HERBICIDAL COMPOSITION

HERBICIDE

English Abstract

- 1 -
Case 5-14381/1+2/=
HERBICIDAL COMPOSITION
Abstract
There are described herbicidal compositions
containing, in addition to
a) a herbicidally effective sulfonylurea of the formula
<IMG> (I)
wherein
X is halogen, C1-C3-haloalkenyl, C1-C3-alkoxycarbonyl,
C3-C4-alkenyloxy, C1-C3-haloalkoxy, C1-C3-haloalkyl-
thio, C1-C3-alkoxy-C1-C2-alkoxy or nitro,
X1 is hydrogen, or together with X forms a bridge member
2-O-CH2CH2-3, <IMG> or <IMG>,
Y is hydrogen or halogen,
E is nitrogen -N= or methine -CH=,
R1 is halogen, C1-C3-alkyl, C1-C3-alkoxy, C1-C4-haloalkoxy
or cyclopropyl, and
R2 is C1-C3-alkyl, C1-C3-alkoxy, C1-C4-haloalkoxy,
cyclopropyl or dimethylamino,
b) an oxime ether acting as an antidote and corresponding
to the formula
<IMG> (II)

- 2 -
wherein n is 1 or 2, R3 and R4 are each hydrogen or
alkyl, R5 and R5 are each hydrogen, halogen, alkyl,
haloalkyl, alkoxy, haloalkoxy, alkylthio, haloalkylthio,
alkylsulfinyl, alkylsulfonyl, haloalkylsulfinyl, halo-
alkylsulfonyl or nitro, R7 and R8 separately are each
alkyl or alkenyl, or together are a 1,2-ethylene or
1,3-propylene group each unsubstituted or substituted by
one or more alkyl groups, and X is a cyano group or a
fluorinated alkyl group which can also contain chlorine;
and also described is the use of these compositions for
the selective control of weeds.

Claims

21489-6491
THE EMBODIMENTS OF THE INVENTION IN WHICH AN EXCLUSIVE
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A herbicidal composition which comprises:
(a) a herbicidally active amount of a sulfonylurea of the
formula I
(I)
<IMG>
wherein
X is halogen, C1-C3-haloalkenyl, C1-C3-alkoxycarbonyl,
C3-C4-alkenyloxy, C1-C3-haloalkoxy, C1-C3-haloalkylthio,
C1-C3-alkoxy-C1-C2-alkoxy or nitro,
X1 is hydrogen, or together with X forms a bridge member
2-O-CH2CH2-3, <IMG> or <IMG>,
Y is hydrogen or halogen,
E is nitrogen -N= or methine -CH=,
R1 is halogen, C1-C3-alkyl, C1-C3-alkoxy, C1-C4-haloalkoxy
or cyclopropyl, and
R2 is C1-C3-alkyl, C1-C3-alkoxy, C1-C4-haloalkoxy, cyclo-
propyl or dimethylamino, and
(b) a herbicide antagonistic amount of an oxime ether of the
formula II
37

<IMG> (II)
wherein n is 1 or 2, R3 and R4 are each hydrogen or C1-C4-alkyl,
R5 and R6 are each hydrogen, halogen, C1-C4-alkyl, C1-C4-halo-
alkyl, C1-C4-alkoxy, Cl-C4-haloalkoxy, C1-C4-alkylthio, C1-C4-
haloalkylthio, C1-C4-alkylsulfinyl, C1-C4-alkylsulfonyl, C1-C4-
haloalkylsulfinyl, C1-C4-haloalkylsulfonyl or nitro, R7 and R8
separately are each C1-C4-alkyl or C3-C4-alkenyl, or together are
a 1,2-ethylene group or 1,3-propylene group each unsubstituted or
substituted by one or more alkyl groups, and X is a cyano group or
a fluorinated C1-C3-alkyl group which can also contain chlorine,
and
(c) if desired, an agriculturally acceptable carrier.
2. A herbicidal composition according to claim 1, wherein
the quantity ratio of antidote to herbicidal active ingredient is
between 1:10 and 10:1.
3. A herbicidal composition according to claim 1, which
contains as herbicidal active ingredient a sulfonyl-urea selected
from the group comprising: N-[2-(2'-chloroethoxy)-phenyl-
sulfonyl]-N'-(4-methyl-6-methoxy-triazin-2-yl)-urea, N-[2-(2'-
methoxyethoxy)-phenyl-sulfonyl]-N'-(4-methyl-6-methoxy-triazin-2-
yl)-urea, N-[2-(2-butenyloxy)-phenyl-sulfonyl]-N'-(4-methyl-6-
38

methoxy-triazin-2-yl)-urea, N-[2-(3-trifluoropropen-1-yl)-phenyl-
sulfonyl]-N'-(4-methyl-6-methoxy-triazin-2-yl)-urea, N-(2,5-di-
chlorophenyl-sulfonyl)-N'-(4 methyl-6-methoxypyrimidin-2-yl)-urea,
N-(2-methoxycarbonyl-phenyl-sulfonyl)-N'-(4-methyl-6-di-
fluoromethoxy-pyrimidin-2-yl)-urea, N-(2-pentafluoroethoxyphenyl-
sulfonyl)-N'-(4,6-dimethoxytriazin-2-yl)-urea, N-(2-chlorophenyl-
sulfonyl)-N'-(4-methyl-6-methoxy-triazin-2-yl)-urea, N-(2-methoxy-
carbonyl-phenyl-sulfonyl)-N'-(4,6-dimethyl-pyrimidin-2-yl)-urea,
N-(2-allyloxy-phenylsulfonyl)-N'-(4-methyl-6-ethoxy-triazin-
2-yl)-urea, N-(2-nitrophenyl-sulfonyl)-N'-(4-methyl-6-difluoro-
methoxypyrimidin-2-yl)-urea and N-(2-methoxycarbonyl-phenyl-
39

sulfonyl)-N'-(4-methyl-6-methoxy-triazin-2-yl)-urea,
N-(2-difluoromethoxyphenylsulfonyl)-N'-(4-methyl-6-
methoxy-pyrimidin-2-yl)-urea, N-(2-methoxyethoxyphenyl-
sulfonyl)-N'-[4-methoxy-6-(2',2',2'-trifluoroethoxy)-
1,3,5-triazin-2-yl]-urea, N-(2-methoxycarbonylphenyl-
sulfonyl)-N'-(4-cyclopropyl-6-methoxy-1,3,5-triazin-2-yl)-
urea, N-(2-difluoromethoxyphenyl-sulfonyl)-N'-(4-cyclo-
propyl-6-methoxy-1,3,5-triazin-2-yl)-urea, N-[2-(3',3',3'-
trifluoroprop-l-en-l-yl)-phenyl-sulfonyl]-N'-(4-methoxy-6-
methyl-1,3,5-triazin-2-yl)-urea, N-(2-methoxycarbonyl-
phenyl-sulfonyl)-N'-(2,4-difluoromethoxy-pyrimidin-2-yl)-
urea, N-(2-difluoromethoxyphenyl-sulfonyl)-N'-(4-dimethyl-
amino-6-methoxy-1,3,5-triazin-2-yl)-urea, N-[2-(1',2'-
dichlorovinyloxy)-phenyl-sulfonyl]-N'-(4-methoxy-6-methyl-
1,3,5-triazin-1-yl)-urea, N-(2,2-dioxo-3-methyl-1-oxa-
2-thia-1,2,3,4-tetrahydro-naphthalen-8-yl)-N'-(4-methoxy-
6-methyl-1,3,5-triazin-2-yl)-urea, N-(2,2-dioxo-3-methyl-
1-oxa-2-thia-1,2,3,4-tetrahydro-naphthalen-8-yl)-N'-
(4-methoxy-6-methyl-pyrimidin-2-yl)-urea, N-(2-methoxy-
carbonylphenyl-sulfonyl)-N'-4,6-dimethoxypyrimidin-2-yl)-
urea, N-(2-methoxycarbonylphenyl-sulfonyl)-N'-(4-methoxy-
6-methylpyrimidin-2-yl)-urea, N-(2-ethoxyphenyl-sulfonyl)-
N'-(4-difluoromethoxy-6-methoxy-pyrimidin-2-yl)-urea,
N-(2-methoxyethoxyphenyl-sulfonyl)-N'-(4,6-dimethoxy-
triazin-2-yl)-urea, N-(2-ethoxyphenyl-sulfonyl)-N'-
(4-chloro-6-methoxypyrimidin-2-yl)-urea, N-(2-ethoxy-
phenylsulfonyl)-N'-(4-difluoromethoxy-6-methylpyrimidin-
2-yl)-urea and N-[2-(2-chloroethylmercapto)-phenyl-
sulfonyl)-N'-(4-methoxy-6-methyl-1,3,5-triazin-2-yl)-urea,
which herbicidal composition also contains as antidote
an oxime ether of the formula II according to claim 1.
4. A herbicidal composition according to claim 1
containing a herbicidal active ingredient of the formula I,

which composition contains, as antidote, an oxime ether
of the formula II according to claim 1, wherein n is 1,
R3, R4 and R6 are hydrogen, R5 is hydrogen, halogen, methyl,
difluoromethyl, trifluoromethyl, chlorodifluoromethyl,
methoxy, difluoromethoxy, trifluoromethoxy, chlorodifluoro-
methoxy, tetrafluoroethyl, tetrafluoroethoxy or trifluoro-
methylsulfonyl, X is a cyano group or perfluorinated
C1-C3-alkyl or chlorodifluoromethyl, and R7 and R8 have
the meanings defined in claim 1.
5. A herbicidal composition according to claim 1
containing a herbicidal active ingredient of the formula I,
which composition contains, as antidote, an oxime ether
of the formula II according to claim 1, wherein n is 1,
R3, R4 and R6 are hydrogen, R5 is hydrogen, fluorine,
chlorine, methyl, difluoromethyl, trifluoromethyl, chloro-
difluoromethyl, methoxy, difluoromethoxy, trifluoromethoxy,
chlorodifluoromethoxy, tetrafluoroethyl, tetrafluoroethoxy
or tetrafluoromethylsulfonyl, X is a cyano group or
trifluoromethyl, chlorodifluoromethyl or pentafluoroethyl,
and R7 and R8 together are a 1,2-ethylene group which is
unsubstituted or substituted by 1-4 methyl groups.
6. A herbicidal composition according to claim 1
containing as active ingredient a sulfonylurea of the
formula I, which composition contains, as antidote,
1-phenyl-1-(1,3-dioxolan-2-yl-methoximino)-2,2,2-tri-
fluoroethane.
7. A herbicidal composition according to claim 1
containing as active ingredient a sulfonylurea of the
formula I, which composition contains, as antidote,
1-(4 chlorophenyl)-1-(1,3-dioxolan-2-yl-methoximino)-
2,2,2-trifluoroethane.
41

8. A herbicidal composition according to claim 1
containing as active ingredient a sulfonylurea of the
formula I, which composition contains, as antidote,
1-(4-chlorophenyl)-1-(2,2-diethoxyethoximino)-2,2,2-
trifluoroethane.
9. A herbicidal composition according to claim 1
containing as active ingredient a sulfonylurea of the
formula I, which composition contains, as antidote,
1-(4-chlorophenyl)-1-(2,2-dimethoxyethoximino)-2,2,2-
trifluoroethane.
10. A herbicidal composition according to claim 1
containing as active ingredient a sulfonylurea of the
formula I, which composition contains, as antidote,
1-(4-fluorophenyl)-1-(1,3-dioxolan-2-ylmethoximino)-
2,2,2-trifluoroethane.
11. A herbicidal composition according to claim 1
containing as active ingredient a sulfonylurea of the
formula I, which composition contains, as antidote,
a-(1,3-dioxolan-2-ylmethoximino)-benzyl cyanide.
12. A herbicidal composition according to claim 1
containing as active ingredient a sulfonylurea of the
formula I, which composition contains, as antidote,
.alpha.-(2,2-dimethoxyethoximino)-benzyl cyanide.
13. A herbicidal composition according to claim 1
containing as active ingredient a sulfonylurea of the
formula I, which composition contains, as antidote,
1-(2-fluorophenyl)-1-(1,3-dioxolan-2-yl-methoximino)-
2,2,2-trifluoroethane.
42

14. A herbicidal composition according to claim 1 containing
as active ingredient a sulfonylurea of the formula I, which
composition contains, as antidote, .alpha.-(1,3-dioxan-2-ylmethoximino)-
benzyl cyanide.
15. A herbicidal composition according to claim 1 containing
as active ingredient a sulfonylurea of the formula I, which
composition contains, as antidote, .alpha.-(5,5-dimethyl-1,3-dioxan-2-
yl methoximino)-benzyl cyanide.
16. A herbicidal composition according to claim 1 containing
as active ingredient a sulfonylurea of the formula I, which
composition contains, as antidote, .alpha.-(2,2-dimethoxyethoximino)-
3,4-dichlorobenzyl cyanide.
17. A herbicidal composition according to claim 1 containing
as active ingredient a sulfonylurea of the formula I, which
composition contains, as antidote,.alpha.-(1,3-dioxolan-2-ylethoximino)-
3,4-dichlorobenzyl cyanide.
18. A herbicidal composition according to claim 1 containing
as active ingredient a sulfonylurea of the formula I, which
composition contains, as antidote, .alpha.-(2,2-dimethyl-1,3-dioxan-2-
ylmethoximino)-4-methoxybenzyl cyanide.
19. A herbicidal composition according to claim 1 containing
as active ingredient a sulfonylurea of the formula I, which
43

composition contains, as antidote, .alpha.-(2,2-diethoxyethoxyimino)-4-
methoxybenzyl cyanide.
20. A process for protecting crops of cultivated plants from
damage caused by sulfonylureas, which process comprises combining
the application of a herbicidally active amount of a sulfonylurea
of the formula I according to claim 1 to the crop area of the
cultivated plants, to the seeds or seedlings of the plants, or to
the plants themselves, with the application of a herbicide-
antagonistic active amount of an oxime ether of the formula II
according to claim 1.
21. A process according to claim 20 for protecting
cultivated plants from damage that could otherwise occur on appli-
cation of a sulfonylurea of the formula I according to claim 1,
which process comprises
a) treating the cultivated area for the plants before or
during application of the sulfonylurea, or
b) treating the seeds or seedlings of the plants themselves
with an effective amount of an oxime ether of the formula II
according to claim 1.
22. A process according to claim 20 for protecting culti-
vated plants from damage that could otherwise occur on application
of a sulfonylurea of the formula I according to claim 1, wherein
the oxime ether used is .alpha.-(1,3-dioxolan-2-ylmethoximino)-benzyl
cyanide.
44

23. A process according to claim 20 wherein from 0.1 to 10
kg/ha of herbicide-antidote active mixture is applied.
24. A process according to claim 20 wherein from 0.25 to 5
kg/ha of herbicide-antidote active mixture is applied.

Description

~2~
-- 1 --
Case 5 14381/1+2/=_
HERBICIDAL COMPOSITION
The present invention relates to a herbicidal compo-
sition containing, besides a herbicidally active sulfonyl-
urea, an oxime ether which acts as an antidote, to the use
of this composition for selectively controlling weeds in
crops of cultivated plants, and to the use of oxime ethers
as antidotes.
Sulfonylureas as herbicidal agents for crops of
cultivated plants are known for example from the U.S.
Patent SpeciEications Nos. 4,127,405, 4,169,719 and
4,238,621, from EP-A 84020 and from the South African Patent
Specifications No. 4874/81 and 127/83. Compared with other
herbicides, the sulfonylurea herbicides have the outstanding
property of being highly effective. Against the advantages
offered, with regard to cost and ecological factors, by
the relatively low level of active substance involved with
the use of sulfonylurea herbicides has to be set the
increased risk of a resulting overdose possibly damaging the
cultivated plants. The occurrence of a harmful side-effect
of sulfonylurea herbicides can depend also on climatic
conditions, on the weather and on the preliminary treatment
of the soil.
After recognition of this problem, attempts were made
a

to find antidotes which would protect the cultivated plants
from the said harmful effects occurring with the use of
sulfonylurea herbicides, without at the same time
lessening the herbicidal effectiveness of these compounds.
In the U.S. Patent Specification No. 4,343,649 there are
described, as being such antidotes, 1,8-naphthalic acid
anhydride, N,N-diallyl-2,2-dichloroacetamide and a-cyano.
These antidotes are used in herbicidal compositions,
together with individual herbicidally effective sulfonyl-
ureas.
The object of the present invention was to find
suitable antidotes against the plant-damaging side-effect
of herbicidally active sulfonylureas.
It has been found that the side-effect, which damages
cultivated plants, of herbicidally active sulfonylureas
of the general formula I can be eliminated or greatly
reduced with the aid of oxime ethers of the general
formula II as antidotes.
The sulfonylureas correspond to the general formula I
5~--6 N--
4! --S02NHCONH~
\ / \ /
3~=~2 N=-
x 1 X \R2
wherein
X is halogen, Cl-C3-haloalkenyl, Cl-C3-alkoxycarbonyl,
C3-C4-alkenyloxy, Cl-C3-haloalkoxy, Cl-C3-haloalkyl-
thio~ Cl-C3-alkoxy-Cl-C2-alkoxy or nitro,
Xl is hydroger-, or together with X forms a bridge member

2-o-CH2CH2-3, 2-OCH-CH2-3 or 2-o-S02CH-CH2-3,
CH3 CH3
Y is hydrogen or halogen,
E is nitrogen -N= or methine -CH=,
~1 is halogen, Cl-C3-alkyl, Cl-C3-alkoxy, Cl-C4-haloalkoxy
or cyclopropyl, and
R2 is Cl-C3-alkyl, Cl C3-alkoxy~ Cl-C4-haloalkoxy,
cyclopropyl or dimethylamino.
Compounds in which Y = H are preferred.
- Halogen can be for example fluorine, chlorine and bromine,
particularly however chlorine.
- By haloalkenyl is meant for example haloethenyl, halo-
propenyl and, preferably, 3,3,3-trifluoropropenyl.
- Alkoxycarbonyl can be for example methoxy, ethoxy, propoxy
or isopropoxycarbonyl, but preferably methoxycarbonyl.
- By alkenyloxy is meant for example: allyloxy, propenyloxy,
buten-2-yloxy, buten-3-yloxy, l-methyl-alkyloxy, 2-methyl-
alkyloxy, l-methylpropenyloxy and 3-methylpropenyloxy,
especially however allyloxy and buten-2-yloxy.
- Haloalkoxy can be for example: halomethoxy, haloethoxy,
halopropoxy and haloisopropoxy, preferably however
chloromethoxy, chloroethoxy, fluoromethoxy or fluoroethoxy;
particularly preferred as X is 2-chloroethoxy and
pentafluoroethoxy, and as Rl difluoromethoxy.
- By alkoxy-alkoxy is meant for example: methoxy-methoxy,
2-methoxy-ethoxy, ethoxy-methoxy, 2-ethoxy-ethoxy,
n-propoxy-methoxy, isopropoxy-methoxy, 2-n-propoxy-ethoxy
and 2-isopropoxy-ethoxy, but especially 2-methoxy-ethoxy.
- Y can be for example hydrogen or halogen, such as fluorine,
chlorine or bromine, in particular hydrogen or chlorine.

-- 4 --
- ~y alkyl is meant for example: methyl, ethyl, n-propyl
or i-propyl, preferably methyl.
- Alkoxy is for example: methoxy, ethoxy, n-propoxy or
i-propoxy, preferably methoxy and ethoxy.
Sulfonylureas which have proved particularly effective
herbicidally are the compounds of the formula I wherein
Y is H.
The following sulfonylureas are especially preferred
herbicides:
N-[2-(2'-chloroethoxy)-phenyl sulfonyl]-N'-(4-methyl-6-
methoxy-triazin-2-yl)-urea, N-[2-(2'-methoxyethoxy)-phenyl-
sulfonyl]-N'-(4-methyl-6 methoxy-triazin-2-yl)-urea,
N-[2 (2-butenyloxy)-phenyl-sulfonyl]-N'-(4-methyl-6-methoxy-
triazin-2-yl)-urea, N-[2-(3-trifluoropropen-1-yl)-phenyl-
sulfonyl]-N'-(4-methyl-6-methoxy-triazin-2-yl)-urea,
N-(2,5-dichlorophenyl-sulfonyl)-N'-(4-methyl-6-methoxy-
pyrimidin-2-yl)-urea, N-(2-methoxycarbonyl-phenyl-sulfonyl)-
N'-(4-methyl-6-difluoromethoxy-pyrimidin-2-yl)-urea,
N-(2-pentafluoroethoxyphenyl-sulfonyl)-N'-(4,6-dimethoxy-
triazin-2-yl)-urea, N-(2-chlorophenyl-sulfonyl)-N'-(4-
methyl-6-methoxy-triazin-2-yl)-urea., N-(2-methoxycarbonyl-
phenyl-sulfonyl)-N'-(4,6-dimethyl-pyrimidin-2-yl)-urea,
N-(2-allyloxy-phenyl-sulfonyl)-N'-(4-methyl~6-ethoxy-
triazin-2-yl)-urea, N-(2-nitrophenyl-sulfonyl)-N'-(4-methyl-
6-difluoromethoxy-pyrimidin-2-yl)-urea and N-(2-methoxy-
carbonyl-phenylsulfonyl)-N'-(4-methyl-6-methoxy-triazin-2-
yl)-urea, N-(2-difluoromethoxyphenylsulfonyl)-N'-(4-methyl-
6-methoxy-pyrimidin-2-yl)-urea, N-(2-methoxyethoxyphenyl-
sulfonyl)-N'-[4-me~hoxy-6-(2'92',2'-trifluoroethoxy)-
1,3,5-triazin-2-yl]-urea, N-(2-methoxycarbonylphenyl-
sulfonyl)-N'-(4-cyclopropyl-6-methoxy-1,3,5-triazin-2-yl)-
urea, N-(2-difluoromethoxyphenyl-sulfonyl)-N'-(4-cyclo-

~22~
-- 5 --
propyl-6-methoxy-1,3,5-triazi.n-2-yl)-urea, N-[2-(3',-
3',3'-trifluoroprop-1-en-1-yl)-phenyl-sulfonyl]-N'-
(4-methoxy-6-methyl-1,3~5-triazin-2-yl)-urea, N-(2-
methoxycarbonylphenylsulfonyl)-N'-(2,4-difluoromethoxy-
pyrimi.din-2-yl)-urea, N-(2-difluoromethoxyphenyl-sulfonyl)-
N'-(4-dimethylamino-6-methoxy-1,3,5-triazin-2-yl)-urea,
N-[2-(1',21-dichlorovinyloxy)-phenylsulfonyl~-N'-(4-
methoxy-6-methyl-1,3,5-triazin~l-yl)-urea, N-(2,2-dioxo-
3-methyl-1-oxa-2-thia-1,2,3,4-tetrahydro-naphthalen-8-yl)-
N'-(4-methoxy-6-methyl-1,3~5-triazin-2-yl)-urea, N-(2,2-
dioxo-3-methyl-1-oxa-2-thia-1,2 a 3,4-tetrahydro-napththalen-
8-yl)-N'-~4-methoxy-6-methyl-pyrimidin-2-yl)-urea,
N-(2-methoxycarbonylphenyl-sulfonyl)-N'-(4,6-dimethoxy-
pyrimidin-2-yl)-urea, N-(2-methoxycarbonylphenyl-sulfonyl)-
N'-(4-methoxy-6-methyl-pyrimidin-2-yl)-urea, N-(2-ethoxy-
phenyl-sulfonyl)-N'-(4-difluoromethoxy-6-methoxy-pyrimidin-
2-yl)-urea, N-(2-methoxyethoxyphenyl-sulfonyl)-N'-(4,6-
dimethoxy-triazin-2-yl)-urea, N-(2-ethoxyphenyl-sulfonyl-
N'-(4-chloro-6-methoxypyridin-2-yl)-urea, N-(2-ethoxy-
phenylsulfonyl)-N'-(4-difluoromethoxy-6-methyl-pyrimidin-
2-yl)-urea and N-[2-(2-chloroethylmercapto)-phenyl-
sulfonyl]-N'-(4-methoxy-6-methyl-1,3,5-triazin-2-yl)-urea.
Oxime ethers which are suggested according to the
present invention as being effective against the plant-
damaging side-effect of herbicidally active sulfonylureas
are those of the formula II
\ O_
- {} - X R O-R (II)
X / 11 13 / 7
/ 4~0 ~(CH)n--CH
R6 0-R8

- 6 ~
wherein n is 1 or 2, R3 and R4 are each hydrogen or
Cl-C4-alkyl9 R5 and R6 are each hydrogen, halogen, Cl-C4-
alkyl~ Cl-C4-haloalkyl, Cl-C4-alkoxy, Cl-C4-haloalkoxy,
Cl-C4-alkylthio, Cl-C4-haloalkylthio, Cl-C4-alkylsulfinyl,
Cl-C4-alkylsulfonyl, C]-C4-haloalkylsulfinyl, Cl-C4-
haloalkylsulfonyl or nitro, R7 and R8 separately are each
Cl-C4-alkyl or C3-C4-alkenyl, or together are a 1,2-
ethylene group or a 1,3-propylene group each unsubstituted
or substituted by one or more alkyl groups, and X is a
cyano group or a fluorinated Cl-C3-alkyl group which
can also contain chlorine.
The radicals R3 - R8, as well as the Cl-C4-alkyl groups
occurring in the radicals R3 - R8, can be straight-chain
or branched-chain and are: methyl, ethyl, n-propyl,
isopropyl, n-butyl, sec-butyl, isobutyl and tert-butyl.
Preferred amongst these alkyl groups are Cl-C2-alkyl
groups, and Rl as an alkyl group is preferably methyl.
This description ofalkyl groups applies also for the
alkyl moieties of other substituent groups according to
the definition of the formula II. Alkenyl can be for
example: allyl, propenyl, i-propenyl, buten-2-yl, 2-methyl-
propen-2-yl and 1-methyl-propen-2-yl, and is preferably
an allyl group.
By halogen is meant for example fluorine, chlorine,
bromine and iodine, especially fluorine or chlorine.
The fluorinated alkyl group X can be for example:
difluoromethyl, trifluoromethyl, chlorodifluoromethyl,
tetrafluoroethyl, pentafluoroethyl and heptafluoropropyl.
Preferred among the stated X groups are perfluorinated
alkyl groups, wherein a fluorine atom can be replaced by a
chlorine atom. Particularly preferred groups X are
trifluoromethyl, chlorodifluoromethyl and pentafluoroethyl.

:~L22~
-- 7 --
The compounds of the :Eormula II in which R7 and R8
together form a 1,2-ethylene or 1,3-propylene group, each
unsubstituted or substituted by one or more alkyl groups,
constitute 1,3-dioxolane or 1,3-dioxane derivatives
and correspond to the formula IIa
~ (R )
~ ~ 19 P
'--C--XR O+CH
~ 3 / \2 (IIa)
/ O~D N O (CH) --CH ~CH2)m
6 CH2
wherein n, R3, R4, R5, R6 and X have the meanings defined
under the formula II, m is zero or 1, p is zero to 4,
and R9 is a Cl-C3-alkyl group, preferably methyl. Preferred
compounds of the formula IIa are those in which m is zero.
Preferred among the compounds of the formula II are
the following subgroups:
a) compounds wherein n is 1, R3, R4 and R6 are hydrogen,
R5 is hydrogen, halogen, methyl, difluoromethyl, trifluoro-
methyl, chlorodifluoromethyl, methoxy, difluoromethoxy,
trifluoromethoxy, chlorodifluoromethoxy, tetrafluoroethyl,
tetrafluoroethoxy or trifluoromethylsulfonyl, X is a
cyano group or perfluorinated Cl-C3-alkyl or chlorodifluoro-
methyl, and R7 and R8 have the meanings defined under the
formula II;
b) compounds wherein n is l, R3, R4 and R6 are hydrogen,
R5 is hydrogen, fluorine, chlorine, methyl, difluoromethyl,
trifluoromethyl, chlorodifluoromethyl, methoxy, difluoro-
methoxy, trifluoromethoxy, chlorodifluoromethoxy, tetra-
fluoroethyl, tetrafluoroethoxy or tetrafluoromethyl-
sulfonyl, X is a cyano group or trifluoromethyl, chloro

~æ2~
-- 8
difluoromethyl or pentafluoroethyl, and R7 and R8 together
are a 1,2-ethylene group which is unsubstituted or
substituted by 1-4 methyl groups;
c) compounds wherein n is 1, R3, R4 and R6 are hydrogen,
R5 is hydrogen, fluorine, chlorine, trifluoromethyl or
trifluoromethoxy, X is a cyano group or trifluoromethyl,
chlorodifluoromethyl or pentafluoroethyl, and R7 and R8
together are a l,2-ethylene group which is unsubstituted
or substituted by L-4 methyl groups;
d) compounds wherein n is 1, R3, R~ and R6 are hydrogen,
R5 is fluorine or chlorine, X is a cyano group or trifluoro-
methyl, chlorodifluoromethyl or pentafluoroethyl, and R7
and R8 together are a 1,2-ethylene group which is unsub-
stituted or substituted by 1-4 methyl groups;
e) compounds wherein n is 1, R3, R4 and R6 are hydrogen,
R5 is in the 3-position and is trifluoromethyl or nitro,
X is a cyano group or trifluoromethyl, chlorodifluoro-
methyl or pentafluoroethyl, and R7 and R8 together are
a 1,2-ethylene group which is unsubstituted or substituted
by 1-4 methyl groups;
f) compounds wherein n is 1, R3, R4 and R6 are hydrogen,
R5 is hydrogen or fluorine, X is a cyano group, and R7 and
R8 together are a 1,2-ethylene group which is unsubstituted
or substituted by 1-4 methyl groups;
g) compounds wherein n is 1, R3, R4 and R6 are hydrogen,
R5 is hydrogen or fluorine, X is a cyano group, and R7 and
R8 together are a 1,2-ethylene group; and
h) compounds wherein n is 1, R3, R~ and R6 are hydrogen,
R5 is fluorine, X is a cyano group, and R~ and R8 together
are a 1,2-ethylene group.

32~
g
Preferred individual compounds are in particular:
l-phenyl-l-(1,3-dioxolan-2-yl-methoxyimino)-2,2,2-
trifluoroethane,
1-(4-chlorophenyl)-1-(1,3-dioxolan-2-yl-methoximino)-
2,2,2-trifluoroethane,
1-(4-chlorophenyl)-1-(2,2-diethoxyethoximino)-2,2,2-
trifluoroethane,
1-(4-chlorophenyl)-1-(2,2-dimethoxyethoximino)-2,2,2-
trifluoroethane,
1-(4-fluorophenyl)-1-(1,3-dioxolan-2-ylmethoximino)-2,2,2-
trifluoroethane,
1-(2-fluorophenyl)-1-(1,3-dioxolan-2-yl-methoximino)-2,2,2-
trifluoroethane,
a-(1,3-dioxolan-2-ylmethoximino)-benzyl cyanide,
a-(2,2-dimethoxyethoximino)-benzyl cyanide,
a-(1,3-dioxan-2-yl-methoximino)-benzyl cyanide,
a-(5,5-dimethyl-1,3-dioxan-2-yl-methoximino)-benzyl cyanide,
a-~2,2-dimethoxyethoximino)-3,4-dichlorobenzyl cyanide,
a-(1,3-dioxolan-2-yl-ethoximino)-3,4-dichlorobenzyl cyanide,
a-(5,5-dimethyl--1,3-dioxan-2-yl-methoximino)-4-methoxy-benz~l
cyanide,
a-(2,2-diethoxyethoximino)-4-methoxybenzyl cyanide.
The oxime ethers of the formula II are suitable for
protecting cultivated plants from the harmful effect of
sulfonylureas. With regard to their use in combination
with the aforementioned herbicides, the oxime ethers of
the formula II can therefore be described as preventives
or antidotes and also as safeners.
Of the compounds of the formula II there exist various

- 10 -
stereoisomeric forms, namely the syn and anti forms of
the oximes from which they are formed; and there also
exist the individual enantiomers of those compounds of
the formula II which possess an asymmetric centre. Such
asymmetric centres are present when R3 has a meaning other
than hydrogen, or when the radicals R7 and R8 differ from
one another, or when the 1,2-ethylene or 1,3-propylene
group formed by the radicals R7 and R8 is asymmetrically
substituted. These stereoisomeric forms are likewise
subject matter of the present invention.
Depending on the purpose of application, such an
antidote of the formula II can be used for the pretreatment
of the seed or seedlings of the cultivated plant (dressing
of the seed or of cuttings), or can be introduced into
the soil before or after sowing, or can be applied on its
own or together with the herbicide before or after
emergence of the plants. The treatment of the plant or
of the seed or seedlings with the antidote can be carried
out therefore essentially independently of the time of
application of the phytotoxic chemicals. The treatment
can however be effected by the simultaneous application
of phytotoxic chemicals and antidote (tank mixture). The
pre-emergence treatment includes both the treatment of
the cultivated area before sowing (ppi = "pre-plant
incorporation") and the treatment of the sown cultivated
area before emergence of the plants.
The applied amounts of antidote in proportion to the
herbicide depend largely on the mode of application. In
the case of field treatment, where the herbicide and
antidote are applied either simultaneously (tank mixture)
or separately, the ratio of the amounts of antidote to
herbicide is within the range of 1:10 to 10:1. The full
protective action is however obtained as a rule with a

:~22~
ratio of antidote to herbicide of 1:3 to 3:1. Which ratio
is most suitable with regard to the optimum effect with
a specific cultivated plant is determined from case to
case, that is to say, depending on the type of herbicide
to be used. With seed dressing and similar specific
protective measures, however, the amounts of antidote
required compared with for example the amounts of herbicide
which would be applied later per hectar of cultivated land
are much smaller. There are generally needed for seed
dressing 0.5 to 50 g of antidote per kg of seed. As a rule,
the maximum protective effect is obtained with amounts as
low as 0.5 to 4 g of antidote per kg oE seed. When the
antidote is to be applied shortly before sowing, by seed
soaking, there are advantageously employed antidote
solutions containing the active ingredient at a concen-
tration of 1 - 10,000 ppm. The full protective action
is as a rule obtained with a concentration o:E antidote
of 10 - 1000 ppm.
Protective measures, such as seed dressing and treatment
of cuttings with an antidote of the formula II, and
possible subsequent field treatment with agricultural
chemicals are as a rule separated by a considerable
interval of time. Pretreated seed and plant material
can subsequently come into contact, in agriculture,
horticulture and forestry, with various chemicals. The
present invention relates therefore also to protective
compositions for cultivated plants, which compositions
contain as active ingredient an antidote of the formula II,
together with customary carrier materials. These prep-
arations can if required additionally contain those
agricultural chemicals against which the cultivated plant
is to be protected.
~ ultivated plants applying within the scope oE the

~2~ 4
- 12 -
present invention are all those which in some form
produce productive materials (seeds, roots, stalks,
tubers, leaves, flowers, or components such as oils,
sugar, starch, protein, and so forth), and which for
this purpose are cultivated and preserved. These plants
include for example varieties of cereals, such as wheat,
rye, barley and oats, in addition particularly rice,
sorghum, maize~ cotton, sugar beet, sugar cane, soybean,
beans, peas, and the like.
The antidote of the invention can be used in all
cases where a cultivated plant of the aforementioned
varieties has to be protected against the harmful action
of sulfonylureas of the formula I.
For the dressing of the seed of the cultivated plant,
the seeds are thoroughly mixed in the desired ratio with
the antidote of the formula II.
For application, the compounds of the formulae I and
II are used either in an unmodified form or preferably
together with auxiliaries customarily employed in
formulation practice, and are thus processed in a known
manner for example into the form of emulsion concentrates,
directly sprayable and dilutable solutions, diluted
emulsions, wettable powders, soluble powders, dusts or
granulates, and also encapsulations in for example poly-
meric substances. The application processes, such as
spraying, atomising, dusting, scattering or pouring, and
likewise the type of composition, are selected to suit
the objectives to be achieved and the given conditions.
The formulations, that ls to say, the compositions
or preparations containing the active ingredients of the
formulae I and II and optionally a solid or liquid additive,
are produced in a known manner, for example by the intimate
mixing and/or grinding of the active ingredients with

- 13 ~
extenders, such as with solvents, solid carriers and
optionally surface-active compounds (tensides).
Suitable solvents are: aromatic hydrocarbons, prefer-
ably the fractions C8 to C12, such as xylene mixtures or
substituted naphthalenes, phthalic esters, such as dibutyl-
or diocty~phthalate, aliphatic hydrocarbons, such as
cyclohexane or paraffins, alcohols and glycols, as well as
ethers and esters thereof, such as ethanol, ethylene glycol,
ethylene glycol monomethyl or -ethyl ethers, ketones,
such as cyclohexanone, strongly polar solvents, such
as N-methyl-2-pyrrolidone, dimethyl sulfoxide or dimethyl-
formamide, as well as optionally epoxidised vegetable oils,
such as epoxidised coconut oil or soybean oil; or water.
The solid carriers used, for example for dusts and
dispersible powders, are as a rule natural mineral
fillers, such as calcite, talcum, kaolin, monomorillonite
or attapulgite. In order to improve the physical
properties, it is also possible to add highly dispersed
silicic acid or highly dispersed absorbent polymers.
Suitable granulated adsorptive carriers are porous types,
for example pumice, ground brick, sepiolite or bentonite;
and suitable nonsorbent carriers are materials such as
calcite or sand. There can also be used a great number
of pre-granulated materials of inorganic or organic
nature, such as in particular dolomite or ground plant
residues.
Suitable surface-active compounds are, depending on the
nature of the active ingredients of the formulae I and II
to be formulated, nonionic, cationic and/or anionic tensides
having good emulsifying, dispersing and wetting properties.
By 'tensides' are also meant mixtures of tensides.
Suitable anionic tensides are both so-called water-

soluble soaps and water-soluble, synthetic, surface-
active compounds.
Soaps which are applicable are the alkali metal,
alkaline-earth metal or optionally substituted ammonium
salts of higher fatty acids (C10-C22), for example the
Na or K salts of oleic or stearic acid, or of natural
fatty acid mixtures, which can be obtained for example
from coconut oil or tallow oil. ~lso to be mentioned are
the fatty acid-methyltaurine salts.
So-called synthetic tensides are however more
frequently used, particularly fatty sulfonates, fatty
sulfates, sulfonated benzimidazole derivatives or
alkylarylsulfonates.
The fatty sulfonates or sulfates are as a rule in the
form of alkali metal, alkaline-earth metal or optionally
substituted ammonium salts, and contain an alkyl group
having 8 to 22 C atoms, 'alkyl' including also the alkyl
moiety of acyl groups, for example the Na or Ca salt of
ligninsulfonic acid, of dodecylsulfuric acid ester or of a
fatty alcohol sulfate mixture produced from natural
fatty acids. Included among these are the salts of
sulfuric acid esters and sulfonic acids of fatty alcohol
ethylene oxide adducts. The sulfonated benzimidazole
derivatives preferably contain 2 sulfonic acid groups
and a fatty acid group having 8 - 22 C atoms. Alkylaryl-
sulfonates are for example the Na, Ca or triethanolamine
salts of dodecylbenzenesulfonic acid, of dibutylnaphthalene-
sulfonic acid or of a naphthalenesulfonic acid-formaldehyde
condensation product.
Also suitable are corresponding phosphates, for example
salts of the phosphoric ester of a p-nonylphenol-(~
ethylene oxide adduct, or phospholipides.

~2~
- 15 -
Suitable nonionic tensides are in particular polyglycol
ether derivatives of aliphatic or cycloaliphatic alcohols,
saturated or unsaturated fatty acids and alkylphenols,
which can contain 3 to 30 glycol ether groups and 8 to 20
carbon atoms in the (aliphatic) hydrocarbon radical and
6 to 18 carbon atoms in the alkyl moiety of the alkylphenols.
Further suitable nonionic tensides are the water-
soluble polyethylene oxide adducts, which contain 20 to
250 ethylene glycol ether groups and 10 to 100 propylene
glycol ether groups, with polypropylene glycol, ethylene-
diaminopolypropylene glycol and alkylpolypropylene glycol
having 1 to 10 carbon atoms in the alkyl chain. The
compounds mentioned usually contain 1 to 5 ethylene
glycol units per propylene glycol unit.
Examples of nonionic tensides which may be mentioned
are: nonylphenolpolyethoxyethanols, castor oil polyglycol
ethers, polypropylene/polyethyleneoxy adducts, tributyl-
phenoxypolyethoxyethanol, polyethylene glycol and octyl-
phenoxypolyethoxyethanol.
Suitable also are fatty acid esters of polyoxyethylene-
sorbitan, such as polyoxyethylenesorbitan-trioleate.
In the case of the cationic tensides, they are in
particular quaternary ammonium salts which contain as
N-substituents at least one alkyl group having 8 to 22
C atoms and, as further substituents, lower, optionally
halogenated alkyl, benzyl or lower hydroxyalkyl groups.
The salts are preferably in the form of halides, methyl
sulfates or ethyl sulfates~ for example stearyltrimethyl-
ammonium chloride or benzyldi(2-chloroethyl)ethylammonium
bromide.
The tensides customarily used in formulation practice
are described, inter alia, in the following publications:

~2~2~2~
- 16 -
" Mc Cutcheon's Detergents and Emulsifiers Annual",
MC Publishing Corp., Ridgewood, New Jersey, 1979; and
Slsely and Wood, "Encyclopedia of Surface Active
Agents", Chemical Publishing Co., Inc. New York, 1964.
These preparations contain as a rule 0.1 to 99%,
particularly 0.1 to 95%, of active ingredients, 1 to 99%
of a solid or liquid additive, and O to 25%, especially
0.1 to 25%, of a tenside.
Whereas commercial products are preferably in the form
of concentrated compositions, the preparations employed
by the end-user are as a rule diluted. The applied forms
can be diluted down to 0.001% of active ingredient. The
amounts applied are as a rule 0.1 to 10 kg of active
ingredient (a.i.) per hectare, preferably 0.25 to 5 kg of
active ingredient (a.i.) per hectare.
The compositions can also contain further additives,
such as stabilisers, antifoam agents, viscosity regulators,
binders and adhesives, as well as fertilisers or other
active ingredients for obtaining special effects.
The active ingredients of the formulae I and II can
be produced by known methods.
Compounds of the formula I are produced in an inert
organic solvent.
One process for obtaining the compounds of the formula
I comprises reacting a phenylsulfonamide of the formula III
Y SO ~H
\ / 2 2
ll (III)
a
~ x
wherein ~ and Y have the meanings defined under the

- 17 -
formula I, in the presence of a base, with an N-pyrimidinyl-
or N-triazinylcarbamate of the formula IV
~R
O N~
// \ 11 // ~
~C NH-- E
I ll \ / (IV)
O ~ ~-
. ~/ \
R
wherein E, Rl and R2 have the meanings defined under the
formula I.
A second process for producing compounds of the
formula I comprises reacting a phenylsulfonylisocyanate
of the formula V
Y
\//\
2~=C=
~/\
x
wherein X and Y have the meanings defined under the
formula L, optionally in the presence of a base, with an
amine of the formula VI
~R
N---
H2N - ~ E (VI)
\ /
N=;
R2
wherein E, Rl and R2 have the meanings defined under the
formula I~
Compounds of the formula I are produced using a further
process by reacting a sulfonamide of the formula III given
above, optionally in the presence of a base, with an

~2Z~
- 18 -
isocyanate or isothiocyanate of the formula VII
Rl
~o
O=C=N E
\ / (VII)
;
R2
wherein E, Rl and R2 have the meanings defined under the
formula I.
Finally, the compounds of the formula I can be obtained
also by reacting an N-phenylsulfonylcarbamate of the
formula VIII
y ~, o ~
\ // \ 11 //
SO ~Uff~- -
: ! 11 2 \ / (VIII),
\\ / \
x
wherein X and Y have the meanings defined under theformula I, with an amine of the given formula VI.
The resulting ureas of the formula I can, if desired,
be converted by means of amines, alkali metal hydroxides
or alkaline-earth metal hydroxides or quaternary ammonium
bases into basic addition salts. This is effected for
example by reaction with the equimolar amount of base
and removal of the solvent by evaporation.
The starting materials of the formulae III, V and
VIII can be produced by the following methods:
The sulfonamides of the formula III used as inter-
mediates are obtained from the corresponding anilines by
diazotisation and exchange of the diazo group for sulfur
dioxide in the presence of a catalyst, such as copper-(I)

- 19 -
chloride, in hydrochloric acid or acetic acid, and reaction
of the formed phenylsulfonyl chloride with an ammonium
hydroxide solution.
The compounds of the formula III can be obtained also
by oxygen-alkylation or -alkenylation of hydroxyphenyl-
sulfonamides with the corresponding halides or sulfuric
acid esters.
The alkoxyphenylsulfonamides for their part can be
obtained from the corresponding alkoxyanilides, as already
mentioned9 or by chlorosulfonylation of alkoxybenzoles,
and reaction of the resulting phenylsulfonyl chlorides
with an ammonium hydroxide solution. Such reactions are
known from J. Am. Chem. Soc. 62, 603 (1940).
The phenylsulfonylisocyanates of the formula V can be
obtained by reactions of the sulfonamides of the formula
III with phosgene in the presence of butylisocyanate, in a
chlorinated hydrocarbon as solvent, at the reflux tempera
ture. Similar methods of preparation are described in
"Newer Methods of Preparative Organic Chemistry", Vol. VI,
223-2~1, Academic Press New York and London.
The N-phenylsulfonylcarbamates of the formula VII are
obtained by reaction of the sulfonamides of the formula II
with diphenylcarbamate in the presence of a base. Similar
processes are mentioned in the Japanese Patent Specification
No. 61 169.
The starting materials of the formulae IV, VI and VII
are known or can be produced by known methods.
Isocyanates of the formula VII can be produced by
reaction of amines of the formula VI with oxalyl chloride
in a chlorinated hydrocarbon. Amines of the formula VI
are known and some are obtainable commercially~ or they

2~
- ~o ~
can be produced by known methods: cp. "The Chemistry of
Heterocyclic Compounds", Vol2 XIV, Interscience Publishers,
New York, London.
These reactions to compounds of the formula I are
advantageously performed in aprotic, inert organic
solvents, such as methylene chloride, tetrahydrofuran,
acetonitrile, dioxane and toluene.
The reaction temperatures are preferably between -20
and +120C. The reactions in general proceeed slightly
exothermically, and can be carried out at room temperature.
For shortening the reaction time or for initiating the
reaction, it is advantageous to apply heat for a short
period up to the boiling point of the reaction mixture.
The reaction times can be shortened also by the addition
of a few drops of a base or of isocyanate as a reaction
catalyst.
The final products can be isolated by means of
concentration by evaporation and/or removal of the solvent
by evaporation, and can be purified by recrystallisation
or trituration of the solid residue in solvents in which
they do not readily dissolve, such as in ethers, aromatic
hydrocarbons or chlorinated hydrocarbons.
The oxime ethers of the formula II are produced by
reacting a salt of an oxime of the formula IX
~_0
~-x (IX),
o~o N-OM
R6
wherein M is an alkali metal cation or alkaline-earth metal
cation, and R4, R5, R6 and X have the meanings given

2~L
- 21 -
under the formula II, with a 2-haloalkylacetal of the
formula X
R~ O-R
Hal ( CH) --CH (X)
\
O-R8
wherein Hal is a halogen atom, especially a chlorine atom
or a bromine atom, and n, R3, R7 and R8 have the meanings
defined under the formula II. Suitable salts of an oxime
of the formula IX are in particular the sodium and
potassium salts. The reaction of the oxime of the formula
IX with the haloacetal of the formula X is advantageously
performed in an inert organic solvent. Polar solvents,
such as acetonitrile, dimethylformamide, dimethyl sulfoxide,
dimethylacetamide, methylpyrrolidone and tetramethylurea,
are especially suitable. The reactants are used as a rule
in an equimolar amount. For the reaction to proceed to
completion, it is however possible to use the cne or the
other reactant in excess. The reaction is advantageously
carried out at elevated temperature, preferably between
50 and 90C. The reaction can also be performed in
another solvent, for example toluene, but at a higher
temperature and with a longer reaction time.
Those oximes of the formula IX in which X has the
meaning defined under the formula II, with the exception
of the cyano group~ can be produced in a known manner by
reaction of the corresponding ketones with hydroxylamine.
The ketones required for this purpose can, depending on
the structure, be produced by various procedures. Thus,
the reaction of Grignard compounds of the formula XI

- 22 -
R~,
~MgHal (XI)
R 5 ~0
wherein Hal is chlorine, bromine or iodine, and R4, R5
and R6 have the meanings defined under the formula II,
with a carboxylic acid X-COOH, an acid chloride X-COCl
or a nitrile X-CN, wherein X has the meaning defined under
the formula II, with the excep~ion of the cyano group,
yields the desired ketones (U.S. Patent No. 3,74~3,361).
The oximes of the formula IX in which X is a cyano
group can be prepared by reaction of a benzyl cyanide of
the formula XII
R~
o ~H ~N (XII),
wherein R4, R5 and R6 have the meanings defined under the
formula II, with butyl nitrile in the presence of a base,
for example sodium methylate or sodium ethylate (S.J. Org.
Chem. 192-193/1937, or U.S. Patent 3,483,246 or German
Offenlegungsschrift No. 2,150,399). It is possible in this
manner to synthesise the following:
l-hydroximino-ortho-fluorobenzyl cyanide,
l-hydroximino-meta-fluorobenzyl cyanide, and
l-hydroximino~para-fluorobenzyl cyanide.
The corresponding o-, m- and p-fluorobenzyl cyanides
are obtainable commercially.
The ring-~luorinated benzyl cyanides for their part

2~244
- 23 -
are obtainable from the correspondingly ring-substituted
benzyl chlorides by reaction with potassium cyanide or
sodium cyanide. The 4-fluorobenzyl cyanide can be
produced for example by chloromethylation of fluoro-
benzene (Bl. [5] 20 C 45 (1953)). The 2- or 3-fluorobenzyl
chloride is produced by side-chain chlorination of the
2- or 3-fluorotoluene obtainable, by a Sandmayer reaction,
from 2- or or 3-aminotoluene.
The more simple oximes can be bought: 2-hydroximino-
acetonitrile is a known intermediate.
The haloalkyl-acetals of the formula X can be produced
by condensation of the corresponding alcohols and
haloaldehydes. The more simple ones, for example
2-bromomethyl-1,3-dioxolane and 2-chloromethyl-1,3-
dioxolane are known as intermediates.
Example 1: Production of N-(1,3-dioxolan-2-yl-methoxy)-
imino-ortho-fluoroacetonitrile.
In a 100 ml round-bottomed flask, 2.3 g (0.1 mol) of
metallic sodium are dissolved in 50 ml of absolute
ethanol, and 18.6 g (0.1 mol) of l-hydroximino-ortho-
fluorophenylacetonitrile are added. After completion of
the addition, stirring is maintained for half an hour at
room temperature, and the solvent is then evaporated off.
There are added dropwise to the solution of the residue in
75 ml of dimethyl sulfoxide, with stirring, 18.4 g
(0.11 mol) of 2-bromomethyl-1,3-dioxolane, and stirring is
continued for 4 hours at an internal temperature of
60-70C. The formed suspension is afterwards cooled and
poured into an ice-water mixture. The reaction product is
obtained from the resulting mixture by extraction with
methylene chloride. The extract is dried over sodium
sulfate and the solvent is evaporated off. There is

~Z~32
- 24 -
obtained as crude product a crystalline precipitate,
which is purified by recrystallisation from ethanol.
The yield is 14.0 g (56% of theory) of N-(1,3-dioxolan-Z-yl-
methoxy)-imino-ortho-fluorophenylacetonitrile, m.p. 46-47~C.
There are obtained in an analogous manner, starting
from l-hydroximino-meta-fluorophenylacetonitrile and
l-hydroxyimino-para-phenylacetonitrile, or the sodium
salts thereof, by reaction with 2-bromomethyl-1~3-dioxolane:
N-(1,3-dioxolan-2-yl-methoxy)-imino-meta-fluorophenyl-
acetonitrile and N-(1,3-dioxolan-2-yl-methoxy)-imino-
para-fluoroacetonitrile, m.p. 68-71C.
Example 2: a-(1,3-Dioxolan-2-ylmethoxyimino)-benzyl
cyanide (Z ~orm).
15.4 g of the sodium salt of a-phenylacetonitrile
oxime (Z form) are dissolved in 70 ml of DMS0; 16.7 g
of bromomethyl-dioxolane are added and the mixture is
stirred at 60C for 4 hours. There are then added 150 ml
of ether and washing is performed three times with 100 ml
of H20 each time. The ether phase is dried with MgS04
and concentrated by evaporation. The crude product
(17.8 g9 m.p. 67C) is crystallised from ether/hexane 1:3
and yields 16.7 g of a-(1,3-dioxolan-2-ylmethoximino)-
benzyl cyanide (Z form), m.p. 76C.

~ 8
- 25 -
Example 3
.
Formulation Examples for active ingredients of the
formula II or for mixtures of these active ingredients
with herbicides of the formula I
a) Wettable powders a) b) c)
active ingredient of the formula II 20% 60% 0.5%
or mixture thereof with a herbicide
of the formula I
sodium lignin sulfonate 5% 5% 5%
sodium lauryL sulfate 3%
sodium diisobutylnaphthalene sulfonate - 6% 6%
octylphenolpolyethyleneglycol ether - 2% 2%
(7-8 mols of ethylene oxide)
highly dispersed silicic acid 5% 27% 27%
~aolin 67%
sodium chloride - - 59.5%
The active ingredient is well mixed with the additives
and the mixture is thoroughly ground in a suitable mill.
Wettable powders which can be diluted with water to give
suspensions of the required concentration are obtained.
b) Emulsion concentrates a) b)
-
active ingredient of the formula II 10% 1%
or mixture thereof with a herbicide
of the formula I
octylphenolpolyethylene glycol ether 3% 3%
(4-5 mols of ethylene oxide)
calcium dodecylbenzene sulfonate 3% 3%
castor oil polyglycol ether 4% 4%
(36 mols of ethylene oxide)
cyclohexanone 30% 10%
xylene mixture 50% 79%
Emulsions of any desired concentration can be obtained
from these concentrates by dilution with water.

~L22~32~
- 26 -
c) Dusts a) b)
actlve ingredient oE the formula II 0.1% 1%
or mixture thereof with a herbicide
of the formula I
talcum 99 9%
kaolin - 99%
Dusts ready for use are obtained by mixing the active
ingredient with the carriers and grinding the mixture in
a suitable mill.
d) Extruder ~ranulate_ a) b)
active ingredient of the formula II 10~/o 1%
or mixture thereof with a herbicide
of the formula I
sodium lignin sulfonate 2% 2%
carboxymethylcellulose 1% 1%
kaolin 87% 96%
The active ingredient is mixed and ground with the
additives, and the mixture is moistened with water. This
mixture is extruded and then dried in a stream of air.
e) Coated granulate
active ingredient of the formula II 3%
or mixture thereof with a herbicide
of the formula I
polyethylene glycol (M.W. 200) 3%
kaolin 9~%
The finely ground active ingredient is evenly applied,
in a mixer, to the kaolin moistened with polyethylene
glycol. Dustfree coated granulates are obtained in this
manner.

- 27 -
f) Suspension concentrates ~) b)
active ingredient of the formula II 40% 5%
or mixture thereof with a herbicide
of the formula I
ethylene glycol 10% 10%
nonylphenolpolyethylene glycol ether ~% 1%
(15 mols of ethylene oxide)
sodium lignin sulfonate 10% 5%
carboxymethylcellulose 1% 1%
37% aqueous formaLdehyde solution0.2% 0.2%
silicone oil in the form of a 75%o.8a/o0.8%
aqueous emulsion
water 32% 77%
The finely ground active ingredient is intimately
mixed with the additives. There is thus obtained a
suspension concentrate from which can be produced, by
dilution wi~h water, suspensions of the concentration
required.
g) Salt solution
active ingredient of the formula II 5%
or mixture thereof with a herbicide
of the formula I
isopropylamine 1%
octylphenolpolyethylene glycol ether 3%
(78 mols of ethylene oxide)
water 91%
Biological Examples
The capability of the compounds of the formula II to
protect cultivated plants against the action of strong
herbicides can be seen from the following Examples. In
the test descriptions, the compounds of the formula II
are designated as antidotes.

2~
. .
- 28
Example ~: Seed dressing with_antidote: herbicide in t_
post-emergence process on maize
~ aize seeds of the "LG 5" variety are mixed in a glass
container with the substance to be tested as antidote.
Seeds and product are thoroughly mixed together by
shaking and rotation. Pots oE the same shape (11 cm
upper diameter) are filled with soil, and the dressed
seeds are sown therein. The herbicide is applied in the
post-emergence process (three-leaf stage of the plant),
and 21 days after application oE the herbicide, the
protective action of the antidote is estimated in per cent.
The plants treated with the herbicide alone and the
completely untreated control plants provide reference
values.
As can be seen from the results summarised in the
Table, the antidote affords a high level of protection.
(a.i. = active ingredient)
Nerbicide:
N-[2-(2-butenyloxy)-phenyl-
sulfonyl]-N'-(4-methyl-6- 1.5 1.0 0.5
methoxy-triazin-2-yl)-urea
kg of a.i./ha
Ant ido t e: _ _ _ _
h- (1,3-dioxolan-2-ylmethox-
i~ino)-ben~yl cyanide (Z form) 4 2 1 4 2 1 4 2
g of a.i./1~g of seeds _ _
rela~ive protective action50 635063 63 63 25 25 25

~L~28~
- 29 -
Herbicide:
N-(2-methoxycarbonyl-phenyl-
sulfonyl)-N'-(4,6-difl~loro- ~.5 0.25 0.125
methoxy-pyrimidin-2-yl)-
kg of a.i./ha
Antidote: _ _ _ _ _
~-(1,3-dioxolan-2-ylmethox-
imino)-benzyl cyanide 4 2 14 2 1 4 2
g of a.i./kg of seeds _ _ _ _ _ _ ~
relative protective action 50 63 12.5 j3 63 50 38 38 38
Example 5: Seed dressin~ with antidote: herbicide in the
pre-emergence process on maize
Maize seeds of the "LG 5" variety are mixed in a glass
container with the substance to be tested as antidote,
Seeds and product are well mixed together by shaking and
rotation. Pots of the same shape (upper diam. 11 cm) are
filled with soil, and the dressed seeds are sown therein.
After the seeds have been covered with soil, the herbicide
is applied in the pre-emergence process. The protective
action of the antidote is estimated in per cent 14 days
after application of the herbicide. The plants treated
with ~he herbicide alone and the cornpletely untreated
plants provide reference values.

- 30 -
The results given in the Table below illustrate the
protective action of the antidote:
Herbicide:
N-[2-(2-butenyloxy)-phenyl-
sulfonyl]-N'-(4-methyl-6- l.S 1.0 0.5
methoxy-triazin~2-yl)-urea
kg of a.i./ha
. __ _ . _ .
Antidote:
a~-(1,3-dioxolan-2-ylmethox-
ililino)-benzyl cyanide (Z form) 4 2 1 4 2 1 4 2 1
g of a.i./kg of seeds
.. _ . _
relative protective action 25 38 38 25 2512.5 25 12~, 12.5
in % .. __
. __.. ~._ . __
Herbicide:
N-(2-methoxycarbonyl-phenyl-
sulfonyl)~N'-4,6 difluoro- 0.25 0.125 0.062
methoxy-pyrimidin-2-yl)-urea
kg of a.i./'na
. _ _
Antidote: 2
~-(1,3-dioxolan-2-yl- 2 2
methoximino)-benzyl cyanide
~ of a.i./kg of seeds
relative protective action 38 38 5
in ~
. __

~L2;2~
- 31 -
Antidote: _
~-(1,3-dioxolan-2-ylmethox- 2 1 O.S 2 1 0.5
ilnino)-benzyl cyanide (Z ~orm)
g of a.i./kg of seeds
_
Herbicide:
N-(2-chlorophenyl-sulfonyl)-0.062 kg a.i./ha 0.031 kg a.i./ha
N'-(4-methyl-6-dimethoxy-
triazin-2~yl)~urea
relative protective action 12.5~ 12.5~ 12.5~ 12.5~ 12.~ 12-5
.
~erbicide:
N-[2-(2'-chloroethoxy)-0,062 kg a.i./ha 0.032 kg a.i./ha
phenyl-sulfonyl]-N'-(4-
methyl-6-methoxy-triazin-
2-yl)-urea
relative protective action: 38~ 25~ 12.5~ 38~ 38%
. . _
~erbicide:
N-[2-(2'-methoxyethoxy)-0.062 kg a i /ha 0.031 kg a i /ha
phenyl-sulfonyl]-N'-(~i- . . . .
methyl-6-methoxy-triazin-2 yl-
urea
relative protective action: 38~ 25~ 12.5~o 38~ 25~ 38~
Example 6: Seed dressin~ with antidote: herbicide in the
pre-emer~ence process on barley
Barley seeds are mixed in a glass container with the
substance to be tested as antidote. Seeds and product
are well mixed together by shaking and rotation. Pots
of the same shape (upper diameter 11 cm) are filled with
soil, and the dressed seeds are sown therein. After the
seeds have been covered with soil, the herbicide is
applied in the pre-emergence process. The protective action
of the antidote is estimated in per cent 14 days after
application of the herbicide. The plants treated with the

32~
herbicide alone and the completely untreated plants
provide reference values.
The results show that a considerable protective
action is afforded by the antidote:
_ ., ..
Herbicide:
N-[2-(2'-methoxyethoxy)-
phenyl-sulfonyl]-N'- 0.125 0.062 0.031
(4-methyl-6-methoxy~
tria~in-2-yl)-urea
kg of a.i./ha
Antldote: ~ _ _
~-(1,3-dioxolan-2-yl)-
~ethoximino)-benzyl 2 1 0.5 2 1 0.5 21 0.5
cyanide (Z fo~m)
g of a.i./kg o~ seeds
.. _._ . _ _
relative protective l12.5 12.5 12.5 12.5 12.5 12.5 38 38 38
action in % _ I _ _ _ _
Exam~ : Seed dressin~ with antidote: herbicide in the
pre-emergence process on sorghum
Sorghum seeds are mixed in a glass container with
the substance to be tested as antidote. Seeds and product
are well mixed together by shaking and rotation. Pots
of the same shape (upper diameter 11 cm) are filled with
soil, and the dressed seeds are sown therein. After the
seeds have been covered with soil, the herbicide is
applied in the pre-emergence process. The protective
action of the antidote is estimated 14 days after the
application of the herbicide. The plants treated with the
herbicide alone and completely untreated plants provide
reference values.

~2~
The results clearly show the protective action obtained
by use of the antidote:
. __ _ I
Antidote:
~-(1,3-dioxolan- 2 1 0.52 1 0.5 2 1 0.5
2-ylmethoximino)-
benzyl cyanide (Z form)
g of a.i./kg of seeds _ _
Herbicide:
N-(2-chlorophenyl- 0.125 0.062 0.031
sulfonyl)-N'-(4- kg a.i./ha kg a.i.~la kg a.i./ha
methyl-6-methoxy-
triazin-2-yl)-urea
relative protective 25~ 12.5~ 25~50~ 50~ 50~ 50~ 65~ 63
action: _
Herbicide:
N-[2-(2'-chloroethoxy- 0.125 0.062 0-031
phenyl--sulfonyl]-N'- kg a.i./ha kg a.i.~la kg a.i./ha
(4-methyl-6-methoxy-
triazin-2-yl)-urea
relative protective 12.5~ 12.5~ 12.5 38~ 38~ 12.5~ 50~ 50~ -
action:
Herbicide:
N-[-2-(2'-methoxy- 0.125 0.062 0.031
ethoxy)-phenyl- kg a.i./ha kg a.i./ha kg a.i./ha
sulfonyl]-N'-(4-methyl-
6-methoxy-triazin-2-
yl)-urea
relative protective action~ 12.5~ - - S0~ 38~ 25~ 75~ 50~ 38

- 34 -
_
Herbicide:
N-[2-(3-trifluoro- 0.1250.062 0.031
propen-l-yl~- kg a.i./hakg a.i./ha kg a.i./ha
phenyl-sulfonyl]-N'-(4-
methyl-6-methoxy-
triazin-2-yl)-urea
action 38~ 63~ 50%38~ 50~ 38~ 12.5~ 25~ 38
_ _ . . _
Herbicide:
N-(2-pentafluoroethoxy-
phenyl-sulfonyl) N'- 0.l25 0.125 0.062
(4,6-dimethoxypyrimidi~ kg a.i./ha kg a.i./ha kg a.i~ha
2-yl)-urea
action 50~ _- 38~ - - 25~ ~
Herbicide- _
N-[2-(2~-methoxyethoxy) .
phenyl-sulfonyl]-N'-(4- 0.062 0.031
methyl-6-methoxy- g a.i./ha g a.i./ha
triazin-2-yl)-urea
_ _
Antidote: relative protective action
a-(2,2-dimethoxy- 50~ 63
ethoxyimino)-benæyl
cyanide
2 g of a.i./kg of seeds
~-(1,3-dioxan-2-yl)-
methoximino)-benzyl 50~ 63
cyanide
2 g of a.i./kg of seeds _
~-(5,5 dimethyl-1,3-
dioxan-2-yl-methox- 50~ 63
imino)-benzyl cyanide
2 g of a.i./kg of seeds
.
~-(2,2-dimethoxy-
ethoxyimino)-3,4- 12.5~ 12.5
dichlorobenzyl cyanide
2 g of a.i./k~ of seeds
~ .

2~
Example 8: Tank mixture in the pre-emergence process
on wheat
. .
Wheat seeds are sown, in a greenhouse, in pots of
the same shape (upper diameter 11 cm) each containing
.5 1 of soil. After the seeds have been covered with
soil, the substance to be tested as antidote and the
herbicide are applied together as a tank mixture to the
surface of the soil. The protective action of the antidote
is estimated in per cent 21 days after application. The
plants treated with the herbicide alone and the completely
untreated plants provide reference values.
A~ clear protective action is obtained as a result
of the antidote:
. Herbicide: . .
N-(2-chlorophenyl-
sulfonyl)-~'-(4-methyl- 0.125 0.0620.031 O.OIS
6-methoxy-triazin-2-yl)-
kg of a.i./ha
.
Antidote:
~-(1,3-dioxolan-2-ylmethoxy-0.125 0.0620.031 O.OlS
imino)-ben~yl cyanide (Z fonn)
._. ,
relative protective action
in % 50 33 ZS 12.5

~%2~
- 36 -
Exam~le 9: Tank mixture in the pre-emergence process
on barley
Barley seeds are sown, in a greenhouse, in pots of
the same shape (upper diameter 11 cm) each containing
0.5 litre of soil. After the seeds have been covered with
soil, the substance to be tested as antidote and the
herbicide are applied together as a tank mixture to the
surface of the soil. The protective action of the antidote
is estimated in per cent 21 days after application. The
plants treated with the herbicide alone and the con~pletely
untreated plants provide reference values.
Antidote:
~-(1,3-dioxolan-2-ylmethoximino)- 0.125 0 062
benzyl cyanide (Z form)
kg of a.i./ha
Herbicide:
N-[-(2'-chloroethoxy)-phenyl-
sulfonyl]-ii'-(4-methyl-6- 0.125 0.062
methoxy-triazin-2-yl)-urea
kg of a.i./ha
relative protective action in % 50 25