CA2048160A1 - Oxalylbishydroxamic acid derivatives, their preparation and plant growth regulators containing them - Google Patents

Oxalylbishydroxamic acid derivatives, their preparation and plant growth regulators containing them

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Publication number
CA2048160A1
CA2048160A1 CA002048160A CA2048160A CA2048160A1 CA 2048160 A1 CA2048160 A1 CA 2048160A1 CA 002048160 A CA002048160 A CA 002048160A CA 2048160 A CA2048160 A CA 2048160A CA 2048160 A1 CA2048160 A1 CA 2048160A1
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weight
phenyl
alkyl
methyl
formula
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French (fr)
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Costin Rentzea
Michael Keil
Albrecht Harreus
Wilhelm Rademacher
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BASF SE
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    • 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
    • A01N37/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
    • A01N37/18—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing the group —CO—N<, e.g. carboxylic acid amides or imides; Thio analogues thereof
    • A01N37/30—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing the group —CO—N<, e.g. carboxylic acid amides or imides; Thio analogues thereof containing the groups —CO—N< and, both being directly attached by their carbon atoms to the same carbon skeleton, e.g. H2N—NH—CO—C6H4—COOCH3; Thio-analogues thereof
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C259/00—Compounds containing carboxyl groups, an oxygen atom of a carboxyl group being replaced by a nitrogen atom, this nitrogen atom being further bound to an oxygen atom and not being part of nitro or nitroso groups
    • C07C259/04—Compounds containing carboxyl groups, an oxygen atom of a carboxyl group being replaced by a nitrogen atom, this nitrogen atom being further bound to an oxygen atom and not being part of nitro or nitroso groups without replacement of the other oxygen atom of the carboxyl group, e.g. hydroxamic acids
    • C07C259/08—Compounds containing carboxyl groups, an oxygen atom of a carboxyl group being replaced by a nitrogen atom, this nitrogen atom being further bound to an oxygen atom and not being part of nitro or nitroso groups without replacement of the other oxygen atom of the carboxyl group, e.g. hydroxamic acids having carbon atoms of hydroxamic groups bound to carbon atoms of rings other than six-membered aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C259/00—Compounds containing carboxyl groups, an oxygen atom of a carboxyl group being replaced by a nitrogen atom, this nitrogen atom being further bound to an oxygen atom and not being part of nitro or nitroso groups
    • C07C259/04—Compounds containing carboxyl groups, an oxygen atom of a carboxyl group being replaced by a nitrogen atom, this nitrogen atom being further bound to an oxygen atom and not being part of nitro or nitroso groups without replacement of the other oxygen atom of the carboxyl group, e.g. hydroxamic acids
    • C07C259/06—Compounds containing carboxyl groups, an oxygen atom of a carboxyl group being replaced by a nitrogen atom, this nitrogen atom being further bound to an oxygen atom and not being part of nitro or nitroso groups without replacement of the other oxygen atom of the carboxyl group, e.g. hydroxamic acids having carbon atoms of hydroxamic groups bound to hydrogen atoms or to acyclic carbon atoms

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Dentistry (AREA)
  • Pest Control & Pesticides (AREA)
  • Plant Pathology (AREA)
  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Agronomy & Crop Science (AREA)
  • General Health & Medical Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Zoology (AREA)
  • Environmental Sciences (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Heterocyclic Carbon Compounds Containing A Hetero Ring Having Nitrogen And Oxygen As The Only Ring Hetero Atoms (AREA)

Abstract

O.Z. 0050/41791 Abstract of the Disclosure: Oxalylbishydroxamic acid derivatives of the general formula I

where R1 and R2 independently of one another are each unsubstituted or substituted alkyl, alkenyl or alkynyl, unsubstituted or substituted cycloalkyl or cycloalkyl-methyl, unsubstituted or substituted cycloalkenyl or cycloalkenylmethyl or unsubstituted or substituted phenyl, phenylalkyl or phenylalkenyl, and their agricul-turally useful salts, processes for their preparation, agents containing them and methods for regulating plant growth.

Description

o.z~ oo~
Oxalylbi~hydroxamic acid derivatives. their preparation and plant growth regulator~ containina them The present invention relates to oxalylbishydrox-amic acid derivatives of the general formula I
Rl-ONH-CO-CO-NHO-R2 where R1 and R2 independently of one another are each Cl-C20-alkyl, C3-Cl~-alkenyl or C3-C8-alkynyl, where the~e group~ may carry from one to five halogen atom~, monocyclic or polycyclic C3-C10-cycloalkyl or C3-Clo-cyclo-alkylmethyl, where these rings may carry from one to three C1-C4-alkyl groups or one phenyl ring, monocyclic or polycyclic C5-C10-cycloalkenyl or Cs-Clo~
cycloalkenylmethyl, where these rings may carry from one to three Cl-C4-alkyl groups or one phenyl ring, and phenyl, phenyl-Cl-C~-alkyl or phenyl-C2-C6-alkenyl, where the aromatic radical~ may carry from one to five halogen atoms and/or from one to three of the following groups:
nitro, Cl-C4-alkyl, Cl-C~-haloalkyl, Cl-C~-alkoxy, Cl-C~-haloalkoxy, Cl-C~-alkylthio or Cl-C, haloalkylthio, where R1 and R2 are not ~imultaneously ethyl, and their agriculturally useful salt~.
The invention furth~rmore relates to processe~
for the preparation of the~e compounds, agents containing th~m and methods for the use of oxalylbishydroxamic acid derivatives of the general formula IA
Rl-ONH--CO--CO-NHO--R2 IA
where R1 and R2 independently of one another are each C1 C20-alkyl, C3-Cl8-alkenyl or C3-C8-alkynyl, where these group3 may carry from one to five halogen atom~, monocyclic or polycyclic C3-C10-cycloalkyl or C3-Clo-cyclo-alkylmethyl, whero these rings may carry from one to three Cl-C4-alkyl groups or one phenyl ring, monocyclic or polycyclic Cs-C10-cycloalkenyl or Cs-Clo~
cycloalkenylme~hyl, where the~e rings may carry from one to three Cl-C4-alkyl groups ur one phenyl ring, and phenyl, phenyl-Cl-C4-alkyl or phenyl-C2-C6-alkenyl, where the aromatic radical~ may carry from one to five halogen 20~8160 - 2 - O.Z. 0050/41791 atom~ and/or from one to three of the following groups:
nitro, C~-C4-alkyl, Cl-C4-haloalkyl, Cl-C~-alkoxy, Cl-C4-haloalkoxy, Cl-C~-alkylthio or Cl-C4-haloalkylthio, and their agriculturally useful salts, as plant growth regulators.
Oxalylhydroxamic acid derivatives are disclosed in the literature as intermediates for syntheses. The preparation of oxalylbisethylhydroxamic acid is also known (Chem. Ber. 27 (1894), 1111).
It is an ob~ect of the present invention to provide novel effective plant growth regulators.
We have found that this ob~ect is achieved by the oxalylbishydroxamic acid derivatives I defined at the outset. We have also found processes for the preparation of oxalylbishydroxamic acid derivatives, agents contain-ing them and methods for using the compounds IA as plant growth regulatorR.
The oxalylbishydroxamic acid derivative~ I are obtainable by variou~ methods. They are particularly advantageously obtained by ona of the processes A and B
de~cribed below.
Proceqs A:
The oxalylbi~hydroxamic acid derivatives of the formula I are obtained, for example, by reacting an oxalylhydroxamic acid derivativ~ of the general formula II in a conventional manner in an inert organic solvent with a hydroxylamine derivative of the general formula III.
Rl--ONH--CO-CO--OCH3+ R2-ONEI2 ----> Rl--ONH-CO--CO-NHO-R2 II III
The reaction is carried out in general at from 0 to 100C, preferably from 20 to 90C.
Examples of ~uitable solvents are halohydro-carbons, in particular chlorohydrocarbon~, eg. 1,1,2,2-tetrachloroethylene,l,l,2,2-tetrachloroethane,dichloro-propane, methylene chloride, dichlorobutane, chloroform, chloronaphthalene, dichloronaphthalene, carbon tetra-~ 3 _ o.z. ~5~417~9 chloride, 1,1,1- or 1,1,2-trichloroethane, trichloro-ethylene, pentachloroethane, o-, m- or p-difluorobenzene, 1,2-dichloroethane,l,l-dichloroethane,1,2-cis-dichloro-ethylene, chlorobenzene, fluorobenzene, bromobenzene, iodobenzene, o-, m- or p-dichlorobenzene, o-, p- or m-dibromobenzene, o-, m- or p-chlorotoluene or 1,2,4-trichlorobenzene, ethers, eg. ethylpropyl ether, methyl tert-butyl ether, n-butyl ethyl ether, di-n-butyl ether, diisobutyl ether, diisoamyl ether, diisopropyl ether, anisole, phenetole, cyclohexyl methyl ether, diethyl ether, ethylene glycol dimethyl ether, tetrahydrofuran, dioxane or thioanisole, nitrohydrocarbons, such as nitromethane, nitroethane, nitrobenzene, o-, m- or p-chloronitrobenzene or o-nitrotoluene, nitriles, such as acetonitrile, butyronitrile, isobutyronitrile, benzo-nitrile or m-chlorobenzonitrile, aliphatic or cyclo-aliphatic hydrocarbons, eg. heptane, pinane, nonane, o-, m- or p-cumene, gasoline fractions boiling within a range from 70 to 190C, cyclohexane, methylcyclohexane, decalin, petroleum ether, hexane, naphtha, 2,2,4-~rLmethylpentane, 2,2,3-trimethylpentane, 2,3,3-trimethylpentane or octane, e~ters, eg. ethyl acetate, ethyl acetoacetate or isobutyl acetate, amides, eg. formamide, methylformamide or dimethylformamide, ketones, eg. acetone or methyl ethyl ketone, and, if reguired, also water and corresponding mixtures. The compounds of the formula I can also be used in excess ac the solvent. Advantageously, the solvent i8 used in an amount of from 100 to 2,000, preferably from 200 to 700, % by weight, based on the starting material II. Example~ of suitable base~ are potassium hydroxide, sodium hydroxide, potascium car-bonate, sodium carbonate, lithium hydroxide, lithium carbonate, sodium bicarbonate, pota~ium bicarbonate, calcium hydroxide, calcium oxide, barium oxide, magnesium hydroxide, magnesium oxide, barium hydroxide, calcium carbonate, magnesium cArbonate, magnesium bicarbonate, magnesium acetate, zinc hydroxide, zinc oxid~, zinc 20481~
- 4 - O.Z. 0050/41791 carbonate, zinc bicarbonate, zinc acetate, sodium for-mate, sodium acetate, trimethylamine, triethylamine, tripropylamine, triisopropylamine, tributylamine, triiso-butylamine, tri-sec-butylamine, tri-tert-butylamine, tribenzylamine, tricyclohexylamine, triamylamine, tri-hexylamine, N,N-dimethylaniline, N,N-diethylaniline, N,N-dipropylaniline, N,N-dimethyltoluidine, N,N-diethyl-toluidine, N,N-dipropyltoluidine, N,N-dimethyl-4-amino-pyridine, N,N-diethyl-4-aminopyridine, N,N-dipropyl-4-aminopyridine, N-methylpyrrolidine, N-ethylpyrrolidine, N-methylpiperidine, N-ethylpiperidine, N-methylpyr-rolidone, N-ethylpyrrolidone, N-methylimidazole, N-ethylimidazole, N-methylmorpholine, N-ethylmorpholine, N-methylhexamethyleneimine, N-ethylhexamethyleneimine, pyridine, quinoline, alpha-picoline, beta-picoline, isoquinoline, pyrimidine, acridine, N,N,N',N'-tetra-methylethylenediamine, N,N,N',N'-tetraethylethylenedi-amine, quinoxaline t N-propyldiisopropylamine, N,N-dimethyleyclohexylamine, 2,6-lutidine, 2,4-lutidine and triethylenediamine.
Advantageously, the base is used in stoichio-metric amounts or in an amount which is not more than 20 mol %, based on starting material II, greater than or les4 than the stoichiometric amount.
It may also be useful to carry out the reaction in the presence of a catalyst.
Preferr~d reaction accelerators are 4-dimethyl-aminopyridine and 4-pyrrolidinopyridine (J. Cossy et al., Synthe~is, 753 et seg. (1989)).
Process B:
The compounds of the formula I in which R1 and R2 have the same meanings are also obtained, for example, by reacting an oxalyl halide of the general formula IV in a conventional manner in an inert organic solvent in the presence of a base with a hydroxylamine of the general formula III.

20~8~
- 5 - O.Z. 0050/41791 Hal-CO-CO-Hal + Rl-ONH2 ---> Rl-ONH-CO-CO-NHO-R
IV III
In formula IV, Hal is halogen, such as fluorine, chlorine, bromine or iodine, preferably chlorine or bromine.
The reaction is carried out in general at from -20 to 100C, preferably from 15 to 80C.
Examples of suitable solvents are those stated above for process A. Acetic acid, ethyl acetate, meth-ylene chloride, toluene, chlorobenzene, tetrahydrofuranand dioxane are particularly suitable.
Suitable ba~es in this process, in addition to those stated above, are potassium acetate and sodium acetate.
In view of the intended use of the compounds IA
in growth-regulating agents, suitable ~ub~tituents are the following radical~:
R1 and R2 independently of one another are each Cl-C20-alkyl, preferably branched or straight-chain Cl-C6-alkyl, such a~ methyl, ethyl, propyl, 1-methylethyl, butyl, l~methylpropyl, 2-methylpropyl, 1,1-dLmethylethyl, pentyl, l-methylbutyl, 2-methylbutyl, 3-methylbutyl, 2,2-dimethylpropyl, 1-ethylpropyl, hexyl, 1,1-dimethylpropyl, 1,2-dimethylpropyl, l-methylpentyl, 2-methylpentyl, 3-methylpentyl t 4-methylpentyl, 1,1-dimethylbutyl, 1,2-dimethylbutyl, 1,3-dLmethylbutyl, 2,2-dimethylbutyl, 2,3 dLmethylbutyl, 3,3-dimethylbutyl, l-ethylbutyl, 2-ethyl-butyl, 1,1,2-trLmethylpropyl, 1,2,2-trimethylpropyl, 1-eth~l-l-methylpropyl or l-ethyl-2-methylpropyl, in particular branched or straight-chain Cl-Cd-alkyl, such as methyl, ethyl, propyl, l-methylethyl, butyl r l-methyl-propyl, 2-methylpropyl or l,l-dLmethylethyl;
C3-C8-alkenyl, in particular C3-C5-alkenyl, such as 2-propenyl, 2-butenyl, 3-butenyl, 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-but~nyl, l-methyl-3-butenyl, 2-methyl 3-butenyl, 3-methyl-3-~0~8160 - 6 - O.Z. OOSO/41791 butenyl, l,l-dimethyl-2-propenyl, 1,2-dimethyl-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, 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,l,l-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, 3,3-dimethyl-2-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-l-methyl-2-propenyl or 1-ethyl-2-methyl-2-propenyl;
C3-CB-alkynyl, in particular C3-C6-alkynyl, such as propyn-yl, 2-butynyl, 3-butynyl, 1-methyl-2-propynyl, 2-pen-tynyl, 3-pentynyl, 4-pentynyl, 1-methyl-2-butynyl, 1-methyl-3-butynyl, 2-methyl-3-butynyl, 1,1-dLmethyl-2-propynyl, 1-ethyl-2-propynyl, 2-hexynyl, 3-hexynyl, 4-hexynyl, 5-hexynyl, 1-methyl-2-pentynyl, 1-me~hyl-3-pentynyl, l-methyl-4-pentynyl, 2-methyl-3-pentynyl~ 2-methyl-4-pentynyl, 3-methyl-4-pentynyl, 4-methyl-2-pentynyl,l,1-dimethyl-2-butynyl,l,l-dimethyl-3-butynyl, 1,2-dimethyl~3-butynyl, 2,2-dim~thyl-3-butynyl, 1-ethyl-2-butynyl, 1-ethyl-3-butynyl, 2-ethyl-3-butynyl or 1-ethyl-l-methyl-2-propynyl, preferably 2 propynyl and 2-butynyl, wh~re the~e groups may carry from one to five halogen atoms, such as fluorine, chlorine, bromine or iodine, preferably fluorine or chlorine;
monocyclic or polycyclic C3-C~O-cycloalkyl, such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclo-heptyl, cyclooctyl, menthyl, norbornyl, adhmantyl or tricyclodecanyl, preierably cyclopropyl or cyclohexyl, or monocyclic or polycyclic C3-C1O-cycloalkylmethyl, such as cyclopropylmethyl, cyclobutylmethyl, cyclopentylmethyl, _ 7 _ O.Z. ~
cyclohexylmethyl, cycloheptylmethyl or cyclooctylmethyl, preferably cyclopropylmethyl or cyclohexylmethyl, where these rings may carry from one to three Cl-C4-alkyl group , such as methyl, ethyl, propyl, 1-methylethyl, butyl, 1-methylpropyl, 2-methylpropyl, l,1-dimethylethyl, preferably methyl or ethyl, in particular methyl, or a phenyl ring;
monocyclic or polycyclic Cs-ClO-cycloalkenyl, preferably 2-cyclohexen-1-yl, or monocyclic or polycyclic C5-C1O-cycloalkenylmethyl, preferably l-cyclohexenylmethyl, 2-cyclohexenylmethyl or 3-cyclohexenylmethyl, where these ring~ may carry from one to thrPe Cl-C4-alkyl group~, such as methyl, ethyl, propyl, 1-methylethyl, butyl, 1-methylpropyl, 2-methylpropyl or 1,1-dLmethyl-ethyl, preferably methyl, or a phenyl ring;
phenyl, phenyl-Cl-C4-alkyl, such as benzyl, 1-phenylethyl, 2-phenylethyl, 1-phenylpropyl, 2-phenylpropyl, 3-phenyl-propyl, l-methyl-1-phenylethyl, 1-phenylbutyl, 2-phenylbutyl, 3-phenylbutyl, 4-phenylbutyl, 1-methyl-1-phenylpropyl, 1-methyl-2-phenylpropyl, 1-methyl-3-phenylpropyl, 2-methyl l-phenylpropyl, 2-methyl-2-phenylpropyl, 2-methyl-3-phenylpropyl or 1,1-dimethyl-2-phenylethyl, preferably benzyl or 2-phenylethyl, or phenyl-C2-C6-alkenyl, in particular phenyl-C2-C4-alkenyl, such as 2-phe~ylethenyl, 2-phenyl-1-propenyl, 2-phenyl-2-propenyl,2-phenyl-1-methylethenyl,2-phenyl-1-butenyl, 2-phenyl-2-butenyl, 2-phenyl-3-butenyl, 2-phenyl-1-methyl-1-propenyl or 2-phenyl-1-methyl-2-propenyl, where the aromatic radicals may carry from one to five halogen atoms, such as fluorine, chlorine, bromine or iodine, preferably fluorine, chlorine or bromine, in particular fluorine or chlorine, and/or from one to three of the following group~: nitro, C1-C4-alkyl, -quch as methyl, ethyl, propyl, l-methylethyl, butyl, 1-methyl-propyl, 2-methylpropyl or l,1-dLmethylethyl, preferably methyl, l-methylethyl or l,l-dimethylethyl;

~81~0 - 8 - O. Z . 0050/41791 Cl-C4-haloalkyl, in particular Cl- or C2-haloalkyl, such a-~
chloromethyl, dichloromethyl, trichloromethyl, f luoro-methyl, difluoromethyl, trifluoromethyl, chlorofluoro methyl, dichlorof luoromethyl, chlorodif luoromethyl, 1-S fluoroethyl, 2-fluoroethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, 2-chloro-2-fluoroethyl, 2-chloro-2,2-dif luoroethyl, 2, 2 -dichloro-2 -f luoroethyl, 2, 2, 2 -tri-chloroethyl or pentafluoroethyl, preferably trifluoro-methyl;
Cl-C~-alkoxy, such as methoxy, ethoxy, propoxy, l-methyl-ethoxy, butoxy, l-methylpropoxy, 2-methylpropoxy or 1,1-dimethylethoxy, preferably methoxy or ethoxy;
C,-C~-haloalkoxy, in particular Cl- or C2-haloalkoxy, such as chloromethoxy, dichloromethoxy, trichlorome~hoxy, chlorofluoromethoxy, dichlorofluoromethoxy, chlorodi-f luoromethoxy, l-f luoroethoxy, 2 -f luoroethoxy, 2, 2-difluoroethoxy, 2,2,2-trifluoroethoxy, 2-chloro-2-f luoroethoxy, 2-chloro-2, 2 -dif luoroethoxy, 2, 2-dichloro-2-fluoroethoxy, 2,2,2-trichloroethoxy or 2 0 pentaf luoroethoxy;
Cl-C4-alkylthio, such as methylthio, ethylthio, propyl-thio, l-methylethylthio, butylthio, 1-methylpropylthio, 2-methylpropylthio or 1, l-dimethylethylthio, preferably methyl~hio, and Cl-C4-haloalkylthio, in partic~lar Cl- or Cz-haloalkylthio, such a~ chloromethylthio, dichloromethylthio, trichloromethylthio, chloro f luoromethylthio, dichloro f luoromethylthio, chlorodifluoromethylthio, 1-fluoroethylthio, 2-f luoroethylthio, 2, 2 -dif luoroethylthio, 2, 2, 2 -trif luoro-ethylthio, 2-chloro-2-fluoroethylthio, 2-chloro-2,2-difluoroethylthio, 2,2-dichloro-2-fluoroethylthio, 2, 2, 2-trichloroethylthio or pentaf luoroethylthio ~`1 In view of the intended use in growth-regulating agents, particularly preferred compound~ IA are those in which Rl has the following meanings:
methyl, ethyl, propyl, l-methylethyl, butyl, 1-methyl-propyl, 2-methylpropyl ~ dimethylethyl, pentyl, g oz o~9~
l-methylbutyl, 2-methylbutyl, 3-methylbutyl, 2,2-dimethylpropyl, l-ethylpropyl, hexyl, l,1-dimethylpropyl, 1,2-dimethylpropyl, l-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, l,l-dimethylbutyl, 1,2-dimethylbutyl, 1,3-dimethylbutyl, 2,2-dLmethylbutyl, 2,3-dimethylbutyl, 3,3-dimethylbutyl, l-ethylbutyl, 2-ethyl-butyl, l,1,2-trimethylpropyl, 1,2,2-trimethylpropyl, 1-ethyl-l-methylpropyl or l-ethyl-2-methylpropyl, in particular methyl, ethyl, propyl, l-methylethyl, butyl, 1-methylpropyl, 2-methylpropyl or l,1-dime hylethyl, 2-propenyl, 2-butenyl, 3-butenyl, 1-methyl-2-propenyl, 2-methyl-2-propenyl, 3-methyl-2-butenyl or benzyl, where these groups may carry from one to five halogen atoms, such as fluorine, chlorine, bromine or iodine, preferably fluorine or chlorine.
Examples of particularly preferred oxalyl-bishydroxamic acid dPrivatives of the general formula IA
are shown in the Table below.

TABLE

Rl-ONH-CO-CO-NHO-R2 ( I ) Rl R2 CH3 n C3~7 CH3 i C3H7 CH3 n C4Hg CH3 i~C4Hg CH3 sec.-C4Hg CH3 n-C5Hll CH3 j_C5H11 CH3 n C6H13 CH3 (CH3~2CH-CH2-cH2-cH2 CH3 n-C7H15 CH3 n-C8H17 CH3 CH3CH2CH2CH2CH(C2H5)cH2 c~3 n-CgHIg CH3 n CIOH21 CH3 n C12H25 c~3 n-Cl~H29 CH3 n C16H33 c~3 n C18H37 c~3 n-C20~41 CH3 CYC I opropylm~thyl CH3 Cyclop~ntyl CH3 Cycloh~xyl CH3 Cyclohexylmathyl CH3 4-Mothylcycloh~xyl CH3 4-Ethylcyelohoxyl CH3 4-t~rt.-Butylcyclohexyl CH3 Altyl CH3 CH3CH~CHCH2 CH3 (CH3)2c3cHcH2 CH3 Geranyl CH3 HCsCCH~-CH3 ~3C~C~H2 c~3 CICH2~CHCH~-~48~60 - 11 - O. Z . 0050/~1791 TABLE ( cont inued ) _ CH3 CH2=C(Cl)cH2 CH3 CH2=C(~r)cH2 CH3 CICH=C(CI)CH2-CH3 Cl22C(CI)CH2-CH3 Cl(CH2)4-CH3 BrCH2~H2~
CH3 Cl-(C~2)6-CH3 Cl-(CH2)8 CH3 Br-(CH2)4~
CH3 3r-(CH2)6 CH3 4CI-C6~4-CH2 CH3 3,4C12-C6H3-CH2 CH3 2,4C12-C6~3-CH2-CH3 4Br-C6H4-CH2 CH3 2,4-~CH3)2-C6H3-CH2-c~3 4-C3H7-C6H4-CH2-CH3 4-t~rt.-C4Hg~S6H4~CH2 CH3 4-CH30-C6H4-C~2-CH3 4-o2N-c6~4-cH2 CH3 C6H5-CH2cH2 C2H5 C2~5 C2H5 n C3~9 C2H5 i-C3Hg C2H5 n-C4Hg C2H5 Sec:.-C4H9 C2H5 i-C4~9 C2H5 H2C'C(cH3i-cH2 i-C3H7 i-C31~7 Allyl All~l 2048~6n - 12 - O.Z. 0050/417gl TABLE (continued) Rl R2 H2C=CCICH2- H2c=cclcH
~/2C=C8rCH2- H2c=c~rcH2-C I CH=CHCH2- C I Cil=CHCH2-CH3CH=CHCH2- CH3cH-cHcH2-H2C=C(cH3)cH2 H2C=C(cH3)cH2 C I CH2cH2cH2 C I CH2cH2cH2 n-C4Hg n-C4Hg i-C4H9 i C4H9 sec . -C 4Hg sec .-C41 !g n-CSHI I n CsHt 1 ~
n-C6H13 n C6H13-Hc--ccH2- HC_CC112-Suitable salts of tho active ingredient~ of tha formula I ar~ ~griculturally useful salts, for example alkali metal salts, ~uch a~ pota~sium or sodium 3alt, alkalino earth metal salt~, 4uch as the calcium, mag-ne~ium or bariu~ s~lt, manganese, copper, zinc or iron salt~ and aImonium, pho~phonium, 3ulfoniu~ or 3ulfoxonium salt3, for e~ample ammonium alt~, tetraalkylammonium ~alt~, benzyltrialkyl~mmonium Qalt3, trial~ylRulfonium iO ~alt~ or trifilkylsulfoxo~um ~alts.
ThQ novel growth regula~ing active ingredient~ IA
or the ag~nts containing them ~an be u~ed, for example, in the for~ of directly ~pr~yabl3 ~olution~, powder~, ~uspQnsion~, includ~ng concentrated aqueou~, oily or other ~u~pen~ions or dispersiQn~, emul~ion~, oil disper-~ions, p~stes, dusting agent~, broadca3ting agent~ or granula~, by spraying, a~omlzing, dusting, broadca~ting or pouri~g. The applic~tion form~ depend on the intended use~; they ~hould in any case ensure v~ry fine di~tribu-tion of the novel ac~i~e ingredients.
The active ingrsdient3 IA are ~uitable in general 204~1~f3 - 13 - O.Z. 0050/41791 for the preparation of directly sprayable ~olutions, emulsions, pastes or oil dispersions. Suitable inert additive~ are mineral oil fractions having a medium to high boiling point, such as kerosene or diesel oil, and coal tar oils and oils of vegetable or animal origin, aliphatic, cyclic and aromatic hydrocarbons, eg. toluene, xylene, paraffin, tetrahydronaphthalene, alkylated naphthalenes or derivatives thereof, methanol, ethanol, propanol, butanol, cyclohexanol, cyclohexanone, chloro-benzene, isophorone or strongly polar solvents, such as N,N-dimethylformamide, dimethyl sulfoxide, N-methyl-pyrrolidone or water.
Aqueous application forms can be prepared from emulsion concentrates, dispersions, pastes, wettable powders or water-dispersible granules by adding water.
For the preparation of emulsions, pastes or oil disper-sions, the substrates, as such or dissolved in an oil or solvent, can be homogenized with water by means of wetting agents, adhesives, dispersants or emulsifiers.
Kowever, it i~ also possible to prepare concentrates which con ist of active sub~tance, wetting agents, adhesives, disper~ant~ or emulsifiers and possible solvents or oil and which are suitable for dilution with water.
Suitable surfactants are the alkali metal, alkaline earth metal and ammonium salts of aromatic sulfonic acids, eg. lignin-, phenol-, naphthalene- and dibutylnaphthaleneYulfonic acid, and of fatty acids, alkyl- and alXylarylsulfonate4, alkylsulfates, lauryl ether ~ulfates and fatty alcohol sulfates, and salt~ of ~ulfated hexa-, hepta- and octadecanols, and of fatty alcohol glycol ethers, condenYates of sulfonated n~ph-thalene and it~ derivatives with formaldehyde, conden-sates of naphthalene or of naph~halenesulfonic acids with phenol and formaldehyde, polyoxyethylene octylphenol ether~, ethoxylated isooctyl-, octyl or nonylphenol, alkylphenol polyglycol ethers, tributylphenyl polyglycol 20~81Ç;~
- 14 - O.Z. 0050/41791 ethers, alkylaryl polyether alcohols, isotridecyl alcohol, fatty alcohol/ethylene oxide condensates, ethoxylated castor oil, polyoxyethylene alkyl ethers or polyoxypropylene, lauryl alcohol polyglycol ether acetate, sorbitol ester, ligninsulfite waste liquors or methylcellulose.
Powder~, broadcasting agents and dusting agents can be prepared by mixing or milling the active sub-stances together with a solid carrier.
Granules, for example coated, impregnated and homogeneous granules, can be prepared by binding the active ingredients to solid carriers. Solid carriers are mineral earths, such as silica gel, silicas, silicates, talc, kaolin, limestone, lLme, chalk, bole, loess, clay, dolomite, kieselguhr, calcium sulfate, magnesium sulfate, magnesium oxide, milled plastics, fertilizers, such as ammonium sulfate, ammonium phosphate, ammonium nitrate or ureas, and vegetable products, ~uch a~ cereal meal, ground bark, woodmeal and nutshell meal, cellulose powder and other ~olid carriers.
The formulations con~ain from 0.1 to 95, prefer-ably from 0.5 to 9Q, % by weight of active ingredient.
The active ingredients are used in a purity of from 90 to 100~, preferably from 95 to 100% (according to the NMR
sp~ctrum).
The novel active ingredients IA can be formu-lated, for example, as follows:
I. 90 part~ by weight of compound No. l.001 are mixed with 10 part~ by weight of N-methyl-a-pyrrolidone, and a solution which is suitable for use in the form of very small drops is obtained.
II. 20 parts by weight of compound No. 1.003 are dissolved in a mixture which consists of 80 parts by weight of xylene, lO parts by weight of the adduct of from 8 to 10 mole~ of ethylene oxide with 1 mole of oleic acid N-monoethanolamide, 5 parts by weight of the calcium salt of dodecyl-~o~s~fin - 15 - O.Z. 0050/41791 benzenesulfonic acid and 5 parts by weight of the adduct of 40 moles of ethylene oxide with 1 mole of castor oil. By pouring the solution into 100,000 parts by weight of water and finely distributing it therein, an aqueous dispersion which contains 0.02% by weight of the active ingredient is obtained.
III. 20 parts by weight of compound No. 1.006 are dissolved in a mixture which consists of 40 parts by weight of cyclohexanone, 30 parts by weight of isobutanol, 20 parts by weight of the adduct of 7 moles of ethyle~e oxide 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 solution into 100,000 parts by weight of water and finely distributing it ~herein, an aqueous dispersion which contains 0.02~ by weight of the active ingredient i5 obtained.
IV. 20 parts by weight of active ingredient No. 1.002 are dissolved in a mixture which consists of 25 parts by weight of cyclohexanone, 65 parts by weight of a mineral oil fraction boiling within a range of from 210 to 280C and 10 parts by weight of the adduct of 40 mole~ of ethylene oxide wi$h 1 mole of castor oil. By pouring the solution into 100,000 parts by weight of water and finely distributing it therein, an aqueous dispersion which contains 0.02% by weight of the active ingredient i9 obtained.
V. 20 parts by weight of the active ingredient No.
1.010 are thoroughly mixed with 3 parts by weight of the sodium salt of diisobutylnaphthalene-a-sulfonic acid, 17 parts by weigh~ of the sodium salt of ligninsulfonic acid obtained from a sulfite waste liquor and 60 parts by weight of ilica gel powder, and the mixture is milled in 20~816~
- 16 - O.Z. 0050/41791 a hammer mill. By finely distributing the mixture in 20,000 parts by weight of water, a spray liquor which contains 0.1% by weight of the active ingredient is obtained.
VI. 3 parts by weight of active ingredient No. 1.013 are mixed with 97 part~ by weight of finely divided kaolin. A dusting agent which contains 3% by weight of the active ingredient is obtained in this manner.
VII. 30 parts by weight of the active ingredient No.
1.009 ars thoroughly mixed with a mixture of 92 parts by weight of silica gel powder and 8 part~
by weight of liquid paraffin, which were sprayed onto the surface of the silica gel. A formula-tion of the active ingredient having good ad-hesion is obtained in this manner.
VIII. 20 partæ by weight of active ingredient No. l.OlS
are thoroughly mixed with 2 part~ by weight of the calcium salt of dodecylbenzenesulfonic acid, 8 parts by weight of a fatty alcohol polyglycol ether, 2 parts by weight of the sodium salt of a phenol/urea/formaldehyde condensate and 68 parts by weight of a paraffinic mineral oil. A stable oily dispersion is obtained.
IX. 90 part~ by weight of compound No. 1.011 are mixed with 10 parts by weight of N-methyl-a-pyrrolidon~, and a solution which is suitable for use in the form of very small drop8 is obtained.
X. 20 parts by weight of compound No. l.OOS are dissolved in a mixture which consists of 80 parts by weight of xylene, 10 parts by weight of the adduct of from 8 to 10 mole~ of ethylene oxide with 1 mole of oleic acid N-monoethanolamide, 5 parts by weight of the calcium salt of dodecyl-ben~enesulfonic acid and 5 parts by weight of the adduct of 40 moles of ethylene oxide with 1 mole of castor oil. By pouring the solution into - 17 - O.z. 0~5~ gb;~
100,000 parts by weight of water and finely distributing it therein, an aqueous dispersion which contains 0.02% by weight of the active ingredient is obtained.
XI. 20 parts by weight of compound No. 1.004 are dissolved in a mixture which con~ists of 40 part~
by weight of cyclohexanone, 30 parts by weight of isobutanol, 20 parts by weight of the adduct of 7 moles of ethylene oxide with 1 mole of iso-octylphenol and 10 part by weight of the adduct of 40 moles of ethylene o~ide with 1 mole of caRtor oil. By pourins the solution into 100,000 parts by weight of water and finely distributing it therein, an aqueous dispersion which contains 0.02% by weight of the active ingredient is obtained.
XII. 20 parts by weight of active ingredient No. 1.007 are dissolved in a mixture which consists of 25 parts by weight of cyclohexanone, 65 parts by weight of a mineral oil fraction boiling within a range of from 210 to 280C and 10 parts by weight of the adduc~ of 40 moles of ethylene oxide with 1 mole of castor oil. By pouring the ~olution into 100,000 parts by weight of water and finely distributing it therein, an aqueous di~persion which contains 0.02~ by weight of the active ingredient is obtained.
XIII. 20 parts by weight oi the active ingredient No.
1.012 are thoroughly mixed with 3 parts by weight of the sodium salt of dii~obutylnaphthalene-a-sulfonic acid, 17 parts by weight of a Rodium salt of lignin~ulfonic acid obtained from a sulfite wa~te liquor and 6U parts by weight of silica gel powder, and th~ mixture is milled in a hammer mill. By finely distributing the mixture in 20,000 part~ by weight of water, a spray liquor which contain~ 0.1% by weight of th~

20481~0 - 18 - O.Z. 0050/41791 active ingredient is obtained.
XIV. 3 parts by weight of active ingredient No. 1.015 are mixed with 97 parts by weight of finely divided kaolinO A dusting agent which contains s 3% by weight of the active ingredient is obtained in this manner.
XV. 30 parts by weight of the active ingredient No.
1.005 are thoroughly mixed with a mixture of 92 parts by weight of silica gel powder and 8 part~
by weight of liquid paraffin, which were sprayed onto the surface of the silica gel. A formula-tion of the active ingredient having good ad-he~ion is obtained in this manner.
XVI. 20 parts by weight of active ingredient No. 1.006 are thoroughly mixed with 2 parts by weight of the calcium salt of dodecylbenzenesulfonic acid, 8 parts ~y weight of a fatty alcohol polyglycol ether, 2 parts by weight of the sodium salt of a phenol sulfonic acid/urea/formaldehydecondensa~e and 68 parts by weight of a paraffinic mineral oil. A stable oily dispersion is obtained.
The growth-regulating agents or the active ingredients can be applied by the premergence or post-emergence method. If the active ingredients are less well tolerated by certain crops, it i pos~ibla to u~e application method~ where the herbicides are sprayed with the aid of the sprayers in such a way that, as far a~
possible, the herbicides do not come into contact with the leave~ of the sensitive crops while the active ingredients reach the leaves of undesirable plants growing underneath or the uncovered soil surface (post-directed, lay-by).
The application r~te~ of active ingredient are from 0.001 to 10, preferably from 0.01 to 5, in par-ticular from 0.05 to 2, kg/ha of active substance (a.s.), depending on the seass~, the target plants and the stage of growth.

~048160 - 19 - O.Z. 0050/41791 The compounds of the formula IA can influence virtually all development stages of a plant in various ways and are therefore used as growth regulators. The wide ~ange of activity of the plant growth regulators depends in particular a) on the plant specie~ and variety, b) on the time of application, based on the stage of development of the plant, and on the season, c) on the place and method of application (eg. seed dressing, soil treatment, foliage application or trunk injectivn in the case of trees), d) on climatic factors, eg. temperature, amount of precipitation and also length of day and light intensity, e) on the soil quality (including fertilizer applica-tion), f~ on the formulation or application form of the active ingredient and finally g) on the concentrations in which the active substance is used.
of the various possible applica~ions of the novel plant growth regulators of the formula IA in cultivation, in agriculture and in horticulture, a few are mentioned below.
A. ~he vegetative growth of the plants can be greatly inhibited with the compounds which can be used according to the invention, this manifesting itself in particular in a reduction in the growth in length. The treated plants accordingly have stunted growth; a darker 3Q leaf coloration i8 al~o ob~erved.
A reduced intensity of growth of gras~e~ along road edges, hedges and canal bank~ and on lawn area~, such as park3, spor~s ground , orchard~, ornamental lawns and airfields, has proven advantageou~ in practice, enabling the labor-inten~ive and expen3ive cutting of lawns to be reduced.
The increase in the strength of crops su~ceptible 20~8160 - 20 - O.Z. 0050/41791 to lodging, such as cereals, corn, sunflowers and soy-bean, is also of economic interest. The resulting shortening and strengthening of the stem reduces or eliminates the danger of lodging (of bending) of plants under unfavorable weather conditions before the harvest.
The use of growth regulators for inhibiting the growth in length and for changing the time of ripening of cotton is also important. This permits completely mechanized harvesting of this important crop.
In the case of fruit trees and other trees, the growth regulator~ reduce the costs of cutting. Further-more, the alternance of fruit trees can be broken by growth regulators.
By using growth regulators, it is also possible to increase or inhibit the lateral branching of plants.
This is of intere~t if it is intended to inhibit the formation of side shoots in favor of leaf growth, for example in tobacco plants.
The frost resistance can also be considerably increased using growth regulators, for example in winter rape. On the one hand, the growth in length and the development of a leaf and plant mass which is too luxuriant ~and hence particularly susceptible to frost) are inhibited. On the other hand, the young rape plants are held back in the vegetative state of development after sowing and before the onset of the winter frosts, in spite of favorable growth condition~. Thi~ also elLminates the danger of frost to plants which tend to undergo a pr~mature decline in the inhibition of blooming and a changeover to the generative phase. In other crop~
too, for example winter cereals, it is advantageous if the stocks are well tillered in the fall by treatment with novel compounds but do not enter the winter with exce~sively luxuriant growth. This make~ it possible to prevent great sensitivity to frost and, owing to the relatively small leaf or plant mass, attack by various diseases, for example fungal disease. Furthermore, the - 21 - O.Z. ~ ~
inhibition of vegetative growth permits denser planting of the soil in many crops, so that it is possible to obtain a greater yield, based on the soil area.
B. Greater yields of both plant parts and plant ingredients can be obtained using the growth regulators.
For example, it is possible to induce the growth of greater amount~ of bud~, blooms, leaves, fruit~, seeds, roots and tubers, to increase the content of sugar in sugar beet, sugar cane and citrus fruits, to increase the protein content in cereals or soybean or to stimulate greater latex flow in rubber trees.
The compounds of the formula IA can increase yields by intervening in the plant metabolism or by promoting or inhibiting vegetative and/or generative growth.
C. Finally, using plant growth regulators it is possible both to shorten or lengthen the stage~ of development and to accelerate or retard the ripening of harvested plant part~ before or after harvesting.
For example, facilitating har~esting is of economic interest, this being permitted by concentrated dropping or a reduction in the adhesion to the tree in citrus fruits, olives or other species and varieties of pomes, drupes and hardshell fruit. The same mechanism, ie. promotion of the formation of abscission tissue between the frui~ or leaf part and the shoot part of the plant i~ also Lmportant for readily controllable defolia-tion of crops such as cotton.
D. Growth regulator~ can also be used for reducing the water consumption of plants. This i~ particularly important for agricultural area~ which have to be artifi-cially irrigated at high expense, for example in arid or semiarid regions. By using the novel substance~, it i~
possible to redllce the inten~ity of irrigation and hence carry out more economical farming. Under the influence of growth regulators, the available water i~ better utilized becau e, inter alia, 204~160 - 22 - o.z. 0050/~1791 - the extent of opening of the stomata i5 reduced, - a thicker epidermis and cuticula are formed, - root penetration of the ~oil is improved and - the microclLmate in the plant stock is advantageously affected by more compact growth.
The growth regulators of the formula IA which are to be used according to the invention can be fed to the crops both via the seed (as seed dressings) and via the soil, ie. through the roots and, particularly preferably, via the foliage by spraying.
Because of the good toleration by plants, the application rate can be greatly varied.
In view of the wide range of methods of applica-tion, the novel compound~ or agents containing them can be used in a large number of crops.
To broaden the action spectrum and to achieve synergistic effect~, the novel active ingredients IA can be mixed with a large number of herbicidal or growth-regulating active ingredients and applied together with these. Examples of suitable components for mixture are diazines, 4H-3,1-benzoxazine derivatives, benzothia-diazinones, 2,6-dinitroanilines, N-phenylcarbamates, thiocarbamates, halocarboxylic acids, triazines, amides, urea~, diphenyl ethers, triazinones, uracils, benzofuran derivatives, cyclohexane-1,3-dione derivatives, quino-linecarboxylic acid derivatives, aryloxy- and hetaryloxy-phenoxypropionic acids and their salts, esters and amides, and others.
It may also be advantageous to apply the active ingredientY IA, alone or in combination with other herbicides, also as a mixture with further crop protec-tion agent~, for example with pesticides or agents for controlling phytopathogenic fungi or bacteria. The miscibility with mineral salt ~olutions, which are used for eliminating nu~rient and trace element deficiencies, i~ also of interest. Nonphytotoxic oils and oil con-centrates can also be added.

2a4sl60 - 23 - O.Z. 0050/41791 Example~ of synthesis The methods described in the Examples of syn-thesis below were used with appropriate modification of the starting compounds in order to obtain further active ingredients IA. The compounds thus obtained are shown in the Tables below together with physical data.

Bis-(propoxyamino)-ethanedione 17.5 g (O.157 mol) of O-propylhydroxylamine hydrochloride, 18.1 g (0.22 mol) of sodium acetate and 10 g (0.0787 mol) of oxalyl chloride were added in succession to 200 ml of acetic acid at 20C. The mixture was stirred for twenty hours at 25C and then filtered under suction and the filtrate was evaporated down under reduced pressure. 200 ml of ethyl acetate were added to the re~idue and the soll~tion was then washed with three times 20 ml of water, dried over Na2SO~, evaporated down under reduced pres~ure and then crystallized in 40 ml of 1 : 1 ethyl acetate/pentane. 8.7 g (54.2~ of theory) of bi~-(propoxyamino)-ethanedione were obtained as colorles3 crystals of melting point 147-150C ~Active Ingredient Example 1.008).

l-(Propoxyamino)-2-(allyloxyamino)-ethanedione 16.1 g (0.1 mol) of methyl propoxyaminooxo-acetate, 16.5 g (0.15 mol3 of O-allylhydkoxylamine hydrochloride and 15 g (0.15 mol) of triethylamine were added in ~ucces~ion to 100 ml of methanol. The mixture wa3 stirred for 20 hours at 60C and then evaporated down.
250 ml of methylene chloride were added to the residue and the solution wa~ washed with twice 50 ml of water, dried over Na2SO4 and evaporated down under reduced pre~sure. 40 ml of 1 : 1 ethyl acetate/pentane were added to the re~idue and the cry~tal3 were filtered off under ~uction and dried. 12 g (59.4~ of theory) of 1-(propoxyamino)-2-(allyloxyamino)-ethanedione were 2~81~
- 24 - O.Z. 0050/41791 obtained as white crystals of melting point 90-91C
(Active Ingredient Example 1.009).

Rl-O-NH-CO-CO-NHO-R2 (I) Example mp.( No. R ~ R2 bp. (C~bdr~
1~0Ol CH3 CH3 166-16~
1.002 C2H5 C2H5 183-185*
1.003 H2C=cBr-cH2- H2C~C~r-cH2- 112-114 1.004 CH3-CH=CH-CH2- CH3-CH~CH-CH2- 1~0-192 1.005 H2C-C(cH3~-cH2 H2C~C(cH3)-cH2 107-t10 1.006 n-C4Hg n-C4Hg 151-153 1.007 HC_C-CH2- HC--C-CH2- 195-197 1.008 CH3CH2CH2 CH3CH2CH2- 147-150 1.009 CH3C~2CH2 CH2=CHCH2- 90- 91 1.010 CH23CHCH2 CH2 CHCH2 1~1-193 1-011 i-C3H7 i-C3H~ 167-169 1.012 CICH~CHCH2 CICH~CHC~2 198-201 1.013 n-C5HIl n-C5H11 138-140 1.014 n-C6H13 n-C6H13 145-148 1.015 ~6H5CH2 C6H5CH2 195-196 W. Lossen et al., Chem. Ber. 27 (1894), 1111 Use Examples The growth-regulating action of the compounds of the Formula I was demonstrated by the following experiment~:
The ac~ive ingredients were prepared ~) as a 0.1% strength solution in acetone or b3 as a 10% strength emulsion in a mixture of 70% by weight of cyclohexanolr 20% by weight of Nekanil~ LN (Lutensol~
AP6, wetting agent having an emul~ifying and dispersing action and based on ethoxylated alkylphenols) and 10% by weight of Emulphor~ EL (Emulan~ EL, emulsifier based on ethoxylated fatty alcohols) and were diluted with acetone in the case of a) and with - 25 - o.z. o~Q0$~1~9~1 water in the case of b) to give the desired concentration.
The culture ve sels used were plastic flower pots (diameter about 12.5 cm; volume about 500 ml) containing loamy sand with about 3.0% of humus as a substrate. The seeds of the test plants were sown separately according to species.
In pre-emergence use, the active ingredients suspended or emulsified in water were applied directly after sowing by means of finely distributing nozzles. The vessels were lightly watered in order to promote germina-tion and growth and then covered with transparent plastic covers until the plants had begun to grow. Covering ensures uniform germination of the test plants.
For the post-emergence treatment, the test plants were not treated with the active ingredients suspended or emulsified in water until a height of growth of from 3 to 15 cm had been reached, depending on the form of growth.
The plantY were kept at 10-25~C or 20-35C, according to species. The test period extended over from 2 to 4 weeks. During thi~ time, the plant~ were tended and their reaction to the individual treatments was evaluated.
The growth-regulating action observed was con-firmed by measuring the height of growth at the end of the test. The measured values thus obtained were ex-pressed as 8 ratio to the height of growth of untreated plants. N-(2-chloroethyl)-N,N,N-trimethylammonium chloride (Example A) was used as a comparative substance for evaluating the growth-regulating action.
The plants used in tho greenhouse experiments were spring whea~ (cv. Ralle~, summer barley (cv Aramir), rice (cv. Bahia), 3unflowers ~cv. Spanners Allzweck) and summer rape (cv. Petranova3.
In post-emergence u~e of 0.4 mg/vessel, compound 1.00~ had a better action than the known growth regulator 20481~G
- 26 - O.Z. 0050/41791 A in the case of spring wheat (cv. Ralle), summer barley (cv. Aramir) and rice (cv. Bahia).
In post-emergence use of 6 mg/vessel, compound 1.005 had a better action than the known growth regulator A in the case of sunflowers (cv. Spanners Allzweck) and summer rape (cv. Petranova).
The color intensity of the leaves increased sLmultaneously with the reduction in the growth in length. The increased chlorophyl content indicates a higher photosynthesi~ rate and hence an increase in yield.

Claims (5)

1. An oxalylbishydroxamic acid derivative of the formula I

where R1 and R2 independently of one another are each C1-C20-alkyl, C3-C18-alkenyl or C3-C8-alkynyl, where these groups may carry from one to five halogen atoms, monocyclic or polycyclic C3-C10-cycloalkyl or C3-C10-cyclo-alkylmethyl, where these rings may carry from one to three C1-C4-alkyl groups or one phenyl ring, monocyclic or polycyclic C5-C10-cycloalkenyl or C5-C10-cycloalkenylmethyl, where these rings may carry from one to three C1-C4-alkyl groups or one phenyl ring, and phenyl, phenyl-C1-C4-alkyl or phenyl-C2-C6-alkenyl, where the aromatic radicals may carry from one to five halogen atoms and/or from one to three of the following groups:
nitro, C1-C4-alkyl, C1-C4-haloalkyl, C1-C4-alkoxy, C1-C4-haloalkoxy, C1-C4-alkylthio or C1-C4-haloalkylthio, where R1 and R2 are not simultaneously ethyl, and its agriculturally useful salts.
2. A process for the preparation of a compound of the formula I as claimed in claim 1, wherein an oxalyl-hydroxamic ester of the formula II

is reacted with a hydroxylamine derivative of the formula III

in a conventional manner in an inert organic solvent.
3. A process for the preparation of a compound of the formula I as claimed in claim 1, in which R1 and R2 have the same meanings, wherein an oxalyl halide of the formula IV
Hal-CO-CO-Hal IV
where Hal is halogen, is reacted in a conventional manner in an inert organic solvent in the presence of a base with hydroxylamine of the formula III

- 28 - O.Z. 0050/41791
4. A plant growth regulator containing an amount, having a regulating effect, of a compound of the formula I as claimed in claim 1 and inert additives.
5. A method for regulating plant growth, wherein the plants, their habitat or their seeds are treated with an amount, having a regulating effect, of an oxalylbis-hydroxamic acid of the formula IA

where R1 and R2 independently of one another are each C1-C20-alkyl, C3-C18-alkenyl or C3-C8-alkynyl, where these groups may carry from one to five halogen atoms, monocyclic or polycyclic C3-C10-cycloalkyl or C3-C10-cyclo-alkylmethyl, where these rings may carry from one to three C1-C4-alkyl groups or one phenyl ring, monocyclic or polycyclic C5-C10-cycloalkenyl or C5-C10-cycloalkenylmethyl, where these rings may carry from one to three C1-C4-alkyl groups or one phenyl ring, and phenyl, phenyl-C1-C4-alkyl or phenyl-C2-C6-alkenyl, where the aromatic radicals may carry from one to five halogen atoms and/or from one to three of the following groups:
nitro, C1-C4-alkyl, C1-C4-haloalkyl, C1-C4-alkoxy, C1-C4-haloalkoxy, C1-C4-alkylthio or C1-C4-haloalkylthio, and their agriculturally useful salts.
CA002048160A 1990-07-31 1991-07-30 Oxalylbishydroxamic acid derivatives, their preparation and plant growth regulators containing them Abandoned CA2048160A1 (en)

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DE4024283A DE4024283A1 (en) 1990-07-31 1990-07-31 OXALYL-BISHYDROXAMSAEUR DERIVATIVES, THEIR PRODUCTION AND PRODUCTS CONTAINING US FOR THE REGULATION OF PLANT GROWTH
DEP4024283.8 1990-07-31

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CN112079747A (en) * 2020-10-20 2020-12-15 浙江工业大学 N-benzyloxy substituted symmetrical oxamide compound and preparation method and application thereof

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DE4226558A1 (en) * 1992-08-11 1994-02-17 Basf Ag Piperazin-2,3-dione as plant growth regulators
US5399589A (en) * 1992-12-17 1995-03-21 Basf Aktiengesellschaft Oxalyl hydrazide-hydroxamic acid derivatives, their preparation and their use as fungicides
CN112142619B (en) * 2020-10-20 2023-01-10 浙江工业大学 1, 1-cyclopropane dicarboxylic acid amide compound and preparation method and application thereof

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112079747A (en) * 2020-10-20 2020-12-15 浙江工业大学 N-benzyloxy substituted symmetrical oxamide compound and preparation method and application thereof
CN112079747B (en) * 2020-10-20 2022-08-16 浙江工业大学 N-benzyloxy substituted symmetrical oxamide compound and preparation method and application thereof

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DE59101927D1 (en) 1994-07-21
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EP0469423A1 (en) 1992-02-05
DE4024283A1 (en) 1992-02-06

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