U.S. patent application number 09/879900 was filed with the patent office on 2002-04-25 for herbicidal sulfonylureas, their preparation and use.
Invention is credited to Gerber, Matthias, Hamprecht, Gerhard, Mayer, Horst, Walter, Helmut, Westphalen, Karl-Otto.
Application Number | 20020049321 09/879900 |
Document ID | / |
Family ID | 6472696 |
Filed Date | 2002-04-25 |
United States Patent
Application |
20020049321 |
Kind Code |
A1 |
Mayer, Horst ; et
al. |
April 25, 2002 |
Herbicidal sulfonylureas, their preparation and use
Abstract
Sulfonylureas of the general formula I 1 where R.sup.1 is a
methyl or ethyl group; R.sup.2 is C.sub.1-C.sub.3-alkoxycarbonyl, a
C.sub.1-C.sub.2-alkyl group which carries 1 to 5 fluorine atoms,
methylsulfonyl, dimethylaminosulfonyl, thiomethyl, methylsulfinyl,
methylsulfonyloxy, trifluoromethoxy, difluoromethoxy,
difluorochloromethoxy, difluorochloromethyl or nitro; R.sup.3 is
hydrogen, methyl, methoxy, ethoxy, fluorine, chlorine or
thiomethyl; W is hydrogen or chlorine and Z is CH or N and their
agriculturally utilizable salts are described.
Inventors: |
Mayer, Horst; (Ludwigshafen,
DE) ; Hamprecht, Gerhard; (Weinheim, DE) ;
Westphalen, Karl-Otto; (Speyer, DE) ; Gerber,
Matthias; (Limburgerhof, DE) ; Walter, Helmut;
(Obrigheim, DE) |
Correspondence
Address: |
Herbert B. Keil
KEIL & WEINKAUF
1101 Connecticut Ave., N.W.
Washington
DC
20036
US
|
Family ID: |
6472696 |
Appl. No.: |
09/879900 |
Filed: |
June 14, 2001 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
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09879900 |
Jun 14, 2001 |
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09517112 |
Mar 7, 2000 |
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09517112 |
Mar 7, 2000 |
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09002836 |
Jan 5, 1998 |
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6043196 |
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09002836 |
Jan 5, 1998 |
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08433521 |
May 12, 1995 |
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08433521 |
May 12, 1995 |
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PCT/EP93/03038 |
Oct 30, 1993 |
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Current U.S.
Class: |
544/211 ;
544/321 |
Current CPC
Class: |
A01N 47/36 20130101;
C07D 521/00 20130101 |
Class at
Publication: |
544/211 ;
544/321 |
International
Class: |
C07D 251/42; C07D
239/47 |
Foreign Application Data
Date |
Code |
Application Number |
Nov 12, 1992 |
DE |
P 42 38 175.4 |
Claims
We claim:
1. A sulfonylurea of the general formula I 24where R.sup.1 is a
methyl or ethyl group; R.sup.2 is C.sub.1-C.sub.3-alkoxycarbonyl, a
C.sub.1-C.sub.2-alkyl group which carries 1 to 5 fluorine atoms,
methylsulfonyl, dimethylaminosulfonyl, methylthio, methyl
sulfoxide, methylsulfonyloxy, trifluoromethoxy, difluoromethoxy,
difluorochloromethoxy, difluorochloromethyl or nitro; R.sup.3 is
hydrogen, methyl, methoxy, ethoxy, fluorine, chlorine or
methylthio; W is hydrogen or chlorine and Z is CH or N and their
agriculturally utilizable salts.
2. A sulfonylurea of the formula I as claimed in claim 1, where
R.sup.2 is methoxycarbonyl, trifluoromethyl, dimethylaminosulfonyl,
trifluoromethoxy, difluoromethoxy or methylsulfonyl.
3. A sulfonylurea of the formula I as claimed in claim 1, where Z
is nitrogen.
4. A sulfonylurea of the formula I as claimed in claim 1, where W
is hydrogen.
5. The process for preparing the sulfonylureas of the formula I as
claimed in claim 1, which comprises reacting a sulfonyl isocyanate
II 25in a manner known per se in an inert organic solvent with
approximately the stoichiometric amount of a 2-amino-1,3,5-triazine
or 2-aminopyrimidine derivative III 26
6. The process for preparing the sulfonylureas of the formula I as
claimed in claim 1, which comprises reacting an appropriate
sulfonamide of the formula IV 27in a manner known per se in an
inert organic solvent with a phenyl carbamate V 28
7. The process for preparing the sulfonylureas of the formula I as
claimed in claim 1, which comprises reacting an appropriate
sulfonamide of the formula IV 29in a manner known per se in an
inert organic solvent with an isocyanate of the formula VI 30
8. A process for preparing salts of the compounds I as claimed in
claim 1, which comprises deprotonating a compound of the formula I
as claimed in claim 1 in a manner known per se in water or an inert
organic solvent using a base.
9. A herbicidal composition containing a sulfonylurea of the
formula I as claimed in claim 1 or its salt and carriers customary
for this purpose.
10. A process for controlling undesired plant growth, which
comprises allowing a herbicidally active amount of a sulfonylurea
of the formula I as claimed in claim 1 or of one of its salts to
act on the plants and/or their environment.
11. A 2-amino-1,3,5-triazine of the formula IIIa 31where W is
hydrogen or chlorine and R.sup.1 is methyl or ethyl.
Description
[0001] The present invention relates to sulfonylureas of the
general formula I 2
[0002] where
[0003] R.sup.1 is a methyl or ethyl group;
[0004] R.sup.2 is C.sub.1-C.sub.3-alkoxycarbonyl, a
C.sub.1-C.sub.2-alkyl group which carries 1 to 5 fluorine atoms,
methylsulfonyl, dimethylaminosulfonyl, thiomethyl, methylsulfinyl,
methylsulfonyloxy, trifluoromethoxy, difluoromethoxy,
difluorochloromethoxy, difluorochloromethyl or nitro;
[0005] R.sup.3 is hydrogen, methyl, methoxy, ethoxy, fluorine,
chlorine or thiomethyl;
[0006] W is hydrogen or chlorine and
[0007] Z is CH or N
[0008] and their agriculturally utilizable salts.
[0009] In U.S. Pat. No. 4,120,691, the nearest structures described
are the triazine compound A and the pyrimidine derivative B (cf.
also U.S. Pat. No. 4,169,719). 3
[0010] In EP-A 48 808, sulfonylureas D having a substituent in the
aromatic moiety are described. 4
[0011] Z=CH or N
[0012] In EP-A 48 143, two N-methylated sulfonylureas E are shown
without closer characterization. 5
[0013] Z=CH or N
[0014] EP-A 388 873 covers benzoic acid esters of the structure F.
6
[0015] R=CH.sub.3 or C.sub.2H.sub.5
[0016] In U.S. Pat. No. 4,310,346, sulfonamides of the type G are
listed. 7
[0017] Z=CH or N
[0018] German Laid-Open Application DE-OS 40 38 430 (WO 92/09608)
describes trifluoromethyl-substituted triazines of type H. 8
[0019] R=halogen, CF.sub.3, alkylsulfonyl or
O(CH.sub.2).sub.2OCH.sub.3
[0020] EP-A 120 814 mentions the compound J without details of
physical data. 9
[0021] It is an object of the present invention to synthesize
sulfonylureas which, compared with the known representatives of
this class of herbicide, have improved properties and are
particularly distinguished by high selectivity in sensitive
crops.
[0022] We have now found that this object can be achieved by the
sulfonylureas of the formula I defined at the outset.
[0023] In the formula I, C.sub.1-C.sub.3-alkoxycarbonyl is
methoxycarbonyl, ethoxycarbonyl, n-propoxycarbonyl or
isopropoxycarbonyl and a C.sub.1-C.sub.2-alkyl group which carries
1 to 5 fluorine atoms is methyl, substituted by 1 to 3 fluorine
atoms, or ethyl, substituted by 1 to 5 fluorine atoms, eg.
trifluoromethyl, difluoromethyl, 2,2,2-trifluoroethyl or
1,1,2,2-tetrafluoroethyl.
[0024] Sulfonylureas of the formula I are particularly preferred in
which R.sup.2 is methoxycarbonyl, trifluoromethyl,
dimethylaminosulfonyl, trifluoromethoxy, difluoromethoxy or
methylsulfonyl, and also sulfonylureas having a triazine
substituent (Z.dbd.N). Compounds I with difluoromethyl substitution
of hetero atoms (W.dbd.H) are additionally particularly
important.
[0025] The sulfonylureas of the formula I according to the
invention are accessible by various routes which are described in
the literature. By way of example, particularly advantageous routes
(A-C) may be illustrated in greater detail in the following. 10
[0026] A: A sulfonyl isocyanate II is reacted in a manner known per
se (EP-A-162 723) with approximately the stoichiometric amount of a
2-amino-1,3,5-triazine or 2-aminopyrimidine derivative III at from
9 to 120.degree. C., preferably from 10 to 100.degree. C. The
reaction can be carried out continuously under normal pressure or
under pressure (up to 50 bar), preferably at from 1 to 5 bar.
[0027] Inert solvents and diluents are expediently used for the
reactions under the respective reaction conditions. Suitable
solvents are, for example, halohydrocarbons, in particular
chlorohydrocarbons, eg. tetrachloroethylene, 1,1,1,2- or
1,1,2,2-tetrachloroethane, dichloropropane, methylene chloride,
dichlorobutane, chloroform, chloronaphthalene, dichloronaphthalene,
carbon tetrachloride, 1,1,1- or 1,1,2-trifluoroethane,
trichloroethylene, pentachloroethane, o-, m- or p-difluorobenzene,
1,2-dichloroethane, 1,1-dichloroethane, 1,2-cis-dichloroethylene,
chlorobenzene, fluorobenzene, bromobenzene or iodobenzene, o-, m-
or p-dichlorobenzene, o-, p- or m-dibromobenzene, o-, m- or
p-chlorotoluene, 1,2,4-trifluorobenzene; ethers, eg. ethyl propyl
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,
thioanisole or .beta.,.beta.'-dichlorodiethyl ether,
nitrohydrocarbons such as nitromethane, nitroethane, nitrobenzene,
o-, m- or p-chloronitrobenzene or o-nitrotoluene; nitriles such as
acetonitrile, butyronitrile, isobutyronitrile, benzonitrile or
m-chlorobenzonitrile; aliphatic or cycloaliphatic hydrocarbons, eg.
heptane, pinane, nonane, or o-, m- or p-cymene, benzene fractions
within a boiling point range from 70 to 190.degree. C.,
cyclohexane, methylcyclohexane, decalin, petroleum ether, hexane,
naphtha, 2,2,4-trimethylpentane, 2,2,3-trimethylpentane,
2,3,3-trimethylpentane or octane; esters, eg. ethyl acetate, ethyl
acetoacetate or isobutyl acetate; amides, eg. formamide,
methylformamide or dimethylformamide; ketones, eg. acetone or
methyl ethyl ketone, and suitable mixtures. The solvent is
expediently used in an amount of from 100 to 2000% by weight,
preferably from 200 to 700% by weight, based on the starting
substance II.
[0028] The compound II required for the reaction is in general
employed in approximately equimolar amounts (using an excess or
deficit of eg. 0 to 20%, based on the respective starting substance
III). The starting substance III can be introduced in one of the
diluents mentioned and the starting substance II then added.
[0029] The process for preparing the novel compounds is expediently
carried out, however, such that the starting substance II is
introduced, if appropriate in one of the abovementioned diluents,
and the starting substance III is then added.
[0030] To complete the reaction, the mixture is subsequently
stirred after the addition of the components for a further 20
minutes to 24 hours at from 0 to 120.degree. C., preferably from 10
to 100.degree. C.
[0031] A reaction accelerator which can be used is advantageously a
tertiary amine, eg. pyridine, .alpha., .beta. or .gamma.-picoline,
2,4- or 2,6-lutidine, 2,4,6-collidine, p-dimethylaminopyridine,
trimethylamine, triethylamine, tri(n-propyl)amine,
1,4-diaza[2.2.2]bicyclooctane [DABCO] or
1,8-diazabicyclo[5.4.0]undec-7-e- ne in an amount of from 0.01 to 1
mol per mole of starting substance II.
[0032] The final substance I is isolated from the reaction mixture
in a customary manner, eg. by removal of solvent by distillation or
directly by filtering off with suction. The residue which remains
can additionally be washed with water or dilute acid to remove
basic impurities. However, the residue can also be dissolved in a
water-immiscible solvent and washed as described. The desired final
substances are obtained here in pure form. If necessary they can be
purified by recrystallization, stirring in an organic solvent which
takes up the impurities or chromatography.
[0033] Preferably, this reaction is carried out in acetonitrile,
methyl tert-butyl ether, toluene or methylene chloride in the
presence of from 0 to 100 mol equivalents, preferably from 0 to 50
mol equivalents, of a tertiary amine such as
1,4-diazabicyclo[2.2.2]octane or triethylamine.
[0034] B: A sulfonamide of the formula IV is reacted in a manner
known per se (EP-A 141 777 or EP-A 101 670) in an inert organic
solvent with approximately the stoichiometric amount of a phenyl
carbamate V and from 0 to 120.degree. C., preferably from 20 to
100.degree. C. The reaction can be carried out continuously or
batchwise at normal pressure or under pressure (up to 50 bar),
preferably at from 1 to 5 bar.
[0035] Bases such as tertiary amines can be added here which
accelerate the reaction and improve the product quality. Suitable
bases for this purpose are those indicated under A, in particular
triethylamine, 2,4,6-collidine, 1,4-diazabicyclo[2.2.2]octane
[DABCO] or 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU), in an amount
of from 0.01 to 1 mol per mole of starting substance IV.
[0036] The solvents or diluents expediently used are those
indicated under A.
[0037] The solvent is used in an amount of from 100 to 2000% by
weight, preferably from 200 to 700% by weight, based on the
starting material IV.
[0038] The compound IV required for the reaction is in general
employed in approximately equimolar amounts (using an excess or
deficit of eg. from 0 to 20%, based on the respective starting
substances V). The starting substance V can be introduced into one
of the abovementioned diluents and the starting substance IV then
added.
[0039] However, the starting substance IV can also be introduced
into one of the solvents mentioned and the carbamate V then added.
In both cases one of the bases mentioned can be added as a catalyst
before or during the reaction.
[0040] To complete the reaction, the mixture is subsequently
stirred after the addition of the components for a further 20
minutes to 24 hours at from 0 to 120.degree. C., preferably from 10
to 100.degree. C., in particular from 20 to 80.degree. C.
[0041] The sulfonylureas of the formula I are isolated from the
reaction mixture using the customary methods, such as described
under A.
[0042] C: A sulfonamide of the formula IV is reacted in a manner
known per se (EP-A 234 352) in an inert organic solvent with
approximately the stoichiometric amount of an isocyanate VI at from
0 to 150.degree. C., preferably from 10 to 100.degree. C. The
reaction can be carried out continuously or batchwise at normal
pressure or under pressure (up to 50 bar), preferably at from 1 to
5 bar.
[0043] Before or during the reaction, bases such as tertiary amines
can be added here which accelerate the reaction and improve the
product quality. Suitable bases for this purpose are those
indicated under A, in particular triethylamine or 2,4,6-collidine,
in an amount of from 0.01 to 1 mol per mole of starting substance
IV.
[0044] The solvents used are expediently those indicated under A.
The solvent is employed in an amount of from 100 to 2000% by
weight, preferably of 200 to 700% by weight, based on the starting
material IV.
[0045] The compound IV required for the reaction is in general
employed in approximately equimolar amounts (using an excess or
deficit of eg. from 0 to 20%, based on the starting materials VI).
The starting substance VI can be initially introduced into one of
the diluents mentioned and the starting substance IV then added.
However, the sulfonamide can also be initially introduced and the
isocyanate VI then added.
[0046] To complete the reaction, the mixture is stirred after the
addition of the components for a further 20 minutes to 24 hours at
from 0 to 120.degree. C., preferably from 10 to 100.degree. C., in
particular from 20 to 80.degree. C. The final product I can be
obtained from the reaction mixture in the customary manner, as
described under A:.
[0047] The sulfonyl isocyanates of the formula II required as
starting substances can be obtained from the corresponding
sulfonamides by phosgenation in a manner known per se (Houben-Weyl
11/2 (1985) 1106, U.S. Pat. No. 4,379,769) or by reaction of the
sulfonamides with chlorosulfonyl isocyanate (DE-A 31 32 944).
[0048] Carbamates of the formula V are accessible by or in a
similar manner to known reactions (eg. EP-A 101 670); however, they
can also be prepared from the corresponding isocyanates VI by
reaction with phenol.
[0049] The isocyanates of the formula VI are obtained from the
amines of the formula III by treatment with oxalyl chloride or
phosgene (in a similar manner to Angew. Chem. 83 (1971) 407, EP-A
388 873).
[0050] The sulfonamides can be obtained by reaction of the
corresponding sulfonyl chlorides with ammonia (Houben-Weyl,
Methoden der organischen Chemie (Methods of organic chemistry),
Volume 9 (1955) 605). The sulfonyl chlorides are obtained by
Meerwein reaction (diazotization of suitable amines and copper
salt-catalyzed sulfochlorination).
[0051] 2-Amino-4-chlorodifluoromethyl-6-methoxy-1,3,5-triazine and
2-amino-4-difluoromethyl-6-methoxy-1,3,5-triazine can be
synthesized as illustrated in the preparation example. The
corresponding 6-ethoxy-substituted 1,3,5-triazines can be prepared
in a similar manner.
[0052] The corresponding pyrimidines of the general formula III are
accessible by the following sequence: 11
[0053] Corresponding reactions are well known (D. J. Brown in "The
Chemistry of Heterocyclic Compounds", Interscience Publishers, New
York, London, Vol. 14, Heterocycl. Chem. 20 (1983) 219).
[0054] The compounds I can be present in the form of their
agriculturally utilizable salts, where in general the nature of the
salt does not matter. Customarily, the salts of those bases will be
suitable which do not adversely affect the herbicidal action of
I.
[0055] The salts of the compounds I are accessible in a manner
known per se (EP-A-304 282, U.S. Pat. No. 4,599,412). They are
obtained by deprotonation of the corresponding sulfonylureas I in
water or an inert organic solvent at from -80.degree. C. to
120.degree. C., preferably from 0.degree. C. to 60.degree. C., in
the presence of a base.
[0056] Suitable bases are, for example, alkali metal or alkaline
earth metal hydroxides, hydrides, oxides or alkoxides such as
sodium, potassium and lithium hydroxide, sodium methoxide, ethoxide
and tert-butoxide, sodium and calcium hydride and calcium oxide.
Salts of transition metals, preferably manganese, copper, zinc and
iron salts and also the ammonium salts which can carry one to three
C.sub.1-C.sub.4-alkyl or hydroxy-C.sub.1-C.sub.4-alkyl substituents
and/or a phenyl or benzyl substituent, preferably
diisopropylammonium, tetramethylammonium, tetrabutylammonium,
trimethylbenzylammonium and trimethyl(2-hydroxyethyl)- ammonium
salts, the phosphonium salts, the sulfonium salts, preferably
tri-(C.sub.1-C.sub.4)-alkylsulfonium salts, and the sulfoxonium
salts, preferably tri-(C.sub.1-C.sub.4)-alkylsulfoxonium salts can
also be employed as basic salts.
[0057] In addition to water, suitable solvents, for example, are
also alcohols such as methanol, ethanol and tert-butanol, ethers
such as tetrahydrofuran and dioxane, acetonitrile,
dimethylformamide, ketones such as acetone and methyl ethyl ketone
and also halogenated hydrocarbons.
[0058] Deprotonation can be carried out at normal pressure or at
pressures of up to 50 bar, preferably at normal pressure up to an
excess pressure of 5 bar.
[0059] The compounds I or the herbicidal compositions containing
them and their environmentally tolerable salts of alkali metals and
alkaline earth metals can very effectively control weeds in crops
such as wheat, rice and maize without damaging the crop plants, an
effect which occurs especially even at low application rates. They
can be applied by spraying, atomizing, dusting, broadcasting or
watering in the form of directly sprayable solutions, powders or
suspensions, even high-percentage aqueous, oily or other
suspensions, or dispersions, emulsions, oil dispersions, pastes,
dusting compositions, broadcasting compositions or granules. The
application forms depend on the intended use; in each case they
should if possible guarantee the finest dispersion of the active
compounds according to the invention.
[0060] The compounds I are generally suitable for preparing
directly sprayable solutions, emulsions, pastes or oil dispersions.
Suitable inert additives are, inter alia, mineral oil fractions of
medium to high boiling point, such as kerosene or diesel oil, and
also coal tar oils and oils of vegetable or animal origin,
aliphatic, cyclic and aromatic hydrocarbons, eg. toluene, xylene,
paraffin, tetrahydronaphthalene, alkylated naphthalenes or their
derivatives, methanol, ethanol, propanol, butanol, cyclohexanol,
cyclohexanone, chlorobenzene, isophorone or strongly polar
solvents, such as N,N-dimethylformamide, dimethyl sulfoxide,
N-methylpyrrolidone or water.
[0061] Aqueous application forms can be prepared from emulsion
concentrates, dispersions, pastes, wettable powders or
water-dispersible granules by addition of water. To prepare
emulsions, pastes or oil dispersions, the substrates as such or
dissolved in an oil or solvent can be homogenized in water by means
of wetting agents, adhesives, dispersants or emulsifiers. However,
concentrates consisting of active substance, wetting agent,
adhesive, dispersant or emulsifier and possibly solvent or oil can
be prepared, which are suitable for dilution with water.
[0062] Suitable surface-active substances are the alkali metal,
alkaline earth metal and ammonium salts of aromatic sulfonic acids,
eg. lignosulfonic, phenolsulfonic, naphthalenesulfonic and
dibutylnaphthalenesulfonic acid, and of fatty acids, alkyl- and
alkyl-arylsulfonates, alkyl-, lauryl ether and fatty alcohol
sulfates, as well as salts of sulfated hexa-, hepta- and
octadecanols, and also of fatty alcohol glycol ethers, condensation
products of sulfonated naphthaline and its derivatives with
formaldehyde, condensation products of naphthalene or of
naphthalenesulfonic acids with phenol and formaldehyde,
polyoxyethylene octylphenol ether, ethoxylated isooctyl-, octyl- or
nonylphenol, alkylphenol or tributylphenyl polyglycol ethers,
alkylaryl polyether alcohols, isotridecyl alcohol, fatty
alcohol/ethylene oxide condensates, ethoxylated castor oil,
polyoxyethylene or polyoxypropylene alkyl ethers, lauryl alcohol
polyglycol ether acetate, sorbitol esters, lignin-sulfite waste
liquors or methylcellulose.
[0063] Powder, broadcasting and dusting compositions can be
prepared by mixing or joint grinding of the active substances with
a solid carrier.
[0064] Granules, eg. coated, impregnated and homogeneous granules
can be prepared by binding the active compounds to solid carriers.
Solid carriers are mineral earths such as silicic acids, silica
gels, silicates, talc, kaolin, limestone, lime, chalk, bole, loess,
clay, dolomite, diatomaceous earth, calcium sulfate and magnesium
sulfate, magnesium oxide, ground synthetic materials, fertilizers,
such as ammonium sulfate, ammonium phosphate, ammonium nitrate,
ureas and vegetable products, such as cereal meal, tree bark meal,
wood meal and nut shell meal, cellulose powder or other solid
carriers.
[0065] The formulations in general contain from 0.1 to 95% by
weight, preferably from 0.5 to 90% by weight, of active compound.
The active compounds are employed here in a purity of from 90 to
100%, preferably from 95 to 100% (according to NMR spectrum).
[0066] Examples of such preparations are:
[0067] I 20 parts by weight of the compound No. 1.01 are dissolved
in a mixture which consists of 80 parts by weight of alkylated
benzene, 10 parts by weight of the additional product of from 8 to
10 mol of ethylene oxide to 1 mol of oleic acid N-monoethanolamide
and 5 parts by weight of the addition product of 40 mol of ethylene
oxide to 1 mol of castor oil. By pouring out the solution and
finely dispersing it in 100,000 parts by weight of water, an
aqueous dispersion is obtained which contains 0.02% by weight of
the active compound.
[0068] II 20 parts by weight of the compound No. 1.01 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
additional product of 7 mol of ethylene oxide to 1 mol of
isooctylphenol and 10 parts by weight of the addition product of 40
mol of ethylene oxide to 1 mol of castor oil. By pouring the
solution into and finely dispersing it in 100,000 parts by weight
of water, an aqueous dispersion is obtained which contains 0.02% by
weight of the active compound.
[0069] III 20 parts by weight of the active compound No. 1.01 are
dissolved in a mixture which consists of 25 parts by weight of
cyclohexanone, 65 parts by weight of a mineral oil fraction of
boiling point 210 to 280.degree. C. and 10 parts by weight of the
addition product of 40 mol of ethylene oxide to 1 mol of castor
oil. By pouring the solution into and finely dispersing it in
100,000 parts by weight of water, an aqueous dispersion is obtained
which contains 0.02% by weight of the active compound.
[0070] IV 20 parts by weight of the active compound No. 1.01 are
well mixed with 3 parts by weight of the sodium salt of
diisobutylnaphthalene-.alpha.-sulfonic acid, 17 parts by weight of
the sodium salt of a lignosulfonic acid from a sulfite waste liquor
and 60 parts by weight of powdered silica gel and the mixture is
ground in a hammer mill. By finely dispersing it in 20,000 parts by
weight of water, a spray liquor is obtained which contains 0.1% by
weight of the active compound.
[0071] V 3 parts by weight of the active compound No. 1.01 are
mixed with 97 parts by weight of finely divided kaolin. In this
manner, a dusting composition is obtained which contains 3% by
weight of the active compound.
[0072] VI 20 parts by weight of the active compound No. 1.01 are
intimately mixed with 2 parts by weight of calcium salt of
dodecylbenzenesulfonic acid, 8 parts by weight of fatty alcohol
polyglycol ether, 2 parts by weight of sodium salt of a
phenol/urea/formaldehyde condensate and 68 parts by weight of a
paraffinic mineral oil. A stable oily dispersion is obtained.
[0073] The application of the herbicidal compositions or of the
active compounds can be carried out pre-emergence or
post-emergence. If the active compounds are less tolerable for
certain crop plants, application techniques can be used in which
the herbicidal compositions are sprayed with the aid of the spray
equipment such that the leaves of the sensitive crop plants are not
affected if possible, while the active compounds reach the leaves
of undesired plants growing under them or the uncovered soil
surface (post-directed, lay-by).
[0074] The application rates of active compound, depending on the
target to be controlled, time of year, target plants and stage of
growth, are from 0.001 to 1.0, preferably from 0.01 to 0.5, kg/ha
of active substance (a.S.).
[0075] In consideration of the variety of application methods, the
sulfonylureas I or compositions containing them can also be
employed in a further number of crop plants for eliminating
undesired plants. Suitable crops are, for example, the
following:
[0076] Allium cepa, Ananas comosus, Arachis hypogaea, Asparagus
officinalis, Beta vulgaris spp. altissima, Beta vulgaris spp. rapa,
Brassica napus var. napus, Brassica napus var. napobrassica,
Brassica rapa var. silvestris, Camellia sinensis, Carthamus
tinctorius, Carya illinoinensis, Citrus limon, Citrus sinensis,
Coffea arabica (Coffea canephora, Coffea liberica), Cucumis
sativus, Cynodon dactylon, Daucus carota, Elaeis guineensis,
Fragaria vesca, Glycine max, Gossypium hirsutum (Gossypium
arboreum, Gossypium herbaceum, Gossypium vitifolium), Helianthus
annuus, Hevea brasiliensis, Hordeum vulgare, Humulus lupulus,
Ipomoea batatas, Juglans regia, Lens culinaris, Linum
usitatissimum, Lycopersicon lycopersicum, Malus spp., Manihot
esculenta, Medicago sativa, Musa spp., Nicotiana tabacum (N.
rustica), Olea europaea, Oryza sativa, Phaseolus lunatus, Phaseolus
vulgaris, Picea abies, Pinus spp., Pisum sativum, Prunus avium,
Prunus persica, Pyrus communis, Ribes sylvestre, Ricinus communis,
Saccharum officinarum, Secale cereale, Solanum tuberosum, Sorghum
bicolor (S. vulgare), Theobroma cacao, Trifolium pratense, Triticum
aestivum, Triticum durum, Vicia faba, Vitis vinifera and Zea
mays.
[0077] To widen the spectrum of action and to achieve synergistic
effects, the substituted sulfonylureas of the formula I can be
mixed with numerous representatives of other herbicidal or
growth-regulating active compound groups and applied together. For
example, suitable mixture components are diazines,
4H-3,1-benzoxazine derivatives, benzothiodiazinones,
2,6-dinitroanilines, N-phenylcarbamates, thiocarbamates,
halocarboxylic acids, triazines, amides, ureas, diphenyl ethers,
triazinones, uracils, benzofuran derivatives, cyclohexane-1,3-dione
derivatives, quinolinecarboxylic acid derivatives, phenyloxy- or
heteroaryloxyphenylpropionic acids and their salts, esters and
amides and others.
[0078] It may additionally be useful to apply the compounds of the
formula I on their own or together in combination with other
herbicides and additionally with other crop protection
compositions, for example with compositions for controlling pests
or phytopathogenic fungi or bacteria. Also of interest is the
miscibility with mineral salt solutions which are employed for
eliminating nutritional and trace element deficiencies.
Non-phytotoxic oils and oil concentrates can also be added.
[0079] Examples of the synthesis of the compounds I are given
below.
[0080] Preparation of the starting substances
[0081] 2-Amino-4-chlorodifluoromethyl-6-methoxy-1,3,5-triazine
[0082] a)
2-Amino-4-chlorodifluoromethyl-6-thiomethyl-1,3,5-triazine
[0083] A suspension of 18.5 g of N-amidinothiourea (adduct with
N-methyl-2-pyrrolidone) (85 mmol) in 90 ml of methanol was treated
with 10.7 g of dimethyl sulfate (85 mmol) and stirred at from 30 to
40.degree. C. for 3 h. 25 g of methyl chlorodifluoroacetate (0.17
mol) was added dropwise to this solution at 0.degree. C., followed
by 30.6 g of a 30% by weight solution of sodium methoxide in
methanol (0.17 mol). The cooling was removed and the mixture was
subsequently stirred at 25.degree. C. for 16 h. The solvent was
removed at 40.degree. C., the residue was stirred with 400 ml of
water, and the product was filtered off with suction and dried at
40.degree. C. in a water-jet vacuum. The crude product (m.p.
118.degree. C.) was employed in Stage b) without purification
(.sup.1H-NMR spectrum (250 MHz, CDCl.sub.3, int. TMS, .delta.
(ppm): 6.74 br (1H); 5.94 br (1H); 2.54 s (3H)).
[0084] b)
2-Amino-4-chlorodifluoromethyl-6-methoxy-1,3,5-triazine
[0085] A solution of 19 g of crude product (84 mmol) from Stage a)
in 100 ml of methanol was treated dropwise at 0.degree. C. with
16.2 g of a 30% strength by weight solution of sodium methoxide in
methanol (90 mmol). The cooling was removed and the mixture was
subsequently stirred at 25.degree. C. for 16 h. A pH of 6 was set
by addition of 4N HCl, the solvent was removed at 40.degree. C. in
a water-jet vacuum and the residue was stirred with 400 ml of
water. The product was filtered off with suction, washed with water
and dried at 40.degree. C. in a water-jet vacuum.
[0086] 13.9 g of the title compound (79% of theory) were thus
obtained of m.p. 130.degree. C. (.sup.1H-NMR spectrum (250 MHz,
CDCl.sub.3, int. TMS, .delta. (ppm): 6.78 br (1H); 6.08 br (1H);
4.03 s (3H)).
[0087] 2-Amino-6-difluoromethyl-6-methoxy-1,3,5-triazine
[0088] a) 2-Amino-4-difluoromethyl-6-trichloromethyl-1,3,5-triazine
A solution of 70.1 g of difluoroacetic anhydride (0.4 mol) in 200
ml of diethyl ether was treated in portions with 40.7 g of
N-(trichloroacetamidino)guanidine (0.2 mol) at 0.degree. C. The
mixture was stirred at from 20 to 25.degree. C. for 3 hours. The
volatile fractions were removed at 40.degree. C. in a water-jet
vacuum, the residue was partitioned between 400 ml of water and 200
ml of methylene chloride and the methylene chloride phase was
carefully neutralized with dilute sodium hydroxide solution (2%
strength by weight). After separating off and drying the methylene
chloride phase over Na.sub.2SO.sub.4, the solvent was distilled off
at 40.degree. C. in a water-jet vacuum. 39.6 g (0.15 mol) (75% of
theory) of a spectroscopically pure crude product were thus
obtained, which can thus be employed in the subsequent reaction
(Stage b) without purification.
[0089] .sup.1H-NMR spectrum (270 MHz, d.sub.6-DMSO, int. TMS,
.delta. (ppm): 8.80 br (2H); 6.78 tr (1H; J.sub.H-F 162 Hz)).
[0090] b) 2-Amino-4-difluoromethyl-6-methoxy-1,3,5-triazine
[0091] A solution of 22.5 g of crude product (85 mmol) from Stage
a) in 100 ml of methanol was treated dropwise at 0.degree. C. with
1.6 g of a 30% strength by weight solution of sodium methoxide in
methanol (9 mmol). The cooling was removed and the mixture was
subsequently stirred at 25.degree. C. for 16 hours. After addition
of a further 1.6 g of a 30% strength by weight solution of sodium
methoxide in methanol (9 mmol), the mixture was subsequently
stirred at 25.degree. C. for 3 hours. A pH of 7 was set by addition
of 3N hydrochloric acid, the solvent was removed in a water-jet
vacuum at 40.degree. C. and the residue was vigorously stirred with
400 ml of water. The product was filtered off with suction, washed
with water and dried at 40.degree. C. in a water-jet vacuum.
[0092] 10.7 g of the title compound (0.61 mol; 71% of theory) were
thus obtained. .sup.1H-NMR spectrum (270 MHz, d.sub.6-DMSO, int.
TMS, .delta. (ppm): 8.02, 7.94 br (2H); 6.55 tr (1H; J.sub.H-F 162
Hz); 3.90 s (3H)).
[0093] Preparation of the sulfonylureas of the formula I
EXAMPLE 1.03
[0094] Methyl
[2-[[(4-chlorodifluoromethyl-6-methoxy-1,3,5-triazin-2-yl)-a-
minocarbonyl]aminosulfonyl]benzoate
[0095] A solution of 4.2 g of
2-amino-4-chlorodifluoromethyl-6-methoxy-1,3- ,5-triazine (20 mmol)
in 20 ml of methylene chloride was treated at 25.degree. C. with a
solution of 4.8 g of 2-methoxycarbonylbenzenesulfony- l isocyanate
(20 mmol) in 5 ml of methylene chlor-ide. The mixture was stirred
at 25.degree. C. for 16 h, the solvent was removed in a water-jet
vacuum at 40.degree. C. and the solid residue was stirred with 100
ml of a hexane/diethyl ether mixture (v:v, 1:1). The separated
product was filtered off with suction, washed with a little ether
and dried. The title compound (3.2 g, 35% of theory) of m.p. 174 to
175.degree. C. was obtained by recrystallizing from
methanol/water.
EXAMPLE 1.05
[0096]
N-[(4-Chlorodifluoromethyl-6-methoxy-1,3,5-triazin-2-yl)aminocarbon-
yl]-2-nitrobenzenesulfonamide
[0097] A solution of 4.2 g of
2-amino-4-chlorodifluoromethyl-6-methoxy-1,3- ,5-triazine (20 mmol)
in 20 ml of methylene chloride was treated at 25.degree. C. with a
solution of 4.6 g of 2-nitrobenzenesulfonyl isocyanate (20 mmol) in
5 ml of methylene chloride. The mixture was subsequently stirred at
25.degree. C. for 16 h, and the deposited product was filtered off
with suction, washed with a little ether and dried at 40.degree. C.
in a water-jet vacuum. 3.1 g of the title compound (35% of theory)
of m.p. 181.degree. C. were thus obtained.
EXAMPLE 1.06
[0098] Sodium
N-[(4-chlorodifluoromethyl-6-methoxy-1,3,5-triazin-2-yl)amin-
ocarbonyl]-2-nitrobenzenesulfonamide
[0099] A suspension of 1.5 g of
N-[(4-chlorodifluoromethyl-6-methoxy-1,3,5-
-triazin-2-yl)aminocarbonyl]-2-nitrobenzenesulfonamide (3.4 mmol)
in 10 ml of methanol was treated at 25.degree. C. with 0.62 g of a
30% strength by weight solution of sodium methoxide (3.4 mmol) in
methanol, whereupon dissolution occurred. The mixture was
subsequently stirred at 25.degree. C. for 30 min and the volatile
fractions were removed at 40.degree. C. in a water-jet vacuum. The
title compound was thus obtained in quantitative yield with a
decomposition point of 169.degree. C.
EXAMPLE 3.01
[0100]
2-[[(4-Difluoromethyl-6-methoxy-1,3,5-triazin-2-yl)aminocarbonyl]am-
inosulfonyl]benzotrifluoride
[0101] A solution of 2.65 g of
2-amino-4-difluoromethyl-6-methoxy-1,3,5-tr- iazine (15 mmol) in 20
ml of acetonitrile was treated at 25.degree. C. with 3.7 g of
2-trifluoromethylbenzenesulfonyl isocyanate (15 mmol). The mixture
was subsequently stirred at 25.degree. C. for 16 h, the solvent was
removed in a water-jet vacuum at 40.degree. C. and the solid
residue was stirred vigorously with 100 ml of diethyl ether. The
product was filtered off with suction, washed with a little ether
and dried. 4.3 g (10 mmol, 67% of theory) of the title compound of
m.p. 143-145.degree. C. were obtained.
EXAMPLE 3.02
[0102] Sodium
N-[(4-difluoromethyl-6-methoxy-1,3,5-triazin-2-yl)aminocarbo-
nyl]aminosulfonylbenzotrifluoride
[0103] A suspension of 1.3 g of
2-[[(4-difluoromethyl-6-methoxy-1,3,5-tria-
zin-2-yl)aminocarbonyl]aminosulfonyl]benzotrifluoride (3 mmol) in
10 ml of methanol was treated at 25.degree. C. with 0.54 g of a 30%
strength by weight solution of sodium methoxide (3 mmol) in
methanol, whereupon dissolution occurred. The mixture was
subsequently stirred at 25.degree. C. for 30 min and the volatile
fractions were removed at 40.degree. C. in a water-jet vacuum. The
title compound was thus obtained in quantitative yield with a
decomposition point of 189-192.degree. C.
[0104] The active compounds mentioned in the following Tables 1 to
4 are obtained by a similar preparative route.
1TABLE 1 I 12 Active Compound No. R.sup.1 R.sup.2 R.sup.3 M.p.
[.degree. C.] 1.01 CH.sub.3 CF.sub.3 H 175-172 1.02 CH.sub.3
CF.sub.3 H 192-193 (d)* 1.03 CH.sub.3 CO.sub.2CH.sub.3 H 174-175
1.04 CH.sub.3 CO.sub.2CH.sub.3 H 171 (d)* 1.05 CH.sub.3 NO.sub.2 H
181 1.06 CH.sub.3 NO.sub.2 H 169 (d)* 1.07 CH.sub.3
SO.sub.2N(CH.sub.3).sub.2 H 152-154 1.08 CH.sub.3
SO.sub.2N(CH.sub.3).sub.2 H 125-130 (d)* 1.09 CH.sub.3 SCH.sub.3
6-SCH.sub.3 >200 1.10 CH.sub.3 OSO.sub.2CH.sub.3 H 1.11 CH.sub.3
OSO.sub.2CH.sub.3 H * 1.12 CH.sub.3 OCF.sub.3 H 1.13 CH.sub.3
OCH.sub.3 H * 1.14 CH.sub.3 OCF.sub.2H H 1.15 CH.sub.3 OCF.sub.2H H
* 1.16 CH.sub.3 SO.sub.2CH.sub.3 H 1.17 CH.sub.3 SO.sub.2CH.sub.3 H
* 1.18 CH.sub.3 CO.sub.2C.sub.2H.sub.5 H 159-167 1.19 CH.sub.3
CO.sub.2C.sub.2H.sub.5 H * 1.20 CH.sub.3 CO.sub.2iC.sub.3H.sub.7 H
1.21 CH.sub.3 CO.sub.2iC.sub.3H.sub.7 H * 1.22 CH.sub.3
CO.sub.2CH.sub.3 5-OCH.sub.3 155-160 1.23 CH.sub.3 CO.sub.2CH.sub.3
5-OCH.sub.3 165-170 (d)* *Na salt
[0105] The compounds shown below can also be obtained in a similar
manner: 13
[0106] or their Na salts, where R.sup.3 has the following
meanings:
[0107] 3-methyl, 5-methyl, 6-methyl, 3-thiomethyl, 5-thiomethyl,
6-thiomethyl, 3-fluoro, 5-fluoro, 6-fluoro, 3-chloro, 5-chloro,
6-chloro, 3-methoxy, 4-methoxy, 5-methoxy, 6-methoxy, 3-ethoxy,
5-ethoxy, 6-ethoxy; 14
[0108] or their Na salts, where R.sup.3 has the following
meanings:
[0109] 3-methyl, 5-methyl, 6-methyl, 3-thiomethyl, 5-thiomethyl,
6-thiomethyl, 3-fluoro, 5-fluoro, 6-fluoro, 3-chloro, 5-chloro,
6-chloro, 3-methoxy, 4-methoxy, 5-methoxy, 6-methoxy, 3-ethoxy,
5-ethoxy, 6-ethoxy; 15
[0110] or their Na salts, where R.sup.3 has the following
meanings:
[0111] 3-methyl, 5-methyl, 6-methyl, 3-thiomethyl, 5-thiomethyl,
6-thiomethyl, 3-fluoro, 5-fluoro, 6-fluoro, 3-chloro, 5-chloro,
6-chloro, 3-methoxy, 4-methoxy, 5-methoxy, 6-methoxy, 3-ethoxy,
5-ethoxy, 6-ethoxy; 16
[0112] or their Na salts, where R.sup.3 has the following
meanings:
[0113] 3-methyl, 5-methyl, 6-methyl, 3-thiomethyl, 5-thiomethyl,
6-thioethyl, 3-fluoro, 5-fluoro, 6-fluoro, 3-chloro, 5-chloro,
6-chloro, 3-methoxy, 4-methoxy, 5-methoxy, 6-methoxy, 3-ethoxy,
5-ethoxy, 6-ethoxy; 17
[0114] or their Na salts, where R.sup.3 has the following
meanings:
[0115] 3-methyl, 5-methyl, 6-methyl, 3-thiomethyl, 5-thiomethyl,
6-thiomethyl, 3-fluoro, 5-fluoro, 6-fluoro, 3-chloro, 5-chloro,
6-chloro, 3-methoxy, 4-methoxy, 5-methoxy, 6-methoxy, 3-ethoxy,
5-ethoxy, 6-ethoxy; 18
[0116] or their Na salts, where R.sup.3 has the following
meanings:
[0117] 3-methyl, 5-methyl, 6-methyl, 3-thiomethyl, 5-thiomethyl,
6-thiomethyl, 3-fluoro, 5-fluoro, 6-fluoro, 3-chloro, 5-chloro,
6-chloro, 3-methoxy, 4-methoxy, 5-methoxy, 6-methoxy, 3-ethoxy,
5-ethoxy, 6-ethoxy; 19
[0118] or their Na salts, where R.sup.3 has the following
meanings:
[0119] 3-methyl, 5-methyl, 6-methyl, 3-thiomethyl, 5-thiomethyl,
6-thiomethyl, 3-fluoro, 5-fluoro, 6-fluoro, 3-chloro, 5-chloro,
6-chloro, 3-methoxy, 4-methoxy, 5-methoxy, 6-methoxy, 3-ethoxy,
5-ethoxy, 6-ethoxy.
2TABLE 2 I 20 (Z = CH) Active Compound No. R.sup.1 R.sup.2 R.sup.3
M.p. [.degree. C.] 2.01 CH.sub.3 CF.sub.3 H 2.02 CH.sub.3 CF.sub.3
H * 2.03 CH.sub.3 CO.sub.2CH.sub.3 H 2.04 CH.sub.3 CO.sub.2CH.sub.3
H * 2.05 CH.sub.3 NO.sub.2 H 2.06 CH.sub.3 NO.sub.2 H * 2.07
CH.sub.3 SO.sub.2N(CH.sub.3).sub.2 H 2.08 CH.sub.3
SO.sub.2N(CH.sub.3).sub.2 H * 2.09 CH.sub.3 SCH.sub.3 6-SCH.sub.3
2.10 CH.sub.3 OSO.sub.2CH.sub.3 H 2.11 CH.sub.3 OSO.sub.2CH.sub.3 H
* 2.12 CH.sub.3 OCF.sub.3 H 2.13 CH.sub.3 OCH.sub.3 H * 2.14
CH.sub.3 OCF.sub.2H H 2.15 CH.sub.3 OCF.sub.2H H * 2.16 CH.sub.3
SO.sub.2CH.sub.3 H 2.17 CH.sub.3 SO.sub.2CH.sub.3 H * 2.18 CH.sub.3
CO.sub.2C.sub.2H.sub.5 H 2.19 CH.sub.3 CO.sub.2C.sub.2H.sub.5 H *
2.20 CH.sub.3 CO.sub.2iC.sub.3H.sub.7 H 2.21 CH.sub.3
CO.sub.2iC.sub.3H.sub.7 H * *Na salt
[0120]
3TABLE 3 I 21 (Z = N) Active Compound No. R.sup.1 R.sup.2 R.sup.3
M.p. [.degree. C.] 3.01 CH.sub.3 CF.sub.3 H 143-145 3.02 CH.sub.3
CF.sub.3 H * 189-192 (d) 3.03 CH.sub.3 CO.sub.2CH.sub.3 H 144-146
3.04 CH.sub.3 CO.sub.2CH.sub.3 H * 168 (d) 3.05 CH.sub.3 NO.sub.2 H
3.06 CH.sub.3 NO.sub.2 H * 3.07 CH.sub.3 SO.sub.2N(CH.sub.3).sub.2
H 160-162 3.08 CH.sub.3 SO.sub.2N(CH.sub.3).sub.2 H * 3.09 CH.sub.3
SCH.sub.3 6-SCH.sub.3 3.10 CH.sub.3 OSO.sub.2CH.sub.3 H 146-148
3.11 CH.sub.3 OSO.sub.2CH.sub.3 H * 3.12 CH.sub.3 OCF.sub.3 H
158-161 3.13 CH.sub.3 OCF.sub.3 H * 120 (d) 3.14 CH.sub.3
OCF.sub.2H H 146-148 3.15 CH.sub.3 OCF.sub.2H H * 161 (d) 3.16
CH.sub.3 SO.sub.2CH.sub.3 H 3.17 CH.sub.3 SO.sub.2CH.sub.3 H * 3.18
CH.sub.3 CO.sub.2C.sub.2H.sub.5 H 167-169 3.19 CH.sub.3
CO.sub.2C.sub.2H.sub.5 H * 158 (d) 3.20 CH.sub.3
CO.sub.2iC.sub.3H.sub.7 H 3.21 CH.sub.3 CO.sub.2iC.sub.3H.sub.7 H *
*Na salt
[0121]
4TABLE 4 I 22 (Z = CH) Active Compound No. R.sup.1 R.sup.2 R.sup.3
M.p. [.degree. C.] 4.01 CH.sub.3 CF.sub.3 H 4.02 CH.sub.3 CF.sub.3
H * 4.03 CH.sub.3 CO.sub.2CH.sub.3 H 4.04 CH.sub.3 CO.sub.2CH.sub.3
H * 4.05 CH.sub.3 NO.sub.2 H 4.06 CH.sub.3 NO.sub.2 H * 4.07
CH.sub.3 SO.sub.2N(CH.sub.3)2 H 4.08 CH.sub.3 SO.sub.2N(CH.sub.3)2
H * 4.09 CH.sub.3 SCH.sub.3 6-SCH.sub.3 4.10 CH.sub.3
OSO.sub.2CH.sub.3 H 4.11 CH.sub.3 OSO.sub.2CH.sub.3 H * 4.12
CH.sub.3 OCF.sub.3 H 4.13 CH.sub.3 OCH.sub.3 H * 4.14 CH.sub.3
OCF.sub.2H H 4.15 CH.sub.3 OCF.sub.2H H * 4.16 CH.sub.3
SO.sub.2CH.sub.3 H 4.17 CH.sub.3 SO.sub.2CH.sub.3 H * 4.18 CH.sub.3
CO.sub.2C.sub.2H.sub.5 H 4.19 CH.sub.3 CO.sub.2C.sub.2H.sub.5 H *
4.20 CH.sub.3 CO.sub.2iC.sub.3H.sub.7 H 4.21 CH.sub.3
CO.sub.2iC.sub.3H.sub.7 H * *Na salt
[0122] Use examples:
[0123] The herbicidal action of the sulfonylureas of the formula I
on the growth of the test plants is shown by the following
greenhouse tests.
[0124] The cultivation containers used were plastic flowerpots
containing loamy sand with about 3.0% humus as a substrate. The
seeds of the test plants were sown separately according to
species.
[0125] In the case of pre-emergence treatment, the active compounds
suspended or emulsified in water were applied directly after sowing
by means of finely dispersing nozzles. The containers were lightly
watered in order to promote germination and growth and then covered
with transparent plastic hoods until the plants had taken root.
This covering causes a uniform germination of the test plants if
this has not been adversely affected by the active compounds.
[0126] For the purpose of post-emergence treatment, the test plants
were first raised, depending on growth form, to a growth height of
from 4 to 15 cm and only then treated with the active compounds
suspended or emulsified in water. To do this, the test plants were
either directly sown and raised in the same containers or they were
first raised separately as seed plants and transplanted into the
test containers a few days before the treatment. The application
rate for post-emergence treatment was 0.06 kg/ha of a.s. (active
substance).
[0127] The plants were kept in a species-specific manner at
10-25.degree. C. or 20-35.degree. C. The test period extended over
2 to 4 weeks. During this time the plants were tended and their
reaction to the individual treatments was assessed.
[0128] Assessment was carried out on a scale of from 0 to 100. 100
here means no germination of the plants or complete destruction of
at least the above-ground parts and 0 means no damage or normal
course of growth.
[0129] The plants used in the greenhouse tests were composed of the
following species:
5 Botanical Name Common Name Abutilon theophrasti Velvetleaf
Sinapis alba White mustard Zea mays Maize
[0130] Using 0.06 kg/ha of a.s. post-emergence, broad-leaved
undesired plants can be very well controlled with Example 1.03,
together with simultaneous outstanding selectivity in the exemplary
crop plant maize.
[0131] In the following tables, results of biological
investigations are compiled in which the active compound according
to the invention Example 1.03 was compared with the compound B
known from U.S. Pat. No. 4,169,719 and the active compound
according to the invention No. 3.01 was compared with the
comparison compound H known from WO 92/09608. 23
6TABLE I Comparison of the herbicidal activity of the exemplary
compound No. 1.03 with the known comparison compound B on
post-emergence application of 0.0313 or 0.0156 kg/ha of a.s.
respectively in the greenhouse. Damage [%] Application rate [kg/ha
of a.s.] Example 1.03 B Test plants 0.0313 0.0156 0.0313 0.0156
Amaranthus retroflexus 100 100 75 70 Galium aparine 95 75 85 40
Polygonum persicaria 80 80 40 40 Sinapis alba 90 90 75 75 Solanum
nigrum 90 90 60 60 Veronica spp. 85 75 50 40
[0132]
7TABLE II Comparison of the herbicidal activity of the exemplary
compound No. 3.01 with the known comparison compound H on
post-emergence application of 0.063 or 0.0313 kg/ha of a.s.
respectively in the greenhouse. Damage [%] Application rate [kg/ha
of a.s.] Example 1.03 B Test plants 0.063 0.0313 0.063 0.0313
Alopecurus myosuroides 98 98 40 0 Galium aparine 95 95 95 95 Ipomea
spp. 98 90 80 80 Sinapis alba 98 98 100 100 Triticum aestivum 0 0 0
0
* * * * *