CA2134915A1

CA2134915A1 - Herbicidal substituted phenylaminosulphonylureas

Info

Publication number: CA2134915A1
Application number: CA002134915A
Authority: CA
Inventors: Hans-Jochem Riebel; Mark-Wilhelm Drewes; Johannes R. Jansen; Markus Dollinger; Hans-Joachim Santel
Original assignee: Individual
Current assignee: Bayer AG
Priority date: 1993-11-05
Filing date: 1994-11-02
Publication date: 1995-05-06
Also published as: EP0661276A1; AU7751394A; BR9404345A; DE4337847A1; JPH07188184A; ZA948720B; CN1107147A; RU94040154A

Abstract

Substituted phenylaminosulphonylureas A b s t r a c t The invention relates to new substituted phenylaminosulphonylureas of the formula (I)

Description

213~15 The invention relates to new substituted phenylamino~
sulphonylureas, to processes for their preparation, and to their use as herbicides.

It has been disclosed that the compound N-(4,6~
dimethoxy-pyrimidin-2-yl)-N'-(2-cyclopropyl-carbonyl-phenylaminosulphonyl)-urea can be used as a selective ~ . t herbicide (cf. EP-A 463287/US Patent 5009699).
Some alkylcarbonylphenylaminosulphonylureas ha~e been disclosed in previous patent applications, but have not 10 gained importance (cf. EP-A 264467/US Patent 4622065). . .
'; ~ ,; ',"'''',''~
The new substituted phenylaminosulphonylureas of general formula (I) ;.

R ~P' ~R2 `~
N~S4N~ ~N~

in which . `-R1 represents hydrogen, halogen, or represents alkyl, lS alkoxy, alkylthio, alkylsulphinyl, alkylsulphonyl, ~ ~ :
alkylamino or dialkylamino, each of which has 1 to 4 carbon atoms in the individual alkyl groups and :~
~, Le A 30 014-FC - 1 - ; -~:

2~34915 ~:~
, ~.

each of which is optionally substituted by halogen ~ ;
or Cl-C3-alkoxy, .

R2 represents hydrogen or halogen, R3 represents halogen, or represents alkyl, alkoxy, alkylthio, alkylsulphinyl, alkylsulphonyl, alkylamino or dialkylamino, each of which has 1 to 4 carbon atoms in the individual alkyl groups and ~ -each of which is optionally subs~ituted by halogen -or Cl-C3-alkoxy, -~

R4 represents hydrogen, amino, halogen or formyl, or represents alkyl, alkoxy, alkylthio, alkyl-sulphinyl, alkylsulphonyl, alkylcarbonyl, alkoxy-carbonyl, alkylcarbonylamino, alkoxycarbonylamino or alkylsulfonylamino, each of which has 1 to 4 carbon atoms in the individual alkyl groups and each of which is optionally substituted by halogen or Cl- C3 - alkoxy, and R5 represents hydrogen, or represents alkyl having 1 ~: ~
to 8 carbon atoms which is optionally substituted :.
by halogen, Cl-C4-alkoxy, Cl-C4-alkylthio, Cl-C4-alkylsulphinyl or Cl-C4-alkylsulphonyl, or represents cycloalkyl, cycloalkyl-Cl-C4-alkyl, cycloalkenyl or cycloalkenyl-Cl-C4-alkyl, each of which has 4 to 7 carbon atoms in the cycloalkyl or ~. ~
cycloalkenyl groups and each of which is : ' h' optionally substituted by halogen and/or Cl-C4- ~

'' ' Le A 30 014-FC - 2 ~

~ `, 2~3~915 ~ ~

alkyl, or represents phenyl or phenyl-C1-C4-alkyl, each of which is optionally substituted by halogen, Cl-C4-alkyl or C1-C4-halogenoalkyl, or represents heterocyclyl or heterocyclyl-C1-C4-alkyl having 2 to 6 carbon atoms and 1 to 3 nitrogen atoms and/or one oxygen or sulphur atom and each of which is optionally substituted by halogen, C1-C4-alkyl or C1-C4-halogenoalkyl, and salts of the compounds of the formula tI) have now ..
10 been found. .

The new substituted phenylaminosulphonylureas of the .
general formula (I) are obtained when aminopyrimidines of the general formula (II) in which .

R1, R2 and R3 have the abovementioned meaning, are reacted with chlorosulphonyl isocyanate, if `~
appropriate in the presence of a diluent, and the :~
chlorosulphonylureas of the general formula (III) `- .
formed in this process Le A 30 014-FC - 3 -`'~

2 1 3 9~ 9 1 ~ r R
~O2-NHKX~NH ~ N'l R3 (tl~
in which --R1, R2 and R3 have the abovementioned meaning;

are reacted with arylamines of the general formula (IV) O

R ~ (IV) in which R4 and R5 have the abovementioned meaning, if appropriate in the presence of an acid acceptor and if appropriate in the presence of a diluent and, if appropriate, the resulting compounds of the formula (I) ~ ~ `t,-are converted into salts by customary methods. `~

A further preparation method for the compounds of the formula (I) according to the invention which is possible is outlined below, where R1, R2, R3, R4 and R5 have the abovementioned meaning and R represents alkyl : Le A 30 014-FC - 4 ~

: -:, . -: :-.. . :-, :,. ..~:,..

2 1 3 ~

(in particular methyl or ethyl), aralkyl (in particular benzyl) or aryl (in particular phenyl)~

o ~ . ~

4~H~ t a-S02N~ ~ R ~R
Q2NH2 i~
",i"
O R1 ~ ,.. ,- ~ .

~NI~SON~ R4~H/~R -~R

~'~,' .`-,' ~ ",, ., "~ ` ~, .,...,~ ..
:.'. ;`;-.-',,.

The new substituted phenylaminosulphonylureas of the I general formula (I) are distinguished by a powerful and ';"-'¦ 5 selective herbicidal activity.

; Surprisingly, the new compounds of the formula (I) show a considerably more powerful herbicidal activity than the compound N-(4,6-dimethoxy-pyrimidin-2-yl)-N'-(2-cyclopropyl-carbonyl-phenylaminosulphonyl)-urea, which -~
is known and which has a similar structure.
~ ;'""'~""'`''`
The invention preferably relates to compounds of the formula (I) in which " ~" ~ .''`' Le A 30 014-FC - 5 - , ~`
: ~ ' , '`,',.''.,''`:

2 1 3 '1 ~

Rl represents hydrogen, fluorine, chlorine or : :
bromine, or represents alkyl, alkoxy, alkylthio, alkylsulphinyl, alkylsulphonyl, alkylamino or :
dialkylamino, each of which has 1 to 3 carbon atoms in the individual alkyl groups and each of :::
which is optionally substituted by fluorine, chlorine, methoxy or ethoxy, ': ~``' R2 represents hydrogen, fluorine, chlorine or ~:
bromine, ~:
10 R3 represents fluorine, chlorine or bromine, or ~ ;
represents alkyl, alkoxy, alkylthio, alkylsulphinyl, alkylsulphonyl, alkylamino or dialkylamino, each of which has 1 to 3 carbon atoms in the individual alkyl groups and each of ::~
which is optionally substituted by fluorine, chlorine, methoxy or ethoxy, ~ -R4 represents hydrogen, amino, fluorine, chlorine, ~
bromine or formyl, or represents alkyl, alkoxy, ::
alkylthio, alkylsulphinyl, alkylsulphonyl, alkyl~
carbonyl, alkoxycarbonyl, alkylcarbonylamino, alkoxycarbonylamino or alkylsulfonylamino, each of which has 1 to 3 carbon atoms in the individual alkyl groups and each of which is optionally substituted by fluorine, chlorine, methoxy or ethoxy, and :~

' , ., ,`.. '. ~.. -Le A 30 014-FC - 6 ~
:.: :: - .-:::

2 13 ~

R5 represents hydrogen, or represents alkyl having 1 to 6 carbon atoms which is optionally substituted by fluorine, chlorine, bromine, C1-C3-alkoxy, Cl - C3 - alkylthio, C1- C3 - alkylsulphinyl or C1- C3 -alkylsulphonyl, or represents cycloalkyl, cyclo-alkyl-C1-C3-alkyl, cycloalkenyl or cycloalkenyl-Cl-C3 -alkyl, each of which has 4 to 6 carbon atoms in the cycloalkyl or cycloalkenyl groups and each of which is optionally substituted by fluorine, chlorine, bromine and/or C1-C3-alkyl, or represents ^~
phenyl or phenyl-C1-C3-alkyl, each of which is ~.-optionally substituted by fluorine, chlorine, ".' .',',~"'.'~'!,.
bromine, C1-C3-alkyl or C1-C3-halo-genoalkyl, or represents heterocyclyl or heterocyclyl-C1-C3~
alkyl, each of which has 3 to 5 carbon atoms and 1 to 3 nitrogen atoms and/or one oxygen or sulphur atom and each of which is optionally su~stituted by fluorine, chlorine, bromine, C1-C3-alkyl or C1-C3-halogenoalkyl. :~

The invention furthermore preferably relates to sodium salts, potassium salts, magnesium salts, calcium salts, ammonium salts, C1-C4-alkyl-ammonium salts, di-(C1-C4-alkyl)-ammonium salts, tri-(C1-C4-alkyl)-ammonium salts, C5- or C6-cycloalkyl-ammonium salts and di-(C1-C2- -~
25 alkyl)-benzyl-ammonium salts of compounds of the ~ *
formula (I) in which R1, R2, R3, R4 and R5 have the meanings given above as being preferred. - ~
; .. ..:. ,;

~,,',`~ .: '' ' ;~ Le A 30 014-FC - 7 -- ... ..

213~913 The invention particularly relates to compounds of the formula ( I ) in which R1 represents hydrogen, chlorine, methyl, ethyl, tri-fluoromethyl, methoxy, ethoxy, difluoromethoxy, methylthio, ethylthio, methylamino, ethylamino or dimethylamino, R2 represents hydrogen, R3 represents chlorine, methyl, ethyl, :~ x trifluoromethyl, methoxy, ethoxy, difluoromethoxy, methylthio, ethylthio, methylamino, ethylamino or dimethylamino, -R4 represents hydrogen, amino, fluorine, chlorine, bromine, methyl, trifluoromethyl, methoxy, methylthio, methylsulphinyl, methylsulphonyl, acetyl or methoxycarbonyl and Rs represents hydrogen, or represents methyl, ethyl, n- or i-propyl, n-, i- or s-butyl or n-, i- or s-pentyl, each of which is optionally substituted by fluorine and/or chlorine, or represents methoxy-methyl, methoxyethyl, ethoxymethyl, ethoxyethyl, methylthiomethyl, methylthioethyl, ethylthio-methyl, ethylthioethyl, methylsulphinylmethyl, ethylsulphinylmethyl, methylsulphonylmethyl or .
ethylsulphonylmethyl, or represents cyclobutyl, -~
cyclobutylmethyl, cyclopentyl, cyclopentylmethyl, .
"'';'''"'''`` '''' ~: Le A 30 014-FC - 8 - -~` 2 1 3 4 ~
,::
cyclopentenylmethyl, cyclohexyl, cyclohexenyl~
methyl, phenyl, benzyl, phenylethyl, furyl, furyl-methyl, thienyl, thienylmethyl, tetrahydrofuryl or tetrahydrofurylmethyl, each of which is optionally substituted by fluorine, chlorine and/or methyl.

A particularly preferred group of compounds according to the invention consists of the compounds of the general formula (Ia) below in which the radicals R1, R2, R3, R4 and R5 have the meaning given above as being particularly preferred.
O R

~SO2-N~NH 1~R ~ ~
R ~;

. ~,~ :,;
' ~"','~ ~ ';
The abovementioned general definitions of radicals, or definitions of radicals whose preferred ranges have ~ .
been given, apply to the end products of the formula (I) and, analogously, to the starting materials or intermediates required in each case for the preparation. These definitions of radicals can be ~'','' '~'!,"
combined with each other, that is to say combinations ~; `
.~. "'', '.-' ' Le A 30 014-FC - 9 ~

;: ' ~ - . : ` : :

2134~15 between ranges given as being preferred are also possible.

The hydrocarbon radicals mentioned in the definitions of the radicals, such as alkyl, also in combinations with hetero atoms, such as in alkoxy, alkylthio or alkylamino, are straight-chain or branched, even when not mentioned expressly.

Halogen generally represents fluorine, chlorine, bromine or iodine, preferably fluorine, chlorine or bromine, in particular fluorine or chlorine.

If, for example, 4-chloro-6-methoxy-2-amino-pyrimidine, chlorosulphonyl isocyanate and 2-propionyl-aniline are used as starting materials, the course of the reaction in the process according to the invention can be outlined by the following equation~
cl cl a~o2-N~o + ~ "-`, ' H2Nl OCH3 a-SO2-Nl~NH J~NJ~C~
O , , .~
~ ~C2Hs ~ ' S~' - NHSO2-N~NH 1 OC~

`.. ~.:- .:

: ~ Le A 30 014-FC - 10 - .

,~ 213~915 :

: -The aminopyrimidines of the formula (II) to be used as starting substances in the process according to the invention are known chemicals for synthesis, some of which are commercially available. ~ -The arylamines of the formula (IV) furthermore required as starting substances are also known chemicals for synthesis, some of which are commercially available (re synthesis, cf. EP-A 325 247; J. Org. Chem. 44 (1979), 578-586 and the preparation examples).

The process according to the invention for the prepara-tion of the new compounds of the formula (I) is preferably carried out using diluents. Suitable diluents are virtually all inert organic sol~ents.
These preferably include aliphatic and aromatic, -~
optionally halogenated hydrocarbons, such as pentane, hexane, heptane, cyclohexane, petroleum ether, benzine, ligroin, benzene, toluene, xylene, methylene chloride, -~ -.
ethylene chloride, ch~oroform, tetrachloromethane, chlorobenzene and o-dichlorobenzene, ethers, such as diethyl ether and dibutyl ether, glycol dimethyl ether and diglycol dimethyl ether, tetrahydrofuran and -dioxane, ketones, such as acetone, methyl ethyl ketone, methyl isopropyl ketone and methyl isobutyl ketone, esters, such as methyl acetate and ethyl acetate, nitriles, such as, for example, acetonitrile and propionitrile, amides, such as, for example, dimethylformamide, dimethylacetamide and N-., ...'~,-., .~,:~,....
,' :. --,, .;

Le A 30 014-FC - 11 - - -~" 213~91~ i methylpyrrolidone, and also dimethyl sulphoxide, tetra-methylene sulphone and hexamethylphosphoric triamide.

Acid acceptors which can be used in the process according to the invention are all acid-binding agents 5 which can conventionally be used for such reactions. `~
Preferably suitable are alkali metal hydroxides, such as, for example, sodium hydroxide and potassium hydroxide, alkaline earth metal hydroxides, such as, for example, calcium hydroxide, alkali metal carbonates 10 and alkali metal alcoholates, such as sodium carbonate -~
and potassium carbonate, sodium tert-butylate and potassium tert-butylate, furthermore aliphatic, aromatic or heterocyclic amines, for example triethylamine, trimethylamine, dimethylaniline, dimethylbenzylamine, pyridine, 1,5-diazabicyclo[4,3,0]-non-5-ene (DBN), 1,8-diazabicyclo-[5,4,0]-undec-7-ene (DBU) and 1,4-diazabicyclo[2,2,2]-octane (DABCO). -. `':, ~.' -.
When carrying out the process according to the `
invention, the reaction temperatures can be varied -`
20 within a substantial range. In general, the process is `~- -carried out at temperatures between -30C and +80C, preferably at temperatures between -10C and +60C. " ' '.: !
: ' " .. , .: .
The process according to the invention is generally carried out under atmospheric pressure. However, it is also possible to carry out the process under elevated or reduced pressure.
.
..... ~
..,..., ..~ ...

'',.~' ;.'' ~'' ,'.~ ' '., Le A 30 014-FC - 12 - ~

r~ 2 1 3 ~ 1 3 To carry out the process according to the invention, the starting substances required in each case are generally employed in approximately equimolar amounts.
However, it is also possible to use one of the two components employed in each case in a larger excess. In general, the reactions are carried out in a suitable diluent in the presence of an acid acceptor, and the reaction mixture is stirred for several hours at the temperature required in each case. Working-up in the process according to the invention is carried out in each case by customary methods (cf. the preparation examples).
.~' '~'',.' If appropriate, salts may be prepared with the compounds of the general formula (I) according to the invention. Such salts are obtained in a simple manner by conventional salt formation methods, for example by dissolving or dispersing a compound of the formula (I) in a suitable solvent, such as, for example, methylene chloride, acetone, tert-butyl methyl ether or toluene, and adding a suitable base. The salts can then be isolated by a concentration or filtration with suction, if appropriate after prolonged stirring.

The active compounds according to the invention can be used, for example, in connection with the following plants~
~,', ."."",/
Dicotyledon weeds of the genera: Sinapis, Lepidium, Galium, Stellaria, Matricaria, Anthemis, Galinsoga, ;~ ~ .'' ' '-~ Le A 30 014-FC - 13 - ~
, , ' :~ .
. ~ ,".

i``) ':~','.. .. : . ,.. ' . ' . ' : ' `: .

`"` 213~91~

Chenopodium, Urtica, Senecio, Amaranthus, Portulaca, Xanthium, Convolvulus, Ipomoea, Polygonum, Sesbania, Ambrosia, Cirsium, Carduus, Sonchus, Solanum, Rorippa, Rotala, Lindernia, Lamium, Veronica, Abutilon, Emex, Datura, Viola, Galeopsis, Papaver, Centaurea, Trifolium, Ranunculus and Taraxacum.

Dicotyledon cultures of the genera: Gossypium, Glycine, Beta, Daucus, Phaseolus, Pisum, Solanum, Linum, Ipomoea, Vicia, Nicotiana, Lycopersicon, Arachis, Brassica, Lactuca, Cucumis and Cucurbita.
.: ., ~.:.' :' Monocotyledon weeds of the genera: Echinochloa, --Setaria, Panicum, Digitaria, Phleum, Poa, Festuca, Eleusine, Brachiaria, Lolium, Bromus, Avena, Cyperus, Sorghum, Agropyron, Cynodon, Monochoria, Fimbristylis, Sagittaria, Eleocharis, Scirpus, Paspalum, Ischaemum, Sphenoclea, Dactyloctenium, Agrostis, Alopecurus and Apera.

Monocotyledon cultures of the genera: Oryza, Zea, Triticum, Hordeum, Avena, Secale, Sorghum, Panicum, s ;~-20 Saccharum, Ananas, Asparagus and Allium.; i;

However, the use of the active compounds according to the invention is in no way restricted to these genera, ~:
but also extends in the same manner to other plants.
,,"
The compounds are suitable, depending on the concen~
tration, for the total combating of weeds, for example , ~

.

Le A 30 014-FC - 14 - ~

~ ', " ~
~:

::

13~913 on industrial terrain and rail tracks, and on paths and squares with or without tree plantings. Equally, the compounds can be employed for combating weeds in peren~
nial cultures, for example afforestations, decorative tree plantings, orchards, vineyards, citrus groves, nut orchards, banana plantations, coffee plantations, tea plantations, rubber plantations, oil palm plantations, cocoa plantations, soft fruit plantings and hopfields, in lawns, turf and pasture-land, and for the selective 10 combating of weeds in annual cultures. .-~

The compounds of the formula (I) according to the invention are particularly suitable for selectively ~ ~ ^
combating monocotyledon and dicotyledon weeds in : ., ~
monocotyledon cultures by the pre- and post-emergence methods.

The active compounds can be converted into the ;;~, customary formulations, such as solutions, emulsions, wettable powders, suspensions, powders, dusting agents, pastes, soluble powders, granules, suspension-emulsion -concentrates, natural and synthetic materials impregnated with active compound, and very fine -~`~
capsules in polymeric substances.

These formulations are produced in a known manner, for ~-~
example by mixing the active compounds with extenders, that is liquid solvents and/or solid carriers, optionally with the use of surface-active agents, that . :~' "."' ' :"' Le A 30 014-FC - 15 -213 19:1~
, is emulsifying agents and/or dispersing agents and/or foam-forming agents.

In the case of the use of water as an extender, organic solvents can, for example, also be used as auxiliary solvents. As liquid solvents, there are suitable in the main: aromatics, such as xylene, toluene or alkylnaphthalenes, chlorinated aromatics and chlorinated aliphatic hydrocarbons, such as chlorobenzenes, chloroethylenes or methylene chloride, alipha-tic hydxocarbons, such as cyclohexane or paraffins, for example petroleum fractions, mineral and vegetable oils, alcohols, such as butanol or glycol as well as their ethers and esters, ketones, such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, strongly polar solvents, such as dimethylformamide and dimethyl sulphoxide, as well as water.
., .

As solid carriers there are suitable~
~ -" .: ',.
fox example ammonium salts and ground natural minerals, 20 such as kaolins, clays, talc, chalk, quartz, - `
attapulgite, montmorillonite or diatomaceous earth, and . -~
ground synthetic minerals, such as highly disperse silica, alumina and silicates, as solid carriers for granules there are suitable: for example crushed and . ::
25 fractionated natural rocks such as calcite, marble, :.:
pumice, sepiolite and dolomite, as well as synthetic granules of inorganic and organic meals, and granules : :, ..
,,.

'..' Le A 30 014-FC - 16 - -~' .' . . ..

~ ',', ' ''` , 213~

of or~anic material 9UCII as sawdust, coconut shells, maize cobs and tobacco stalks; as emulsifying and/or foam-forming agents there are suitable: for example nonionic and anionic emulsifiers, such as polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, for example alkylaryl polyglycol ethers, alkylsulphonates, alkyl sulphates, arylsulphonates as well as albumen hydrolysis products;
as dispersing agents there are suitable: for example lignin-sulphite waste liquors and methylcellulose.

Adhesives such as carboxymethylcellulose and natural and synthetic polymers in the form of powders, granules or latexes, such as gum arabic, polyvinyl alcohol and polyvinyl acetate, as well as natural phospholipids, such as cephalins and lecithins, and synthetic phospholipids, can be used in the formulations. Further additives can be mineral and vegetable oils.

It is possible to use colorants such as inorganic pig-ments, for example iron oxide, titanium oxide and Prus-sian Blue, and organic dyestuffs, such as alizarindyestuffs, azo dyestuffs and metal phthalocyanine dye-stuffs, and trace nutrients such as salts of iron, manganese, boron, copper, cobalt, molybdenum and zinc.

The formulations in general contain between 0.1 and 95 per cent by weight of active compound, preferably between 0.5 and 90%.

Le A 30 014-FC - 17 -v _.

.1 . -.~-.
:

:
'., :-, 2 13 ~

For combating weeds, the active compounds according tothe invention, as such or in the form of their formula-tions, can also be used as mixtures with known herbicides, finished formulations or tank mixes being possible.

Suitable herbicides for the mixtures are known herbicides, for example anilides such as, for example, diflufenican and propanil; arylcarboxylic acids such as, for example, dichloropicolinic acid, dicamba and picloram; aryloxyalkanoic acids such as, for example, 2,4 D, 2,4 DB, 2,4 DP, fluroxypyr, MCPA, MCPP and triclopyr; aryloxy-phenoxy-alkanoic esters such as, for example, diclofop-methyl, fenoxaprop-ethyl, fluazifop-butyl, haloxyfop-methyl and quizalofop-ethyl; azinones such as, for example, chloridazon and norflurazon;
carbamates such as, for example, chlorpropham, desmedipham, phenmedipham and propham;
chloroacetanilides such as, for example, alachlor, acetochlor, butachlor, metazachlor, metolachlor, pretilachlor and propachlor; dinitroanilines such as, for example, oryzalin, pendimethalin and trifluralin;
diphenyl ethers such as, for example, acifluorfen, bifenox, fluoroglycofen, fomesafen, halosafen, lactofen and oxyfluorfen; ureas such as, for example, chlortoluron, diuron, fluometuron, isoproturon, linuron and methabenzthiazuron; hydroxylamines such as, for example, alloxydim, clethodim, cycloxydim, sethoxydim and tralkoxydim; imidazolinones such as, for example, imazethapyr, imazamethabenz, imazapyr and imazaquin;

Le A 30 014-F~ - 18 -~;'.'~' ' ' ' ' ' , ' ' ' ' ,, ' .
,,~
':,'' ' ~:
~,.,: ., .
.~,,-.,,.--, ~. .:

-" 213~91~

nitriles such as, for example, bromoxynil, dichlobenil and ioxynil; oxyacetamides such as, for example, mefenacet; sulphonylureas such as, for example, amido-sulfuron, bensulfuron-methyl, chlorimuron-ethyl, chlor-sulfuron, cinosulfuron, metsulfuron-methyl, nicosulfuron, primisulfuron, pyrazosulfuron-ethyl, thifensulfuron-methyl, triasulfuron and tribenuron-methyl; thiocarbamates such as, for example, butylate, cycloate, di-allate, EPTC, esprocarb, molinate, prosulfocarb, thiobencarb and tri-allate; triazines such as, for example, atrazine, cyanazine, simazine, simetryn, terbutryn and terbutylazine; triazinones such as, for example, hexazinone, metamitron and metribuzin;
others such as, for example, aminotriazole, benfuresate, bentazone, cinmethylin, clomazone, clopyralid, difenzoquat, dithiopyr, ethofumesate, fluorochloridone, glufosinate, glyphosate, isoxaben, pyridate, quinchlorac, quinmerac, sulphosate and tridiphane.

Mixtures with other known active compounds, such as fungicides, insecticides, acaricides, nematicides, bird repellants, plant nutrients and agents which improve soil structure, are also possible.

The active compounds can be used as such, in the form of their formulations or in the use forms prepared therefrom by further dilution, such as ready-to-use solutions, suspensions, emulsions, powders, pastes and Le A 30 014-FC - 19 -. -, .
., ' ~,' .' . ~,.

-`~ 213'~915 granules. They are used in the customary manner, for example by watering, spraying, atomizing or scattering.

The active compounds according to the invention can be applied either before or after emergence of the plants.
They can also be incorporated into the soil before sowing.

The amount of active compound used can vary within a -substantial range. It depends essentially on the nature ~
of the desired effect. In general, the amounts used are ~:
10 between 10 g and 10 kg of active compound per hectare ~
of soil surface, preferably between 50 g and 5 kg per -ha.

The preparation and use of the active compounds according to the invention can be seen from the following examples.

Preparation Examples:

Example 1 O

N~SO2NI~ 1N~OCH3 4.2 g (33 mmol) of 2-amino-4-methoxy-6-methylpyrimidine -are added at -5C with stirring to a mixture of 4.3 g Le A 30 014-FC 20 -. . ., ,~,, ,:: .

~ 213'~315 (30 mmol) of chloros~llphollyl isocyanate and 50 ml of methylene chloride. The mixture is stirred for 30 minutes at 0C.

Then, 4.7 g (30 mmol) of 2-amino-propiophenone, 3.5 g (35 mmol) of triethylamine and 50 ml of methylene chloride are added, and stirring of the reaction mixture is continued for 18 hours at 20C.
''"'.

The product is then washed using water and 10% strength hydrochloric acid, dried using sodium sulphate and filtered.

The filtrate is concentrated in vacuo, the residue is crystallized by digestion with ethanol, and the product is isolated by filtration with suction.

6.9 g (58.5~ of theory) of N-(4-methoxy-6-methyl-pyrimidin-2-yl)-N'-(2-propionyl-phenylaminosulphonyl)-urea of melting point 126C are obtained.

Other examples of the compounds of the formula (I) which can be prepared analogously to Example 1 and following the general description of the preparation process according to the invention are those listed in Table 1 below.

* ~
O R

H 54~C~H 1~R3 (I) -Le A 30 014-FC - 21 -~''';':~' ' - .
'-, ~ ' '' , ~; .

~,.......... .
~, .~...
., 213'191~

Ta~le 1: Examples of the compounds of the formula (I) Ex.- Rl R2 R3(Position-) RS melting- - -No. R4 point(C) -,"

Cl H OCH3 H CH3 158 -~-9 Cl H OCH3 H C2H5 152 OCH3 H OCH3 (6-)CI C2H5 162 11 OCH3 H CH3 (6-)CI C2H5 157 12 OCH3 H OCH3 (5-)Cl CH3 172 ---~
13 OCH3 H OCH3 (5-)CI CH(CH3)2 166 ~-~
14 CH3 H OCH3 H CH(cH3)2 149 15 OCH3 H OCH3 (6-)F CH3 16 OCH3 H OCH3 (6-)CH3 CH3 184 . ~:
` 17 OCH3 H OCH3 (6-)CI CH3 174 -18 OCH3 H OCH3 (6-)OCH3 CH3 .. _ .. . , . _ .. . . .. . . ..
~;~ Le A 30 014-FC - 22 -- :

. ,.~ , ~ , : ;

`" 2134~1~

Tablel(Continuntion) .
Ex.- Rl R2 R3 (Position-) R5 melting-No. R4 point(C) 19 OCH3 H OCH3 (6-)SCH3 CH3 162 OCH3 H OCH3 (6-)COOCH3 CH3 21 OCH3 H OCH3 (6-)F C2H5 155 22 OCH3 H OCH3 (6-)CH3 C2H5 164 23 OCH3 H OCH3 (6-)OCH3 C2H5 24 OCH3 H OCH3 (6-)SCH3 C2H5 220 OCH3 H OCH3 (6-)COOCH3 C2Hs ..
26 OCH3 H OCH3 (4-)CI n-C4Hg 165 27 OCH3 H OCH3 (5-)CI CH(CH3)2 160 28 CH3 H OCH3 (6-)F CH3 -29 CH3 H OCH3 (6-)CI CH3 30 CH3 H OCH3 (6-)CH3 CH3 136 - -.
31 CH3 H OCH3 (6-)OCH3 CH
32 CH3 H OCH3 (6-)SCH3 CH3 33 CH3 H OCH3 (6-)COOCH3 CH3 ç~.
~ 34 CH3 H OCH3 (6-)F C2H5 161 : 3S CH3 H OCH3 (6-)CH3 C2H5 212 LeA30 014-FC

.
: , ~.~
.. ..

- 213~

Table I (Continuation) , .
Ex.- Rl R2 R3 (Position-) RS melting-No. R4 point(C) 36 CH3 H OCH3 (6-)OCH3 C2H5 37 CH3 H OCH3 (6-)SCH3 C2H5 .
38 CH3 H OCH3 (6-)COOCH3 C2H5 39 Cl H OCH3 (6-)F CH3 Cl H OCH3 (6-)CI CH3 154 41 Cl H OCH3 (6-)CH3 CH3 145 42 Cl H OCH3 (6-)OCH3 CH3 43 Cl H OCH3 (6-)SCH3 CH3 .~.-44 Cl H OCH3 (6-)COOCH3 CH3 -45 Cl H OCH3 (6-)P C2H5 180 46 Cl H OCH3 (6-)CI C2H5 184 ~ .
47 Cl HOCH3 (6-)CH3 C2H5 158 48 Cl HOCH3 (6-?OCH3 C2H5 49 Cl HOCH3 (6-)SCH3 C2H5 196 -50 Cl HOCH3 (6-)COOCH3 C2Hs H H CH3 (6-)F CH3 52 H H CH3 (6-)CI CH3 ~ , Le A 30 014-FC - 24 -: ' ,~ " . , . _, . .
~ ' i - -;~ , , .:,, - .. .
.. ~ ..
. j~-::'~ ` '`'` , .

213~91~

T~biel (Continuation) Ex.- Rl R2 R3 (Position-) RS melting-No~ R4 point (C) 53 H H CH3 (6-)CH3 CH3 54 H H CH3 (6-)OCH3 CH3 H H CH3 (6-)SCH3 CH3 .
56 H H CH3 (6-)COOCH3 CH3 58 H H CH3 (6-)F C2H5 59 H H CH3 (6-)CI C2H5 H H CH3 (6-)CH3 C2H5 61 H H CH3 (6-)OCH3 C2H5 62 H H CH3 (6-)SCH3 C2Hs ~:
63 H H CH3 (6-)COOCH3 C2Hs : -~

H H OCH3 (6-)F CH3 66 H H OCH3 (6-)CI CH3 ~-67 H H OCH3 (6-)CH3 CH3 68 H H OCH3 (6-)SCH3 CH3 ~: 69 H H OCH3 (6-)OCH3 CH3 Le A30014-FC

,~
....

--" 2134~1~

Table I (Continuation) .
Ex~- Rl R2 R3 (Position-) R5 melting-No~ R4 point(C) ' H H OCH3 (6-)COOCH3 CH3 72 H H OCH3 (6-)F C2H5 73 H H OCH3 (6-)CI C2H5 74 H H OCH3 (6-)OCH3 C H
H H OCH3 (6-)SCH3 C2H5 76 H H OCH3 (6-)CH3 C2H5 77 H H OCH3 (6-)COOCH3 C2H5 78 CH3 H CH3 (6-)F CH3 ~ -79 CH3 H CH3 (6-)Cl CH3 158 -80 CH3 H CH3 (6-)CH3 CH3 128 81 CH3 H CH3 (6-)SCH3 CH3 82 CH3 H CH3 (6-)OCH3 CH3 83 CH3 H CH3 (6-)COOCH3 CH3 ~.
CH3 H CH3 (6-)F C2H5 160 ~ ~ ~
85 CH3 H CH3 (6-)CI C2H5 -86 CH3 H CH3 (6-)OCH3 C2H5 .

Le A 30 014-FC

~'~ ~ ' ', , `
~'''-'''' , .
~','"'," , Tnble I (Continuation) Ex.- Rl R2 R3(Position-) RS melting-No. R4 point(C) g7 CH3 H CH3(6-)SCH3 C2H5 174 88 CH3 H CH3(6-)CH3 C2H5 178 89 CH3 H CH3(6-)COOCH3 C2H5 91 CF3 H CF3(6-)F CH3 92 CF3 H CF3(6-)CI CH3 93 CF3 H CF3(6-)CH3 CH3 94 CF3 H CF3(6-)SCH3 CH3 CF3 H CF3(6-)OCH3 CH3 96 CF3 H C~3(6-)COOCH3 CH3 97 ~F3 H CF3 H C2H5 98 CF3 H CF3(6-)F C2H5 99 CF3 H CF3(6-)Cl C2H5 100 CF3 H CF3(6-)OCH3 C2H5 101 CF3 H CF3(6-)SCH3 C2H5 102 CF3 H CF3(6-)CH3 C2H5 ..
103 CF3 H CF3(6-)COOCH3 C2H5 LeA30 014-FC

,~
;. ~. .
v',~

~. .-. ,~ . . `

" 213~1S

Tnblel(Continuation) Ex.- Rl R2 R3 (Position-) R5 melting-No. R4 point(C) -105 CF3 H OCH3(6-)F CH3 106 CF3 H OCH3(6-)CI CH3 107 CF3 H OCH3(6-)CH3 CH3 108 CF3 H OCH3(6-)SCH3 CH3 109 CF3 H OCH3(6-)OCH3 CH3 110 CF3 H OCH3(6-)COOCH3 CH3 111 CF3 H OCH3 H C2H5 ~ :;
112 CF3 H OCH3(6-)F C2H5 113 CF3 H OCH3(6-)CI C2H5 114 CF3 H OCH3(6-)OCH3 C2H5 115 CF3 H OCH3(6-)SCH3 C2H5 :~: 116 CF3 H OCH3(6-)CH3 C2H5 117 CF3 H OCH3(6-)COOCH3 C2H5 ;~

119 OCHF2 H OCHF2(6-)F CH3 120 OCHF2 H OCHF216-)CI CH3 . ~:
LeA30014-FC

.~,~".,, ~, ~j,,;-'.,, ', '.
.

--" 213~91~

Tablel(Continuntion) P~ A, . ~
Ex.- Rl R2 R3 (Position-) R5 melting-No. R4 point(C) 121 OCHF2 H OCHF2 (6-)CH3 CH3 122 OCHF2 H OCHF2 (6-)SCH3 CH3 123 OCHF2 H OCHF2 (6-)OCH3 CH3 124 OCHF2 H OCHF2 (6-)COOCH3 CH3 -.

126OCHF2 H OCHF2 (6-)F C2H5 127OCHF2 H OCHF2 (6-)CI C2H5 ~.
128OCHF2 H OCHF2 (6-)OCH3 C2H5 129OCHF2 H OCHF2 (6-)SCH3 C2H5 130OCHF~ H OCHF2 (6-)CH3 C2H5 131OCHF2 H OCHF2 (6-)COOCH3 C2H5 132 OCH3 H NHCH3 H CH3 .
133OCH3 H NHCH3 (6-)F CH3 134OCH3 H NHCH3 (6-)CI CH3 135OCH3 H NHCH3 (6-)CH3 CH3 136OCH3 H NHCH3 (6-)SCH3 CH3 137OCH3 H NHCH3 (6-)OCH3 CH3 LeA30 014-FC

. - . , .
;,-. .
~ '; , .
~'' ` , -`' 213~15 -Tablel(Contimlation) Ex~- Rl R2 R3 (Position-) R5 melting-No. R4 point(C) 138 OCH3 H NHCH3 (6-)COOCH3 CH3 140 OCH3 H NHCH3 (6-)F C2H5 141 OCH3 H NHCH3 (6-)Cl C2HS
142 OCH3 H NHCH3 (6-)OCH3 C2H5 143 OCH3 H NHCH3 (6-)SCH3 C2H5 144 OCH3 H NHCH3 (6-)CH3 C2H5 145 OCH3 H NHCH3 (6-)COOCH3 C2H5 147 OC2H5 H NHCH3 (6-)F CH3 148 OC2Hs H NHCH3 (6-)CI CH3 149 OC2H5 H NHCH3 (6-)CH3 CH
150 OC2H5 H NHCH3 (6-)SCH3 CH3 - -.
151 OC2Hs H NHCH3 (6-)OCH3 CH3 152 OC2H5 H NHCH3 (6-)COOCH3 CH3 154 OC2H5 H NHCH3 (6-)F C2H5 Le A 30 014-F

, . ..

~ A
~" - ~'' ' ~ '~' ~ . . ~' ' , ' ' ~,','' , ' ~ ' ' ' `
',' ` ' " ' 213~91~

Table I (Continuation) Ex. - R I R2R3(Position-) R5 melting-No. R4 point (C) 155 OC2H5 HNHCH3 (6-)Cl C2H5 156 OC2~5 HNHCH3(6-)OCH3 C2H5 157 OC2H5 HNHCH3(6-)SCH3 C2H5 ~ ~p 158 OC2Hs HNHCH3(6-)CH3 C2H5 159 OC2H5 HNHCH3(6-)COOCH3 C2H5 161 OCH3 HOCH3 H C3H7n 156 162 CH3 HOCH3 H C3H7n 149 163 CH3 H H H C3H7n 155 ~ `
164 OCH3 HOCH3 (6-)F c3H7n 142 165 OCH3 HOCH3 (6-)Cl c3H7n 133 166OCH3 HOCH3(6-)CH3 c3H7n 72 167OCH3 HOCH3 ~ 3 192 168OCH3 HOCH3 H ~ 188 169OCH3 HCH3 H ~ 172 "';' `' ~`' `.
Le A 30 014-FC --31- . .~

213'1~1S

Table I (Continuatio~
Ex.- Rl R2 R3 (Position-) R5 melting-No. R4 point (C) -170OCH3 H OCH3 H CH(cH3)2 150 171OCH3 H OCH3 H (CH2)3CH3 156 172OCH3 H OCH3 H ~ 152 ~ ~ ' 173OCH3 H OCH3 (4-)C1 147 . -174OCH3 H OCH3 (3-)F CH(CH3)2 175OCH3 H OCH3 (5-)CI CH3 163 176OCH3 H OCH3 (4-)CH3 CH(CH3)2 177OCH3 H OCH3 (4-)OCH3 CH(CH3)2 - ~- -178OCH3 H OCH3 (4-)OCH3 CH3 --,~ . . ~ .
179OCH3 H CH3 (4-)CI (CH2)3cH3 ~L.,,~
180OCH3 H CH3 (4-)CI ~
', .
181OCH3 HOCH3 H ~ 170 182OCH3 HOCH3 H {~ 165 ~ -183OCH3 HOCH3 H t-C4Hg 103 ~ -Le A 30 014-FC - --32- - ::-'- . .

; ~
,, .. ~
.,.. - ~ .

213~91S

Tablel(Continuntion) Ex~- Rl R2 R3 ~osition-) R5 melting-No. R4 point (C) ; ~;, . . . _ .

184OCH3 H OCH3 ~ ~ 172 185OCH3 H OCH3 H. ~ 150 186OCH3 H OCH3 ~4-)OCH3 n-C4Hg 149 187OCH3 H OCH3 (5-)OCH3 i-C3H7 165 188 CH3 H OCH3 (4-)OCH3 CH(CH3)2 162 189OCH3 H OCH3 (5-)CH3 CH(CH3)2 153 190 CH3 H OCH3 (5-)CH3 CH(CH3)2 164 191OCH3 H OCH3 (6-)C2H5 CH(C~3)2 152 192OCH3 H OCH3 (6-)CH(CH3)2 CH(CH3)2 176 193OCH3 H OCH3 (6-)C4Hg-s CH(CH3)2 162 194OCH3 H OCH3 (3-)OCH3 CH3 147 -195OCH3 H OCH3 (5-)OCH3 n-C4Hg 170 .--196OCH3 H OCH3 (3-)OCH3 n-C4Hg 158 197OCH3 H OCH3 (5-)C2Hs CH(CH3)2 176 198OCH3 H OCH3 (4-) CH(CH3)2 164 ~
NHCOOC2H5 ` . " ` . .

LeA30014-FC . :
-33- . ~-. . . ~ .- ~ -;, i . . - . .

213 I~l~

Table I (Continuation) Ex.- Rl R2 R3 (Position-) R5 melting-No. R4 point(C) 199OCH3 H OCH3 (6-)C2H5 CH3 159 200OCH3 H OCH3 (6-)C2HS C2H5 160 .
201OCH3 H OCH3 (6-)C2H5 n-C4Hg 116 202OCH3 H OCH3 (6-)CH(CH3)2 C2H5 161 203OCH3 H OCH3 (6-)CH(CH3)2 CH3 157 204OCH3 H OCH3 (6-) CH(CH3)2 160 205 Cl H OCH3 (6-)C2H5 C2H5 148 206OCH3 H OCH3 (6-)CH3 -(CH2)3-Cl 67 207OCH3 H OCH3 H ~3 128 :

208 CH3 HOCH3 H H 105 - ~- -209OCH3 HOCH3 (6-)CH3 H 147 210Cl HOCH3 H H 158 ~.
211Cl HOCH3 (6-)CH3 H 194 212OCH3 HOCH3 (6-)C3H7-n CH3 144 213OCH3 HOCH3 (6-)C3H7-n C2H5 151 ~ , 214OCH3 HOCH3 (6-)C3H7 n C3H7~n 148 . . ~.

` :~
LeA30014-~C -:
-34- :

t. ! . ~ ' ' ,;'. -~ `
.~''' ~` . ' ` ' ` ' . `
',..................................... ` .` ' ' ' ' ' ' 213 ~91~ ~

Table L (Continuation) Ex.- R I R2 R3(Position-) R5 melting-No. R4 point (C) 215 CH3 H OCH3(6-)C3H7-n CH3 133 '.
216 CH3 H OCH3(6-)C3H7-n C2H5 144 217 CH3 H OCH3(6-)C3H7-n C3H7~n 143 218OCH3 H OCH3(6-)C3H7-n CH(CH3)2 140 219 CH3 H OCH3(6-)C3H7-n CH(CH3)2 135 220 Cl H OCH3 H -CH2SCH3 136 221 CH3 H OCH3(6-)CH3 C3H7-n 128 222 Cl H OCH3(6-)CH3 C3H7-n 122 ~ ~-223OCH3 H OCH3(6-)SC2Hs C3H7~n 150 224 Cl H OCH3(6-)Sc2Hs C3H7-n 125 225 CH3 H CH3 H ~ 190 - , 226Cl HOCH3 H ~ 186 ~ ~.

227CH3 BrCH3 H C2H5 178 228CH3 BrCH3 (6-)F C2H5 168 : - .
229CH3 BrCH3(6-)CH3 C2H5 154 230OCH3 HOCH3(6-)soc2Hs C3H7-n 128 :

.
Le A 30 014-FC -` : . .
-35- ~ ~, '' ```'~'`' P~
.,, ~,;

213'~91~

Tab!e_L (Continuation) Ex.- Rl R2 R3 (Position-) R5 melting-No. R4 point(C) 231OCH3 H OCH3 (6-)SO2C2H5 C3H7~n 125 232OCH3 H OCH3 (6-)SCH3 C3H7~n 148 233 CH3 H OCH3 (6-)SCH3 C3H7-n 137 234OCH3 H OCH3 (6-)SO2CH3 C3H7~n 132 235 Cl H OCH3 H C3H7-n 129 236 Cl H OCH3 (6-)SCH3 C3H7~n 139 237 Cl H OCH3 (6-)Cl C3H7-n 148 238 CH3 H OCH3 (6-)Cl C3H7-n 145 239 CH3 H OCH3 (6-)Sc2H5 C3H7-n 168 240 CH3 H OCH3 (6-)F C3H7-n 149 241 Cl H OCH3 (6-)F C3H7-n 148 242OCH3 H OCH3 (6-)SO2CH3 CH3 182 244OCH3 H OCH3 (6-)Br C2H5 185 245 CH3 H OCH3 (6-)Br C2H5 169 246 Cl H OCH3 (6-)Br C2H5 161 247 CH3 H CH3 (6-)Br C2H5 181 Le A 30 014-FC

:. - -.. . . ..
~' '' " ' ` , , , ,. . . .

:.

~13'i315 Table I (Continuation) Ex.- R I R2 R3(Position-) R5 melting-No. R4 point(C) 248 OCH3 H OCH3 (6-)Br CH3 195 249 CH3 H OCH3 (6-)Br CH3 191 250 OCH3 H OCH3(6-)CH3 -CH2SCH3 148 251 Cl H OCH3(6-)CH3 -CH2SCH3 102 252 CH3 H OCH3(6-)CH3 -CH2SCH3 85 253 Cl H OCH3(6-)CH3 -CH2SOCH3 112 ~ ~:
254 OCH3 H OCH3 (6-)Br C3H7-n 174 255 Cl H OCH3 (6-)Br C3H7-n 152 256 CH3 H OCH3 (6-)Br C3H7-n 148 - .. -257 Cl H OCH3 (6-)Br CH3 182 -:
258 CH3 H CH3 (6-)Br CH3 177 259 Cl H OC2H5(6-)SCH3 CH3 150 ; ~ - -260 Cl H OC2H5(6-)CI C2H5 174 261 Cl H OC2H5(6-)CI CH3 174 262 Cl H OC2H5 H C2H5 124 -- :
263 Cl H CH3 H C2H5 161 .
264 Cl H CH3 H CH3 196 ' ' '~

Le A 30 014-FC

. -. .-~ ' . ' .
.
...

2134~1S

Table I (Continuation) Ex. - R I R2 R3(Position-) R5 melting-No. R4 point (C) : ".: -;
265 Cl H CH3 (6-)CH3 CH3 201 266 Cl H CH3 (6-)SCH3 CH3 158 267 Cl H CH3 (6-)SCH3 C2H5 140 269 Cl H OCH3 H -CH2C1 194 270 CH3 H OCH3 H -CH2C1 177 .

272 Cl H CH3 H -CH2C1 140 273 Cl H OC2H5 H -CH2C1 112 275 OCH3 H OCH3 (6-)CH3 -CH2C1 178 ` ~
276 Cl HOCH3 (6-)CH3 -CH2C1 128 ~`-277 CH3 HOCH3 (6-)CH3 -CH2C1 153 278 CH3 H CH3 (6-)CH3 -CH2C1 164 -279 Cl H CH3 (6-)CH3 -CH2C1 171 -280 Cl HOC2H5(6-)CH3 -CH2C1 136 281 CH3 HOC2H5(6-)CH3 -CH2C1 15S ` -;
''~' :, Le A 30 014-FC
--3~--` '` ' ' ' , ~:',, -: - ` ' 213'191~

Table I (Continuation) Ex.- Rl R2 R3(Position-) R5 melting-No. R4 point (C) 282OCH3 H OCH3 (6-)CI -CH2C1 155 283 Cl H OCH3 (6-)F -CH2C1 158 284OCH3 H OCH3 (6-)Br -CH2C1 155 . -. -285 Cl H OCH3 (6-)Br -CH2C1 105 ,~ ' "" .-' . ', .
: -' '"''""'"'''-''"-.- .. ..-.

-.~, ..--.-;
,: -- -,~ ..

; ~:-,. - ~, ..-- : ~
-"- ' ,. '',', Le A 30 014-FC

' ' . .
.' " ,-` ' . ' `''' ' " ', . "
, 213'1915 Starting ~4stances of ~le formula (IV):

Example(IV-1) (C~

A mixture of 100 ml (0.1 mol) of boron trichloride and 100 ml of 1,2-dichloroethane is cooled to 0C. 12.3 g 5 (0.1 mol) of 4-methoxyaniline are added dropwise with ~-stirring in the course of 15 minutes at this temperature. A solution of 10.4 g (0.15 mol) of ~.
isobutyronitrile in 100 ml of 1,2-dichloroethane is then added dropwise and, after the mixture has been -- ~i stirred for 5 minutes, 14.7 g (0.11 mol) of aluminium -~ ~
trichloride are added to the mixture in portions at `
0C. The reaction mixture is then stirred for 5 hours '-at 80C and subsequently subjected to ice-cooling, and 300 ml of water are added dropwise. The organic phase - : ~
15 is then separated off, and the aqueous phase is -~ -reextracted three times using methylene chloride. The --combined organic phases are dried over sodium sulphate and filtered, and the filtrate is concentrated. The ;~
residue is separated by column chromatography (silica 20 gel; hexane/ethyl acetate: 4:1 by volume). ~ ~-¦~ 5.3 g (27.5~ of theory) of4-methoxy-2-isobutyroyl-~ aniline are obtained. ---~
. ~ .
.

Le A 30 014-FC

1. . . .

;'''''''" ' ' ' ' .~ .
: `
.~
, .:. ~:.

E a~Q_~
O
\~
'' - ~ '.
N~

10.9 g (72 mmol) of 2-cyano-4-chloro-aniline are dis-solved in 30 ml of diethyl ether, and the mixture is cooled to 0C. 100 ml of a two-molar solution of 5 cyclopentylmagnesium chloride in diethyl ether are --added dropwise at this temperature, and the reaction -mixture is stirred for a further 4. 5 hours at 20C. ~ -After the mixture has been cooled to 0C, 150 ml of 10% ;
strength hydrochloric acid are added dropwise, and the 10 mixture is stirred for one hour at 20C. After the ~
mixture has again been cooled to 0C, 25 g of sodium ~ -hydroxide are added to the mixture, the organic phase is separated off, the aqueous phase is reextracted - -three times using diethyl ether, and the combined ~
lS organic phases are dried over sodium sulphate and ~ -concentrated. ~ ; --~.- . .~, The residue is separated by column chromatography .~'.~,r."~
(silica gel; hexane/ethyl acetate: 4:1 by volume). ---C ~
11.9 g (74~ of theory) of 4-chloro-2-cyclopentanoyl~
20 aniline of melting point 73C are obtained. -Other compounds of the formula (Iv) which can be prepared analogously to Example (IV-l) or (IV-2) are those listed in Table 2 below. ~--O

R ~ (IV) Le A 30 014-FC

~ :, 'S ' , , - ' , ~ ` : `' "' '~ -. . ., ," .~

.,, ~ . .

213'191~

Table 2: Examples of the compound~ of the formula (IV) .. ,.. ~ . ~ _ _ Ex. (Position) R5 Melting ¦ ;.
¦NO. Rq point ¦IV-3 H CH(CH3)2 (oil) 5¦ IV - 4 ( 4 - ) Cl CH ( CH3 ) 2 6 4 C
IV-6 H ~ SgC

IV- 7 ( 4 - ) Cl CH
¦ IV-8 (4-) Cl (CH2) 3CH3 69C
IV-g t4-)Cl ~ 73C

10IV-10 (5-)Cl CH (CH3) 2 (oil) I I .
¦ IV-11 ( 3 - ) F CH ( CH3 ) 2 IV- 12 ( 5 - ) Cl CH
I .
IV- 13 ( 4 - ) OCH3 CH ( CH3 ) 2 ( oil ) IV- 14 ( 4 - ) OCH3 CH ( CH3 ) 2 ( oil ) . _ _ 15IV- 15 ( 4 - ) OCH3 CH3 ( oil ) IV-16 H CH2SCH3 ( oil ) .

Le A 30 014-FC
-~2-, ` ~ .
....

2 1 3 '~

Table 2: Continuation) _ Ex. (Position) R5 Melting ¦ .
No R

IV-17 ¦H CH2SCH3 (oil) l : .
IV-l~ (6-)F C3H7n l ~ -.
IV-19 (6-)Cl C3H7n ¦¦
IV-20 (6-)CH3 C3H7n I .
11 ,, -, IV-21 H -CH2 ~ 86C ~ ~

I . .
IV-22 (6-)Cl C2H
IV-23 (6-)F C2Hs I ::
IV-24 H d~ 4 03 H 1~'C

¦d=l 29 Le A 30 014-FC
~43-~fi~
.,'~ `:
i~
~ . .

213'1~ 1~

Table 2: Contilluatioll) _ Ex (Position) R5 Melting No. R4 p(~oC)t IV-27 (6-) Cl CH3 I
IV-28 (6-) CH3 CH, 48 I
IV-29 (6-) SCH3 C3H7 - n IV-30 (6-) SCH3 CH3 IV-31 (6-) CH3 -CH2SCH3 :
IV-32 (6-)Br C3H7-n S9 - :' - ~ i " ' Use Examples In the use examples, the compound (A) below is used as comparison substance:

O S~

M~S02~KX}NH ~OC~ (A) N-(4,6-Dimethoxy-pyrimidin-2-yl)-N'-(2-cyclopropyl-carbonyl-phenylaminosulphonyl)-urea (disclosed in EP-A 463287/US Patent 5009699).

Le A 30 014-FC

'~
.
' .
.

213'1~1~

Example A

Post-emergence test -~

Solvent: 5 parts by weight of acetone ;
Emulsifier: 1 part by weight of alkylaryl polyglycol ether ~ -': -To produce a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated amount of solvent, the stated amount of I -emulsifier is added and the concentrate is diluted with ~
lO water to the desired concentration. -. ':
Test plants which have a height of 5 - 15 cm are ~
sprayed with the preparation of the active compound in ~-such a way as to apply the particular amounts of active -compound desired per unit area. The concentration of the spray liquor is chosen such that the particular amounts of active compound desired are applied in 2,000 l of water/ha. After three weeks, the degree of -damage to the plants is rated in ~ damage in comparison to the development of the untreated control.
20 The figures denote -0~ = no action (like untreated control) -~-100~ = total destruction.
: ', .
In this test, a considerably more powerful action -.-.
against weeds than in the case of compound (A) which is ~r.
25 known, combined with a very good tolerance by crop ::-plants, such as, for example, wheat, is shown, for example, by the compounds of Preparation Examples 1 and 2.

Le A 30 014-FC

,: ' ~;.. ;: .
l ~
I ~

2134~1S

E~ample s Solvent: 5 parts by weigllt of acetone Emulsifier: 1 part by weight of alkylaryl polyglycol ether 5 To produce a suitable preparation of active compound, ;
1 part ~y weight of active compound is mixed with the stated amount of solvent, the stated amount of emulsifier is added and the concentrate is diluted with -water to the desired concentration.
' '-. :.' Seeds of the test plants are sown in normal soil.
After 24 hours the soil was watered with the preparation of the active compound. It is expedient to keep constant the amount of water per unit area. The concentration of the active compound in the preparation is of no importance, only the amount of active compound applied per unit area being decisive. After three weeks, the degree of damage to the plants is rated in damage in comparison to the development of the untreated control. The figures denote:

0~ = no action (like untreated control) ---100~ = total destruction.

In this test, a considerably more powerful action - against weeds than in the case of compound (A) which is known, combined with a very good tolerance by crop plants, such as, for example, wheat, is shown, for example, by the compounds of Preparation Examples 1 and 2.
It will.be apprecisted that the instant specification and claims are set forth by way of illustration and not limi-tation, and that various modifications and changes may be made without departing from the spirit and scope of the present invention.
_,, , , . ... . _ . . . , .. _ . . . _, . . . . . .
Le A 30 014-FC
_46-i~tj. ~ -.. .
. ,~

, .

Claims

1. A substituted phenylaminosulphonylurea of the general formula (I) (I) in which R1 represents hydrogen, halogen, or represents alkyl, alkoxy, alkylthio, alkylsulphinyl, alkylsulphonyl, alkylamino or dialkylamino, each of which has 1 to 4 carbon atoms in the individual alkyl groups and each of which is optionally substituted by halogen or C1-C3-alkoxy, R2 represents hydrogen or halogen, R3 represents halogen, or represents alkyl, alkoxy, alkylthio, alkylsulphinyl, alkylsulphonyl, alkylamino or dialkylamino, each of which has 1 to 4 carbon atoms in the individual alkyl groups and each of which is optionally substituted by halogen or C1-C3-alkoxy, R4 represents hydrogen, amino, halogen or formyl, or represents alkyl, alkoxy, alkylthio, alkylsulphinyl, alkylsulphonyl, alkylcarbonyl, alkoxycarbonyl, alkyl-carbonylamino, alkoxycarbonylamino or alkylsulfonylamino, each of which has 1 to 4 carbon atoms in the individual alkyl groups and each of which is optionally substituted by halogen or C1-C3-alkoxy, and R5 represents hydrogen, or represents alkyl having 1 to 8 carbon atoms which is optionally substituted by halogen, C1-C4-alkoxy, C1-C4-alkylthio, C1-C4-alkylsulphinyl or C1-C4-alkylsulphonyl, or represents cycloalkyl, cyclo-alkyl-C1-C4-alkyl, cycloalkenyl or cycloalkenyl-C1-C4-alkyl, each of which has 4 to 7 carbon atoms in the cycloalkyl or cycloalkenyl groups and each of which is optionally substituted by halogen and/or C1-C4-alkyl, or represents phenyl or phenyl-C1-C4-alkyl, each of which is optionally substituted by halogen, C1-C4-alkyl or C1-C4-halogenoalkyl, or represents heterocyclyl or heterocyclyl-C1-C4-alkyl having 2 to 6 carbon atoms and 1 to 3 nitrogen atoms and/or one oxygen or sulphur atom and each of which is optionally substituted by halogen, C1-C4-alkyl or C1-C4-halogenoalkyl, or a salt thereof.

2. A compound of the formula (I) according to claim 1, wherein R1 represents hydrogen, fluorine, chlorine or bromine, or represents alkyl, alkoxy, alkylthio, alkylsulphinyl, alkylsulphonyl, alkylamino or dialkylamino, each of which has 1 to 3 carbon atoms in the individual alkyl groups and each of which is optionally substituted by fluorine, chlorine, methoxy or ethoxy, R2 represents hydrogen, fluorine, chlorine or bromine, R3 represents fluorine, chlorine or bromine, or represents alkyl, alkoxy, alkylthio, alkylsulphinyl, alkylsulphonyl, alkylamino or dialkylamino, each of which has 1 to 3 carbon atoms in the individual alkyl groups and each of which is optionally substituted by fluorine, chlorine, methoxy or ethoxy, R4 represents hydrogen, amino, fluorine, chlorine, bromine or formyl, or represents alkyl, alkoxy, alkylthio, alkylsulphinyl, alkylsulphonyl, alkylcarbonyl, alkoxy-carbonyl, alkylcarbonylamino, alkoxycarbonylamino or alkylsulfonylamino, each of which has 1 to 3 carbon atoms in the individual alkyl groups and each of which is optionally substituted by fluorine, chlorine, methoxy or ethoxy, and R5 represents hydrogen, or represents alkyl having 1 to 6 carbon atoms which is optionally substituted by fluorine, chlorine, bromine, C1-C3-alkoxy, C1-C3-alkylthio, C1-C3-alkylsulphinyl or C1-C3-alkylsulphonyl, or represents cycloalkyl, cycloalkyl-C1-C3-alkyl, cycloalkenyl or cycloalkenyl-C1-C3-alkyl, each of which has 4 to 6 carbon atoms in the cycloalkyl or cycloalkenyl groups and each of which is optionally substituted by fluorine, chlorine, bromine and/or C1-C3-alkyl, or represents phenyl or phenyl-C1-C3-alkyl, each of which is optionally substituted by fluorine, chlorine, bromine, C1-C3-alkyl or C1-C3-halogenoalkyl, or represents heterocyclyl or heterocyclyl-C1-C3-alkyl, each of which has 3 to 5 carbon atoms and 1 to 3 nitrogen atoms and/or one oxygen or sulphur atom and each of which is optionally substituted by fluorine, chlorine, bromine, C1-C3-alkyl or C1-C3-halogenoalkyl, or a salt thereof.

3. A compound of the formula (I) according to claim 1, wherein R1 represents hydrogen, chlorine, methyl, ethyl, tri-fluoromethyl, methoxy, ethoxy, difluoromethoxy, methyl-thio, ethylthio, methylamino, ethylamino or dimethyl-amino, R2 represents hydrogen, R3 represents chlorine, methyl, ethyl, trifluoromethyl, methoxy, ethoxy, difluoromethoxy, methylthio, ethylthio, methylamino, ethylamino or dimethylamino, R4 represents hydrogen, amino, fluorine, chlorine, bromine, methyl, trifluoromethyl, methoxy, methylthio, methyl-sulphinyl, methylsulphonyl, acetyl or methoxycarbonyl and R5 represents hydrogen, or represents methyl, ethyl, n- or i-propyl, n-, i- or s-butyl or n-, i- or s- pentyl, each of which is optionally substituted by fluorine and/or chlorine, or represents methoxymethyl, methoxyethyl, ethoxymethyl, ethoxyethyl, methylthiomethyl, methyl-thioethyl, ethylthiomethyl, ethylthioethyl, methyl-sulphinylmethyl, ethylsulphinylmethyl, methylsulphonyl-methyl or ethylsulphonylmethyl, or represents cyclobutyl, cyclobutylmethyl, cyclopentyl, cyclopentylmethyl, cyclopentenylmethyl, cyclohexyl, cyclohexenylmethyl, phenyl, benzyl, phenylethyl, furyl, furylmethyl, thienyl, thienyl-methyl, tetrahydrofuryl or tetrahydrofurylmethyl, each of which is optionally substituted by fluorine, chlorine and/or methyl, or a salt thereof.

4. A compound of the formula (Ia) (Ia) R1, R2, R3, R4 and R5 have the meanings given in claim 3, or a salt thereof.

5. The compound N-(4-methoxy-6-methyl-pyrimidin-2-yl)-N'-(2-propionyl-phenylaminosulphonyl)-urea of the formula

6. A compound of formula I as defined in claim 1 wherein R1 and R3 are each -OCH3, R2 and R4 are each hydrogen and R5 is -C2H5.

7. A herbicidal composition comprising a herbicidally effective amount of a compound according to any one of claims 1 to 6 in admixture with a suitable carrier or diluent.

8. A herbicidal composition comprising a herbicidally effective amount of a compound according to any one of claims 1 to 6 in admixture with a solid diluent or carrier, a liquified normally gaseous diluent or carrier, or a liquid diluent or carrier containing a surface active agent.

9. A method of combating weeds which comprises applying to the weeds, or to a habitat thereof, a herbicidally effective amount of a compound according to any one of claims 1 to 6.

10. A method of combating weeds which comprises applying to the weeds, or to a habitat thereof, a herbicidally effective amount of a composition containing a compound according to any one of claims 1 to 6 in admixture with a suitable carrier or diluent.

11. A method of combating weeds which comprises applying to the weeds, or to a habitat thereof, a herbicidally effective amount of a composition containing between 0.1 and 95% by weight of a compound according to any one of claims 1 to 6 in admixture with a suitable carrier or diluent.

12. A method of combating weeds which comprises applying to the weeds, or to a habitat thereof, a herbicidally effective amount of a composition containing between 0.5 and 90% by weight of a compound according to any one of claims 1 to 6 in admixture with a suitable carrier or diluent.

13. A method of combating weeds which comprises applying to the weeds, or to a habitat thereof, a herbicidally effective amount of a compound according to any one of claims 1 to 6 wherein the compound is applied as a pre-emergence herbicide.

14. A method of combating weeds which comprises applying to the weeds, or to a habitat thereof, a herbicidally effective amount of a compound according to any one of claims 1 to 6 wherein the compound is applied as a post-emergence herbicide.

15. A method of combating weeds which comprises applying to the weeds, or to a habitat thereof, a herbicidally effective amount of a compound according to any one of claims 1 to 6 wherein the compound is applied to an area of cultivation at a rate of between 10 g and 10 kg/ha.

16. A method of combating weeds which comprises applying to the weeds, or to a habitat thereof, a herbicidally effective amount of a compound according to any one of claims 1 to 6 wherein the compound is applied to an area of cultivation at a rate of between 50 g and 5 kg/ha.

17. A process for preparing a compound of formula I as defined in claim 1, wherein R1, R2, R3, R4 and R5 are as defined in claim 1 which process comprises reacting an aminopyrimidine of the formula (II) (II) in which R1, R2 and R3 have the meaning given in claim 1, with chlorosulphonyl isocyanate, and the chloro-sulphonylurea of the general formula (III) so obtained (III) in which R1, R2 and R3 have the meaning given in claim 1, is reacted with an arylamine of the general formula (IV) (IV) in which R4 and R5 have the meaning given in claim 1, and, where required, forming a salt thereof.

18. A process for preparing a herbicidal composition comprising admixing a compound of the general formula (I) according to any one of claims 1 to 6 together with an extender and/or surface-active agent.