydrocarbons, such as hexane and cyclohexane, esters, such as ethyl acetate, and ethers, such as diethyl ether, dioxane and tetrahydro~
furan. The reaction is preferably carried out in methanol using sodium bicarbonate as the base.
The reaction is complete af~er a few hours. The desired compound can be isolated, for example by evapora-ting down the mixture, distributing the re~idue in methylene chloride/water and di tilling off the solvent under reduced pressure.
However, the free hydroxylamine base, for example in the form of an aqueou~ solu~ion, can also be used directly for this reaction; depending on the solvent u~ed for the compound II, a single-phase or two-phase reaction mixture i5 obtained.
Examples of suitable ~olvents for this varian~
are alcohol~, such a methanol, ethanol, isopropanol and cyclohexanol, aliphatio and aroma~ic hydrocarbon3 and chlorohydrocarbon~, such a~ hexane, cyclohexane, meth-ylene chloride, toluene and dichloroethane, esters, such a~ ethyl acetate, nitrile3, such a~ acetonitrile, and cyclic ethQrs, such a~ dioxane and tetrahydrofuran.
Alkali metal ~alts of the compounds I can be obtained by treating the 3-hydroxy compound~ with sodium hydroxide, potas~ium hydroxide or a ~odium or pota~ium alcoholate in aqueous solution or in an organic solvent, such as methanol, ethanol, acetone or toluene.
Other metal salt~, such a~ mangan2se, coppPr, zinc, iron, calcium, magnesium and barium salt3, can be prepared from the ~odium salt~ in a conventional manner, !
2~ 7~3 - 5 - O.Z. 0050/4159~
aR can ammonium and pho~phonium salts using ammonia or phosphonium, sulfonium or sulfoxonium hydroxide.
The compounds of type II can be prepared, for example, from the corresponding cyclohexane-1,3-dione~ of the formula IV
OH
R2 ~ IV, Y o where Y is hydrogen or methoxycarbonyl, by known methods, for example as described in Tetrahadron Lett. (1975), 2491.
It is also possible to prepare the compounds of the formula II by the enol e~ter intermediate~ V which are obtained in the reaction of compounds of the formula IV with acyl chloride3 VI in the presence of a basa and are then subjec~ed to a rearrangemen~ reaction with certain Lmidazole or pyridine derivatives (Japanese Preliminary Published ~pplication 79/063 052).
R2~ + R~CI - ~ R2~ ~ a IV VI V II
The compounds of tha formula IV are obtained by a num~er of known process s~eps, starting from known intermediates.
The synthesis of the hydroxylamines I~I is carried out according to the reaction ~cheme below, for example by A) alkylation of N-hydrox~phthalimide VII with suitabla phenylbutyl halide~ YIII and sub~equ~nt elLmina-tion of the protective group, for example with hydrazine or ethanolamine, sLmilarly to Examples in EP-A-244 786 or Houben-Weyl, Methodan der organischen Chemie, Volume X/l, page 1152 et seq. or , .
2~7~
i - 6 ~ O.Z. 0050/41598 B) hydrogenation of N-4-phenylbutenylo~yphthal-imides Xa, b, whose preparation is descri~ed in DE-A 38 38 310, by means of suitable catalysts, eg. palladium on active carbon, in suitable inert solvent~, such as methanol, tetrahydrofuran or dioxane, and subsequent elimination of the protective group as described above.
The hydrogenation is advantageously carried out at from 20C to the boiling point of the solvent, in particular at room temperature, by a conventional method, under atmospheric, superatmospheric or reduced pressureO
A pressure rAnge of from 1 to lO, in particulax 1 to 2, bar ig preferred.
Reaction scheme:
RouteA) O N~H + Ha 1~0 --~ D N ~ ~( X ) n IX
O O H 2N~OH
VII YIII ~a~. 1 , R out e B ) D N-O~l ~ ( X ) n or III
(X)n _ o Xb In the cyclic hydroximide~ VII, D is, for ex-I, `'; ' ' ' ~ .
2~ 7~
7 _ o . z . 0050/41598 ample, C2-C3-alkylene, C2-alkenylene or a 5-membered or 6-membered ring which contains not more than 3 double bonds and may contain 1 nitrogen atom, for example phenylene, pyridinylene, cyclopentylene, cyclohexylene or cyclohexenylene. Examples of suitable substances a-e the following:
o o o N -OH ¦¢N~ N--OH
O O O
O¢ N-OH ¢N{)H (;~N-OH
O O O
C~N_OH
The cleavage of the cyclic imide ethers VIII is carried out similarly to a proce~s de~cribed in EP-A 244 786, using alkanolamine~. After thi~ proce~ , hydroxyl-amines III can be i~olated a3 free bases or, after precipitation with acid~, a~ salt~. Readily crystalliz-ing salt~ are obtained by reacting the bases with oxalic acid.
In view of the biological activity, preferred cyclohexenone~ of the formula I are those in which Rl is alkyl, such as methyl, ethyl, propyl or n-bu~yl, in particular ethyl or propyl, X is halogen, such a~ fluorinel chlorine, bromine or iodine, in particular fluorine or chlorine, n is from 1 to 5, in particular 1, 2 or 3, the sub-stituent3 being identical or different where there i~ a .
' 7 ~ ~
I - 8 - o.Z~ 0050/41598 plurality of radicals X, R2 is alkyl a~ st~ted under Rl, which may carry an alko~y or alkylthio group stated below, preferably in the 1-, 2--or 3-position, in particular 2-ethylthiopxopyl, or S cyclohexyl which may carry from 1 ~o 3 methyl or hydroxyl groups, in particular 4-methylcyclohexyl or 3,4-di-hydroxycyclohexyl, 5-membered hetaryl~ such as pyrazolyl or isoxazolyl, a 6-membered heterocyclic struc~ure, such as tetrahydro-pyran-3-yl, tetrahydropyran-4-yl or tetrahydrothiopyran-3-yl, phenyl or pyridyl, where the cyclic radicals may carry from one to three alkyl, alkoxy, alkylthio and/or haloalkyl group~ and, in the case of 6-membered radical~, al~o halogen as stated under X or hydroxyl, for example alkyl, such as methyl ethyl, propyl, 1-methylethyl, butyl, l-methylpropyl, 2-meth~lpropyl or 1,1-dLmethyl-ethyl, in particular methyl or l,l-dimethyle~hyl, alkoxy, such as methoxy, ethoxy, propoxy, l-methylethoxy, butoxy, l-methylpropoxy, 2-me~hylpropoxy or 1,1-dimethyl-ethoxy, in particular methoxy, ethoxy, l-methylethoxy or l,l-dimethylethoxy, alkylthio, such a~ methylthio, ethyl~hio, propylthio, 1-methylethylthio, butylthio, 1-methylpropylthio,2-methyl-propylthio or 1,1-dimethylethylthio, in particular methylthio, or haloalkyl ~uch as fluoromethyl, difluorome~hyl, tri-fluoromethyl, chlorodifluoromethyl, dichloro~luoromethyl or trichloromethyl, in p3rticular difluoromethyl or trifluoromethyl.
2,4,6-Trimethylphenyl is particularly preferred.
The 5-membered heteroaromatic radical~ R2 may carry ths following radicals a3 substituent~:
halogen a~ ~tated under X, in particular fluorine or chlorine.
In the case of the phenyl and pyridyl radicals, - 2~7~
_ 9 _ o.z. 0050/41598 suitable substituents in addition to the abovementioned group~ are the following radicals:
alkynyloxy, such as 2-propynyloxy, in particular proparg-yloxyphenyl or amino which may carry one or two acyl radicals, such as acetyl or benzoyl.
Particularly preferred cyclohexenone oxime ethers of the formula I are summarized in the Table below:
11 , ~ ' ' . , ;
9 ~
- 10 - O.Z. 0050/~1598 ,_ ~
-- E E
._ _ _ _ ~ _ _ _, U o ` I :~ T r ~ ~ I S ~ ~t . o ~
~, _ _ _; - ~ ~ ~ ~J
, ~ t r --E ~` o o o o o o o o ` o o a-tO _ I ~- S
L ~ ~
_ ? ~ V ~ ~ V ~ D ~ --t aE _ _, _ _ _ _ _ _ _ Z ~ ~
OOOOOOOOOOOO
L L L L t L h h h h F~l h L L
O O O O O O O O C:l O O O C~
C~ -- S -- -~
_ _ _ _ _ _ ~., _ C C ~
~ ~I L L ~ * ~ ~ ~ ~ t L L L
' C O ~b e ~ C C ' ' 0~ 0 90~ 0 L L ~-- ~-- L L L L L L ~
r- L L L L L L L L L L L L L
0~0 ~ ~ S ~ ,~ L L
~11 ~ ~ ~ +~ ~ ~ .~
~ C~~ ~ ~ L ~ L ~ L
_. ~ cL ~ ~ w ~ L~ 1 ~ w ~:L w ~
C~ -- o o O C:~
- 11 - O.Z. 0050/~1598 T .~ T _ ~T ~ r ~_ I N -r N I--'~ ~ ` `
N ~ ._ ~V~:1 E --~ E ` E~ ~ EiE e ~
-- E -- E -- E ---- -- ~ ~ ,~, --a~ ~ o o o oo _~ ~
O
^ I ~ I I T
` E ` ~. E ~ ~ ~ ~ E
E -- ~ E ~ E ~ -- E -- E Ea -- --_ ~ -- E
E~ ~ o 0- 0 Cr~ ~ ~1 0 -- O --N t~l N
:r: I r r ^ ~ r ^ T I ~: ~ I S I T -- ~ -- I --' ~o ~o ~ ~ ~ ~ r ~ T
_~ E ~ E ` ~ ' ~ ~ E ~ E ~ ~ ~ E ~ ~ ~ '~
ui ~ - - -s z _ o ~ o ~ o o _ -- ~ -- -- o .~
h O O O
O O O O O O C~ O O O i J ,~
~ h ~ h O O OO O O O ~ri'~i ~ri s ~ a I ~ ~ ~
,_ ~
I I I Ii ~ I I I I i ~ ' L ~7 ~ ~ ~ ~ ~ L ~t L L L L ~ L L. L L ~
O O O C~ O O O O O O ~-- O O O
L L L L L rl r~ L
s s c '' ~ r s s c s :-~ c s ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ C ~ ~ ~
S_ ~ L L L L L L L L ~ L L L
a~
E~
O ~ ~. ~ L ~ ~ ~ L ~ L L ~ L
~i ~i ~ ~ ~ ~ ~_ ~ i i i i i i i i U;
X _ _ _ _ ~
t! I . . `
. ~ , 2 ~ 3 12 - o . z . 0050/41598 s ~ ~ 2 ~ ~ r ~: ~
v ~ E ~ ~ E ~ E
7 ~ _ ~ u~ In In o o ~ ~o u o _ I ~ T
~ T I
E
_ U~
E
~0 '-- ^ I ^ ~ 1 ^ I ^ ^ V ^ --. * ~` V ~ E V V ~ E ~ ~ ~ V _ E -- I~ -- -- --,_ z ~ ~ ~ - -- O ~~ CO cr o _ o o- _ _ ~ _ ~ o~
~_ o 1~ o r~ 1~ o 1~ o 1~ _ _ _ 1~ o 1~ _ c c ~ .c o ~ o o . i C~u O. r I S E X o 1~ L
C CL ~ O ~ ~. C~, ~
L e ~ L
~ X ~ L' C
a. ~. e L I-- ~ L ~ 0 ~) O O O
~ I I :,. ~ e o o ~ v v CI i O S ~ ::1 ~ ,:~
C C ci o ~ L L $ ~ O O ~L ~ ~d ~
r~ ~ I I (O J ~V
ffi E~
O O ~ g c O ~:: ~ o r V _. ~ t ~ ~ L ~ ( ~ ~L. ~ ~
~ CL ~ I~J ~i ~ hi CLl~i ~Li ~ ~i ~i _l , ~ ~ . . ' .
I) , :
, - 13 - O. z . 0050/41598 8`
U~
_.
T
_~
E
C~
,~
:~ r _ _ ~ ~ u~ In s 2 o r.
.. O
~:
X ~
.;~r L
C~
. . V
t ~ I_ 2 .~
g - CL
U
~ $
E~ Z -~ *
,~
I, ' ' ' ',;
2~7~
i - 14 - O.Z. 0050J41598 The cyclohexenone oxime ethex~ I are suitable as herbicides, in particular for con~rolling plant species from among the Gramineae (grasses).
The cyclohexenone derivatives I or the herbicides containing them can be used, for example, in the form of directly sprayable solution~, powders, suspensions, including concentrat0d aqueous, oily or other suspensions or dispersions, emulsions, oil dispersions, pas~es, dusting agents, broadcasting a~en~s or granules, by spraying, atomizing, du~ing, broadca ting or pouring.
The application forms depend on the intended uses; they should in any case ensure very fine distribution of the novel active ingredients.
Compounds I are suitable in general for the preparation of directly sprayable ~olution~, emulsions, pastes or oil disper~ions. Suitable inext additives are mineral oil fractions having a medium to high boiling point, such as kerosene or diesel oil, as well as coal tar oils and oils of vegetable or animal origin, aliphat-ic, cyclic and aromatic hydrocarbons, eg. toluene,xylene, paraffin, tetrahydronaphthalene, alkylated naphthalenes and derivatives thereof, methancl, ethanol, propanol, butanol, cyclohe~anol, cyclohexanone, chloro-benzene, isophorone or strongly polar solvents, such as N,N-dLmethylformamide, dLmethyl sulfoxide, N-methylpyr-rolidone or water.
Aqueous application forms can be prepared from emulsion concentrates, dispersions, pastes, w ttable powder~ or water-dispersible granules by adding water.
For th~ prepaxation of emulsion~, pa tes or oil disper-sion~, the sub~trates, as such or in ~olution in oil or solvent, can be homogenized in water by means of wetting agents, adhesive~, di~persant~ or emulsifiersO However, it is also po~sible for concentrates which consi~t of active substances, wetting agent~, adhesives, disper~ants or emulsifier~ and may consi t of solvents or oil and which are suitable for dilution wi~h water to be 2~7~3 - 15 - o. z . 0050/41598 prepared.
Suitable surfactants are the alkali metal, alkaline earth metal and ammonium salts o~ aromatic sulfonic acids, fox example lignin-, phenol-, naph-thalene- and dibutylnaphthalenesulfonic acid, and of fatty acids, alkyl- and alkylarylsulfonates, alkyl-sulfates, lauryl ether sulfates and fatty alcohol ~ul-fates, and salts of sulfated hexa-, hepta- and octa-decanols, and of fatty alcohol glycol ethers, condensates of sulfonated naphthalene and it~ derivatives with formaldehyde, condensate~ of naphthalene or of naph-thalenesulfonic acids with phenol and formaldehyde, polyoxyethyleneoctylphenolethers,ethoxylated isocotyl-, octyl-or nonylphenol, alkylphenol polyglycol e~hers, tributylphenyl polyglycol ether~, alkylaryl polyether alcohols, isotrideoyl alcohol, fatty alcohol/ethylene oxide condensates, ethoxylated ca~tor oil, polyoxy-ethylene alkyl ethers or polyoxypropylene~ lauryl alcohol polyglycol ether aceta~e, ~orbitol e ters, ligninsulfite waste liquor~ or methylcellulose.
Powder~, broadcasting agent~ and duating agents can be prepared by mixing or milling the active sub-stances together with a solid carrier.
Granule~, for example, coated, impregnated and homogeneous granules, can be prapared by binding the active ingredients to solid carriers. Solid carriers are mineral earths, such as ~ilica , ~ilica gel~, silicates, talc, kaolin, limestone, lime, chalk, bole, loess, clay, dolomite, diatomaceou~ earth, calcium ~ulfate, magnesium sulfate, magne ium oxide, milled pla~tic~, fertilizers, such a~ ammonium sulfate, ammonium phosphate, ammonium nitrate, ureas and vegetable product~, ~uch as cereal meal, ground bark, woodmeal and nu~shell meal, cellulo~e powder and other ~olid carriers.
The formulation~ contain from 0.02 to 95, prefer-ably from 0.5 to 90, ~ by weight of active ingredient.
The active ingredients ar~ used in a puri~y of from 90 to I~ : : , .
I - 16 - O.Z. 0050/~159~
100%, preferably from 95 to 100% (according to ~he NMR
spectrum).
The novel compounds I can be formulated, fox example, as follows:
I. 90 parts by weight of compound No. 1.05 are mixed with 10 parts by weight of N-msthyl-~-pyrrolid-one, and a solution suitable for use in the form of very small drops i~ obtained.
II. 20 parts by weight of compound No. 1.03 are dissolved in a mixture which consists of sn part~
by weight of ~ylene, 10 parts by weight of the adduct of rom 8 to 10 moles o~ ethylene oxide with 1 mole of oleic acid N-monoethanolamide, 5 parts by weight of the calcium salt of dodecyl-benzenesulfonic acid and 5 parts by weight o an adduct of 40 moles of ethylene oxide with 1 mole of castor oil. By pouring the ~olution into 100,000 part~ by weight of water and finely distributing it therein, an aqueous di~persion which contain~ 0.02% by weight of the active ingredient is obtained.
III. 20 parts by weight of compound No. 1.11 are dis~olved in a mixture which con~i~ts of 40 part~
by weight of cyclohQxanone, 30 part~ by weight of isobutanol, 20 part~ by weight of ~he adduct of 7 moles of ethylene oxid~ with 1 mole of iso-octylphenol and 10 parts by weight of the adduct of 40 mole~ of ethylene oxide with 1 mole of castor oil. By pouring the ~olution into 100,000 part~ by weight of water and finely distributing it therein, an aqueous disper~ion which contain~
0.02% by weight of th~ active ingredienk is obtained.
IV. 20 part~ by w~ight of ac~ive ingredient No. 1.11 are dissolved in a mixture which consist~ of 25 part~ by weight of cyclohe~anone, 65 part~ by wei~ht of a mineral oil fraction boiling within ! ~ .
, 7 ~ 3 I - 17 - O.Z. 0050/41598 a range from 210 to 280C and 10 parts by weight of ~he adduct of 40 mole~ of ethylene oxide with 1 mole of castor oil. By pouring the solution into 100,000 parts by weight of water and finely S distributing it ~herein, an aqueous dispersion which contain~ 0.02~ by weight of the active ingredient is obta ned.
V. 20 parts by weight of active ingredient No. 1.05 ar~ thoroughly mixed with 3 par~s by weight of the sodium ~alt of diisobutylnaphthalene-~-sulfonic acid, 17 parts by weight of the sodium salt of ligninsulfonic acid obtained fro~ a sulfite waste liquor and 60 part~ by weight of silica gel powder, ~nd the mixture is milled in-a hammer mill. ~y finely distributing the mixture in 20,000 parts by weight of water, a spray liquor which contain~ 0.1~ by weight of ~he active ingredient is obtainad.
VI. 3 parts by welght of active ingredien~ No. 1.03 ara mixed with 97 part~ by weigh~ of finely divided kaolin. A dusting agent which contain~
3~ by weight of ~he active ingredient i~ obtained in this manner.
VII. 30 part~ by weight of active ingredient No. 1.05 are thoroughly mixed with a mixture of 92 parts by weight of ~ilica gel powder and 8 parts by weight of liquid paraffin which ha~ been sprayed onto the ~urface of thi~ ~ilica gel. a formula-tion of the active ingredient ha~ing good ad-hesion i3 obtained in this manner.
VIII. 20 part~ by weight of active ingredient NoO 1~03 are thoroughly mixed with 2 parts by weight of the ~alcium salt of dode~ylbenzene~ulfonic acid, 8 parts by weight of a fatty alcohol polyglycol ether, 2 parts by weight of the sodium salt of a phenol/urea/formal~ehyde conden~ate and 68 parts by weight o~ a paraffinic mineral oil. A ~table , , .
- :
, 2,'~7~3 I - 18 - O.Z. 0050/41598 oily dispersion is obtained.
Th0 agent~ can be applied by the preemergence or postemergence method. If the active ingredients are less well tolerated by certain crops, it is also possible to use application methods in which the herbicides are sprayed with the aid of the sprayers in such a way that there is as far as possible no contact with the leav~s of the sen~itive crops while the active ingredient~ reach the leaves of undesirable plants growing underneath or reach the uncovered soil area (post-directed, lay-by~.
The application rates of active ingredient are from 0.001 to 3, preferably from 0.01 to 2.0, kg/ha, depending on the season, the target plants and the stage of growth.
In view of the prac~icable ac~ion spec~rum for weed control, the toleration by crops or the desired effect on the growth ~hereof and because of the wide range of application metho~s, the novel compounds can be used in a large number of cxops. Example of suitable crops are the following:
Botanical name Common name Allium cepa onions Anana~ comosu~ pineapples Arachis hypogaea peanut~ (groundnuts) Asparagus off icinali8 asparagus Beta vulgari~ spp. alti sima ~ugarbeets Beta ~ulgari~ pp. rapa fodder beets Brassica napu~ var. napus rapeseed 30 BrasYica napus var. napobra~ica swedes Brassica rapa var. silve~tris beets Camellia sinensi~ tea plants Carthamus tinctoriu~ ~afflower Carya illinoinensi~ pecan tree~
Citrus limon lemon trces Citru~ ~inensi4 orang~ tree~
Coffea arabica (Coffea canephora, Coffea liberica) coffee plants Cucumis sativus cucumbers 2 ~ 3 I - 19 - O.Z. 0050/41598 Botanical name Common name Cynodon dactylon sermudagrass in turf and lawn~
Daucus carota carrots Elaeis guineensis oil palm~
Fragaria vesca ~trawberrie3 Glycine max soybean~
Gossypium hirsutum (Gossypium arboreum cotton Gossypium herbaceum Gossypium viti~olium) Helianthus annuus sunflowers Helianthus tuberosus Jerusalem artichoke Hevea brasiliensis rubber plants Hordeum vulgare baxley Humulus lupulus hops Ipomoea batatas sweet potatoes Juglans regia walnut trees Lens culinari~ lentils Linum usitatissimum flax Lycopersicon lycoper~icum tomatoes Malus spp. apple tree~
Manihot esculenta cas~ava Medicago ~ativa alfalfa (lucerne) Musa spp. banana plants Nicotiana tabacum tobacco (N. rustica) Olaa europaea olive trees Oryza ~ativa rice Pha~eolu~ lunatu~ limabeans Phaseolus vulgari~ 3napbeans, green bean~, dry beans Picea abiQs Norway spruce Pinus spp. pine trees Pisum ~ativum English pea~
Prunus avium cherry tree~
~,, .
., `
, 7 ~ 3 I - 20 O.Z. 0050/4159 Botanical name Common name Prunus dulci~ almond trees Prunus per~ica peach trees Pyrus communis pear trees Ri~es sylve~tre redcurrants Ricinus communis castor-oil plants Saccharum afficinarum sugar cane Secale cereale rye Solanum tuberosum Irish potatoes Sorghum bicolor (s. vulgare) sorghum Theobroma cacao cacao plants Trifolium pratense red clover Triticum aestivum wheat Triticum durum durum wheat Vicia faba tick beans Vitis vinifera grapes Zea may3 Indian corn, sweet corn, maize To broaden the action spec~rum and to achieve synergi~tic efects, the cyclohexenone derivative~ of the formula I can be mixed both with one another and with member~ of other groups of herbicidal or growth-regulating active ingredient~ and applied together.
Example~ of suitable component~ for the mixture are diazine~, 4H-3,1-ben~oxazine derivatives, benzothia-diazinone~, 2,6-dinitroaniline~, N-phenylcarbamates, thiocarbamates, halocarboxylic acid~, triazine~, amides, ureas, diphenyl ether~, triazinone~, uracils, benzofuran derivative~, quinolinecarboxylic acids, sulfonylurea derivatives, cyclohexenones, (hetero)aryloxyphenoxypropionic acids, their ~alts, e~ters and amide~ and others.
It may also be useful to apply the cyclohexenone derivative~ o~ the formula I, or herbicides containing them, alone or together in combination with other herl-icide~ or mixed with further crop protection agent~, for example with pesticidea, agents for controlling .. , !l :
~ ..
.
2 V ~ 3 I - 21 - O.Z. 0050/41598 phytopathogenic fungi or bactericides. The miscibility with mineral ~alt solution~ which are used for eliminat ing nutrient and trace elemen~ deficiencies is also of interest. It is also possible to add nonphytotoxic oils and oil concentrates.
EXAMPLES
~ ,-o-(cH2)4 ~ xn (I) whe~e Rl i5 Cl-C6-X is halogen, n is from 1 to 5, R2 is Cl~C~-alkoxy-Cl-C6-alkyl or Cl-C4 alkyl~hio-Cl-C~-alkyl, C3-C7-cycloalkyl or C5-C7-cycloalkenyl, and these groups may additionally carry from one to three radicAls selected from the group con~isting of Cl-C~-alkyl, Cl-C4~
alkoxy, Cl-C4-alkylthio, Cl-C4-haloalkyl, hydroxyl and halogen, a 5-membered saturated heterocyclic structure which contains one sr two hetero atoms ~elected from the group consisting of oxygen and sulfur and may additionally carry from one to three radicals selected from the group consisting C1-C4-alkyl, Cl-C4-alkoxy, Cl-C4-alkylthio and Cl-C4-haloalkyl, a 6-membered or 7-me~bered saturated or mono- or diunsaturated hoterocyclic structure containing one or two~.hetero atom~ selected from the group con~isting of oxygen and sulfur, and the heterocyclic ~tructure may additionally carry ~rom one to three radicals selected from the group con~i~tinq of hydroxyl, halogen, C~-C4-alkyl, Cl-C4-alkoxy, C~-C4-al~ylthio and C1-C4-haloalkyl, 30 a 5-membered heteroaromatic ~tructure containing one to three hetero atoms selected from the group consisting of two nitrogen atom~ and one oxygen or ~ulfur atom, and this ring may additionally carry from one to three radicals ~elected from the group consi~ting of halogen, cyano, Cl-C4-alkyl, Cl-C4-alkoxy, Cl-C4-alkylthio, : .
`` 2~79~3 - 2 - O. Z . 0~50/41598 Cl-C4-haloalkyl, C2-C6-alkenyl, C2-Ca-aIkenyloxy, CZ-C6-haloalkenyl and Cl-C4-alkoxy- C1-C4-alkyl, phenyl or pyridyl ~ and the~e group~ may additionally carry from one to three radicals selected from the group consisting of halogen, nitro, cyano, Cl-C4-alkyl, Cl-C4-alkoxy, Cl-C4-alkylthio, Cl-C4-haloalkyl, C3-C6 alkenyloxy, C3-C6-alXynyloxy and -NR3R4, where R3 is hydrogen, C1-C4-alkyl, C3-C6-alk~nyl or C3-C6-alkynyl and R4 is hydrogen, C1 C4-alkyl, C3-C6-alkenyl, C3-C6-alkynyl, C1 C6-acyl or benzoyl, and ~he aromatic ring may addition-ally carry from one to three radical~ selected from the group consisting of nitro, cyano, halogen, Cl-C4-alkyl, Cl-Cb-alkoxy, Cl-C4-alkylthio and C1-C4-haloalkyl, and ~heir agriculturally usable salts and esters of Cl-C1O-carboxylic acid and inorganic acid~.
The present invention furthermora relates to a process for their preparation and their use as crop protection a~ents.
The novel cyclohexenone~ I obviously have acidic character, ie. they can form simple reaction products, such a~ salts of alkali metal or alkaline earth metal compounds or enol e~ters.
Tha compounds of the formula I may occur in a plurality of tautomeric forms, all of ~hich are embraced by the claim.
DE-A 38 38 309 describes herbicidal cyclohexenone oxi~ne ethers whoRe general formula cover~ the axyl-butyleneoximinocyclohexanediones I defined at tha outset.
Compound of the formula I' X
2~4 ~ I' o R
where X is p-trifluoromethyl or p-tert-butyl, n i 0 or 1 and R1 and R2 have the meanings stated under I, are 2 ~ 3 I - 3 - O.Z. 0050/41598 mentioned in particular.
It i~ an object of the present invention to synthesize cyclohexenon~ oxime ether~ which have high sel~ctivity compared with the known members of thi~ class of substances in controlling weeds in gramineous crop~, such as rice.
We have found that thi~ object is achieved by the novel cyclohexenone oxime ether of the formula I which are defined at the outset and which have a good herbicid-al action, preferably against specie~ from the gra sfamily (Gramineae). They are tolerated and hence selec-tive in broad-leaved crops and in monocotyledon culture~
which do not belong to the Gramineae. They also include compounds which exhibit selectivity also in gramineous crops and at ~he same time centrol undesirable gras~e~.
The cyclohexenone~ of the formula I can be prepared in a conventional manner from derivatives of the formula II (EP-A 80 301, EP-A-125 094, EP-A-142 741, US-A 4 249 937, EP-A 137 174 a~d EP-A 177 913) and the corresponding hydro~ylamines of the formula III (EP-A 169 521).
R2 ~ ~ ~ H2NO(CH2)4 ~ ~ R2 ~ ~o(CH2)4 ~ xn II III I
The reaction is advantageously carried out in the heterogeneou~ pha~a in a solvent, at an adequate tempera-ture below about 80C, in the pre~ence of a base, and the hydroxylamine III i~ used in the form of it~ ammonium salt.
Examples of ~uitabla ba~es are carbonates, bicarbonates, acetat0~, alcoholates or oxide~ of alkali or alkaline ear~h metals, in particular ~odium hydroxide, potas~ium hydroxide, magnesium oxide and calcium oxide.
Organic ba~es, ~uch a~ pyridine or tertiary amine~, can . ,: , . , . ,:
,. . . , :
2~1 7~3 I ~ 4 - U.Z. 0050/41598 also be used~ The ba~e i~ added, for example, in an amount of from 0.5 to 2 mole equivalents, based on the ammonium compound.
Examples of suitable solv2nt~ are dLmethyl S sulfoxide, alcohol~, such a methanol, ethanol and isopropanol, aromatic hydrocarbons, such as benzene and toluene, chlorohydrocarbons, ~uch as chloroform and dichloroethane, aliphatic hydrocarbons, such as hexane and cyclohexane, esters, such as ethyl acetate, and ethers, such as diethyl ether, dioxane and tetrahydro~
furan. The reaction is preferably carried out in methanol using sodium bicarbonate as the base.
The reaction is complete af~er a few hours. The desired compound can be isolated, for example by evapora-ting down the mixture, distributing the re~idue in methylene chloride/water and di tilling off the solvent under reduced pressure.
However, the free hydroxylamine base, for example in the form of an aqueou~ solu~ion, can also be used directly for this reaction; depending on the solvent u~ed for the compound II, a single-phase or two-phase reaction mixture i5 obtained.
Examples of suitable ~olvents for this varian~
are alcohol~, such a methanol, ethanol, isopropanol and cyclohexanol, aliphatio and aroma~ic hydrocarbon3 and chlorohydrocarbon~, such a~ hexane, cyclohexane, meth-ylene chloride, toluene and dichloroethane, esters, such a~ ethyl acetate, nitrile3, such a~ acetonitrile, and cyclic ethQrs, such a~ dioxane and tetrahydrofuran.
Alkali metal ~alts of the compounds I can be obtained by treating the 3-hydroxy compound~ with sodium hydroxide, potas~ium hydroxide or a ~odium or pota~ium alcoholate in aqueous solution or in an organic solvent, such as methanol, ethanol, acetone or toluene.
Other metal salt~, such a~ mangan2se, coppPr, zinc, iron, calcium, magnesium and barium salt3, can be prepared from the ~odium salt~ in a conventional manner, !
2~ 7~3 - 5 - O.Z. 0050/4159~
aR can ammonium and pho~phonium salts using ammonia or phosphonium, sulfonium or sulfoxonium hydroxide.
The compounds of type II can be prepared, for example, from the corresponding cyclohexane-1,3-dione~ of the formula IV
OH
R2 ~ IV, Y o where Y is hydrogen or methoxycarbonyl, by known methods, for example as described in Tetrahadron Lett. (1975), 2491.
It is also possible to prepare the compounds of the formula II by the enol e~ter intermediate~ V which are obtained in the reaction of compounds of the formula IV with acyl chloride3 VI in the presence of a basa and are then subjec~ed to a rearrangemen~ reaction with certain Lmidazole or pyridine derivatives (Japanese Preliminary Published ~pplication 79/063 052).
R2~ + R~CI - ~ R2~ ~ a IV VI V II
The compounds of tha formula IV are obtained by a num~er of known process s~eps, starting from known intermediates.
The synthesis of the hydroxylamines I~I is carried out according to the reaction ~cheme below, for example by A) alkylation of N-hydrox~phthalimide VII with suitabla phenylbutyl halide~ YIII and sub~equ~nt elLmina-tion of the protective group, for example with hydrazine or ethanolamine, sLmilarly to Examples in EP-A-244 786 or Houben-Weyl, Methodan der organischen Chemie, Volume X/l, page 1152 et seq. or , .
2~7~
i - 6 ~ O.Z. 0050/41598 B) hydrogenation of N-4-phenylbutenylo~yphthal-imides Xa, b, whose preparation is descri~ed in DE-A 38 38 310, by means of suitable catalysts, eg. palladium on active carbon, in suitable inert solvent~, such as methanol, tetrahydrofuran or dioxane, and subsequent elimination of the protective group as described above.
The hydrogenation is advantageously carried out at from 20C to the boiling point of the solvent, in particular at room temperature, by a conventional method, under atmospheric, superatmospheric or reduced pressureO
A pressure rAnge of from 1 to lO, in particulax 1 to 2, bar ig preferred.
Reaction scheme:
RouteA) O N~H + Ha 1~0 --~ D N ~ ~( X ) n IX
O O H 2N~OH
VII YIII ~a~. 1 , R out e B ) D N-O~l ~ ( X ) n or III
(X)n _ o Xb In the cyclic hydroximide~ VII, D is, for ex-I, `'; ' ' ' ~ .
2~ 7~
7 _ o . z . 0050/41598 ample, C2-C3-alkylene, C2-alkenylene or a 5-membered or 6-membered ring which contains not more than 3 double bonds and may contain 1 nitrogen atom, for example phenylene, pyridinylene, cyclopentylene, cyclohexylene or cyclohexenylene. Examples of suitable substances a-e the following:
o o o N -OH ¦¢N~ N--OH
O O O
O¢ N-OH ¢N{)H (;~N-OH
O O O
C~N_OH
The cleavage of the cyclic imide ethers VIII is carried out similarly to a proce~s de~cribed in EP-A 244 786, using alkanolamine~. After thi~ proce~ , hydroxyl-amines III can be i~olated a3 free bases or, after precipitation with acid~, a~ salt~. Readily crystalliz-ing salt~ are obtained by reacting the bases with oxalic acid.
In view of the biological activity, preferred cyclohexenone~ of the formula I are those in which Rl is alkyl, such as methyl, ethyl, propyl or n-bu~yl, in particular ethyl or propyl, X is halogen, such a~ fluorinel chlorine, bromine or iodine, in particular fluorine or chlorine, n is from 1 to 5, in particular 1, 2 or 3, the sub-stituent3 being identical or different where there i~ a .
' 7 ~ ~
I - 8 - o.Z~ 0050/41598 plurality of radicals X, R2 is alkyl a~ st~ted under Rl, which may carry an alko~y or alkylthio group stated below, preferably in the 1-, 2--or 3-position, in particular 2-ethylthiopxopyl, or S cyclohexyl which may carry from 1 ~o 3 methyl or hydroxyl groups, in particular 4-methylcyclohexyl or 3,4-di-hydroxycyclohexyl, 5-membered hetaryl~ such as pyrazolyl or isoxazolyl, a 6-membered heterocyclic struc~ure, such as tetrahydro-pyran-3-yl, tetrahydropyran-4-yl or tetrahydrothiopyran-3-yl, phenyl or pyridyl, where the cyclic radicals may carry from one to three alkyl, alkoxy, alkylthio and/or haloalkyl group~ and, in the case of 6-membered radical~, al~o halogen as stated under X or hydroxyl, for example alkyl, such as methyl ethyl, propyl, 1-methylethyl, butyl, l-methylpropyl, 2-meth~lpropyl or 1,1-dLmethyl-ethyl, in particular methyl or l,l-dimethyle~hyl, alkoxy, such as methoxy, ethoxy, propoxy, l-methylethoxy, butoxy, l-methylpropoxy, 2-me~hylpropoxy or 1,1-dimethyl-ethoxy, in particular methoxy, ethoxy, l-methylethoxy or l,l-dimethylethoxy, alkylthio, such a~ methylthio, ethyl~hio, propylthio, 1-methylethylthio, butylthio, 1-methylpropylthio,2-methyl-propylthio or 1,1-dimethylethylthio, in particular methylthio, or haloalkyl ~uch as fluoromethyl, difluorome~hyl, tri-fluoromethyl, chlorodifluoromethyl, dichloro~luoromethyl or trichloromethyl, in p3rticular difluoromethyl or trifluoromethyl.
2,4,6-Trimethylphenyl is particularly preferred.
The 5-membered heteroaromatic radical~ R2 may carry ths following radicals a3 substituent~:
halogen a~ ~tated under X, in particular fluorine or chlorine.
In the case of the phenyl and pyridyl radicals, - 2~7~
_ 9 _ o.z. 0050/41598 suitable substituents in addition to the abovementioned group~ are the following radicals:
alkynyloxy, such as 2-propynyloxy, in particular proparg-yloxyphenyl or amino which may carry one or two acyl radicals, such as acetyl or benzoyl.
Particularly preferred cyclohexenone oxime ethers of the formula I are summarized in the Table below:
11 , ~ ' ' . , ;
9 ~
- 10 - O.Z. 0050/~1598 ,_ ~
-- E E
._ _ _ _ ~ _ _ _, U o ` I :~ T r ~ ~ I S ~ ~t . o ~
~, _ _ _; - ~ ~ ~ ~J
, ~ t r --E ~` o o o o o o o o ` o o a-tO _ I ~- S
L ~ ~
_ ? ~ V ~ ~ V ~ D ~ --t aE _ _, _ _ _ _ _ _ _ Z ~ ~
OOOOOOOOOOOO
L L L L t L h h h h F~l h L L
O O O O O O O O C:l O O O C~
C~ -- S -- -~
_ _ _ _ _ _ ~., _ C C ~
~ ~I L L ~ * ~ ~ ~ ~ t L L L
' C O ~b e ~ C C ' ' 0~ 0 90~ 0 L L ~-- ~-- L L L L L L ~
r- L L L L L L L L L L L L L
0~0 ~ ~ S ~ ,~ L L
~11 ~ ~ ~ +~ ~ ~ .~
~ C~~ ~ ~ L ~ L ~ L
_. ~ cL ~ ~ w ~ L~ 1 ~ w ~:L w ~
C~ -- o o O C:~
- 11 - O.Z. 0050/~1598 T .~ T _ ~T ~ r ~_ I N -r N I--'~ ~ ` `
N ~ ._ ~V~:1 E --~ E ` E~ ~ EiE e ~
-- E -- E -- E ---- -- ~ ~ ,~, --a~ ~ o o o oo _~ ~
O
^ I ~ I I T
` E ` ~. E ~ ~ ~ ~ E
E -- ~ E ~ E ~ -- E -- E Ea -- --_ ~ -- E
E~ ~ o 0- 0 Cr~ ~ ~1 0 -- O --N t~l N
:r: I r r ^ ~ r ^ T I ~: ~ I S I T -- ~ -- I --' ~o ~o ~ ~ ~ ~ r ~ T
_~ E ~ E ` ~ ' ~ ~ E ~ E ~ ~ ~ E ~ ~ ~ '~
ui ~ - - -s z _ o ~ o ~ o o _ -- ~ -- -- o .~
h O O O
O O O O O O C~ O O O i J ,~
~ h ~ h O O OO O O O ~ri'~i ~ri s ~ a I ~ ~ ~
,_ ~
I I I Ii ~ I I I I i ~ ' L ~7 ~ ~ ~ ~ ~ L ~t L L L L ~ L L. L L ~
O O O C~ O O O O O O ~-- O O O
L L L L L rl r~ L
s s c '' ~ r s s c s :-~ c s ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ C ~ ~ ~
S_ ~ L L L L L L L L ~ L L L
a~
E~
O ~ ~. ~ L ~ ~ ~ L ~ L L ~ L
~i ~i ~ ~ ~ ~ ~_ ~ i i i i i i i i U;
X _ _ _ _ ~
t! I . . `
. ~ , 2 ~ 3 12 - o . z . 0050/41598 s ~ ~ 2 ~ ~ r ~: ~
v ~ E ~ ~ E ~ E
7 ~ _ ~ u~ In In o o ~ ~o u o _ I ~ T
~ T I
E
_ U~
E
~0 '-- ^ I ^ ~ 1 ^ I ^ ^ V ^ --. * ~` V ~ E V V ~ E ~ ~ ~ V _ E -- I~ -- -- --,_ z ~ ~ ~ - -- O ~~ CO cr o _ o o- _ _ ~ _ ~ o~
~_ o 1~ o r~ 1~ o 1~ o 1~ _ _ _ 1~ o 1~ _ c c ~ .c o ~ o o . i C~u O. r I S E X o 1~ L
C CL ~ O ~ ~. C~, ~
L e ~ L
~ X ~ L' C
a. ~. e L I-- ~ L ~ 0 ~) O O O
~ I I :,. ~ e o o ~ v v CI i O S ~ ::1 ~ ,:~
C C ci o ~ L L $ ~ O O ~L ~ ~d ~
r~ ~ I I (O J ~V
ffi E~
O O ~ g c O ~:: ~ o r V _. ~ t ~ ~ L ~ ( ~ ~L. ~ ~
~ CL ~ I~J ~i ~ hi CLl~i ~Li ~ ~i ~i _l , ~ ~ . . ' .
I) , :
, - 13 - O. z . 0050/41598 8`
U~
_.
T
_~
E
C~
,~
:~ r _ _ ~ ~ u~ In s 2 o r.
.. O
~:
X ~
.;~r L
C~
. . V
t ~ I_ 2 .~
g - CL
U
~ $
E~ Z -~ *
,~
I, ' ' ' ',;
2~7~
i - 14 - O.Z. 0050J41598 The cyclohexenone oxime ethex~ I are suitable as herbicides, in particular for con~rolling plant species from among the Gramineae (grasses).
The cyclohexenone derivatives I or the herbicides containing them can be used, for example, in the form of directly sprayable solution~, powders, suspensions, including concentrat0d aqueous, oily or other suspensions or dispersions, emulsions, oil dispersions, pas~es, dusting agents, broadcasting a~en~s or granules, by spraying, atomizing, du~ing, broadca ting or pouring.
The application forms depend on the intended uses; they should in any case ensure very fine distribution of the novel active ingredients.
Compounds I are suitable in general for the preparation of directly sprayable ~olution~, emulsions, pastes or oil disper~ions. Suitable inext additives are mineral oil fractions having a medium to high boiling point, such as kerosene or diesel oil, as well as coal tar oils and oils of vegetable or animal origin, aliphat-ic, cyclic and aromatic hydrocarbons, eg. toluene,xylene, paraffin, tetrahydronaphthalene, alkylated naphthalenes and derivatives thereof, methancl, ethanol, propanol, butanol, cyclohe~anol, cyclohexanone, chloro-benzene, isophorone or strongly polar solvents, such as N,N-dLmethylformamide, dLmethyl sulfoxide, N-methylpyr-rolidone or water.
Aqueous application forms can be prepared from emulsion concentrates, dispersions, pastes, w ttable powder~ or water-dispersible granules by adding water.
For th~ prepaxation of emulsion~, pa tes or oil disper-sion~, the sub~trates, as such or in ~olution in oil or solvent, can be homogenized in water by means of wetting agents, adhesive~, di~persant~ or emulsifiersO However, it is also po~sible for concentrates which consi~t of active substances, wetting agent~, adhesives, disper~ants or emulsifier~ and may consi t of solvents or oil and which are suitable for dilution wi~h water to be 2~7~3 - 15 - o. z . 0050/41598 prepared.
Suitable surfactants are the alkali metal, alkaline earth metal and ammonium salts o~ aromatic sulfonic acids, fox example lignin-, phenol-, naph-thalene- and dibutylnaphthalenesulfonic acid, and of fatty acids, alkyl- and alkylarylsulfonates, alkyl-sulfates, lauryl ether sulfates and fatty alcohol ~ul-fates, and salts of sulfated hexa-, hepta- and octa-decanols, and of fatty alcohol glycol ethers, condensates of sulfonated naphthalene and it~ derivatives with formaldehyde, condensate~ of naphthalene or of naph-thalenesulfonic acids with phenol and formaldehyde, polyoxyethyleneoctylphenolethers,ethoxylated isocotyl-, octyl-or nonylphenol, alkylphenol polyglycol e~hers, tributylphenyl polyglycol ether~, alkylaryl polyether alcohols, isotrideoyl alcohol, fatty alcohol/ethylene oxide condensates, ethoxylated ca~tor oil, polyoxy-ethylene alkyl ethers or polyoxypropylene~ lauryl alcohol polyglycol ether aceta~e, ~orbitol e ters, ligninsulfite waste liquor~ or methylcellulose.
Powder~, broadcasting agent~ and duating agents can be prepared by mixing or milling the active sub-stances together with a solid carrier.
Granule~, for example, coated, impregnated and homogeneous granules, can be prapared by binding the active ingredients to solid carriers. Solid carriers are mineral earths, such as ~ilica , ~ilica gel~, silicates, talc, kaolin, limestone, lime, chalk, bole, loess, clay, dolomite, diatomaceou~ earth, calcium ~ulfate, magnesium sulfate, magne ium oxide, milled pla~tic~, fertilizers, such a~ ammonium sulfate, ammonium phosphate, ammonium nitrate, ureas and vegetable product~, ~uch as cereal meal, ground bark, woodmeal and nu~shell meal, cellulo~e powder and other ~olid carriers.
The formulation~ contain from 0.02 to 95, prefer-ably from 0.5 to 90, ~ by weight of active ingredient.
The active ingredients ar~ used in a puri~y of from 90 to I~ : : , .
I - 16 - O.Z. 0050/~159~
100%, preferably from 95 to 100% (according to ~he NMR
spectrum).
The novel compounds I can be formulated, fox example, as follows:
I. 90 parts by weight of compound No. 1.05 are mixed with 10 parts by weight of N-msthyl-~-pyrrolid-one, and a solution suitable for use in the form of very small drops i~ obtained.
II. 20 parts by weight of compound No. 1.03 are dissolved in a mixture which consists of sn part~
by weight of ~ylene, 10 parts by weight of the adduct of rom 8 to 10 moles o~ ethylene oxide with 1 mole of oleic acid N-monoethanolamide, 5 parts by weight of the calcium salt of dodecyl-benzenesulfonic acid and 5 parts by weight o an adduct of 40 moles of ethylene oxide with 1 mole of castor oil. By pouring the ~olution into 100,000 part~ by weight of water and finely distributing it therein, an aqueous di~persion which contain~ 0.02% by weight of the active ingredient is obtained.
III. 20 parts by weight of compound No. 1.11 are dis~olved in a mixture which con~i~ts of 40 part~
by weight of cyclohQxanone, 30 part~ by weight of isobutanol, 20 part~ by weight of ~he adduct of 7 moles of ethylene oxid~ with 1 mole of iso-octylphenol and 10 parts by weight of the adduct of 40 mole~ of ethylene oxide with 1 mole of castor oil. By pouring the ~olution into 100,000 part~ by weight of water and finely distributing it therein, an aqueous disper~ion which contain~
0.02% by weight of th~ active ingredienk is obtained.
IV. 20 part~ by w~ight of ac~ive ingredient No. 1.11 are dissolved in a mixture which consist~ of 25 part~ by weight of cyclohe~anone, 65 part~ by wei~ht of a mineral oil fraction boiling within ! ~ .
, 7 ~ 3 I - 17 - O.Z. 0050/41598 a range from 210 to 280C and 10 parts by weight of ~he adduct of 40 mole~ of ethylene oxide with 1 mole of castor oil. By pouring the solution into 100,000 parts by weight of water and finely S distributing it ~herein, an aqueous dispersion which contain~ 0.02~ by weight of the active ingredient is obta ned.
V. 20 parts by weight of active ingredient No. 1.05 ar~ thoroughly mixed with 3 par~s by weight of the sodium ~alt of diisobutylnaphthalene-~-sulfonic acid, 17 parts by weight of the sodium salt of ligninsulfonic acid obtained fro~ a sulfite waste liquor and 60 part~ by weight of silica gel powder, ~nd the mixture is milled in-a hammer mill. ~y finely distributing the mixture in 20,000 parts by weight of water, a spray liquor which contain~ 0.1~ by weight of ~he active ingredient is obtainad.
VI. 3 parts by welght of active ingredien~ No. 1.03 ara mixed with 97 part~ by weigh~ of finely divided kaolin. A dusting agent which contain~
3~ by weight of ~he active ingredient i~ obtained in this manner.
VII. 30 part~ by weight of active ingredient No. 1.05 are thoroughly mixed with a mixture of 92 parts by weight of ~ilica gel powder and 8 parts by weight of liquid paraffin which ha~ been sprayed onto the ~urface of thi~ ~ilica gel. a formula-tion of the active ingredient ha~ing good ad-hesion i3 obtained in this manner.
VIII. 20 part~ by weight of active ingredient NoO 1~03 are thoroughly mixed with 2 parts by weight of the ~alcium salt of dode~ylbenzene~ulfonic acid, 8 parts by weight of a fatty alcohol polyglycol ether, 2 parts by weight of the sodium salt of a phenol/urea/formal~ehyde conden~ate and 68 parts by weight o~ a paraffinic mineral oil. A ~table , , .
- :
, 2,'~7~3 I - 18 - O.Z. 0050/41598 oily dispersion is obtained.
Th0 agent~ can be applied by the preemergence or postemergence method. If the active ingredients are less well tolerated by certain crops, it is also possible to use application methods in which the herbicides are sprayed with the aid of the sprayers in such a way that there is as far as possible no contact with the leav~s of the sen~itive crops while the active ingredient~ reach the leaves of undesirable plants growing underneath or reach the uncovered soil area (post-directed, lay-by~.
The application rates of active ingredient are from 0.001 to 3, preferably from 0.01 to 2.0, kg/ha, depending on the season, the target plants and the stage of growth.
In view of the prac~icable ac~ion spec~rum for weed control, the toleration by crops or the desired effect on the growth ~hereof and because of the wide range of application metho~s, the novel compounds can be used in a large number of cxops. Example of suitable crops are the following:
Botanical name Common name Allium cepa onions Anana~ comosu~ pineapples Arachis hypogaea peanut~ (groundnuts) Asparagus off icinali8 asparagus Beta vulgari~ spp. alti sima ~ugarbeets Beta ~ulgari~ pp. rapa fodder beets Brassica napu~ var. napus rapeseed 30 BrasYica napus var. napobra~ica swedes Brassica rapa var. silve~tris beets Camellia sinensi~ tea plants Carthamus tinctoriu~ ~afflower Carya illinoinensi~ pecan tree~
Citrus limon lemon trces Citru~ ~inensi4 orang~ tree~
Coffea arabica (Coffea canephora, Coffea liberica) coffee plants Cucumis sativus cucumbers 2 ~ 3 I - 19 - O.Z. 0050/41598 Botanical name Common name Cynodon dactylon sermudagrass in turf and lawn~
Daucus carota carrots Elaeis guineensis oil palm~
Fragaria vesca ~trawberrie3 Glycine max soybean~
Gossypium hirsutum (Gossypium arboreum cotton Gossypium herbaceum Gossypium viti~olium) Helianthus annuus sunflowers Helianthus tuberosus Jerusalem artichoke Hevea brasiliensis rubber plants Hordeum vulgare baxley Humulus lupulus hops Ipomoea batatas sweet potatoes Juglans regia walnut trees Lens culinari~ lentils Linum usitatissimum flax Lycopersicon lycoper~icum tomatoes Malus spp. apple tree~
Manihot esculenta cas~ava Medicago ~ativa alfalfa (lucerne) Musa spp. banana plants Nicotiana tabacum tobacco (N. rustica) Olaa europaea olive trees Oryza ~ativa rice Pha~eolu~ lunatu~ limabeans Phaseolus vulgari~ 3napbeans, green bean~, dry beans Picea abiQs Norway spruce Pinus spp. pine trees Pisum ~ativum English pea~
Prunus avium cherry tree~
~,, .
., `
, 7 ~ 3 I - 20 O.Z. 0050/4159 Botanical name Common name Prunus dulci~ almond trees Prunus per~ica peach trees Pyrus communis pear trees Ri~es sylve~tre redcurrants Ricinus communis castor-oil plants Saccharum afficinarum sugar cane Secale cereale rye Solanum tuberosum Irish potatoes Sorghum bicolor (s. vulgare) sorghum Theobroma cacao cacao plants Trifolium pratense red clover Triticum aestivum wheat Triticum durum durum wheat Vicia faba tick beans Vitis vinifera grapes Zea may3 Indian corn, sweet corn, maize To broaden the action spec~rum and to achieve synergi~tic efects, the cyclohexenone derivative~ of the formula I can be mixed both with one another and with member~ of other groups of herbicidal or growth-regulating active ingredient~ and applied together.
Example~ of suitable component~ for the mixture are diazine~, 4H-3,1-ben~oxazine derivatives, benzothia-diazinone~, 2,6-dinitroaniline~, N-phenylcarbamates, thiocarbamates, halocarboxylic acid~, triazine~, amides, ureas, diphenyl ether~, triazinone~, uracils, benzofuran derivative~, quinolinecarboxylic acids, sulfonylurea derivatives, cyclohexenones, (hetero)aryloxyphenoxypropionic acids, their ~alts, e~ters and amide~ and others.
It may also be useful to apply the cyclohexenone derivative~ o~ the formula I, or herbicides containing them, alone or together in combination with other herl-icide~ or mixed with further crop protection agent~, for example with pesticidea, agents for controlling .. , !l :
~ ..
.
2 V ~ 3 I - 21 - O.Z. 0050/41598 phytopathogenic fungi or bactericides. The miscibility with mineral ~alt solution~ which are used for eliminat ing nutrient and trace elemen~ deficiencies is also of interest. It is also possible to add nonphytotoxic oils and oil concentrates.
EXAMPLES
4-Phenylbutoxyamine ~ONH 2 Method A:
167.S g (1.21 mol) of potas~ium carbonate and 2 g of potassium iodide were added to 302 g (1.85 mol) of N-hydroxyphthalimide in 1.9 1 of anhydrous N-methyl-pyrrolidone. After the reaction mixture had been heated to 50C, 395.2 g tl.85 mol) of 4-phenylbutyl bromide were added and this tPmperature was maintained for a further 6 hours. After cooling, the mixture was poured onto 6 l of ice wa~er and taken up with dichloroethane, and the organic phase wa~ washed with dilute sodium hydroxide solution, dried and evapora~ed dow~ under reduced pres-sure. Yield: 379 g of N-~4~phenylbu~o~y)-phthalLmide (73%).
250-MHz lH-NNR (DMSO-d~) (ppm) = 1.65-1.85 (m, 4H); 2.66 (t, 2H); 4.18 (t, 2H) 7.1-7.4 (m, 5H); 7.86 (~, 4H) 81,8 g (1.34 mol) of e~hanolamine were added to 396 g (1.34 mol) of the phthalLmidoether obtained above in 1,300 ml of ethyl acetate. The reaction mixture was heated at 60C for 5 hours. Thereafter~ stirring was carried out for 24 hour~ at room temperature, the precipitated cry~tal~ were filtered off under suction and washed with a little ethyl acetate and a vigor~us ~tre~m of hydrogen chloride gas was pa~ed through the combined mother liquors ~or 15 minute~, during which tha intarnal tempera~ure should not exc0ed 40C. ~he precipitated - 22 - O.Z. 0050/41598 crystals were filtered off under suction, washed with a little ethyl acetate and dried under reduced pressure.
Yield : 148.5 g of 4-phenylbutoxyamine hydrochloride (55~). Mp.: g3 94C.
250-MHz lH-NMR (DMSO-d~) ~ppm) - 1.5-1.7 (m, 4H); 2.58 (t, 2H); 4.04 (t, 2H) 7.1-7.3 ~m, 5H); 11.1 (broad s, 3H) 4-(4-Fluorophenyl)-butoxyamine F~3(C~12) 4--ONH2 Method B: Hydrogenation N-(4-(4-Fluorophenyl)-butoxy)-phthalimide 2 g of palladium on ac~ive carbon (10% ~trength) were added to a solution of 71.5 g (0.23 mol) of N-(4-(4-fluorophenyl~-3-butenyloxy~-phthalLmide(preparedaccord-ing to German ~aid~Open Application DOS 3,838,310) in 300 ml of tetrahydrofuran. Hydrogenation was carried ou~
under slightly superatmospheric pre~sure until 1.2 times the theoretical amount of hydrogen had been consumed. The mixture was fil~ered under ~uction over kie~elguhr, the filtrate wa~ evaporated down and the crude product was recrystallized from isopropanol.
Yield: 62.8 g 187~); mp.: 67-68C
2S0-MHz lH-NNR (DMSO-d~) (ppm) = 1.8-1.9 (m, 4H); 2.65 (t, 2H); 4.15 (t, 2H) 7.0-7.35 (m, 4H); 7.86 (s, 4H) 61.8 g (0.197 mol) of the phthalimidoether previously prepared were introduced a little at a tLme into 92 mol of ethanolamine. The mixture was heated at 60C for 3 hour~, after which it wa~ allowed to cool and was then poured into 400 ml of ice water and extracted with dichloroethane. The combined organic phase~ were wa~hed with saturated ~odium chloride ~olution, dried and evaporated down under reduced pre~sure. ~he 4-~4-fluoro-phenyl)-butoxyamine was obtained as an oil.
., .
7 ~ 3 - 23 - o.z. 0050/ds15g8 250-MHz lH-PIMR (CDCl3) ~ppm) = 1.5--1.74 (m/ 4~; 2.61 (t, 2H); 3.68 (t, 2H) 5.4 (broadL s, 2E~); 6.9-7.2 (m, 4H) 4- ( 4-Chlorophenyl ) -butoxyamine Ct~
~(CH2) 4{~NH2 4-(4-Chlorophenyl)-buto~yamine wa~ obtained as an oil in a total yield of 60% similarly ~o the Example described above, starting from N-(4 (4-chlorophenyl)-butenyloxyphthalLmide (German Laid-Open Applica~ion DOS
3,838,310).
250-MHz lH-NNR (CDCl3) (ppm) = 1.65-1.85 (m, 4H); 2~66 (t, 2H); 4.lB (t, 2H) 7.1-7.4 (m~ 5H); 7.86 (~, 4H) N-(4-(4-Chlorophenyl~-butoxyphthalimide C ~ cH 2 ) 4~N~3 Mp.: 72~73C (isopropanol) 250-MHz lH-NMR (DMSO-d6) (ppm) = 106-1.85 (m, 4H); 2.6a (t~ 2H~; 4.17 (t, 2H) 7.2-7.4 (m, 4H); 7.88 (s, 4H) 2-{1-[4-(4-Fluorophenyl)-butoximino]-butyl}-5-tetrahydro-thiopyran-3-yl-3-hydroxycyclohex-2~enone (compound 1.04) 2.2 g (12 mmol) of 4-(4~fluorophe~yl)-butoxyamine were added to a solution of 3 g tll mol) of 2 butyryl-3-hydroxy-5-tetrahydrothiopyran-3-ylcyclohex-2-enone in 100 ml of dry methanol. ~he mixture was stirred for 16 hours at room temperature and was then evaporat*d to drynes~ under reduced pres~ure. The residue wa~ taken up in diethyl ether and the ~olution was chromatographed over silica gel. Yield . 3.6 g (80% o~ theory).
The cyclohexenone compounds shown in Table 1 can be obtained similarly to thi~ method.
. .
.. . .
.
- ~ . .
7 ~ 3 - 24 - O.Z. 0050/41598 Use Examples The herbicidal action of the cyclohexenone oxime ethers of the formula I could be demonstrated by yreen-house experiment~:
The culture ve ~els used were plas~ic flowerpots containing loamy sand with about 3% of humus as a sub-strate. The seeds of the test plan~s were sown separate-ly according to species.
In the cAse of preemergence trea~ment, the active ingredients ~uspended or emul~ified in water were applied directly after sowing, by means of nozzles providing a fine distribution. The vessel~ were lightly watered in order to promote germination and growth and then covered with transparent plastic covers un~il the plants had begun to grow. This covering ensures uniform germination of the ~est plant~, unles~ this i~ adversely affected by the active ingredients.
For the purpo~e of postemergence treatment, the test plant~ wers treated with the active ingredients suspended or emul~ified in water, bu~ only after reaching a height of growth of from 3 to 15 cm, depending on the growth form. The application rate for the postemergence treatment was 0.06 kg/ha of active substance.
The plants were kept at 10-25C or 20-35C, depending on the specie~. The te~t period extended over 2-4 weeks. During this time, the plants were tended and their reaction to the individual treatments ~as e~aluated.
Evaluation was based on a cale from 0 to 100.
100 means no emergence of the plant~ or complete destruc-tion of at lea~t the above-ground parts and 0 means no damage or normal growth.
The plants used in the greenhouse experiments consisted of the following 3pecies:
2~793 I - 25 - O.z. 0050/41598 Latin name _ Commen name Oryza sativa rice Echinochloa crus-galli barnyardgra~s Setaria italica foxtail millet When 0~06 kg/ha of active substance is used in the postemergence method, undesirable gramineous plants can be very readily controlled using Example 1.11, 1.03 and 1.05, with simultaneous toleration by the example crop rice.
, .
167.S g (1.21 mol) of potas~ium carbonate and 2 g of potassium iodide were added to 302 g (1.85 mol) of N-hydroxyphthalimide in 1.9 1 of anhydrous N-methyl-pyrrolidone. After the reaction mixture had been heated to 50C, 395.2 g tl.85 mol) of 4-phenylbutyl bromide were added and this tPmperature was maintained for a further 6 hours. After cooling, the mixture was poured onto 6 l of ice wa~er and taken up with dichloroethane, and the organic phase wa~ washed with dilute sodium hydroxide solution, dried and evapora~ed dow~ under reduced pres-sure. Yield: 379 g of N-~4~phenylbu~o~y)-phthalLmide (73%).
250-MHz lH-NNR (DMSO-d~) (ppm) = 1.65-1.85 (m, 4H); 2.66 (t, 2H); 4.18 (t, 2H) 7.1-7.4 (m, 5H); 7.86 (~, 4H) 81,8 g (1.34 mol) of e~hanolamine were added to 396 g (1.34 mol) of the phthalLmidoether obtained above in 1,300 ml of ethyl acetate. The reaction mixture was heated at 60C for 5 hours. Thereafter~ stirring was carried out for 24 hour~ at room temperature, the precipitated cry~tal~ were filtered off under suction and washed with a little ethyl acetate and a vigor~us ~tre~m of hydrogen chloride gas was pa~ed through the combined mother liquors ~or 15 minute~, during which tha intarnal tempera~ure should not exc0ed 40C. ~he precipitated - 22 - O.Z. 0050/41598 crystals were filtered off under suction, washed with a little ethyl acetate and dried under reduced pressure.
Yield : 148.5 g of 4-phenylbutoxyamine hydrochloride (55~). Mp.: g3 94C.
250-MHz lH-NMR (DMSO-d~) ~ppm) - 1.5-1.7 (m, 4H); 2.58 (t, 2H); 4.04 (t, 2H) 7.1-7.3 ~m, 5H); 11.1 (broad s, 3H) 4-(4-Fluorophenyl)-butoxyamine F~3(C~12) 4--ONH2 Method B: Hydrogenation N-(4-(4-Fluorophenyl)-butoxy)-phthalimide 2 g of palladium on ac~ive carbon (10% ~trength) were added to a solution of 71.5 g (0.23 mol) of N-(4-(4-fluorophenyl~-3-butenyloxy~-phthalLmide(preparedaccord-ing to German ~aid~Open Application DOS 3,838,310) in 300 ml of tetrahydrofuran. Hydrogenation was carried ou~
under slightly superatmospheric pre~sure until 1.2 times the theoretical amount of hydrogen had been consumed. The mixture was fil~ered under ~uction over kie~elguhr, the filtrate wa~ evaporated down and the crude product was recrystallized from isopropanol.
Yield: 62.8 g 187~); mp.: 67-68C
2S0-MHz lH-NNR (DMSO-d~) (ppm) = 1.8-1.9 (m, 4H); 2.65 (t, 2H); 4.15 (t, 2H) 7.0-7.35 (m, 4H); 7.86 (s, 4H) 61.8 g (0.197 mol) of the phthalimidoether previously prepared were introduced a little at a tLme into 92 mol of ethanolamine. The mixture was heated at 60C for 3 hour~, after which it wa~ allowed to cool and was then poured into 400 ml of ice water and extracted with dichloroethane. The combined organic phase~ were wa~hed with saturated ~odium chloride ~olution, dried and evaporated down under reduced pre~sure. ~he 4-~4-fluoro-phenyl)-butoxyamine was obtained as an oil.
., .
7 ~ 3 - 23 - o.z. 0050/ds15g8 250-MHz lH-PIMR (CDCl3) ~ppm) = 1.5--1.74 (m/ 4~; 2.61 (t, 2H); 3.68 (t, 2H) 5.4 (broadL s, 2E~); 6.9-7.2 (m, 4H) 4- ( 4-Chlorophenyl ) -butoxyamine Ct~
~(CH2) 4{~NH2 4-(4-Chlorophenyl)-buto~yamine wa~ obtained as an oil in a total yield of 60% similarly ~o the Example described above, starting from N-(4 (4-chlorophenyl)-butenyloxyphthalLmide (German Laid-Open Applica~ion DOS
3,838,310).
250-MHz lH-NNR (CDCl3) (ppm) = 1.65-1.85 (m, 4H); 2~66 (t, 2H); 4.lB (t, 2H) 7.1-7.4 (m~ 5H); 7.86 (~, 4H) N-(4-(4-Chlorophenyl~-butoxyphthalimide C ~ cH 2 ) 4~N~3 Mp.: 72~73C (isopropanol) 250-MHz lH-NMR (DMSO-d6) (ppm) = 106-1.85 (m, 4H); 2.6a (t~ 2H~; 4.17 (t, 2H) 7.2-7.4 (m, 4H); 7.88 (s, 4H) 2-{1-[4-(4-Fluorophenyl)-butoximino]-butyl}-5-tetrahydro-thiopyran-3-yl-3-hydroxycyclohex-2~enone (compound 1.04) 2.2 g (12 mmol) of 4-(4~fluorophe~yl)-butoxyamine were added to a solution of 3 g tll mol) of 2 butyryl-3-hydroxy-5-tetrahydrothiopyran-3-ylcyclohex-2-enone in 100 ml of dry methanol. ~he mixture was stirred for 16 hours at room temperature and was then evaporat*d to drynes~ under reduced pres~ure. The residue wa~ taken up in diethyl ether and the ~olution was chromatographed over silica gel. Yield . 3.6 g (80% o~ theory).
The cyclohexenone compounds shown in Table 1 can be obtained similarly to thi~ method.
. .
.. . .
.
- ~ . .
7 ~ 3 - 24 - O.Z. 0050/41598 Use Examples The herbicidal action of the cyclohexenone oxime ethers of the formula I could be demonstrated by yreen-house experiment~:
The culture ve ~els used were plas~ic flowerpots containing loamy sand with about 3% of humus as a sub-strate. The seeds of the test plan~s were sown separate-ly according to species.
In the cAse of preemergence trea~ment, the active ingredients ~uspended or emul~ified in water were applied directly after sowing, by means of nozzles providing a fine distribution. The vessel~ were lightly watered in order to promote germination and growth and then covered with transparent plastic covers un~il the plants had begun to grow. This covering ensures uniform germination of the ~est plant~, unles~ this i~ adversely affected by the active ingredients.
For the purpo~e of postemergence treatment, the test plant~ wers treated with the active ingredients suspended or emul~ified in water, bu~ only after reaching a height of growth of from 3 to 15 cm, depending on the growth form. The application rate for the postemergence treatment was 0.06 kg/ha of active substance.
The plants were kept at 10-25C or 20-35C, depending on the specie~. The te~t period extended over 2-4 weeks. During this time, the plants were tended and their reaction to the individual treatments ~as e~aluated.
Evaluation was based on a cale from 0 to 100.
100 means no emergence of the plant~ or complete destruc-tion of at lea~t the above-ground parts and 0 means no damage or normal growth.
The plants used in the greenhouse experiments consisted of the following 3pecies:
2~793 I - 25 - O.z. 0050/41598 Latin name _ Commen name Oryza sativa rice Echinochloa crus-galli barnyardgra~s Setaria italica foxtail millet When 0~06 kg/ha of active substance is used in the postemergence method, undesirable gramineous plants can be very readily controlled using Example 1.11, 1.03 and 1.05, with simultaneous toleration by the example crop rice.
, .
Claims (3)
1. A cyclohexenone oxime ether of the formula I
(I) where R1 is C1-C6-alkyl, X is halogen, n is from 1 to 5, R2 is C1-C4-alkoxy-C1-C6-alkyl or C1-C4-alkylthio-C1-C6-alkyl, C3-C7-cycloalkyl or C5-C7-cycloalkenyl, and these groups may additionally carry from one to three radicals selected from the group consisting of C1-C4-alkyl, C1-C4-alkoxy, C1-C4-alkylthio, C1-C4-haloalkyl, hydroxyl or halogen, a 5-membered saturated heterocyclic structure which contains one or two hetero atoms chosen from oxygen or sulfur and may additionally carry from one to three radicals selected from the group consisting of C1-C4-alkyl, C1-C4-alkoxy, C1-C4-alkylthio or C1-C4-haloalkyl, a 6-membered or 7-membered saturated or mono- or diunsaturated heterocyclic structure containing one or two hetero atoms selected from the group consisting of oxygen or sulfur, and the heterocyclic structure may additionally carry from one to three radicals selected from the group consisting of hydroxyl, halogen, C1-C4-alkyl, C1-C4-alkoxy, C1-C4-alkylthio or C1-C4-haloalkyl, a 5-membered heteroaromatic structure containing one to three hetero atoms selected from the group consisting of two nitrogen atoms or one oxygen or sulfur atom, and this ring may additionally carry from one to three radicals selected from the group consisting of halogen, cyano, C1-C4-alkyl, C1-C4-alkoxy, C1-C4-alkylthio, C1-C4-haloalkyl, C2-C6-alkenyl, C2-C6-alkenyloxy, C2-C6-haloalkenyl or - 27- O.Z. 0050/41598 Cl-C4-alkoxy-Cl-C4-alkyl, phenyl or pyridyl, and these groups may additionally carry from one to three radicals selected from the group consisting of halogen, nitro, cyano, C1-C1-alkyl, Cl-C4-alkoxy, Cl-C4-alkylthio, Cl-C4-haloalkyl, C3-C6-alkenyloxy, C3-C8-alkynyloxy or -NR3R4, where R3 is hydrogen, Cl-C4-alkyl, C3-C5-alkenyl or C3-C8-alkynyl and R4 is hydrogen, Cl-C4-alkyl, C3-C6-alkenyl, C3-C6-alkynyl, C1-C6-acyl or benzoyl, and the aromatic ring may addition-ally carry from one to three radicals selected from the group consisting of nitro, cyano, halogen, Cl-C4-alkyl, Cl-C4-alkoxy, C1-C4-alkylthio or C1-C4-haloalkyl, and its agriculturally usable salts and esters of Cl-C10-carboxylic acids and inorganic acids.
(I) where R1 is C1-C6-alkyl, X is halogen, n is from 1 to 5, R2 is C1-C4-alkoxy-C1-C6-alkyl or C1-C4-alkylthio-C1-C6-alkyl, C3-C7-cycloalkyl or C5-C7-cycloalkenyl, and these groups may additionally carry from one to three radicals selected from the group consisting of C1-C4-alkyl, C1-C4-alkoxy, C1-C4-alkylthio, C1-C4-haloalkyl, hydroxyl or halogen, a 5-membered saturated heterocyclic structure which contains one or two hetero atoms chosen from oxygen or sulfur and may additionally carry from one to three radicals selected from the group consisting of C1-C4-alkyl, C1-C4-alkoxy, C1-C4-alkylthio or C1-C4-haloalkyl, a 6-membered or 7-membered saturated or mono- or diunsaturated heterocyclic structure containing one or two hetero atoms selected from the group consisting of oxygen or sulfur, and the heterocyclic structure may additionally carry from one to three radicals selected from the group consisting of hydroxyl, halogen, C1-C4-alkyl, C1-C4-alkoxy, C1-C4-alkylthio or C1-C4-haloalkyl, a 5-membered heteroaromatic structure containing one to three hetero atoms selected from the group consisting of two nitrogen atoms or one oxygen or sulfur atom, and this ring may additionally carry from one to three radicals selected from the group consisting of halogen, cyano, C1-C4-alkyl, C1-C4-alkoxy, C1-C4-alkylthio, C1-C4-haloalkyl, C2-C6-alkenyl, C2-C6-alkenyloxy, C2-C6-haloalkenyl or - 27- O.Z. 0050/41598 Cl-C4-alkoxy-Cl-C4-alkyl, phenyl or pyridyl, and these groups may additionally carry from one to three radicals selected from the group consisting of halogen, nitro, cyano, C1-C1-alkyl, Cl-C4-alkoxy, Cl-C4-alkylthio, Cl-C4-haloalkyl, C3-C6-alkenyloxy, C3-C8-alkynyloxy or -NR3R4, where R3 is hydrogen, Cl-C4-alkyl, C3-C5-alkenyl or C3-C8-alkynyl and R4 is hydrogen, Cl-C4-alkyl, C3-C6-alkenyl, C3-C6-alkynyl, C1-C6-acyl or benzoyl, and the aromatic ring may addition-ally carry from one to three radicals selected from the group consisting of nitro, cyano, halogen, Cl-C4-alkyl, Cl-C4-alkoxy, C1-C4-alkylthio or C1-C4-haloalkyl, and its agriculturally usable salts and esters of Cl-C10-carboxylic acids and inorganic acids.
2. A herbicide containing a herbicidal amount of one or more compounds of the formula I as claimed in claim 1 and inert additives.
3. A method for controlling undesirable plant growth, wherein the undesirable plant or their habitat are or is treated with a herbicidal amount of a cyclo-hexenone derivative of the formula I as claimed in claim 1.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE4014988A DE4014988A1 (en) | 1990-05-09 | 1990-05-09 | CYCLOHEXENONE OXIMETHER, METHOD FOR THE PRODUCTION THEREOF, AND ITS USE AS HERBICIDE |
| DEP4014988.9 | 1990-05-09 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2041793A1 true CA2041793A1 (en) | 1991-11-10 |
Family
ID=6406110
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002041793A Abandoned CA2041793A1 (en) | 1990-05-09 | 1991-05-03 | Cyclohexenone oxime ethers, their preparation and their use as herbicides |
Country Status (12)
| Country | Link |
|---|---|
| EP (1) | EP0456089B1 (en) |
| JP (1) | JP3001661B2 (en) |
| KR (1) | KR0172959B1 (en) |
| AR (1) | AR247740A1 (en) |
| AT (1) | ATE136303T1 (en) |
| BR (1) | BR9101870A (en) |
| CA (1) | CA2041793A1 (en) |
| DE (2) | DE4014988A1 (en) |
| ES (1) | ES2085925T3 (en) |
| HU (1) | HU212627B (en) |
| RU (2) | RU2126790C1 (en) |
| ZA (1) | ZA913483B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8084649B2 (en) | 2007-03-09 | 2011-12-27 | Syngenta Crop Protection, Inc. | Herbicides |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE4135265A1 (en) * | 1991-10-25 | 1993-04-29 | Basf Ag | cyclohexenone |
| DE19510183A1 (en) * | 1994-03-31 | 1995-10-05 | Basf Ag | New imino:alkyl-aminomethyl-cyclohexenone derivs. |
| AU705642B2 (en) * | 1994-10-28 | 1999-05-27 | Commonwealth Scientific And Industrial Research Organisation | Bisallyloxyimides |
| AUPM910994A0 (en) * | 1994-10-28 | 1994-11-24 | Commonwealth Scientific And Industrial Research Organisation | Bisallyloxyimides |
| DE19545212A1 (en) * | 1995-12-05 | 1997-06-12 | Basf Ag | Cyclohexenone oxime ether metal salts |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3324707A1 (en) * | 1983-07-08 | 1985-01-17 | Basf Ag, 6700 Ludwigshafen | CYCLOHEXAN-1,3-DIONE DERIVATIVES, METHOD FOR THE PRODUCTION THEREOF AND THEIR USE FOR COMBATING UNWANTED PLANT GROWTH |
| AU566671B2 (en) * | 1983-07-18 | 1987-10-29 | Ici Australia Limited | Cyclohexene-1,3-dione derivatives |
| DE3762742D1 (en) * | 1986-04-24 | 1990-06-21 | Ciba Geigy Ag | ACYL-CYCLOHEXANDIONE AND THEIR OXIMAETHER WITH HERBICIDAL AND REGULATING EQUIPMENT REGULATING EFFECT. |
| DE3838309A1 (en) * | 1988-11-11 | 1990-05-31 | Basf Ag | CYCLOHEXENONE OXIMETHER, METHOD FOR THE PRODUCTION THEREOF, AND ITS USE AS HERBICIDE |
-
1990
- 1990-05-09 DE DE4014988A patent/DE4014988A1/en not_active Withdrawn
-
1991
- 1991-04-30 ES ES91106992T patent/ES2085925T3/en not_active Expired - Lifetime
- 1991-04-30 DE DE59107638T patent/DE59107638D1/en not_active Expired - Lifetime
- 1991-04-30 EP EP91106992A patent/EP0456089B1/en not_active Expired - Lifetime
- 1991-04-30 AT AT91106992T patent/ATE136303T1/en not_active IP Right Cessation
- 1991-05-03 CA CA002041793A patent/CA2041793A1/en not_active Abandoned
- 1991-05-08 RU RU93039127A patent/RU2126790C1/en active
- 1991-05-08 BR BR919101870A patent/BR9101870A/en not_active Application Discontinuation
- 1991-05-08 JP JP3102606A patent/JP3001661B2/en not_active Expired - Fee Related
- 1991-05-08 ZA ZA913483A patent/ZA913483B/en unknown
- 1991-05-08 AR AR91319635A patent/AR247740A1/en active
- 1991-05-08 RU SU914895321A patent/RU2049394C1/en active
- 1991-05-08 HU HU911546A patent/HU212627B/en not_active IP Right Cessation
- 1991-05-09 KR KR1019910007481A patent/KR0172959B1/en not_active IP Right Cessation
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8084649B2 (en) | 2007-03-09 | 2011-12-27 | Syngenta Crop Protection, Inc. | Herbicides |
Also Published As
| Publication number | Publication date |
|---|---|
| HU212627B (en) | 1996-09-30 |
| DE59107638D1 (en) | 1996-05-09 |
| HUT57003A (en) | 1991-11-28 |
| JPH04225942A (en) | 1992-08-14 |
| AR247740A1 (en) | 1995-03-31 |
| RU2126790C1 (en) | 1999-02-27 |
| RU2049394C1 (en) | 1995-12-10 |
| DE4014988A1 (en) | 1991-11-14 |
| ES2085925T3 (en) | 1996-06-16 |
| KR0172959B1 (en) | 1999-02-01 |
| ZA913483B (en) | 1993-01-27 |
| BR9101870A (en) | 1991-12-17 |
| KR910019995A (en) | 1991-12-19 |
| JP3001661B2 (en) | 2000-01-24 |
| EP0456089B1 (en) | 1996-04-03 |
| ATE136303T1 (en) | 1996-04-15 |
| EP0456089A1 (en) | 1991-11-13 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US4624696A (en) | Cyclohexenone derivatives and their use for controlling undesirable plant growth | |
| US5364833A (en) | Cyclohexenone oxime ethers, their preparation and their use as herbicides | |
| CA1230344A (en) | Cyclohexane-1,3-dione derivatives and their use for controlling undesirable plant growth | |
| US4596877A (en) | Herbicidal cyclohexanone substituted tetrahydro-thiopyran derivatives, compositions, and method of use therefor | |
| CA2041794A1 (en) | Cyclohexenone oxime ethers, their preparation, intermediates for their preparation and their use as herbicides | |
| CA2129121A1 (en) | Mixtures of optically active cyclohexenone oxime ethers, their preparation and intermediates therefor, and use thereof as herbicides | |
| CA1291139C (en) | Cyclohexane-1,3-dione derivatives, processes for their manufacture, and their use for controlling undesirable plant growth | |
| EP0716653B1 (en) | Substituted 1-amino-3-phenyluracils with herbicidal activities | |
| CA2041630A1 (en) | Cyclohexenone oxime ethers, their preparation, intermediates for their preparation and their use as herbicides | |
| CA2041793A1 (en) | Cyclohexenone oxime ethers, their preparation and their use as herbicides | |
| CS255000B2 (en) | Herbicide and method of its efficient substances production | |
| US4898610A (en) | Cyclohexane-1,3-dione derivatives and their use for controlling undesirable plant growth | |
| US5085689A (en) | Cyclohexenone compounds and their use as herbicides or plant growth regulators | |
| US4602935A (en) | Cyclohexane-1,3-dione derivatives and their use for controlling undesirable plant growth | |
| US4545806A (en) | 5-(Oxo or thio heterocycle) cyclohexane-1,3-dione derivatives and their use for controlling undesirable plant growth | |
| WO1993016033A1 (en) | Cyclohexenone oxime ethers, methods of preparing them and their use as herbicides | |
| US4650513A (en) | Cyclohexenones and their use for controlling undesirable plant growth | |
| US4842638A (en) | Herbicidal tetrahydro(thio)pyran-2,4-dione derivatives | |
| CA2127543A1 (en) | Cyclohexenone oxime ethers, their preparation, and use thereof as herbicides | |
| CA1251800A (en) | Cyclohexenone derivatives and their use for controlling undesirable plant growth | |
| US5604183A (en) | Cyclohexenone oxime ethers | |
| HU201299B (en) | Herbicides and compositions regulating the growth of plants containing derivatives of cyclohexonon and process for production of the active substances | |
| US4994106A (en) | Cyclohexenone compounds, their preparation and their use for controlling undesirable plant growth | |
| CA1157482A (en) | 5-aryl-cyclohexane-1,3-dione derivatives, herbicides containing these compounds, and the preparation of these compounds | |
| US5677263A (en) | S-tetrahydropyranone cyclohexenone oxime ethers and their use as herbicides |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| FZDE | Discontinued |