Sulfonylureas having heterocyclic substituents, and their use in agriculture

Compounds of the formula ##STR1## wherein R.sub.1 is (among others) (halo)cycloalkyl or (halo)cycloalkenyl, R.sub.2 and R.sub.3 are preferably hydrogen, X is preferably oxygen and R.sub.4 is substituted pyrimidyl or s-triazinyl, are valuable herbicides and growth regulators.

It has already been disclosed that phenylsulfonylureas having heterocyclic 
substituents, such as, for example, 
N-(4-chloro-6-i-propylamino-1,3,5-triazin-2-yl)-N-i-propyl-N'-(4-chlorophe 
nylsulfonyl)urea, have herbicidal or plant-growth regulating properties 
(cf. Netherlands Patent 121,788, German Offenlegungsschrift No. 2,715,786, 
European Pat. Nos. 1,485, 1,514, 1,515, 4,163, 7,687, 9,419, 10,560, 
23,140, 23,141 and 23,422). 
It has now been found that cyclo- and bicycloalkylsulfonylureas having 
heterocyclic substituents are also suitable as herbicides and plant-growth 
regulators. 
Thus the present invention relates to compounds of the formula I 
##STR2## 
wherein R.sub.1 denotes a saturated cycloaliphatic radical having 3 to 12 
C atoms or a cycloaliphatic radical having 5-12 C atoms, which is 
monounsaturated or polyunsaturated and all of which can optionally be 
substituted by up to 4 halogen atoms and/or by one or more (C.sub.1 
-C.sub.4)-alkyl or halogenoalkyl (the latter having 1-3 halogen atoms) or 
by a (C.sub.1 -C.sub.4)-alkoxycarbonyl radical; a bicyclic saturated or 
monounsaturated or di-unsaturated aliphatic radical having 7 to 12 C 
atoms, which can optionally carry up to 6 halogen atoms or one or more 
(C.sub.1 -C.sub.4)-alkyl radicals or in which a CH.sub.2 bridge can be 
replaced by oxygen, R.sub.2 and R.sub.3 denote H or (C.sub.1 
-C.sub.4)-alkyl, X denotes O or S, R.sub.4 denotes a six-membered 
heterocyclic ring containing 2-3 nitrogen atoms, which is optionally 
substituted 1-3 times by halogen, NO.sub.2, CN, CHO, (C.sub.1 
-C.sub.4)-alkylamino, (C.sub.1 -C.sub.4)-dialkylamino, a (C.sub.1 
-C.sub.4)-alkyl radical (which is optionally substituted by halogen, 
(C.sub.1 -C.sub.3)-alkoxy, (C.sub.1 -C.sub.3)-alkylthio, (C.sub.1 
-C.sub.3)-alkylamino, (C.sub.1 -C.sub.3)-dialkylamino or (C.sub.1 
-C.sub.4)-alkoxycarbonyl), a (C.sub.1 -C.sub.4)-alkoxy or (C.sub.1 
-C.sub.4)-alkylthio radical (which are optionally substituted by halogen 
or (C.sub.1 -C.sub.4)-alkoxycarbonyl), or (C.sub.1 
-C.sub.4)-alkoxycarbonyl, and, if R.sub.2 denotes hydrogen, their 
physiologically tolerated salts with bases. 
"Halogen" preferably denotes fluorine, chlorine or bromine. 
Those compounds are particularly preferred in which R.sub.1 denotes a 
saturated or monounsaturated (C.sub.5 -C.sub.8)-cycloaliphatic or (C.sub.7 
-C.sub.8)-bicyclic radical which is unsubstituted or substituted once or 
more times by Cl or CH.sub.3, it being possible for Cl to be present, 
preferably, up to three times and CH.sub.3 up to 9 times. 
Examples of sulfonylureas having heterocyclic substituents of the formula I 
according to the invention which may be mentioned in addition to the 
compounds described in the experimental section are the following: 
N-[(4-methoxy-6-methyl-1,3,5-triazin-2-yl)aminocarbonyl]-1,2-dichlorocyclo 
hexylsulfonamide; 
N-[(2,6-dimethyl-5-chloropyrimidin-2-yl)aminocarbonyl]-3-bromo-1-cyclohexe 
nylsulfonamide; 
N-[(4-methyl-6-methylthio-1,3,5-triazin-2-yl)aminocarbonyl]-1,3-cyclohexad 
ienylsulfonamide; 
N-[(4-methyl-6-dimethylamino-1,3,5-triazin-2-yl)-aminocarbonyl]-2-chlorocy 
clopentylsulfonamide; 
N-[(-5,6-dimethyl-1,2,4-triazin-3-yl)aminothiocarbonyl]-1-cyclopentenylsul 
fonamide; 
N-[(-4,6-dimethoxy-5-chloropyrimidin-2-yl)methylaminocarbonyl]-1-cyclopent 
enylsulfonamide; 
N-[(-4,5-dimethyl-6-methoxypyrimidin-2-yl)aminocarbonyl]-1-cycloheptenylsu 
lfonamide; 
N-[(4-methyl-5-nitro-6-chloropyrimidin-2-yl)aminocarbonyl]-2-chlorocyclooc 
tylsulfonamide; 
N-[(4-methoxycarbonyl-6-methyl-1,3,5-triazin-2-yl)aminocarbonyl]-1-cyclooc 
tenylsulfonamide; 
N-[(4-chloro-6-isopropylamino-1,3,5-triazin-2-yl)aminocarbonyl]-1-cyclooct 
enylsulfonamide; 
N-[(-4-trifluoromethyl-6-methylpyrimidin-2-yl)aminocarbonyl]-3-cyclohexeny 
lsulfonamide; 
N-[(4,6-di-methylmercapto-1,3,5-triazin-2-yl)aminocarbonyl]-cyclohexylsulf 
onamide; 
N-[(4-methylpyrimidin-2-yl)aminocarbonyl]-3,4-dichlorocyclohexylsulfonamid 
e; 
N-[(4-methoxy-5-n-butyl-6-methylpyrimidin-2-yl)aminocarbonyl]-1,2-dibromoc 
yclohexylsulfonamide; 
N-[(4-methoxycarbonylmethoxy)-6-methylpyrimidin-2-yl)aminocarbonyl]-1-cycl 
ohexenylsulfonamide, sodium salt; 
N-[(4-methoxy-6-methyl-1,3,5-triazin-2-yl)methylaminocarbonyl]-1-cyclohexe 
nylsulfonamide; 
N-[(4-methoxy-6-methylpyrimidin-2-yl)aminocarbonyl]-cyclopentylsulfonamide 
; N-[(4-ethyl-6-methoxy-1,3,5-triazin-2-yl)aminocarbonyl]-cyclopentylsulfon 
amide; 
N-[(4-methoxy-6-methylpyrimidin-2-yl)aminocarbonyl]-1,2-dichlorocyclopenty 
lsulfonamide; 
N-[(4-methoxy-6-methylpyrimidin-2-yl)-aminocarbonyl]-2-chlorocyclopentylsu 
lfonamide; 
N-[(4,6-dimethoxy-1,3,5-triazin-2-yl)aminocarbonyl]-2-chlorocyclodecylsulf 
onamide; 
N-[(4-methoxy-6-methylpyrimidin-2-yl)aminocarbonyl]-3-chlorobicyclo[2.2.1] 
hept-2-ylsulfonamide; 
N-[(4-methoxy-6-methyl-1,3,5-triazin-2-yl)-aminocarbonyl]-bicyclo[2.2.1]he 
pt-5-en-2-ylsulfonamide; 
N-[(4,6-dimethylpyrimidin-2-yl)aminocarbonyl]bicyclo[2.2.2]oct-2-ylsulfona 
mide; 
N-[(4-methoxy-6-methyl-1,3,5-triazin-2-yl)aminocarbonyl]-2,3,3-trimethylbi 
cyclo[2.2.1]-hept-2-ylsulfonamide; 
N-[(4-methoxy-6-methylpyrimidin-2-yl)aminocarbonyl]bicyclo[2.2.1]hept-2-yl 
sulfonamide; 
N-[(5,6-dimethyl-1,2,4-triazin-3-yl)aminocarbonyl]-4,5-dichlorobicyclo[2.2 
.1]heptylsulfonamide; 
N-[(4,6-dimethylpyrimidin-2-yl)aminocarbonyl]-2,2,5,5-tetramethyl-3-cycloh 
exenylsulfonamide; 
N-[(4-methoxymethyl-6-methyltriazin-2-yl)aminocarbonyl]-2-chlorocyclohexen 
ylsulfonamide; 
N-[(4-methoxy-6-methylpyrimidin-2-yl)aminocarbonyl]-2-chloro-3-methyl-4-cy 
clohexenylsulfonamide; 
N-[(4,6-dimethyl-1,3,5-triazin-2-yl)aminocarbonyl]-2,4,5-trichloro-3-methy 
lcyclohexylsulfonamide; 
N-[(4-methoxy-6-methylpyrimidin-2-yl)aminocarbonyl]-2-chlorocyclooctylsulf 
onamide; 
N-[(4,6-dimethyl-1,3,5-triazin-2-yl)aminocarbonyl]-cyclopropylsulfonamide; 
N-[(4-methoxy-6-methyl-1,3,5-triazin-2-yl)aminocarbonyl]-2-methyl-5-isopro 
pylcyclohexylsulfonamide; 
N-[(4,6-dimethyl-pyrimidin-2-yl)aminocarbonyl]bicyclo[3.2.2]non-2-ylsulfon 
amide. 
The new compounds of the general formula I can be synthesized from starting 
materials known in themselves or which have been prepared by known 
processes. The processes for preparation comprise 
(a) reacting compounds of the formula 
EQU R.sub.1 --SO.sub.2 --N.dbd.C.dbd.O (II) 
or 
##STR3## 
with compounds of the formula 
##STR4## 
or 
(b) reacting compounds of the formula 
##STR5## 
with compounds of the formula 
EQU S.dbd.C.dbd.N--R.sup.4 (VI) 
or 
##STR6## 
wherein R.sub.3 denotes (C.sub.1 -C.sub.4)-alkyl, or 
(c) reacting compounds of the formula 
##STR7## 
wherein R.sub.5, R.sub.6 and R.sub.7 denote hydrogen, halogen or (C.sub.1 
-C.sub.4)-alkyl with compounds of the formula 
##STR8## 
wherein R.sub.8 to R.sub.13 represent hydrogen, halogen or CH.sub.3 and 
one of the radicals R.sub.9 to R.sub.12 can also be (C.sub.2 
-C.sub.4)-alkyl or (C.sub.1 -C.sub.4)-alkoxycarbonyl or R.sub.8 and 
R.sub.13 together represent a (C.sub.1 -C.sub.6)-alkylene group, in which 
a --CH.sub.2 group can also be replaced by oxygen, and, if desired, 
converting the compounds of the formula I obtained into other compounds of 
the formula I by splitting off hydrogen halide, adding halogen or hydrogen 
onto multiple bonds when present, alkylating in the R.sub.2 position or 
forming a salt. 
In respect of (a) the reaction of the compounds II or III and IV is 
preferably carried out in inert aprotic solvents such as, for example, 
acetonitrile, dichloromethane, toluene, tetrahydrofuran or dioxane at 
temperatures between 0.degree. C. and the boiling point of the solvent. 
When starting materials of the formula III are used, the reaction is 
carried out in the presence of an acid acceptor such as, for example, 
potassium carbonate, pyridine or triethylamine. 
In respect of (b) the reaction of the compounds V with VI or VII is also 
carried out in the abovementioned inert solvents with the addition of 
basic compounds such as, for example, potassium carbonate, pyridine or 
triethylamine at temperatures between 0.degree. C. and the boiling point 
of the solvent. 
In respect of (c) the reaction of the compounds VIII and IX is preferably 
carried out in inert solvents such as, for example, toluene, xylene, 
dioxane or dichloromethane at temperatures between room temperature and 
the boiling point of the solvent. If appropriate, the reaction can be 
carried out in the presence of catalysts such as, for example, aluminum 
trichloride, or in autoclaves under elevated pressure. 
The subsequent splitting off of hydrogen halide (HCL, HBr) from radicals 
R.sub.1 containing halogen is carried out in a known manner, for example 
with alkali metal alcoholate, alcoholic sodium hydroxide or potassium 
hydroxide solution, triethylamine or other agents which split off acid, 
optionally in the presence of a further inert solvent or diluent (for 
example toluene) at temperatures between room temperature and the boiling 
point. 
Halogen (Cl.sub.2, Br.sub.2), hydrogen halide or hydrogen can be added onto 
multiple bonds in the R.sub.1 position, which are present or which are 
formed subsequently, under normal pressure or under elevated pressure, 
where appropriate, in the presence of a catalyst, for example Pd/charcoal 
or Raney nickel in a manner which is also known and thus, if desired, 
provide new compounds of the formula I. The bromination or chlorination is 
carried in inert organic solvents such as, for example, dichloromethane or 
chloroform, with irradiation, for example with ultraviolet light, or in 
the presence of compounds which decompose to give radicals, for example, 
azodiisobutyronitrile, at temperatures between 0.degree. C. and the 
boiling point of the solvent. The addition of hydrogen halide is carried 
out in the presence of inert solvents (for example toluene) using gaseous 
HCl or HBr at low temperatures, optionally in the presence of a peroxide 
catalyst. 
For subsequent alkylation in the R.sub.2 position, the reaction is 
preferably carried out in inert solvents such as, for example, dioxane or 
dimethylformamide, with addition of an inorganic base, for example sodium 
hydride or potassium carbonate, at temperatures from 20.degree. C. up to 
the boiling point of the solvent. Examples of alkylating agents used are 
dimethyl sulfate, methyl iodide or ethyl bromide. 
Compounds of the formula I, in which R.sub.2 denotes hydrogen, can form 
salts in which H is replaced by a cation which is suitable for 
agriculture. These salts are generally salts of metals, ammonium or 
organic amines and are preferably prepared in inert solvents such as, for 
example, water, methanol or acetone at temperatures of 
20.degree.-100.degree.. Examples of suitable bases for preparing the salts 
according to the invention are potassium carbonate, ammonia or 
ethanolamine. 
The starting materials of the formula IV are known or can be prepared by 
processes which are known in principle, for example by cyclization of 
appropriate guanidine derivatives with appropriate substituted 
1,3-diketones (cf. for example "The Chemistry of Heterocyclic Compounds", 
vol. XVI (1962) and Supplement I (1970)) or by derivatization of cyanuric 
chloride (cf. for example "The Chemistry of Heterocyclic Compounds", L. 
Rapoport: "s-Triazines and Derivatives" (1959)). 
The sulfonyl isocyanates of the formula II are also mostly known or can be 
prepared in a simple manner by processes which are known in principle (cf. 
German Auslegeschriften Nos. 1,211,165, 1,230,016 and 1,297,601). 
The sulfonylcarbamoyl or sulfonylthiocarbamoyl chlorides of the formula III 
can be prepared by customary methods from the alkali metal salts of the 
corresponding sulfonamides of the formula V, which are known from the 
literature, by reaction with phosgene or thiophosgene. 
The isothiocyanates of the formula VI which are required for the reactions 
according to process (b) are known or are accessible by known processes 
(cf. Tetrahedron 29, 691 (1973); Japan Kokai Sho-51-143686). 
The same applies to the heterocyclic carbamoyl chlorides and thiocarbamoyl 
chlorides of the formula VII (cf. for example German Auslegeschriften Nos. 
1,149,718 and 2,238,870). 
The .alpha.,.beta.-unsaturated sulfonylureas of the formula VIII are 
described in the Patent Application Nos. P 31 11 451.2. 
The heterocyclic sulfonylurea derivatives according to the invention 
exhibit an excellent herbicidal activity and a very good selectivity in 
important crops which are grown on a large scale. Thus they are suitable 
for the selective control of dicotyledonous and graminaceous annual and 
perennial weeds, especially in crops of agricultural importance such as, 
for example, wheat, barley, rye, rice, corn, sugar beet and soya bean. In 
this context, it is immaterial whether the substances are applied by 
pre-sowing, pre-emergence or post-emergence spraying. If the compounds 
according to the invention are applied to the surface of the earth in a 
pre-sowing or pre-emergence process and before the weed plants have 
germinated, the sprouting of the seedlings is not prevented. The weeds 
grow to the cotyledon stage but then stop growing and finally die 
completely after 3-5 weeks. When the active compounds are applied to the 
green parts of the plant in a post-emergence process, again a drastic 
termination of growth occurs rapidly after treatment and the weed plants 
remain at the stage of growth present at the time of application or die 
completely after a certain time so that, by this means, competition by 
weeds, which is injurious to the crop plants, is removed very early and 
permanently. 
Furthermore, the substances according to the invention exhibit outstanding 
growth-regulating properties for crop plants. They intervene to regulate 
the plants' own metabolism and can thus be employed to produce specific 
effects on the plant constituents and to facilitate harvesting, such as, 
for example, by inducing desiccation and growth shortening. Moreover, they 
are suitable for general control and inhibition of undesired vegetative 
growth without at the same time killing the plants. Inhibition of 
vegetative growth makes a large contribution to many monocotyledonous and 
dicotyledonous crops, since, by this means, storage can be decreased or 
completely avoided. The growth-regulating effect of the compounds as 
growth inhibitors of cereals, corn, soya bean, cotton and lawns and their 
ability to increase the content of desired constituents, such as 
carbohydrates and protein in crop plants, should be particularly 
emphasized. Finally, the compounds show a very great improvement of the 
fruit abscission, specially for citrous fruits, or reduction of the 
retaining power. 
Thus the invention also relates to herbicidal or growth-regulating agents 
which contain a compound of the formula I in combination with customary 
formulating auxiliaries and inert compounds and their use in agriculture. 
The agents according to the invention generally contain the active 
compounds of the formula I to an extent of 2 to 95% by weight. They can be 
used in the customary formulations as powders for spraying, emulsifiable 
concentrates, sprayable solutions, dusting agents or granules. 
The powders for spraying are formulations which can be uniformly dispersed 
in water and which contain, in addition to the active compound and a 
diluent or inert compound, wetting agents, for example polyoxyethylated 
alkylphenols, polyoxyethylated fatty alcohols, alkylsulfonates or 
alkylphenylsulfonates and dispersants, for example sodium ligninsulfonate, 
sodium 2,2'-dinaphthylmethane-6,6'-disulfonate, sodium 
dibutylnaphthalenesulfonate or also sodium oleylmethyltaurate. 
Emulsifiable concentrates are prepared by dissolving the active compound in 
an organic solvent, for example butanol, cyclohexanone, dimethylformamide, 
xylene or also high-boiling aromatic compounds or hydrocarbons with the 
addition of one or more emulsifiers. Examples of emulsifiers which can be 
used are: 
Calcium alkylarylsulfonates, such as Ca dodecylbenzenesulfonate, or 
nonionic emulsifiers, such as fatty acid polyglycol esters, alkylaryl 
polyglycol ethers, fatty alcohol polyglycol ethers, condensation products 
of propylene oxide and ethylene oxide, condensation products of fatty 
alcohols, propylene oxide and ethylene oxide, alkyl polyethers, sorbitan 
fatty acid esters, polyoxyethylene sorbitol fatty acid esters or 
polyoxyethylene sorbitol esters. 
Dusting agents are obtained by milling the active compound with finely 
divided solid materials, for example talc, natural clays, such as kaolin, 
bentonite, pyrophillite or diatomaceous earths. 
Granules can be prepared either by spraying the active compound onto 
absorbent granules of inert material or by applying concentrates of the 
active compounds, using adhesives, for example, polyvinyl alcohol, sodium 
polyacrylate or also mineral oils, onto the surface of vehicles, such as 
sand or kaolinite, or of granules of inert material. Suitable active 
compounds can also be prepared in the manner customary for the preparation 
of granulated fertilizers, if desired mixed with fertilizers. 
For herbicidal agents, the concentrations of the active compounds in the 
commercial formulations can vary. 
In powders for spraying, the concentration of active compound varies, for 
example, between about 10% and 80%, the remainder comprising the 
formulation additives mentioned above. In emulsifiable concentrates, the 
concentration of active compound can also be about 10% to 80%. 
Formulations as dusts contain about 2-20%. In granules, the content of 
active compound depends, to some extent, on whether the active compound is 
liquid or solid and which granulating auxiliaries, fillers and the like 
are used. 
The commercial concentrates when used as herbicides are, when appropriate, 
diluted in a customary manner, for example using water for powders for 
spraying and emulsifiable concentrates. Formulations as dusts and granules 
and spraying solutions are not further diluted with inert substances 
before use. The amount which is required to be used varies with the 
outside conditions, such as temperature, humidity and the like. In 
general, it is between 0.01 and 10 kg/hectare, preferably about 0.1 to 5.0 
kg/hectare of active compound. 
It can be advantageous for some areas of use to use the new herbicides 
together with one or more herbicides, for example as a tank mixture or in 
the form of a ready-to-use formulation in order to obtain further 
advantageous effects. 
The active compounds according to the invention can be combined with other 
herbicides, insecticides and fungicides. 
Concentrations between 0.01 and 1.25 kg/hectare are suitable for use as 
growth regulators. Aqueous dispersions of powders for spraying or 
dilutions of emulsifiable concentrates are preferably used. These are used 
post-emergence. The preferred crops are corn and tobacco.

PREATION EXAMPLES 
EXAMPLE 1 
N-[(4-Methoxy-6-methylpyrimidin-2-yl)aminocarbonyl]-2-chlorocyclohexylsulfo 
namide 
41.7 g (0.3 mole) of 2-amino-4-methoxy-6-methylpyrimidine were suspended in 
500 ml of dichloromethane and a solution of 71.5 g (0.32 mole) of 
2-chlorocyclohexylsulfonyl isocyanate in 200 ml of dichloromethane was 
added dropwise at 0.degree. C. The reaction mixture was stirred a further 
18 hours at room temperature, cooled to 0.degree. C. and n-hexane was 
added. The precipitated reaction product was filtered off with suction and 
washed with n-hexane. 
84.9 g (78% of theory) of 
N-[(4-methoxy-6-methylpyrimidin-2-yl)aminocarbonyl]-2-chlorocyclohexylsulf 
onamide were obtained, having a melting point of 145.degree.-148.degree.. 
EXAMPLE 2 
N-[(4-Methoxy-6-methylpyrimidin-2-yl)aminocarbonyl]-1-cyclohexenylsulfonami 
de 
36.2 g (0.1 mole) of 
N-[(4-methoxy-6-methylpyrimidin-2-yl)aminocarbonyl]-2-chlorocyclohex-1-yls 
ulfonamide (see Example 1) were suspended in 300 ml of methanol and 8 g 
(0.2 mole) of sodium hydroxide dissolved in 40 ml of water were added at 
room temperature. The reaction mixture was then stirred under reflux for 8 
hours, evaporated in vacuo and taken up in 250 ml of water. After 
filtration and acidification with 2N HCl to pH 5, extraction was carried 
out with ethyl acetate and then the extracts were dried over sodium 
sulfate and evaporated. After adding n-hexane, 17.2 g (52.7% of theory) of 
N-[(4-methoxy-6-methylpyrimidin-2-yl)aminocarbonyl]-1-cyclohexenylsulfonam 
ide were obtained, having a melting point of 163.degree.-166.degree. C. 
EXAMPLE 3 
N-[(4,6-Dimethylpyrimidin-2-yl)aminocarbonyl]-7-oxabicyclo[2.2.1]hept-2-en- 
6-ylsulfonamide 
30.7 g (0.25 mole) of 2-amino-4,6-dimethylpyrimidine were dissolved in 350 
ml of dichloromethane and a solution of 52 g (0.26 mole) of 
7-oxabicyclo[2.2.1]hept-2-en-6-ylsulfonyl isocyanate (Diels-Alder adduct 
of vinylsulfonyl isocyanate and furan) in 100 ml of dichloromethane was 
added at 0.degree. C. with stirring. The mixture was stirred a further 12 
hours at room temperature, cooled to 0.degree. C. and n-hexane was added. 
The precipitated reaction product was filtered off with suction, washed 
with n-hexane and dried. 73.6 g (90.8% of theory) of 
N-[(4,6-dimethylpyrimidin-2-yl)aminocarbonyl]-7-oxabicyclo[2.2.1]hept-2-en 
-6-ylsulfonamide having a melting point of 125.degree.-145.degree. C. were 
obtained. 
EXAMPLE 4 
N-[(4-Methylthio-6-methyl-1,3,5-triazin-2-yl)aminocarbonyl]-3 (or 
4)-methyl-3-cyclohexenylsulfonamide 
7.81 g (0.05 mole) of 2-amino-4-methylthio-6-methyl-1,3,5-triazine were 
suspended in 150 ml of dichloromethane and a solution of 11.05 g (0.055 
mole) of 3 (or 4)-methyl-3-cyclohexen-1-ylsulfonyl isocyanate (mixture of 
isomers; Diels-Alder adduct of isoprene to vinylsulfonyl isocyanate) in 50 
ml of dichloromethane was added at 0.degree. C. The mixture was stirred a 
further 18 hours at room temperature and was worked up in analogy to 
Example 1. 13.2 g (74% of theory) of 
N-[(4-methylthio-6-methyl-1,3,5-triazin-2-yl)aminocarbonyl]-3 (or 
4)-methyl-3-cyclohexenylsulfonamide were obtained, having a melting point 
of 156.degree.-160.degree. C. 
EXAMPLE 5 
N-[(4,6-Dimethylpyrimidin-2-yl)aminocarbonyl]-2-chlorocycloheptylsulfonamid 
e 
14.3 g (0.06 mole) of 2-chlorocycloheptylsulfonyl isocyanate in 100. ml of 
dichloromethane were initially introduced and 7.4 g (0.06 mole) of 
2-amino-4,6-dimethylpyrimidine were added in portions at 0.degree. C. The 
mixture was stirred initially at 0.degree. C. for 2 hours and then at room 
temperature for 18 hours. The organic phase was then extracted with 
3.times.40 ml of 2N H.sub.2 SO.sub.4, washed to neutrality and the organic 
layer was dried over Na.sub.2 SO.sub.4. Then 50 ml of n-hexane was added 
and the solvent was distilled off in vacuo. 13.3 g (61% of theory) of 
N-[(4,6-dimethylpyrimidin-2-yl)aminocarbonyl]-2-chlorocycloheptylsulfonami 
de were obtained (viscous oil). 
EXAMPLE 6 
N-[(4,6-Dimethylpyrimidin-2-yl)aminocarbonyl]-2-chlorocyclodecylsulfonamide 
15.4 g (0.05 mole) of 2-chlorododecylsulfonyl isocyanate in 100 ml of 
dichloromethane were initially introduced and 6.2 g (0.05 mole) of 
2-amino-4,6-dimethylpyrimidine were added in portions at 0.degree. C. The 
mixture was initially stirred at 0.degree. C. for 2 hours and then at room 
temperature for 18 hours and was then worked up in analogy to Example 5. 
15.2 g (71% of theory) of 
N-[(4,6-dimethylpyrimidin-2-yl)aminocarbonyl]-2-chlorocyclododecylsulfonam 
ide were obtained (pale yellow solid material, melting point 84.degree. 
C.). 
EXAMPLE 7 
N-[(4,6-Dimethylpyrimidin-2-yl)aminocarbonyl]-3-chlorobicyclo[2.2.1]hept-2- 
ylsulfonamide 
14.1 g (0.06 mole) of 3-chlorobicyclo[2.2.1]hept-2-ylsulfonyl isocyanate in 
100 ml of dichloromethane were initially introduced and 7.4 g (0.06 mole) 
of 2-amino-4,6-dimethylpyrimidine were added in portions at 0.degree. C. 
The mixture was initially stirred at 0.degree. C. for 2 hours and then at 
room temperature for 18 hours and then worked up in analogy to Example 5. 
14.1 g (66% of theory) of 
N-[(4,6-dimethylpyrimidin-2-yl)aminocarbonyl]-3-chlorobicyclo[2.2.1]hept-2 
-ylsulfonamide were obtained (viscous oil). 
The following compounds were, or can be, obtained in an analogous manner 
TABLE 1 
__________________________________________________________________________ 
##STR9## 
Example Melting 
No. R.sub.1 R.sub.2 
R.sub.3 
R.sub.4 point (.degree.C.) 
__________________________________________________________________________ 
##STR10## 
H H 
##STR11## 155-163 
9 " H H 
##STR12## 118-123 
10 " H H 
##STR13## 159-162 
11 " H H 
##STR14## 143-144 
12 
##STR15## 
H H 
##STR16## glass-like 
13 
##STR17## 
H H 
##STR18## 48-52 (Decomp.) 
14 " H H 
##STR19## viscous oil 
15 
##STR20## 
H H 
##STR21## 103 
16 
##STR22## 
H H 
##STR23## 142-144 
17 
##STR24## 
H H 
##STR25## 165-169 
18 " H H 
##STR26## 150 
19 " H H 
##STR27## 159-167 
20 
##STR28## 
H H 
##STR29## viscous oil 
21 " H H 
##STR30## viscous oil 
22 
##STR31## 
H H 
##STR32## 195 
23 " H H 
##STR33## 143 
24 " H H 
##STR34## 173-176 
25 " H H 
##STR35## 89-92 
26 " H H 
##STR36## 161-164 
27 
##STR37## 
H H 
##STR38## 54-57 
28 " H H 
##STR39## 88-91 
29 
##STR40## 
H H 
##STR41## viscous oil 
30 
##STR42## 
H H 
##STR43## 146-150 
31 " H H 
##STR44## 135-145 
32 
##STR45## 
H H 
##STR46## resin 
33 " H H 
##STR47## 152-154 
34 " H H 
##STR48## 
35 
##STR49## 
H H 
##STR50## 
36 
##STR51## 
H H 
##STR52## 
37 
##STR53## 
H H 
##STR54## 78-80 
38 " H CH.sub.3 
##STR55## 
39 
##STR56## 
H H 
##STR57## 
40 " H H 
##STR58## 137-138 
__________________________________________________________________________ 
FORMULATION EXAMPLES 
EXAMPLE A 
An emulsifiable concentrate was obtained from: 
15 parts by weight of active compound 
75 parts by weight of cyclohexane as the solvent, and 
10 parts by weight of oxyethylated nonylphenol (10 EO) as emulsifier 
EXAMPLE B 
A wettable powder, which was easily dispersible in water, was obtained by 
mixing 
25 parts by weight of active compound 
64 parts by weight of kaolin-containing quartz as inert material 
10 parts by weight of potassium ligninsulfonate, and 
1 part by weight of sodium oleylmethyltaurate as wetting agent and 
dispersant 
and milling in a pinned disk mill. 
EXAMPLE C 
A dusting agent was obtained by mixing 
10 parts by weight of active compound and 90 parts by weight of talc as 
inert material 
and grinding in a beater mill. 
EXAMPLE D 
Granules are composed of, for example, 
about 2-15 parts by weight of active compound and 
about 98-85 parts by weight of inert granular materials, such as, for 
example, attapulgite, pumice and quartz sand. 
BIOLOGICAL EXAMPLES 
(a) Herbicidal activity 
The damage to the weed plants and the tolerance by the crop plants were 
classified by scoring from 0-5. 
The significance of these scores is as follows: 
0=no effect (damage) 
1=0-20% effect 
2=20-40% effect 
3=40-60% effect 
4=60-80% effect 
5=80-100% effect 
The abbreviations have the following meanings: 
LOM=ryegrass (lolium multiflorum) 
STM=starwort (stellaria media) 
SIA=charlock (sinapis arvensis) 
AS=active substance 
1. Pre-emergence process 
Seeds or pieces of rhizomes of monocotyledonous and dicotyledenous weeds 
were scattered on loam and covered with soil. The compounds according to 
the invention formulated as wettable powders were applied in the form of 
aqueous suspensions or emulsions to the surface of the soil. The amount of 
water used per pot corresponded on conversion to 600-800 l/hectare. After 
the treatment, the test pots were placed in a glasshouse and the test 
plants were cultivated under good conditions for growth (temperature: 
about 23.degree. C.; relative atmospheric humidity 60-80%). After about 3 
weeks, the plant damage was scored visually. Untreated controls served as 
a comparison in this test. 
The pre-emergence results are compiled in Table 2. It is apparent that the 
compounds according to the invention exhibit a good herbicidal activity 
against both monocotyledenous and also dicotyledenous weeds when the 
active compounds were administered in a pre-emergence process. 
TABLE 2 
______________________________________ 
Pre-emergence effect of the compounds according to the 
invention against monocotyledenous and dicotyledenous 
weeds 
Dose of AS 
Example kg/hectare LOM STM 
______________________________________ 
1 2.5 3 4 
9 2.5 2 3 
10 2.5 3 2 
16 2.5 5 5 
19 2.5 5 5 
3 2.5 4 4 
30 2.5 5 5 
31 2.5 5 4 
28 2.5 2 3 
32 2.5 5 5 
33 2.5 5 5 
37 2.5 5 5 
______________________________________ 
2. Post-emergence process 
Seeds of monocotyledenous and dicotyledenous weeds were sown in pots and 
raised in a glasshouse under good conditions for growth. A few weeks after 
sowing, the test plants were treated at the three-leaf stage. The products 
according to the invention, which were formulated as powders for spraying 
or as emulsion concentrates, were sprayed onto the green parts of the 
plants at various dosages and, after about 3 weeks standing in a 
glasshouse under optimum conditions for growth (temperature: about 
23.degree. C.; relative atmospheric humidity 60-80%), the effect of the 
products were scored visually in comparison to untreated controls. 
The agents according to the invention showed good herbicidal effectiveness 
against a wide spectrum of economically important annual and perennial 
weeds and unwanted grasses (Table 3): 
TABLE 3 
______________________________________ 
Herbicidal activity of the compounds according to the 
invention against monocotyledenous and dicotyledenous 
weeds in the post-emergence process 
Dose of AS 
Product kg/hectare LOM SIA 
______________________________________ 
9 2.5 1 5 
10 2.5 3 4 
19 2.5 5 5 
3 2.5 3 5 
30 2.5 4 5 
31 2.5 5 5 
27 2.5 0 4 
32 2.5 5 5 
33 2.5 5 5 
37 2.5 5 5 
______________________________________ 
(b) Plant-growth regulating action 
3. Inhibition of growth of cereals 
In dish trials in a glasshouse, young cereal plants (wheat, barley and rye) 
in the 3-leaf stage were sprayed until dripping wet with the compounds 
indicated in Table 1 in the concentrations of active compound mentioned 
(kg/hectare). 2-Chloroethyltrimethylammonium chloride was employed as the 
comparison compound. After the untreated control plants had grown to a 
height of about 55 cm, the added growth of all plants was measured and the 
growth inhibition was calculated as a percentage of the added growth of 
the control plants. In addition, the phytotoxic activity of the compounds 
was observed. The results are compiled in Table 4. For the report of 
growth inhibition, 100% denotes a standstill in growth and 0% denotes a 
growth corresponding to that of the untreated control plants. 
TABLE 4 
______________________________________ 
Inhibition of growth of cereals 
Compound Concentration 
Growth inhibition 
Phyto- 
according 
used (kg/hec- 
in % toxic 
to Example 
tare) Wheat Barley 
Rye activity 
______________________________________ 
3 0.62 22 24 22 no 
0.31 11 21 18 damage 
28 1.25 19 18 15 no 
damage 
19 1.25 15 10 11 no 
damage 
Comparison: 
(2-Chloro- 
2.50 27 8 10 no 
ethyl)tri- 
1.25 23 0 0 damage 
methylammo- 
nium chloride 
______________________________________ 
4. Inhibition of growth of bush beans 
10-15 cm bush beans were sprayed until dripping wet with the formulations 
of the active compounds. After 2 weeks, the added growth was measured and 
the growth inhibition was calculated as a percentage of the added growth 
of the control plants. The results are compiled in Table 5. 
TABLE 5 
______________________________________ 
Inhibition of growth of bush beans 
Concentra- Growth Phyto- 
Compound accor- tion used inhibi- toxic 
ding to Example (kg/hectare) 
tion in % 
action 
______________________________________ 
3 0.62 40 no 
Comparison: 0.34 20 damage 
##STR59## 2.50 34 no damage 
______________________________________ 
5. Inhibition of growth of lawns 
A lawn mixture, which contained 5 representative species, was, after three 
cutbacks, sprayed until dripping wet with a formulation of an active 
compound. After 3-4 weeks, the added growth was measured and the growth 
inhibition was calculated as a percentage of the added growth of the 
control plants. 100% denotes a standstill in growth and 0% denotes growth 
corresponding to that of the untreated control plants. 
TABLE 6 
______________________________________ 
Inhibition of growth of lawns 
Phyto- 
Compound accor- 
Concentration 
Growth inhi- 
toxic 
ding to Example 
used (kg/hectare) 
bition in % 
action 
______________________________________ 
3 0.62 82 no 
Comparison: 0.31 70 damage 
Maleic 2.50 60 severe 
hydrazide damage 
______________________________________ 
6. Increase in the sugar content of sugarcane 
Procedure 
Sugarcane plants were raised under glasshouse conditions at 
25.degree.-35.degree. C. and about 65% atmospheric humidity. Various 
amounts of the formulated agents were suspended in water which 
additionally contained about 0.25% by weight of a surface active agent 
(nonylphenol). 
In each case, 0.3 ml of the suspension was applied with the aid of a spray 
in the region of the spindle at the level of the last visible leaf blade 
("dewlap") (10 plants per concentration). On harvesting after 3 weeks, the 
leaves of both the treated plants and also of the untreated controls were 
removed and the internodes were analyzed in groups for their sucrose 
content. The results are presented in Table 7. 
TABLE 7 
______________________________________ 
Compound accor- 
Concentration used 
Sugar content in 
ding to Example 
(kg/hectare) % at harvesting 
______________________________________ 
3 0.62 145 
19 0.62 239 
Control 100 
______________________________________ 
7. Stimulation of the liberation of ethylene 
Calamondine oranges were immersed in a solution of active compound 
containing 2,000 ppm of active compound for 2 minutes. The ethylene 
produced by the fruit was then found each day for 5 days by gas 
chromatography. 
The results in Table 8 represent mean values from a total of 3 test series. 
TABLE 8 
______________________________________ 
Compound accor- 
Ethylene production (relative 
ding to Example 
units) 1-5 days overall 
______________________________________ 
Control 2.4 
3 12.4 
10 9.0 
Comparison: 
Glyoxime 3.8 
______________________________________ 
The compounds according to the claim showed a significantly higher effect 
on the liberation of ethylene, both initially and long-term, than the 
comparison agent. The overall amount of ethylene produced also clearly 
exceeded that of the comparison agent. Since ethylene, which is also 
produced by the plant, is involved in the processes of ripening and 
abscission to a determining extent, the test serves to demonstrate the 
accelerated and comprehensive formation of separating tissue, which is 
induced by the compounds according to the application, and thus the 
initiation of the process of abscission.