CA2051988A1 - Benzaldoxime ether derivatives - Google Patents

Benzaldoxime ether derivatives

Info

Publication number
CA2051988A1
CA2051988A1 CA002051988A CA2051988A CA2051988A1 CA 2051988 A1 CA2051988 A1 CA 2051988A1 CA 002051988 A CA002051988 A CA 002051988A CA 2051988 A CA2051988 A CA 2051988A CA 2051988 A1 CA2051988 A1 CA 2051988A1
Authority
CA
Canada
Prior art keywords
alkyl
methyl
carry
formula
alkoxy
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
Application number
CA002051988A
Other languages
French (fr)
Inventor
Joachim Rheinheimer
Matthias Gerber
Karl Eicken
Uwe J. Vogelbacher
Karl-Otto Westphalen
Helmut Walter
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
BASF SE
Original Assignee
Individual
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Individual filed Critical Individual
Publication of CA2051988A1 publication Critical patent/CA2051988A1/en
Abandoned legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D251/00—Heterocyclic compounds containing 1,3,5-triazine rings
    • C07D251/02—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings
    • C07D251/12—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
    • C07D251/26—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with only hetero atoms directly attached to ring carbon atoms
    • C07D251/30—Only oxygen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D403/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00
    • 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
    • A01N43/54—1,3-Diazines; Hydrogenated 1,3-diazines
    • 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
    • A01N43/64—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with three nitrogen atoms as the only ring hetero atoms
    • A01N43/66—1,3,5-Triazines, not hydrogenated and not substituted at the ring nitrogen atoms
    • 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
    • C07C251/34—Oximes with oxygen atoms of oxyimino groups bound to hydrogen atoms or to carbon atoms of unsubstituted hydrocarbon radicals
    • C07C251/48—Oximes with oxygen atoms of oxyimino groups bound to hydrogen atoms or to carbon atoms of unsubstituted hydrocarbon radicals with the carbon atom of at least one of the oxyimino groups bound to a carbon atom of a six-membered aromatic ring
    • 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
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D239/00—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings
    • C07D239/02—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings
    • C07D239/24—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members
    • C07D239/28—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, directly attached to ring carbon atoms
    • C07D239/46—Two or more oxygen, sulphur or nitrogen atoms
    • C07D239/52—Two oxygen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D239/00—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings
    • C07D239/02—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings
    • C07D239/24—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members
    • C07D239/28—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, directly attached to ring carbon atoms
    • C07D239/46—Two or more oxygen, sulphur or nitrogen atoms
    • C07D239/60—Three or more oxygen or sulfur atoms

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Agronomy & Crop Science (AREA)
  • Pest Control & Pesticides (AREA)
  • Plant Pathology (AREA)
  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Dentistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Zoology (AREA)
  • Environmental Sciences (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Plural Heterocyclic Compounds (AREA)

Abstract

O.Z. 0050/41919 ABSTRACT OF THE DISCLOSURE: Benzaldoxime ether derivatives of the formula I

I

(R1 is succiniminoxy; unsubstituted or substituted hetaryl; OR5, in which R5 is substituted or unsubstituted cycloalkyl, alkyl, alkenyl, alkynyl, phenyl or an oxime group; OR8, in which R8 is hydrogen, an alkali metal or alkaline earth metal cation, ammonium or organic ammonium;
R2, R3 are each C1-C4-alkyl, C1-C2-haloalkyl, C1-C4-alkoxy, C1-C2-halo-alkoxy, C1-C4-alkylamino, di-(C1-C4-alkyl)amino and/or C1-C4-alkylthio;
R4 is C1-C8-alkyl, C3-C6-alkenyl, C3-C6-haloalkenyl, unsubstituted or substituted benzyl;
X is oxygen or sulfur;
Z is nitrogen or a methine group), the manufacture of these substances, intermediates therefor, and the use of compounds I as herbicides and bioregulators.

Description

2 ~
O.z. 0050/41919 Benzaldoxime ether derivatives The present invention relates to benzaldoxime ether derivative~ of the formula I

~X (/ ~Z
R40N=CH CORl R 3 S where R1 is succini~idoxy;
a 5-membered heteroaromatic st,ructure which contains two or three nitrogen atoms and may carry one or two halogen atoms andtor one or two of the following radicals: C~-C4-al~yl, Cl-C4-haloalkyl, Cl-C4-alkoxy, C1-C4-haloalkoxy and/or C1-C4-alkylthio;
a radical -oR5 in which R5 is C3-C12-cycloalkyl which may carry from one to three Cl-C~-alkyl radicals;
Cl-C1O-alkyl which may carry from one to five halogen atom~ and/or one of the following radicals:
Cl-C~-alkoxy, Cl-C4-alkylthio, cyano, Cl-C~-alkylcarbonyl, C3-Cl2-cycloalkyl, C1-Ca-alkoxycarbonyl, phenyl, phenoxy or phenylcarbonyl, where the aromatic radicals in turn may carry from one to five halogen atoms and/or from one to three of the following radîcals:
C1-C4-alkyl, C1-C4-haloalkyl, C1-C4-alkoxy, C1-C~-haloalkoxy and/or Cl-C4-alkylthio;
C2-C~-alkyl which carries one of the following radicals in the 2-position:
Cl-C6alkoximino, C3-C6-alkenyloximino, C3-C6haloalkenyloximino or benzyloximino;
C3-C9-alkenyl or C3-C6-alkynyl, where ~hese groups in turn may carry from one to five halogen atoms;

~3~ X
- 2 - O.Z. 0050/41919 phenyl which i~ unsubstituted or monosub-stituted to tri~ubstituted by Cl-C4-alkyl or Cl-C4-alkoxy or monosu~stituted to pentasubstituted by halogen; or -N=CR~R7, in which R6 and R7 are each Cl-C20-alkyl which may carry phenyl, Cl-C4-alkoxy and/or Cl-C4-alkylthio, or are each phenyl or together form a C3-Cl2-alkylene chain which may carry from one to three Cl-C3-alkyl groups;
of a radical -OR~, in which Ra i3 hydrogen, an alkali metal cation, one equivalent of an alkaline earth metal cation, ammonium or an organic ammonium .
ion;
R2 and R3 are each Cl C4-alkyl, Cl- or C~-haloalkyl, Cl C4-alkoxy, Cl- or C2-haloalkoxy, Cl-C4-alkylamino, di-(C1-C4-alkyl)-amino and/or C1-C4-alkylthio;
R4 i8 C1-C3-alkyl, C3-C~-alkenyl, C3-C6-haloalkenyl or benzyl which may carry from one to three of the following substituents in the phenyl ring: JC1-C3-alkyl, halogen or Cl-C~-alkoxy;
X is oxygon or sulfur; and Z i8 nitrogen or a methine group =CH-~
Tha pre~ent invention furthermore relate~ to processes for the preparation of these compound~, their use a~ herbicide~ and growth regulator~ and compounds of the formula IV

~XRl 1 IV
R 40N=CH COR 1 as intermediate~ for the preparation of the compound~ I
in which Rl1 i~ hydrogen, acetyl or methyl.
The literature (EP-A 223 406, EP-A 287 072, EP-A
287 079, EP-A 249 708 and EP-A 360 163) describes herbi-cidal aromatic carboxylic acid darivative~. However, 2 ~ 8 ~
_ 3 _ o.z. 0050/41919 they do not contain oxime ether groups and their herbi-cidal action i5 unsati~factory.
It is an ob~ect of the present invention to provide further, particularly active compounds having improved herbicidal properties combined with plant growth-regulating properties.
We have found that this ob~ect is achieved by the compounds I defined at the outset.
We have also found processes for the preparation of the compounds I, intermediates of the formula IV, herbicides containing the co~pound I, methods for con-trolling undesirable plant growth, the use of the com-pounds I as the herbicides, agents for influencing plant growth and methods for regulating plant growth.
In view of the intended use of the benzaldoxime ether derivatives I as herbicides and growth regulators, the following radicals are preferred substituents:
R1 is succinimidoxy;
5-membered hetaryl, such as pyrrolyl, pyrazolyl, imLdazolyl or triazolyl, in particular imidazolyl or pyrazolyl, where the aromatic radical i~ bonded via nitrogen and may in turn carry one or two halogen atoms, in particular fluorine or chlorine, and/or one or two of the following radicals:
C1-C~-alkyl, such as methyl, ethyl, propyl, l-methyl-ethyl, butyl, 1-methylpropyl, 2-methylpropyl and 1,l-dimethylethyl, preferably methyl, ethyl or 1-methylethyl;
C1-C~-haloalkyl, preferably C1- or C2-haloalkyl, such a~ fluoromethyl, difluoromethyl, trifluoromethyl, chlorodifluoromethyl, dichlorofluoromethyl, tri-chloromethyl, l-fluoroethyl, 2-fluoroethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, 2-chloro-2,2-difluoroethyl, 2,2-dichloro-2-fluoroethyl, 2,2,2-trichloroethyl or pentafluoroethyl, in par~icular difluoromethyl, trifluoromethyl, 2,2,2-trifluoro-ethyl or pentafluoroethyl;

:;:

~/ ~ r~ g ~
- 4 - O.Z. 0050/41919 Cl-C4-alkoxy, such as methoxy, ethoxy, propoxy, 1-methylethoxy or butoxy;
Cl-C4-haloalkoxy, in particular Cl- or C2-haloalkoxy, such as difluoromethoxy, trifluoromethoxy, chlorodi-fluoromethoxy, dichlorofluoromethoxy, l-fluoro-ethoxy, 2-fluoroethoxy, 2,2-difluoroethoxy, 1,1,2 r 2 -t etrafluoroethoxy, 2,2,2-trifluoroethoxy, 2-chloro-1,1,2-trifluoroethoxy or pentafluoroethoxy, in particular trifluoromethoxy, and/or C1-C4-alkylthio, such as methylthio, ethylthio, propylthio, 1-methylethylthio, butylthio, 1-methyl-propylthio, 2-methylpropylthio or 1,1-dimethylethyl-thio, in particular methylthio or ethylthio;
a radical -oR5, in which R5 is preferably C3-C5-cycloalkyl, such as cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl, which may carry ~rom one to three C1-C4-alkyl radical~, in particular methyl or ethyl;
Cl-C1O-alkyl, ~uch as methl, ethyl, propyl, 1-methyl-ethyl, butyl, l-methylpropyl, 2-methylpropyl, 1,1-dimethylethyl, n-pentyl, l-methylbutyl, 2-methyl-butyl, 3-methylbutyl, 1,2-dimethylpropyl, 1,1-dimethylpropyl, 2,2-dimet ffllpropyl, 1-ethylpropyl, n-hexyl, 1-methylpentyl, 2-methylpentyl, 3-methyl-pentyl, 4-methylpentyl, 1,2-dimethylbutyl, 1,3-dimethylbutyl,2,3-dimethylbutyl,1,1-dimethylbutyl, 2,2-dimethylbutyl, 3,3-dimethylbutyl, 1,1,2~
trimethylpropyl, 1,2,2-trimethylpropyl, 1-ethylbutyl, 2-ethylbutyl, 1-ethyl 2-methylpropyl, n-heptyl, 1-methylhexyl, 2-methylhexyl, 3-methylhexyl, 4-methylhexyl, 5-methylhexyl, 1-ethylpentyl, 2-ethylpentyl, 1-propylbutyl, octyl, nonyl or decyl, preferably C1-C~-alkyl, such as methyl, ethyl, propyl, 1-methylethyl, butyl, 1-methylpropyl, 2-methylpropyl, 1,1-dimethylethyl, pentyl, 1-methyl-butyl, 2-methylbutyl, 3-methylbutyl, 2,2-dimethyl-propyl, 1-ethylpropyl, hexyl, 1,1-dimethylpropyl, a.~
- 5 - O.z. 0050/41919 1,2-dimethylpropyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1,1-dimethylbutyl, 1,2-dimethylbutyl, 1,3-dimethylbutyl, 2,2-dLmethyl-butyl, 2,3-dLmethylbutyl, 3,3-dLmethylbutyl, l-S ethyl~utyl, 2-ethylbutyl, 1,1,2-trLmethylpropyl, 1,2,2 trimethylpropyl, l-ethyl-l-methylpropyl or 1-ethyl-2-methylpropyl, which in the case of Cl may carry from one to three halogen atoms and in the case o~ C2-C10 may carry from one to five halogen atoms, in particular fluorine or chlorine, and/or one of the following radicals:
Cl-C4-alkoxy, in particular methoxy, ethoxy or 1-methylethoxy;
C1-C4-alkylthio, in particular methylthio or ethylthio;
cyano;
C1-CB-alkylcarbonyl, ~uch as methylcarbonyl, ethylcarbonyl, propylcarbonyl, l-methylethyl-carbonyl, butylcarbonyl, 1-methylpropylcarbonyl, 2-methylpropylcarbonyl, 1,1-dimethylethyl-carbonyl, pentylcarbonyl, 1-methylbutylcarbonyl, 2-methylbutylcarbonyl, 3-methylbutylcarbonyl, 1,1-dimethylpropylcarbonyl, 1,2-dimethylpropyl-carbonyl, 2,2-dimethylpropylcarbonyl, 1-ethyl-propylcarbonyl, hexylcarbonyl, 1-methylpentyl-carbonyl,2-methylpentylcarbonyl,3-methylpentyl-carbonyl, 4-methylpentylcarbonyl, 1,1-dimethyl-butylcarbonyl, 1,2-dimethylbutylcarbonyl, 1,3-dimethylbutylcarbonyl, 2,2-dimethylbutylcarbonyl~
2,3-dimethylbutylcarbonyl, 3,3-dimethylbutyl-carbonyl, 1-ethylbutylcarbonyl, 2-ethylbutyl-carbonyl, 1/1,2-trimethylpropylcarbonyl, 1,2,2-trLmethylpropylcarbonyl, 1-ethyl-1-methylpropyl-carbonyl or 1-ethyl-2-methylpropylcarbonyl;
C3-C8-cycloalkyl, such as cyclopropyl, cyclopentyl or cyclohexyl;
Cl-C~-alkoxycarbonyl, such as methoxycarbonyl, 2~5~
- 6 - O.Z. 0050/41919 ethoxycarbonyl, propoxycarbonyl, 1-methylethoxy-carbonyl, butoxycarbonyl, 1-methylpropoxy-carbonyl, 2-methylpropoxycarbonyl, l,l-dimethyl-ethoxycarbonyl, n-pentyloxycarbonyl, 1-methyl-butoxycarbonyl,2-methylbutoxycarbonyl,3-methyl-butoxycarbonyl,l,2-dimethylpropoxycarbonyl,1,1-dimethylpropoxycarbonyl, 2,2-dimethylpropoxy-carbonyl, l-ethylpropoxycarbonyl, n-hexyloxy-carbonyl, l-methylpentyloxycarbonyl, 2-methyl-pentyloxycarbonyl, 3-methylpentyloxycarbonyl, 4-methylpentyloxycarbonyl, 1,2-dimethylbutoxy-carbonyl, 1,3-dimethylbutoxycarbonyl, 2,3-di-methylbutoxycarbonyl, l,l-dimethylbutoxycarbonyl, 2,2-dimethylbutoxycarbonyl, 3,3-dimethylbutoxy-carbonyl, 1,1,2-trimethylpropoxycarbonyl, 1,2,2-trimethylpropoxycarbonyl, l-ethylbutoxycarbonyl, 2-ethylbutoxycarbonyl, 1-ethyl-2-meth~lpropoxy-carbonyl, n-heptyloxycarbonyl, l-methylhexyloxy-carbonyl, 2-methylhexyloxycarbonyl, 3-methyl-hexyloxycarbonyl, 4-methylhexyloxycarbonyl, 5-methylhexyloxycarbonyl, l-ethylpentyloxycarbonyl, 2-ethylpentyloxycarbonyl, l-propylbutoxycarbonyl or octyloxycarbonyl, in particular Cl-C4-alkoxy-carbonyl, ~uch as methoxycarbonyl, ethoxy-carbonyl,propoxycarbonyl,l-methylethoxycarbonyl or l-methylpropoxycarbonyl;
phenyl, phenoxy, phenylcarbonyl, 2-, 3- or 4-fluorophenyl, 2-, 3- or 4-chlorophenyl, 2-, 3- or 4-methylphenyl, 2-, 3- or 4-methylphenoxy, 2-, 3-or 4-methylphenylcarbonyl, 2-, 3- or 4-tri-fluoromethylphenyl, 2-, 3- or 4-trifluoromethyl-phenoxy, 2-, 3- or 4-trifluoromethylphenyl-carbonyl, 2-, 3- or 4-methoxyphenyl, 2-, 3~ or 4-methoxyphenoxy or 2-, 3- or 4-methylthiophenyl;
C2-C6-alkyl, in particular C2-C4-alkyl, which i~
sub~tituted in the 2-position by C1-C~-alkoximino, in particular C~-C~-alkoximino, ~uch a~ methoximino, â~
- 7 - O.Z. 0(:)50/41919 ethoxi~nino, propoximino or butoximino; C3-C6-alkenyl-oximino, preferably C3- or C4-alkenyloximino, such as 2-propenyloximino, 2-butenyloximino or 3-butenyl-oximino; C3-C6-haloalkenyloximino, in particular C3-haloalkenyloximino, such as 3,3-dichloro-2-propenyl-oximino or 2,3,3-trichloro-2-propenyloximino, or benzyloximino;
C3-C6-alkenyl, such as 2-propenyl, 2-butenyl, 3-butenyl, l-methyl-2-propenyl, 2-methyl-2-propenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, 1-methyl-2-butenyl, 2-methyl-2-butenyl, 3-methyl-2-butenyl, 1-methyl-3-butenyl, 2-methyl-3-butenyl, 3-methyl-3-butenyl, 1,1-dimethyl-2-propenyl, 1,2-dimethyl-2 propenyl, 1-ethyl-2-propenyl, 2-hexenyl, 3-hexenyl, 4-hexenyl, 5-hexenyl, 1-methyl-2-pentenyl, 2-methyl-2-pentenyl, 3-methyl-2-pentenyl, 4-methyl-2-penten-yl, 1-methyl-3-pentenyl, 2-methyl-3-pentenyl, 3-methyl-3-pentenyl, 4-methyl-3-pentenyl, 1-methyl-4-pentenyl, 2-methyl-4-pentenyl, 3-methyl-4-pentenyl, 4-methyl-4-pentenyl, 1,1-dimethyl-2-butenyl,1,1-dimethyl-3-butenyl, 1,2-dimethyl-2-butenyl,1,2-dimethyl-3-butenyl, 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, 1-ethyl-3-butenyl, 2-ethyl-2-butenyl, 2-ethyl-3-butenyl, 1,1,2-trimethyl-2-propenyl, l-ethyl-1-methyl-2-propenyl or 1-ethyl-2-methyl-2-propenyl, in particular C3-C4-alkenyl, quch a~ 2-propenyl, 2-butenyl, 1-methyl-2-propenyl, 2-methyl-2-propenyl, and 3-methyl-2-butenyl and 3-methyl-2-pentenyl;
C3-C3-alkynyl, such as 2-propynyl, 2-butynyl, 3-butynyl, 1-methyl-2-propynyl, l-pentynyl, 2-pentyn-yl, 3-pentynyl, 4-pentynyl, 1-methyl-2-~utynyl, 1-methyl-3-butynyl, 2-methyl-3-butynyl, 3-methyl-1-butynyl, 1,1-dimethyl-2-propynyl, 1-ethyl-2-propynyl, l-hexynyl, 2--hexynyl, 3-hexynyl, 4-~rj ~ ~ hJ3 - 8 - O. Z . 0050/41919 hexynyl, 5-hexynyl, 1-methyl-2-pentynyl, l-methyl-3-pentynyl, 1-methyl-4-pentynyl, 2-methyl-3-pentynyl, 2-methyl-4-pentynyl, 3-methyl-1-pentynyl, 3-methyl-4-pentynyl, 4-methyl-1-pentynyl, 4-methyl-2-pentynyl, 1,1-dimethyl-2-butynyl, 1,1-dimethyl-3-butynyl, 1,2-dimethyl-3-butynyl, 2,2-dimethyl-3-butynyl, 3,3-dimethyl-1-butynyl, 1-ethyl-2-butynyl, l-ethyl-3-butynyl, 2-ethyl-3-butynyl and 1-ethyl-1-methyl-2-propynyl, in particular C3- or C4-alkynyl, such as 2-propynyl, 2-butynyl or 3-butynyl, where 2-propynyl may carry from one to three halogen atoms and the alkenyl and remaining alkynyl groups may carry from one to five halogen atoms, in particular fluorine or chlorine;
phenyl which is unsubstituted or monosubstituted to tri~ubstituted by Cl-C4-alkyl, such a~ methyl, ethyl, propyl or butyl or by Cl-C4-alkoxy, such as methoxy, ethoxy, propoxy or butoxy, or monosubstituted to pentasubstituted by halogen, in particular fluorine or chlorine;
-N=CR8R7, where RB and R7 are each C1-C20-alkyl, preferably C1-C~5-alkyl, in particular C1-C10-alkyl as stated above, which may carry a phenyl radical, Cl-C~-alkoxy as ~tated above and/or C1-C4-alkylthio aR ~tated above, or are each phenyl, or together form C3-Cl2-alkylene, preferably C4-C,-alkylene, which may carry from one to three C1-C3-alkyl groups, preferably methyl or ethyl;
a radical -ORa, where R8 is hydrogen, a cation of an alkali metal, such as sodium or potassium, a cation of an alkaline earth metal, such as magnesium or calcium, ammonium or an organic ammonium ion, ~uch a~ tri-Cl-C4-alkyl-ammonium, preferably triethylammonium or tributyl-ammonium, - 9 - O.Z. 0050/41919 R2 and R3 are each C1-C4-alkyl, ~uch as methyl, ethyl, propyl, 1-methylethyl, butyl, 1-methylpropyl, 2-methylpropyl or 1,1-dimethylethyl;
C1- or C2-haloalkyl, such a~ chloromethyl, dichloro-methyl, trichloromethyl, chlorofluoromethyl, fluoro-methyl, difluoromethyl, trifluoromethyl, dichloro-fluoromethyl, chlorodifluorome~hyl, 1-fluoroethyl, 2-fluoroethyl, 2,2-difluoroethyl, 2,2,2-trifluoro-ethyl, 2-chloro-2-fluoroethyl, 2-chloro-2,2-di-fluoroethyl, 2,2-dichloro-2-fluoroethyl, 2,2,2-trichloroethyl or pentafluoroethyl, in particular trifluoromethyl;
Cl-C4-alkoxy, such as methoxy, ethoxy, propoxy, 1-methylethoxy, butoxy, l-methylpropoxy, 2-methyl-propoxy or 1,1-dimethylethoxy;
C1- or C2-haloalkoxy, s~ch a~ chloromethoxy, dichloromethoxy, trichloromethoxy, fluoromethoxy, difluoromethoxy, trifluoromethoxy, chlorofluoromethoxy, dichlorofluoromethoxy, chlorodifluoromethoxy, 1-fluoroethoxy, 2-fluoroethoxy, 2,2-difluoroethoxy, 2,2,2-trichloroethoxy, 2-chloro-2-fluoroethoxy, 2-chloro-2,2-difluoroethoxy, 2,2-dichloro-2-fluoroethoxy, 2,2,2-trichloroethoxy or pentafluoroethoxy, in ~5 particular trifluoromethoxy;
C1-C4-alkylamino, ~uch a~ methylamino, ethylamino, propylamino, 1-methylethylamino, butylamino, 1-methylpropylamino, 2-methylpropylamino or 1,1-dimethylethylamino;
di-(Cl-C4-alkyl)-amino, such as N,N-dimethylamino, N,N-diethylamino, N,N-dipropylamino, N,N-di-(1-methylethyl)-amino, N,N-dibutylamino, N,N-di-(1-methylpropyl)-amino, N,N-di-(2-methylpropyl)-amino, N,N-di-(1,1-dimethylethyl)-amino, N-ethyl-N-methylamino, N-methyl-N-propylamino, N-methyl-N-(1-methylethyl)-amino,N-butyl-N-methylamino,N-methyl-N-(1-methylpropyl)-amino, N-methyl-N-8 ~
- 10 - O.Z. 0050/41919 (2-methylpropyl)-amino, N-(1,l-dimethylethyl)-N-methylamino, N-ethyl-N-propylamino, N-ethyl-N-(1-methylethyl)-amino, N-butyl-N-ethylamino, N-ethyl-N-(1-methylpropyl)-amino, N-ethyl-N-(2-methyl-propyl)-amino, N-ethyl-N-(1,l-dLmethylethyl)-amino, N-(l-methylethyl)-N-propylamino, N-butyl-N-propyl-amino, N-(l-methylpropyl)-N-propylamino, N-(2-methypropyl-N-propylamino, N-~1,1-dLmethylethyl)-N-propylamino, N-butyl-N-(1-methylethyl)-amino, N-(l-methylethyl)-N-(1-methylpropyl)-amino, N-(1-methylethyl)-N-(2-methylpropyl)-amino, N-(l,1-dimethylethyl)-N-(l-methylethyl)-amino, N-butyl-N-(1-methylpropyl)-amino, N-butyl-N-(2-methylpropyl)-amino, N-butyl-N-(1,1-dimethylethyl)-amino, N-(l-methylpropyl)-N-(2-methylpropyl)-amino, N-(1,1-dimethylethyl)-N-(1-methylpropyl)-amino or N-(l,l-dimethylethyl)-N-(2-methypropyl)-amino, in particular di-(C~- or C2-alkyl)-amino, such as N,N-dimethylamino, N,N-diethylamino or N-methyl-N-ethylamino;
Cl-C4-alkylthio, such a~ methylthio, ethylthio, propylthio, 1-methylethylthio, butylthio, l-methyl-propylthio, 2-methylpropylthio or 1,1-dimethylethyl-thio;
R4 i~ Cl-C~-alkyl, such as methyl, ethyl, propyl, 1-methylethyl, butyl, 1-methylpropyl, 2-methylpropyl, 1,1-dimethylethyl, n-pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 1,2-dimethylpropyl, 1,1-dimethylpropyl, 2,2-dimethylpropyl, 1-ethylpropyl, n hexyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1,2-dimethylbutyl, 1,3-dimethylbutyl, 2,3-dimet:hylbutyl, 1,1-dimethylbutyl,2,2-dimethylbutyl,3,3-dim0thylbutyl, 1,1,2-trimethylpropyl, 1,2,2-trimethylpropyl, 1-ethylbutyl, 2-ethylbutyl, 1-ethyl-2-methylpropyl, n-heptyl, 1-methylhexyl, 2-methylhexyl, 3-methyl-hexyl, 4-methylhexyl, 5-methylhexyl, 1-ethylpentyl, ' ' ' ', , , .

- 11 - O.Z. 0050/41919 2-ethylpentyl, l-propylbutyl or octyl, in particular Cl-C4-alkyl, such as methyl, ethyl, propyl, 1-methyl-ethyl, butyl, l-methylpropyl, 2-methylpropyl or 1,1-dimethylethyl;
C3-C~-alkenyl, such as 2-propenyl, 2-butenyl, 3-b~tenyl, 1-methyl-2-propenyl, 2-methyl-2-propenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, 1-methyl-2-butenyl, 2-methyl-2-butenyl, 3-methyl-2-butenyl, 1-methyl-4-butenyl, 2-methyl-3-butenyl, 3-methyl-3-butenyl, 1,l-dimethyl-2-propenyl, 1,2-dLmethyl-2-propenyl, l-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, l-methyl-3-pentenyl, 2-methyl-3-pentenyl, 3-methyl-3-pentenyl, 4-methyl-3-pentenyl, 1-methyl-4-pentenyl, 2-methyl-4-pentenyl, 3-methyl-4-pentenyl, 4-methyl-4-pentenyl, 1,1-dimethyl-2-butenyl, 1,1-dimethyl-3-butenyl, 1,2-dLmethyl-2-butenyl, 1,2-dimethyl-3-butenyl, 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, l-ethyl-2-butenyl, 1-ethyl-3-butenyl, 2-ethyl-2-butenyl,2-ethyl-3-butenyl,1,1,2-trimethyl-2-propenyl, 1-ethyl-1-methyl-2-propenyl and l-ethyl-2-methyl-2-propenyl, in particular C3- or C4-alkenyl, such as 2-propenyl, 2-butenyl, 3~butenyl, 1-methyl-propenyl or 2-methyl-2-propenyl;
C3-C6-haloalkenyl, such a~ 2-chloroallyl or E- or Z-3-chloroallyl;
benzyl which i9 unsub~tituted or monosub~tituted to trisub~tituted in the phenyl ring by Cl-C3-alkyl, halogen or C1-C4-alkoxy, such as 2-, 3- or 4-methyl-benzyl, 2-, 3- or 4-fluorobenzyl, 2-, 3- or 4-chlorobenzyl or 2-, 3- or 4-methoxybenzyl;
35 X is preferably oxygen or sulfur; and Z is preferably nitrogen or the methine group =CH-.
Owing to the C=N double bond, the 3tarting r~
~ 12 ~ O.Z. 0050~41919 compounds II may be present as E/Z isomer mixtures or as pure E or 2 isomer~, so that the corresponding compounds I are obtained either as EfZ isomer mixtures or as E or Z isomers. The present invention relates both to the individual isomeric compounds and to mixtures thereof.
The compounds I are obtained, for example, by reacting an aromatic carboxylic acid derivative II with a compound III in the presence of a base in a convention-al manner.

~X H N~
)~< + R 9--</ \Z ~ I
R40N=CH CORI N--~R3 II III
R9 is a nucelofugic leaving group, for example halogen, such as chlorine, bromine or iodine, aryl- or alkyl-sulfonyl, such as toluenesulfonyl or methylsulfonyl or another equivalent leaving group.
The compounds II are obtained in general by known methods, such as ether or ester cleavage (where R11~H), from the compounds IV, which are obtainable from the corresponding known aldehydes:

~XRII ~ R40NHz ~)~R
CHO COR 1 R 40N=CH COR 1 IV
Compounds of the formula III having a reactive sub-stituent R3 are known or are readily obtainable by known methods.
Suitable bases are alkali metal or alkaline earth metal hydride~, such as NaH or CaH2, alkali metal hydrox-ides, such as NaOH or KOH, alkali metal alcoholate~, such as potassium tert-butylate, alkali metal carbonates, such as NazCO3 or K2C03, alkali metal amides, such as NaNH2 or lithium diisopropylamide, or tertiary amines, such as triethylamine. When an inorganic base is used, a phase transfer cataly~t, such as an organic ammonium salt or a 2~3 - 13 - O.Z. 0050/41919 crown ether, may be added, with the result that the reaction is frequently accelerated.
If the compounds I are the carboxylic acids I' (R8 = H), the other compounds according to the definition can also be prepared therefrom, for example, by first converting the carboxylic acid I' in a conventional manner into an activated form, such as a halide, prefer-ably the acyl chloride, or imidazolide, and then reacting the latter with an alcohol R50H, such a~ ethanol, propar-gyl alcohol or allyl alcohol, a di- or triazole, such as imidazole or 1,2,4-triazole, or N-hydroxysuccinLmide.
These two steps can also be simplified, for example, by allowing the carboxylic acid to act on the hydroxy compound in the presence of a water-eliminating agent, such as a carbodiimide or a phosphonic anhydride.
Furthermore, the carboxylic acids I' can first be converted in a conventional manner into a salt, preferably an alkali metal salt, and the latter then reacted with a compound R10-R5 to give the compounds I.
In this reaction, the bases used in the reaction of the compound~ II and III may likewise be employed. In the compound R10-R5 used, R10 is a nucleofugic leaving group, such as chlorine, bromine, iodine or aryl- or alkyl3ulfonyl, such as toluenesulfonyl or methylsulfonyl, and R5 is one of the radicals stated under R5, with the exception of unsubstituted and substituted phenyl and -N-CR~R7.
~ he compounds R10-R5 used are known or can be prepared by known methods.

2~

14 O.z. 0050/41919 The herbicidal and growth-regulating compounds I, or agents containing them, may be applied for instance in the form of directly sprayable solu-tions, powders, suspensions (including high-percentage aqueous, oily or other suspensions), dispersions, emulsions, oil dispersions, pastes, 5 dusts, broadcasting agents, or granules by spraying, atomizing, dusting, broadcasting or watering. ~he forms of application depend entirely on the purpose for which the agents are being used, but they must ensure as fine a distribution of the active ingredients according to the invention as possible.
For the preparation of solutions, emulsions, pastes and oil dispersions to be sprayed direct, mineral oil fractions of medium to high boiling point, such as kerosene or diesel oil, further coal-tar oils, and oils of vege-table or animal origin, aliphatic, cyclic and aromatic hydrocarbons such 15 as toluene, xylene, paraffin, tetrahydronaphthalene, alkylated naphtha-lenes and their derivatives, methanol, ethanol, propanol, butanol, cyclo-hexanol, cyclohexanone, chlorobenzene, isophorone, etc., 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, oil dispersions, wettable powders or water-dispersible granules by adding water. To prepare emulsions, pastes and oil dispersions the ingredients as such or dissotved in an oil or solvent may be homogenized in water by 25 means of wetting or dispersing agents, adherents or emulsifiers. Concen-trates which are suitable for dilution with water may be prepared from active ingredient, wetting agent, adherent, emulsifying or dispersing agent and possibly solvent or oil.
30 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-sulfonic acid, and of fatty acids, alkyl and alkylaryl sulfonates, and alkyl, lauryl ether and fatty alcohol sulfates, and salts of sulfated 35 hexadecanols, heptadecanols, and octadecanols, salts of fatty alcohol glycol ethers, condensation products of sulfonated naphthalene and naphthalene derivatives with formaldehyde, condensation products of naphthalene or naphthalenesulfonic acids with phenol and formaldehyde, ' polyoxyethylene octylphenol ethers, ethoxylated isooctylphenol, ethoxyl-40 ated octylphenol and ethoxylated nonylphenol, alkylphenol polyglycol ethers, tributylphenyl polyglycol ethers, alkylaryl polyether alcohols, isotridecyl alcohol, fatty alcohol ethylene oxide condensates, ethoxylated castor oil, polyoxyethylene alkyl ethers, ethoxylated polyoxypropylene, lauryl alcohol polyglycol ether acetal, sorbitol esters, lignin-sulfite waste liquors and methyl cellulose.
''' , i ., .

O.Z. 0050/41919 Powders, dusts and broadcasting agents may be prepared by mixing or grinding th~ active ingredients with a solid carrier.
Granules, e.g., coated, impregnated or homogeneous granules, may be 5 prepared by bonding the active ingredients to solid carriers. Examples of solid carriers are mineral earths such as silicic acids, 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 10 sulfate, ammonium phosphate, ammonium nitrate, and ureas, and vegetable products such as grain meals, bark meal, wood meal, and nutshell meal, cellulosic powders, etc.
The formulations contain from 0.1 to 95, and preferably 0.5 to 90, % by15 weight of active ingredient. The active ingredients are used in a purity of 90 to 100, and preferably 95 to 100, % (according to the NMR spectrum).
formulations may be prepared for example as follows:
20 I. 90 parts by weight of compound no. 1 is mixed with 10 parts by weight of N-methyl-alpha-pyrrolidone. A mixture is obtained which is suitable for application in the form of very fine drops.
II. 20 parts by weight of compound no. 2 is dissolved in a mixture 25 consisting of 80 parts by weight of xylene, 10 parts by weight of the adduct of 8 to 10 moles of ethylene oxide and 1 mol0 of oleic acid-N-monoethanolamide, 5 parts by weight of the calcium salt of dodecylbenzene-sulfonic acid, and 5 parts by weight of the adduct of 40 moles of ethylene oxide and 1 mole of castor oil. By finely distributing the solution in 30 water, a dispersion iS obtained.
III. 20 parts by weight of compound no. 9 is dissolved in a mixture consisting of 40 parts by weight of cyclohexanone, 30 parts by weight of isobutanol, 20 parts by weight of the adduct of 7 moles of ethylene oxide 35 and 1 mole of isooctylphenol, and 10 parts by weight of the adduct of 40 moles of ethylene oxide and 1 mole of castor oil.
IV. 20 parts by weight of compound no. 10 is dissolved in a mixture consisting of 25 parts by weight of cyclohexanone, 65 parts by weight of a 40 mineral oil fraction having a boiling point between 210 and 280~C, and 10 parts by weight of the adduct of 40 moles of ethylene oxide and 1 mole of castor oil.

16 o.z. 0050/41919 V. 20 parts by weight of compound no. 17 is well mixed with 3 parts by weight of the sodium salt of diisobutylnaphthalene-alpha-sulfonic acid, 17 parts by weight of the sodium salt of a lignin-sulfonic acid obtained from a sulfite waste liquor, and 60 parts by weight of powdered silica 5 gel, and triturated in a hammer mill. By uniformly distributing the mixture in 20,000 parts by weight of water, a spray liquor is obtained containing 0.1% by weight of the active ingredient.
VI. 3 parts by weight of compound no. 23 is intimately mixed with 10 97 parts by weight of particulate kaolin. A dust is obtained containing 3%
by weight of the active ingredient.
VII. 30 parts by weight of compound no. 1 is intimately mixed with a mixture consisting of 92 parts by weight of powdered silica gel and 15 8 parts by weight of paraffin oil which has been sprayed onto the surface of this silica gel. A formulation of the active ingredient is obtained having good adherence.
VIII. 20 parts by weight of compound no. 2 is intimately mixed with 20 2 parts of the calcium salt of dodecylbenzenesulfonic acid, 8 parts of a fatty alcohol polyglycol ether, 2 parts of the sodium salt of a phenol-sulfonic acid-urea-formaldehyde condensate and 68 parts of a paraffinic minerat oil. A stable oily dispersion is obtained.
25 The active ingredients or the herbicidal and growth-regulating agents conta~ning them may be applied pre- or postemergence. If certain crop plants 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 p1ants are if 30 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 of herbicidal active ingredient depend on the ob-jective to be achieved, the time of the year, the plants to be combated 35 and their growth stage, and are from 0.001 to 3, preferably 0.005 to 2, kg of active ingredient per hectare.
The growth-regulating carboxylic acid derivatives of the formula I may exercise a variety of influences on practically all plant development 40 stages, and are therefore used as growth regulators. The diversity of action of growth regulators depends especially on a) the type and variety of plant;
b) the time applied, with reference to the development stage of the plants and the time of the year;

8 ~

17 O.Z. 0050/41919 c) the place and method of application (seed treatment, soil treatment, application to foliage, or trunk injection in the case of trees);
d) climatic factors, e.g., average temperature, amount of precipitate, day length and light intensity~;
5 e) soil conditions (including fertili~ation~;
f) the formulation of the active ingredient; and g) the concentration at which the active ingredient is applied.
A description of some of the various possibilities of using the growth 10 regulators according to the invention in agriculture and horticulture is given below.
A. Vegetative plant growth can be inhibited to a considerable extent, a fact which is manifested particularly in a reduction in plant height.
The treated plants thus have a compact habit; furthermore, the leaf color is darker.
Of advantage in practice is for example the reduction in grass growth on roadsides, hedges, canal embankments and on areas such as parks, sportsgrounds, fruit orchards, lawns and airfields, thuS reducing expensive and time-consuming mowing.
A further feature of economic interest is the increase in the rigor of crops which tend to lodge, such as cereals, Indian corn, sunflowers and soybeans. The shortening and strengthening of the stem thus caused reduces or eliminates the danger of lodging under unfavorable weather conditions.
The use of growth regulators is also important for inhibiting plant height and changing the time of ripening in cotton. It is thus pos-sible for this important crop to be harvested completely mechanically.
In fruit and other trees, pruning costs can be reduced with growth regu1ators. With growth regulators, it is also possible to break up the alternate breeding rhythm of fruit trees.
Growth regulators may also increase or inhibit lateral branching. This is of interest whén, for instance in tobacco plants, it is desired to inhibit the formation of lateral shoots (suckers) in favor of leaf development.
With growth regulators, it is possible for instance in winter rape to considerably increase the resistance to freeze injury. On the one hand, upward growth and the development of a too luxuriant (and thus particularly frost-susceptible) leaf or plant mass are inhibited; on the other, the young rape plants are kept, in spite of favorable -, -18 O.Z. 0050/41919 growth conditions, in the vegetative development stage before winter frosts begin. The danger of freeze injury is thus eliminated in plants which tend to lose premature1y their inhibition to bloom and pass into the generative phase. In other crops, too, e.g., winter cereals, it is advantageous if the plants are well tillered in the fall as a result of treatment with the compounds according to the invention, but enter winter with not too lush a growth. This is a preventive measure against increased susceptibility to freeze injury and - because of the relatively low leaf or plant mass - attack by various (especially fungus) diseases. The inhibition of vegetative growth also makes closer planting possible in numerous crops, which means an increase in yield, based on the area cropped.
B. Better yields both of plant parts and plant materials may be obtained with the novet agents. It is thus for instance possible to induce increased formation of buds, blossom, leaves, fruit, seed grains, roots and tubers, to increase the sugar content of sugarbeets, sugarcane and citrus fruit, to raise the protein content of cereals and soybeans, and to stimulate the increased formation of latex in rubber trees.
The benzaldoxime ether derivatives I may raise the yield by influen-cing plant metabolism or by promoting or inhibiting vegetative and/or generative plant growth.
C. It is also possible with growth regulators to shorten or lengthen growth stages and to acceterate or retard the ripening process in plant parts elther before or after harvesting.
A factor of economic interest is for example the facilitation of har-vesting made possible by a chemical, temporally concentrated loosening (abscission) of the adherence of stalks to the branches of citrus fruit, olive trees, and other kinds of pomes, drupes and indehiscent fruit. The same mechanism, i.e., promotion of the formation of separ-ation layers between fruit or leaf and stem of the plant, is also es-sential for a readily controllable defoliation of crop plants, e.g., cotton.
;

D. Further, transpiration in crop plants may be reduced with growth regulators. This is particularly important for plants growing in agricultural areas which are expensive to irrigate, e.g., in arid or semi-arid areas. Irrigation frequency can be reduced by using the compounds according to the invention, making for lower costs. As a result of the use of growth regulators, the water available can be ':

~ ,, , .. .

~ r~ 3 1~ ~3 ~

19 O.Z. 0050/41919 better utilized, because, inter alia, - the size of the stomata opening is reduced;
- a thicker epidermis and cuticle are formed;
- penetration of the soil by the roots is improved;
- the micro-climate in the stand is favorably influenced by the more compact growth.
The growth regulators to be used according to the invention may be applied not only to the seed (as a disinfectant), but also to the soil, i.e., via 10 the roots, and - the method particularly preferred - to the foliage by spraying.
As a result of the good tolerance by crop plants~ the application rate may vary within wide limits.
In view of the numerous application methods possible, the compounds according to the invention, or agents containing them, may be used in a large number of crops. Those which follow are given by way of example:
20 Botanical name _ Common name Allium cepa onions Ananas comosus pineapples Arachis hypogaea peanuts (groundnuts) Asparagus officinalis asparagus 25 Avena sativa oats Beta vulgaris spp. altissima sugarbeets Beta vulgar{s spp. rapa fodder beets Brassica napus var. napus rapeseed Brassica napus var. napobrassica swedes 30 Brassica napus var. rapa turnips Brassica rapa var. silvestris Camellia sinensis tea plants Carthamus tinctorius safflower Carya illinoinensis pecan trees 35 Citrus limon lemons Citrus sinensis orange trees Coffea arabica (Coffea canephora, Coffea liberica) coffee plants Cucumis sativus cucumbers 40 Cynodon dactylon Bermudagrass Daucus carota Garrots Elais guineensis oil palms Fragaria vesca strawberries Glycine max soybeans - ~ ~ 3 O.Z. 0050/41919 Gossypium hirsutum (Gossypium arboreum, Gossypium herbaceum, Gossypium vitifolium) cotton Helianthus annuus sunflowers Hevea brasiliensis rubber plants 5 Hordeum vulgare barley Humulus lupulus hops Ipomoea batatas sweet potatoes Juglans regia walnut trees Lactuca sativa lettuce 10 Lens culinaris lentils Linum usitatissimum flax Lycopersicon lycopersicum tomatoes Malus spp. apple trees Manihot esculenta cassava 15 Medicago sativa atfalfa (lucerne) Musa spp. banana plants Nicotiana tabacum (N. rustica) tobacco Olea europaea olive trees Oryza sativa rice 20 Phaseolus lunatus limabeans Phaseolus vulgaris snapbeans, green beans, dry beans Picea abies Norway spruce Pinus spp. pine trees 25 Pisum sativum English peas Prunus avium cherry trees Prunus persica peach trees Pyrus communis pear trees Ribes sylvestre redcurrants 30 Ricinus communis castor-oil plants Saccharum officinarum sugar cane : Secale cereale rye Solanum tuberosum Irish potatoes Sorghum bicolor (s. vulgare) sorghum 35 Theobroma cacao cacao plants Trifolium pratense red clover Triticum aestivum wheat Triticum durum durum wheat Vicia faba tick beans 40 Vitis vinifera grapes Zea mays Indian corn, sweet corn, .,.. ,,.,. - ~
' .
.

3 '~ 9 ~ ~

21 O . Z . 0050/41 91 9 To increase the spectrum of action and to achieve synergistic effects, the compounds I may be mixed with each other, or mixed and applied together with numerous representatives of other herbicidal or growth-regulating active ingredient groups. Examples of suitable components are diazines, 5 4H-3,1-benzoxazine derivatives, benzothiadiazinones, 2,6-dinitroanilines, N-phenylcarbamates, thiolcarbamates, halocarboxylic acids, triazines, amides, ureas, diphenyl ethers, triazinones, uracils, benzofuran deriva-tives, cyclohexane-1,3-dione derivatives, quinolinecarboxylic acids, sulfonylurea derivatives, (hetero)-aryloxyphenoxypropionic acids and IO salts, esters, amides thereof, etc.
It may also be useful to apply the compounds I, either alone or in com-bination with other herbicides or crop protection agents, in admixture with other crop protection agents, e.g., agents for combating pests or lS 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 added.
Synthesis examples The instructions given in the synthesis examples below were used, afterappropriate modifications to the starting materials, to obtain further compounds I. These compounds are given in the following table with their physical data. Compounds without these data may be synthesized analogous-25 ly. The structures given in the table describe particularly preferredactive ingredients of the formula I.
A) Synthesis of compounds IV
30 Example 1 Ethyl 2-ethoxyiminomethyl-6-hydroxybenzoate a) Ethyl 2-acetoxy-6-formylbenzoate 38.1 g of N-methylmorpholine-N-oxide was added to 1.5 liters of chloroform, and dried azeotropically. Granulated molecular sieve 4A
(1/8" balls) (250 ml, measured volumetrically) was introduced and the solution was stirred overnight at room temperature. A third of the solution was separated for later use. 47.2 g of ethyl 2-acetoxy-6-bromomethylbenzoate (cf. T. Eicher et al, Synthesis 1988, pp. 525-529) was then added. The mixture was stirred for 3.5 hours at 55-60~C, the retained third of the oxidant was added, the mixture was stirred for a further 3 hours at the same temperature, and oxidant was again added (21.2 g of N-methylmorpholine-N-oxide dissolved in 1.1 liters of .
.
', .:

-22 O.Z. 0050/41919 chloroform and dried as described above, an equivalent amount of mole-cular sieve being employed). After 3 hours at 55-60C, the solution was decanted off from the molecular sieve, which was then washed four times, each time with 400 ml of methylene chloride. The combined organic phases were washed four times, each time with 150 ml of 5%
strength phosphoric acid and then three times with the same amount of saturated sodium chloride solution, dried over sodium sulfate and evaporated down under reduced pressure. Yield: 27 9.
10 b) Ethyl 2-acetoxy-6-ethoxyiminomethylbenzoate Molecular sieve 4A (190 ml, measured volumetrically) was added to 10.0 9 of the ethyl 2-acetoxy-6-formylbenzoate obtained under a) in 320 m1 of toluene. 2.8 9 of ethoxyamine was then added. The mixture was stirred for 30 minutes at room temperature, for 30 minutes at 45C
and then overnight at room temperature. The mixture was then decanted off from the molecular sieve, which was carefully washed with toluene.
Evaporation under reduced pressure gave 8.8 g of the desirPd product as an oil.
c) Ethyl 2-ethoxyiminomethyl-6-hydroxybenzoate A solution of 1.5 9 of sodium bicarbonate in 120 ml of water was added to a solution of 5.0 g of ethyl 2-acetoxy-6-ethoxyiminomethylbenzoate in 100 ml of methanol. The mixture was stirred for 2.5 hours at 45C
and then poured into 600 ml of 5% strength orthophosphoric acid, followed by extraction with ethyl acetate, drying over sodium sulfate and evaporation under reduced pressure. Yield: 3.6 g.
lH-NMR ~CDCI3): ~ = 1.33 (t); 1.42 (t); 4.22 (q); 4.42 (q), 7.02 (d);
7.23 (d); 7.41 (t); 8.61 (s); 10.20 (s).
The fotlowing compound was prepared analogously:
Example 2 35 Ethyl 2-tert-butoxyiminomethyl-6-hydroxybenzoate lH-NMR (CDC13): ~ = 1.36 (S); 1.42 (t); 4.42 (q); 7.00-7.43 (m), 8.60 (s);
11.15 (s).
Example 3 40 2-Ethoxyiminomethyl-6-hydroxybenzoic acid 4.9 9 of 50% strength sodium hydroxide solution was added to a solution of 8.6 9 of ethyl 2-acetoxy-6-ethoxyiminomethylbenzoate (cf. Example 1) in 60 ml of methanol and 20 ml of water. The mixture was stirred for 5 hours $ ~

23 O.Z. 0050/41919 at 75C, most of the methanol was removed under reduced pressure, and the mixture was diluted with 200 ml of cold water. The product was precipi-tated with 10% strength hydrochloric acid, separated off, washed with a small amount of water, and then stirred three times with n-pentane and 5 filtered. It was then dried under reduced pressure. Yield: 3.7 g.
lH-NMR (CDCl3): ~ = 1.38 (t); 4.30 (q); 7.05-7.50 (m), 8.65 (s).
The following were prepared in the same way:
Example 4 2-Allyloxyiminomethyl-6-hydroxybenzoic acid lH-NMR (CDC13): ~ = 4.70 (d); 5.25-5.45 (m); 5.95-6.15 (m); 7.05-7.55 (m), 8.65 (s).
Example 5 2-t.Butoxyiminomethyl-6-hydroxybenzoic acid 1H-NMR (CDCl3): ~ = 1.40 (s); 7.10-7.55 (m); 8.47 (s).
20 Example 6 2-(4-Chlorobenzyloxy)iminomethyl-6-hydroxybenzoic acid 1H-NMR (CDCl3): ~ = 5.18 (s); 7.05-7.60 (m), 8.67 (s).
B) Synthesis of compounds I
Example 7 Ethyl 2-t.-butoxyiminomethyl-6-(4,6-dimethoxypyrimidin-2-yloxy)benzoate (cf. Table, No. 9) 30 0.90 g of potassium tert-butylate was added to a solution of 2.00 9 of ethyt 2-t.-butoxyiminomethyl-6-hydroxybenzoate in 50 ml of dimethyl sulfoxide, and the mixture was stirred for 10 minutes at room temperature.
1.75 g of 4,6-dimethoxy-2-methylsulfonylpyrimidine was then added and the whole stirred for 2 hours at room temperature. The reaction mixture was 35 added to 600 ml of 5% strength orthophosphoric acid and extracted with ethyl acetate, and the organic phase was washed with water. After drying over sodium sulfate the product was avaporated down under reduced pres-sure. It was further purified by chromatography on silica gel using toluene/hexane as elutant. Yield: 2.4 g.
1H-NMR (CDCl3): ~ = 1.15 (t); 1.33 (s); 3.80 (s); 4.22 (q); 5.78 (s);
7.25-7.65 (m), 8.23 (s).

~,3 ^~ 3 24 O.Z. 0050/4191g Example 8 2-t.-Butoxyiminomethyl-6-(4,6-dimethoxypyrimidin-2-yloxy)benzoic acid (cf. Table, No. 10) 5 2.63 9 of potassium tert-butylate was added to a solution of 2.65 9 of 2-t.-butoxyiminomethyl-6-hydroxybenzoic acid in 60 ml of dimethyl sulf-oxide gelost, and the mixture was stirred for 20 minutes at room tempera-ture. 2.56 g of 4,6-dimethoxy-2-methylsulfonylpyrimidine was then added and the whole stirred for 30 minutes at room temperature. The reaction 10 mixture was added to 800 ml of 5% strength orthophosphoric acid, and the precipitate was filtered off, washed with water and dried under reduced pressure. For purification, it was then dissolved in diethyl ether and filtered, the filtrate was evaporated down under reduced pressure, and the residue was washed with cyclohexane. Removal of the remaining solvent 15 under reduced pressure gave 1.9 g of solid; melting point 63C.

u~

~ ~ I_ a- o '`
o In _ _ _ _ ~
O ~ ~ ~ OC~ ~ ~ U:) O .
O >~ .
sn. o ~1 ~ E c ~o E
o In <D
O I :~: I I T II I

x OOOOOO~nooooooo _. ~ r~ ~ ~ r~ ~~ . ~ ~ :~ ~ O L
U'l ~ C S C C S ~ C S ~ 8 ~ C L ~:L
c~: ~ ~ ~ E E C ~---O T
~ I T T I T I ~ I I I
~: O C~ O O O O O ~ OO O O O O
-- X

.~ Z X
`L ~0 O
Q~ Xo ~S
c - E x E o o a~ c ,C :~ x' ._ O` L S ~ O ~, _ ~ ~ ~ ~ L I I T ~ 1~
~ ~: O ~ ~ E cL o o o aJ o O ~ o O
c ..
8 E o o o o ~ o D o 0 ~ o _ _ _ _ ,r <J~ *
_I ~ O O
~ 4 00 ~ ~n ~ ~ ~ .
g v~ ll ll .
:~. a. ~ ~7 ~ t~ E E ~
O
u~
~O T I I I T T I ~- I I I I I I I I I t/~
O E
~ OOOOOOOOOOOOOOO~O
._ _ _ 4-~ s _ _ ~ ~ ~
~, L L ~ D D
. ~ O O o o ~ ..
_ O C _ _ E
~ ~ .
D ~ J S C ~, ~O O U _ ~ C ~ E ~ ~ C r -- 10 ~ ~0 1.1 ~ ~'J D ~ O E E C a~ > _ J~l T T T T T I T T T T T I T I 4a ~Y OOOOOOOOOOOOOOOOO X
O
~7 .
X X ~ :.
X - C
O
_ C ~ I
C a L o L

X _ X C o _ E D ~ ~-- E O
~ 3 ~ ,c /~
o :~, x '--E E
, I I T L I I I S
~ O O O ~ O O O O O O ~ D O ~ l ~_ C E

D E _ _ _ _ ~ _ _ _ _ _ _ _ _ _ _ _ _ E
O O ~ ~ ~ O c~ oo a o _ *

- ~?

27 O.Z. 0050/41919 Examples illustrating herbicidal action The herbicidal action of compounds I according to the invention is demonstrated in greenhouse experiments:
The vessels employed were plastic flowerpots having a volume of 300 cm3 and filled with a sandy loam containing about 3.0% humus. The seeds of the test plants were sown separately, according to species.
10 For the postemergence treatment, plants were used which had been sown in the pots and grown there, or they were grown separately as seedlings and transplanted to the pots a few days before treatment. The plants were grown, depending on growth form, to a height of 3 to 15 cm before being treated with the compounds, suspended or emulsified in water. The 15 application rate for postemergence treatment was 0.25 kg/ha.
The pots were set up in the greenhouse, heat-loving species at 20 to 35C, and species from moderate climates at 10 to 25C. The experiments were run for from 2 to 4 weeks. During this period the plants were tended and their 20 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 used in the experiments were as follows:
Abbreviation Botanical name Common name _ AMARE Amaranthus retroflexus redroot pigweed CHEAL Chenopodium album lambsquarters (goosefoot) 30 SOLNI Sotanum nigrum black nightshade .. . . .
.

.

Claims (10)

1. Benzaldoxime ether derivatives of the formula I

I

where R1 is succinimidoxy;

a 5-membered heteroaromatic structure which contains two or three nitrogen atoms and may carry one or two halogen atoms and/or one or two of the following radicals: C1-C4-alkyl, C1-C4-haloalkyl, C1-C4-alkoxy, C1-C4-haloalkoxy and/or C1-C4-alkylthio;
a radical -OR5, in which R5 is C3-C12-cycloalkyl which may carry from one to three C1-C4-alkyl radicals;
C1-C10-alkyl which may carry from one to five en halogen atoms and/or one of the following radicals:
C1-C4-alkoxy, C1-C4-alkylthio, cyano, C1-C8-alkylcarbonyl, C3-C12-cycloalkyl, C1-C8-alk-oxycarbonyl, phenyl, phenoxy or phenylcarbonyl, where the aromatic radicals in turn may carry from one to five halogen atoms and/or from one to three of the following radicals: C1-C4-alkyl, C1-C4-haloalkyl, C1-C4-alkoxy, C1-C4-haloalkoxy and/or C1-C4-alkylthio;
C2-C6-alkyl which carries one of the following radicals in the 2-position: C1-C6-alkoxyimino, C3-C6-alkenyloxyimino, C3-C6-haloalkenyloxyimino or benzyloxyimino;
C3-C6-alkenyl- or C3-C6-alkynyl, where these groups in turn may carry from one to five halogen atoms;

29 O.Z. 0050/41919 phenyl which is unsubstituted or monosubstituted to trisubstituted by C1-C4-alkyl or C1-C4-alkoxy or mono-substituted to pentasubstituted by halogen; or -N=CR6R7, in which R6 and R7 are each C1-C20-alkyl which may carry phenyl, C1-C4-alkoxy and/or C1-C4-alkylthio, or are each phenyl or together form a C3-C12-alkylene chain which may carry from one to three C1-C3-alkyl groups;
or a radical -OR8, in which R8 is hydrogen, an alkali metal cation, one equivalent of an alkaline earth metal cation, ammonium or an organic ammonium ion;
R2, R3 are each C1-C4-alkyl, C1-C2-haloalkyl, C1-C4-alkoxy, C1-C2-haloalkoxy, C1-C4-alkylamino, di-(C1-C4-alkyl)-amino and/or C1-C4-alkylthio;

R4 is C1-C8-alkyl C3-C6-alkenyl C3-C6-haloalkenyl or benzyl which may carry from one to three of the following sub-stituents in the phenyl ring: C1-C3-alkyl, halogen or C1-C4-alkoxy;
X is oxygen or sulfur; and Z is nitrogen or a methine group =CH-.
2. A process for the manufacture of compounds of the formula I as set forth in claim 1, wherein a compound of the formula II
II

is reacted in conventional manner with a heterocyclic structure of the formula III

III, O.Z. 0050/41919 where R9 is a nucleofugic leaving group, in the presence of a base.
3. A process for the manufacture of compounds of the formula I as set forth in claim 1, wherein the free carboxylic acid of the formula I' I' is first converted in conventional manner into the halide or another activated form of the carboxylic acid, which is then reacted with an alcohol R5OH, a di- or triazole or N-hydroxysuccinimide.
4. A process for the manufacture of compounds of the formula I as set forth in claim 1, wherein the free carboxylic acid I' is first con-verted in conventional manner into a salt and the latter is then reacted with a compound R10 - R5', where R10 is a nucleofugic leaving group and R5 is:
C3-C12-cycloalkyl which may carry from one to three C1-C4-alkyl radicals;
C1-C10-alkyl which may carry from one to five halogen atoms and/or one of the following radicals:
C1-C4-alkoxy, C1-C4-alkylthio, cyano, C1-C8-alkylcarbonyl, C3-C12-cycloalkyl, C1-C8-alkoxycarbonyl, phenyl, phenoxy or phenylcarbonyl, where the aromatic radicals in turn may carry from one to five halogen atoms and/or from one to three of the following radicals: C1-C4-alkyl, C1-C4-haloalkyl, C1-C4-alkoxy, C1-C4-haloalkoxy and/or C1-C4-alkylthio;
C2-C6-alkyl which carries one of the following radicals in the 2-position: C1-C6-alkoxyimino, C3-C6-alkenyloxyimino, C3-C6-halo-alkenyloxyimino or benzyloxyimino; or C3-C6-alkenyl or C3-C6-alkynyl, where these groups in turn may carry from one to five halogen atoms.

31 O.Z. 0050/41919
5. A compound of the formula IV

IV, where R11 is hydrogen, acetyl or methyl.
6. A herbicidal composition containing a compound of the formula I as set forth in claim 1.
7. A process for combating unwanted plant growth, wherein the unwanted plants and/or their habitat are treated with a herbicidally effective amount of a derivative I as set forth in claim 1.
8. The use of benzaldoxime ether derivatives of the formula I as set forth in claim 1 as herbicides.
9. An agent for influencing plant growth containing a benzaldoxime ether derivative of the formula I as set forth in claim 1.
10. A process for regulating plant growth, wherein a regulatorily effect-ive amount of a benzaldoxime ether derivative of the formula I as set forth in claim I is allowed to act on the seed, the plants and/or their habitat.
CA002051988A 1990-09-29 1991-09-20 Benzaldoxime ether derivatives Abandoned CA2051988A1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DEP4030929.0 1990-09-29
DE4030929A DE4030929A1 (en) 1990-09-29 1990-09-29 BENZALDOXIMETHERDERIVATE

Publications (1)

Publication Number Publication Date
CA2051988A1 true CA2051988A1 (en) 1992-03-30

Family

ID=6415297

Family Applications (1)

Application Number Title Priority Date Filing Date
CA002051988A Abandoned CA2051988A1 (en) 1990-09-29 1991-09-20 Benzaldoxime ether derivatives

Country Status (6)

Country Link
EP (1) EP0479055A1 (en)
JP (1) JPH04273862A (en)
KR (1) KR920006349A (en)
CA (1) CA2051988A1 (en)
DE (1) DE4030929A1 (en)
HU (1) HU913108D0 (en)

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3872113A (en) * 1972-05-30 1975-03-18 Endo Lab Hydroxy- and acetoxy-phthalaldehydric acid, O-(substituted) oximes
DE3851773T2 (en) * 1987-04-14 1995-04-20 Ihara Chemical Ind Co 2-phenoxypyrimidine derivatives and herbicidal compositions.
EP0346789B1 (en) * 1988-06-16 1994-04-20 BASF Aktiengesellschaft Salicylic-acid derivatives and their sulfur analogues
PH27460A (en) * 1989-12-28 1993-07-09 Kumiai Chemical Industry Co Pyrimidine derivatives and herbicidal composition containing the same

Also Published As

Publication number Publication date
KR920006349A (en) 1992-04-27
EP0479055A1 (en) 1992-04-08
DE4030929A1 (en) 1992-04-02
HU913108D0 (en) 1992-01-28
JPH04273862A (en) 1992-09-30

Similar Documents

Publication Publication Date Title
CA1336093C (en) Salicylic acid derivatives and their sulfur analogs
CA2018960C (en) Salicylaldehyde derivatives and salicylic acid derivatives and their sulfur analogs, their preparation and their use as herbicides and bioregulators
KR100325555B1 (en) 3- (hetero) arylcarboxylic acid derivatives, methods for their preparation and intermediates used for their preparation
CA2012596A1 (en) Herbicidal and plant growth-regulating azolylmethyloxiranes
US5360913A (en) Salicyclic acid derivatives
US5085685A (en) Carboxylic acid derivatives
KR100332330B1 (en) 3- (hetero) aryloxy (thio) carboxylic acid derivatives, methods for their preparation and intermediates used for their preparation
US5559218A (en) 2-aroylcyclohexanediones and their use as herbicides or plant growth-regulating agents
CA2027446C (en) Cyclohexenone compounds and their use as herbicides or plant growth regulators
US5290755A (en) Salicylic acid derivatives as selective herbicides
CA1289560C (en) Cyclohexenone derivatives, the preparation and use thereof as herbicides and plant growth regulators
US5188657A (en) Herbicidal sulfonylureas and their use
US5276007A (en) Herbicidal sulfonylureas
US5100458A (en) Salicyclic acid derivatives and their use as herbicides and bioregulators
US5362876A (en) Salicylaldehyde and salicylic acid derivatives and sulfur analogs thereof, their preparation and intermediates therefor
US5318945A (en) Thiocarboxylic acid derivatives
CA2051988A1 (en) Benzaldoxime ether derivatives
CA1334421C (en) N-substituted 3,4,5,6-tetrahydrophthalimide derivatives
RU2146255C1 (en) 3-halogen-3-hetarylcarboxylic acid derivatives, and herbicidal agent

Legal Events

Date Code Title Description
FZDE Dead