Note: Descriptions are shown in the official language in which they were submitted.
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.
-10- -Z-
TABLE
Rl-ONH-CO-CO-NHO-R2 ( I )
Rl R2
CH3 CH3
CH3 C2H5
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 )
R 2
_
CH3 CH2=C(Cl)cH2
CH3 CH2=C(~r)cH2
CH3 CICH=C(CI)CH2-
CH3 Cl22C(CI)CH2-
CH3 CICH2CH2
CH3 C13CCH2-
CH3 CICH2CH2CH2-
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 C6H5-CH2-
CH3 4CI-C6~4-CH2
CH3 3CI-C6H4-CH2
CH3 3,4C12-C6H3-CH2
CH3 2,4C12-C6~3-CH2-
CH3 4F-C6H4-CH2-
CH3 4Br-C6H4-CH2
CH3 4-CH3-C6H4-CH2-
CH3 2,4-~CH3)2-C6H3-CH2-
CH3 4-C2H5-C6H4-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-
C6H5-CH2- C6H5-CH2-
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.
EXAMPLE 1
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).
EXAMPLE 2
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).
TABLE 1
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.
