CA2129528C - Herbicidal n-[(pyrimidin-2-yl)aminocarbonyl]-benzenesulfonamides - Google Patents

Abstract

Herbicide N-[(pyrimidin-2-yl)aminocarbonyl] benzene sulphonamides of general formula I, wherein the substituents represent the following: R1 represents methyl or ethyl; R2 represents hydrogen or methyl; R3 represents optionally substituted alkyl; or a group ER6; in which E stands for O or S, and R6 represents optionally fluorine-susbtituted alkyl except difluoromethoxy or, if E represents O and simultaneously, R5 represents trifluoromethyl, can represent methyl sulphonyl, ethyl sulphonyl, trifluoromethyl sulphonyl; allyl sulphonyl, or propargyl sulphonyl; or NO2 or OH; or a dialkyl group, if R5 represents fluorine; or a C1-C2- alkyl sulphonyl group which can contain 1-3 halogen atoms; R4 represents hydrogen, methyl, ethyl, methoxy, ethoxy, fluorine, chlorine, methylthio, ethylthio, or C1-C2-halogen alkoxyl; R5 represents fluorine or trifluoromethyl, as well as their environmentally acceptable salts and process for their manufacture and their use.

Description

Herbicidal N-ftgvrimidin-2-yl]aminocarbonyll benzenesulfonamides The present invention relates to N-[(pyrimidin-2-yl)aminocarbonyl]benzenesulfonamides of the general formula I

II
SO2--NH--C-I~ --C/
N- I

ORi where R1 is methyl or ethyl;
R' is hydrogen or methyl;
R3 is Cl-C,-alkyl which may carry from one to three methoxy groups or fluorine atoms;
or R3 is a group ER6 in which E is O or S, R6 being C1-C2-alkyl, which may carry from 1 to 3 or 1 to 5 fluorine atoms, with the exception of difluoromethoxy, and, if E is O and at the same time R5 is trifluoromethyl, R6 may furthermore be methylsulfonyl, ethylsulfonyl, trifluoro-methylsulfonyl, allylsulfonyl or propargylsulfonyl;
N02 or OH;
or R3 is di-C1-C3-alkylaminosulfonyl if R5 is fluorine;
or R3 is C1- or C2-alkylsulfonyl which may carry 1-3 halogen atoms;
R° is hydrogen, methyl, ethyl, methoxy, ethoxy, fluorine, chlorine, methylthio, ethylthio or C1-Cz-haloalkoxy;
and Rs is fluorine or trifluoromethyl, and their environmentally compatible salts.
The present invention furthermore relates to a process for the preparation of the compounds I and to their use as herbicides.
The prior art includes a number of patents which relate to sulfonylureas having a herbicidal action.
EP-A 44 808 lists the compounds A -D in the form of a table, without further characterization.
OCH3 A: R1 - CFA; RZ - OCF2C1 N B: R1 - F; RZ - OCF2C1 SOZNHCONH---~/ ~ C : Rl - CF3 ; R2 - OCHF2 1 0 N - D: R1 - F; RZ - OCHF2 The sulfonylurea E is mentioned in EP-A 44 807, likewise without physical characteristics.

N
SOzNHCON'H--~/ ~ E
N

EP-A 338 424 describes methyl benzoates, for 20 example F.

N
SOZNHCONH ~---~/
N- F
ocH3 DE-A 39 00 472 relates to benzoates and benzamides and o-halogen-substituted sulfonylureas, for example having the structures G-I.

2a R~

G : Rl - C02CH3 ; R2 - H
N H: Rl - C1; RZ - H
S02NHCONH--~~
N - I: R1 - CON(CH3)Z; RZ - 3-F

EP-A 101 308 describes higher sulfones, for example J-M.

, ~~~~~~V
-' '3 ° Ooze o05 43041 ~-~ ~~rSO Rl ' OR2 J : ~C' ~ xs-i:3lH~; R~ ..., ~;~3 it : Rl - CH ( CH3 ) CHaCH~ ; RZ - CHI
N .
S02NHCONH----~/ ~ L: Rl ~ CH? --!~ , RZ ~ CH3 N '° M: R1 - C(CH3)3; RZ ' C2Hs F
US-s 4 120 691 (DS-A 27 15 786) mentions the sulfonylureas N and O.
C1 OCH3 .
N
SQ2NHCONH---~~ ~ N
N - a N
S02NHCONH--~/
CH; N -U.S. Patent 4,310,346 discloses sulfonamides havia~g the structure P.
so2N a ocH3 s ~02NHCONH-~-~/ ~ P
CFA
bim~thgrlcarba~noyl-substituted sulfonylureas havi.r~g the etructur~ R
' pS02N (CHg3 2 OCH~
~ N
S02NHCONH---~, N_ are disclosed in U.S. Patent 4,515,624.
Sulfonylurea derivatives substituted by fluoro-alkoxy, sulfamoyl, aeyl or alkyl in the ortho position of the phenyl radical are represented by general structural formulae in EP-A 173 312, US-B 4 515 624, US.-U 4 425 153 i i and EP-A 44 209, respectively, without any detailed information on specific structures.
The earlier German Applications DE40 38 430A of December 1, 1990 and DE 41 05 518 A of February 22, 1991 describe herbicidal sulfonamides which, compared with the novel compounds, have different substituents in the ortho position of the phenyl radical and/or in the 3/5 posi-tions of the triazine radical.
It is an object of the present invention to synthesize sulfonylureas which have improved properties compared with the known members of this herbicide class.
We have found that this object is achieved by the N-[(pyrimidin-2-yl~aminocarbonyl]benzenesulfonamides of the formula I which are defined at the outset.
In view of their intended use, suitable sub-stituents are, for example, the following radicals:
Rl is methyl or ethyl;
R~ is hydrogen or methyl;
R' is C1-C'-alkyl, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl or tert-butyl, which may carry from one to three methoxy groups or fluorine atoms;
a group ER6 in which E is 0 or S, R6 being C1-CZ-alkyl, which if R6 is methyl may carry 1 to 3 fluorine atoms and if R6 is ethyl may carry 1 to 5 fluorine atoms, with the exception of difluoromethoxy, and, if E = 0 and at the same time RS - trifluoromethyl, R6 may furthermore be methylsulfonyl, trifluoromethylsulfonyl, ethylsulfonyl, allylsulfonyl or propargylsulfonyl;
NOZ or OH;
di-(C1-C,-alkyl)aminosulfonyl, such as dimethylamino-sulfonyl or diethylaminosulfonyl if RS is fluorine;
C1-CZ-alkylsulfonyl, such as methylsulfonyl or ethyl-sulfonyl, where up to three hydrogen atoms may be replaced by halogen atoms;
R' is hydrogen, methyl, ethyl, methoxy, ethoxy, fluorine, chlorine, methylthio, ethylthio or C1-Cz-haloalkoxy such ~l~~~h~
- 5 - O.Z. 0050/43041 as t.~ra.f~.uorome~thoxy or difluoromethoxy; and RS is fluorine or trifluoromethyl.
Halogen is in general fluorine, chlorine, bromine or iodine, in particular fluorine, chlorine or bromine.
~ Compounds with Rl = methyl and R~ = hydrogen are preferred.
Preferred definitions of R3 are: methylsulf onyloxy, trifluaromethyl, trifluoromethoxy, thiomethyl, vitro, methylsulfonyl, ethylsul'fonyl, methoxymethyl and P1,~1-dimethylsulfamoyl.
Particularly preferred compounds I arise as a result of the following combinations of radicals:
a) Rl = methyl, Ra, R° = H, R3 = methylsulfonyloxy, RS = . .
trifluoromethyl;
b) R1 - methyl, R2, R~ = H, R3 - trifluoromethyl, Rg = ,' trifluoromethyl or fluorine;
c); Rl = methyl, R2, R° ° H, R3 = trifluoro~nethoxy, RS =
trifluoromethyl or fluorine;
d ) R~ _ methyl, R2 ~ H, R~ = thiomethyl or methoxy, R° _ s-methyltha:o, R5 - trifluoromethyl or fluorine;
a) RL - methyl, R2, R° - H, R3 - methoxymethyl, RS - .
trifluoromethyl or fluorine;
f) Rs _ methyl, Rz, R° - H, R3 = vitro, RS = trifluorome-thyl or fluorine;
g) Rl methyl, R28 R° - H, R' - methyl- or ethylsul f~nyl, RS _ tra:fluorc~methyl or fluorine;
h ~ . R' - in~thyl, R2, R4 = g, R3 = fit, I~-dimethylsulfamoyl, ~5 ~ fluorine The novel su3.fonylureas of the formula I are obtainable by various methods which.are described in the literature. Particularly advantageous methods (A-D) are described in detail below by way of example~

~ ~~~~.~~~
- ? - o.z. 0050/43041 I~,a . ~~ s~slfo~ay:E isocyaa~aate l.:t is x~eac;c~ri xri a cc~ar~r~sax-,'g,'x. ..
tional manner (EP-A-162 723) with about the stoichio-metric amount of a 2-aminopyrimidine derivative III at from 0 to 120°C, preferably from 10 to 1.00°C. The reaction can be carried out under atmospheric pxessure or superatmospheric pressure (up to 50 bar), preferably at from 1 to 5 bar, continuously or batchwise.,..,.
Solvents and diluents which are inert under the particular reaction conditions' are advantageously used for the reactions. Examples of suitable solvents are halohydrocarbons, in particular chlorohydrocarbons, eg.
tetrachloroethylene, 1,1,2,x- or 1,1,1,2-tetrachloro-ethane, dichloropropane, methylene chloride, dichloro-butane, chloroform, chloronaphthalene, dichloro-naphthalene, carbon tetrachloride, 1,1,1- or 1,1,2-trichloroethane, trichloroethylene, pentachloroethane, o-, m- or p-difluorobenzene, 1,2-dichloroethane, 1,I-dichloroethane, 1,2-cis--dichloroethylene, chlorobenzene, fluorobenzene, br~iaobenzene, iodobenz~ne, o-, m- or p-dichlorobenzene, o-, p- or m-dibramobenz~ne, o-, m- or p-chlorotoluene or 1,2,4-trichlorobenzene; ethers, eg.
ethyl propyl ether, methyl: tert-butyl ether, n-butyl ethyl ether, di-n-butyl. ether, diisobutyl ether, diiso-amyl ether, dii~opxoplrl ether, anisole, phenetole, ~yclohexyl,methyl ethero diethyl ether, ethylene glycol da.~ethyl ether, tet~ahyelrofuran, dioxan~, thioanisole or a.~:-dichlvr~die~hyl ~tlaer; nitrohydrocarbons, such as :.:;
raitrometlaane, nitr~ethane, . nitrobenzene, o-, m- or p--chlbronitr~benzene or o~nitrotoluene; nitriles, such as acetonitrile, btttyronitrile, isabutyronitrile, benzo-nitrile or m-chlorobenzonitrile; aliphatic or cyclo-aliphatic'hydrocarbons, eg. heptane, pinane, nonane, o-,.
m- ~r p-cyr~ene, gasoline fractions boiling within a range froze: 70 to 190°C, cycloh~xane, azaethylcyclohexane, decalin, petroleum ether, hexane, naphtha, 2,2,4-tri-methylpentane, 2, 2, 3~triaa~ethylpentane, 2, 3, 3-tra.methyl-Pehtane or octane; esters, eg. ethyl acetate, ethyl ,. .
y r .. ~, f..::
1 3..
a a0...
T , r!. -,.
f . .
n.. "5 1.
i.., :.
Y ..
..:. . , : ., . .;.. ~, ..::. . , ~ ~;.. .: ,.
. . i.
f s ..1 ~ Y''P,:
'..9 ~. ;h, r w. :~i.:. , .. . ,.. . /. ~ . ... ., . .,... .. .....w . G ,.-.~.. ......,... . ~
_>.r.~....".. ...,.,. w....r. .. , ., , .:

... ... .,,,.... ...,. . ,.. ,,, ... .. ..... .... ..... . .
' - 8 -' OeZ. 0050!43041 acetaacetate or ~.sobuty~. acetate; amides, eg. for~~amide, "fir.
methylformamide or dimethylformamide; ketones, eg.
acetone or methyl ethyl ketone, and corresponding mix-tutee. The solvent is advantageously used in an amount of from 100 to 2, 000, preferably from 200 to 700, ~ by wei.c~ht, based on the starting material II.
The compound II required for the,reaction is generally used in about equianolar amounts (for example from 80 to 120, based on the particular starting mater-7.0 ial TII). The starting material ITT in one of the above-mentioned diluents may be initially taken and the start-ing material II then added:
However, the process for the preparation of the novel compounds is advantageously carried out by initial I5 ly taking the starting material II, if necessary in one of the abovementioned diluents, and then adding the starting material III:
To terminate -the reaction, stirring is carried out for a further 20 ma.nutes to 24~ hours at from 0 to 20 120°C, p=eferably from 10 t~ 100°C, after the addition of the components.
A. tertiary amine, eg: pyridine, a,~i-y-picoline, 2,4- or 2,6-lutidine, 2,4,6-collidine, p-dimethylamino-py~idi.ne, trimethylamine, triethylamine, tri-n-propyl-25 amine, 1,4-diaza[22.2,bi:cyclooctane [DABCO~ or l,8-diazabicycto[5:4.0~undec--7.~ene, gay advantage~usly be used as a reaction accelerator, in an amount of from 0.01 to l mol per mol of starting material IT.
The end product I is isolated from the reaction 30 mixture in a conventional manner, for example by distil ling off solvents or directly by filtration unde~c suc tion.' The residue can be washed with water or dilute.
amid to remove basic impurities: However, the residue can also be dissolved in a water-immiscible solvent and 35 waahed in the manner desdribed. The desired end products are obtained Mere in pure form; if necessary, they can be purified by recrystallszation, stirring in an organic ~~.~~~2~~
- Oa~e 0050!43041 solv~~t.yahich takes up the impurities or chromatography.
This reaction is preferably carried out in aceto- , nitrite, methyl tent-butyl ether, toluene or methylene chloride, in the presence of from 0 to 100, preferably from 0 to 50, molar equivalents of a tertiary amine, such y as 1,4-dia~abicyclo[2.2.2]octane or triethylamine.
B: A corresponding suifonyl carbamate of .:the formula IV is reacted in a conventional manner (EP-A-120 814, EP-A-101 407), in an inert o~ga~ic solvent at from 0 to 120°C, preferably from 10 to 100°G, with a 2-amino pyrimidine derivative III. Bases, such as tertiary aanines, may be added here, with the result that the , reaction is accelerated and the product quality improved.
Suitable bases for this purpose are, for example, tertiary amines as stated under A, in particular tri ethylamine or 1,4-diazabicyclo~2.2.2]octane, in an amount of from 0.0I to 1 mot per mot of starting material IV. .
Advantageously used solvents are those stated under A.
The solvent is used in an amount ~f from 100 to 2, 000, preferably from 200 to ?00, ~ by raeight, based on .
the starting material IV.
The compound IV required for the reaction is used in general in about equimolar amounts (for example from 50 to'120%, based on the particular starting material III). The starting material IV in one of the above-mehtz~ned diluents may be initially taken and the start-ing material ILI then added.
gowever, the starting material III in one of the stated solvents or diluents may also be initially taken and the sulfonyl carbamate, IV added.. , In both cases, a base may be added as a catalyst hefore or during the ruction.
The end product I can be obtained from the reaction mixture in a conventional manner, as stated under Ao A sulfonamide of the formula V is .reacted in a .-.-.... ~emrr..ww.. ,. .....,.,.:.J.3'.-.,. ...:iJ. , ....J.~:~Y. . .r.:":j ,4~.~.:~... . < t;:...

~~:~~~~~
- 10 - O.Z. 0050/43041 conv.~ntional manner (Ep-A-141 777 and EP-A-101 670), in an inert organic solvent, with about the stoichiometric amount of a phenyl carbamate VI at from 0 to 120°C, preferably from 20 to 100°C. The reaction can be carried out at atmospheric or superatmospheric pressure (up to 50 bar), preferably at from 1 to 5 bar, continuously or batchwise.
Bases such as tertiary amines, which accelerate the reaction and improve the product quality, may be ZO added here. Suitable bases for this purpose are those stated 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 (DHU), in an amount of from 0.01 to 1 mol per mol of starting material V.
Advantageously used solvents or diluents are those stated under A:
The solvent is used in an amount of from 100 to 2,.000, preferabl~t from 200 to ?00, ~ by weight, based on the starting material V:
The compound V'required for the reaction is used in general in about equimolar amounts (for example from to 120%, based on the particular starting materials VI). The starting material VI in one of the above mentioned diluents may be initially taken and the start ing material V then added:
However,, the starting' material; V in one of the stated solvents may also be initially taken and the carbamate VI then added. In both cases, one of the stated bases may be added as a catalyst before or during 3~ the reaction.
To terminate, the reaction, stirring is earrie.d out for a further 20 minutes to 24 hours at from 0 to I20°C, preferably from 10 to 100°C, in particular from 20 to 80°C, after the addition of the components.
The sulfonylureas of the formula I are isolated from the reaction mixture by conventional. methods as described under A.

D: ~ sulfonamide of the formula V is reacted in a conventional manner (EP-A-234 352), in an inert organic solvent, with about the stoichiometric amount of an iso-cyanate VII at from 0 to 150°C, preferably from 10 to 100°C. The reaction can be carried out under atmospheric or superatmospheric pressure (up to 50 bar), preferably at from 1 to 5 bar, continuously or batchwise.
Bases such as tertiary amines, which accelerate the reaction and improve the product quality, may be added before or during the reaction. Suitable bases for this purpose are those stated under A, in particular triethylamine or 2,4,6-collidine, in an amount of from 0.01 to 1 mol per mol of starting material V.
Advantageously used solvents are those stated under A. The solvent is used in an amount of from 100 to 2,000, preferably from 200 to 700, % by weight, based on the starting material V.
The compound V required for the reaction is used in general in about equimolar amounts (for example from 80 to 120$, based on the starting materials VII). The starting material VII in one of the stated diluents may be initially taken and the starting material V then added. However, the sulfonamide may also be initially taken and the isocyanate VII then added.
To terminate the reaction, stirring is carried out for a further 20 minutes to 24 hours at from 0 to 120°C, preferably from 10 to 100°C, in particular from 20 to 80°C, after the addition of the components. The end product I can be obtained from the reaction mixture in the conventional manner, as described under A.
The sulfonyl isocyanates of the formula II which are required as starting materials can be obtained in a conventional manner from the corresponding sulfonamides by phosgenation (Houben-Weyl 11/2 (1985) 1106, US 4 379 769 ) or by reacting the sulfonamides with chloro sulfonyl isocyanate (German Laid-Open Application DE 3,132,944).
The sulfonamides of the formula V can be obtained ~1 ~3~~~~
- 12 - .O.Z. 0050/43041 by r~ae:~ing the correspondling sulfon~r:l chlorides w.~th ammonia ,,(M. Quaedvlieg in Houben-Weyl, Methoden der organischen Chemie, Georg Thieme Verlag, Stuttgart, 9_ (1955), 398-400, F. Muth, ibid., 605 et seq.j. However, it is also possible for an o-halobenzenesulfonamide to be.
subjected to a nucleophilic substitution reaction, for example with an alcohol or thiol, and, for,example, far the resulting corresponding thioether to be oxidized to the sulfoxide or sulfone (cf. process examples).
The corresponding sulfonyl chlorides for pregara-Lion of the sulfonamides of the formula V are obtained in general by a Meerwein reaction (diazotization of suitable . y amides and sulfochlorination with sulfur dioxide under catalysis by a copper salt: F_. Muth in Houben-Weyl, 15. Methoden der organischen Chemie, Georg Thieme Verlag, Stuttgart, ~ (1955), 579, S. Pawlenko in Houben-Weyl,' Methoden der organischen Chemie, Georg.Thieme Verlag, Stuttgart, Vol. E 11/2 (1985), 1069), from the corres ponding sulfonic acids (F~ Muth in Houben-Weyl, Methoden der organischen Chemie, Geo~rg Thieme Verlag, Stuttgart, 9 ( 1955 j , 564 j , by chlorosulf ovation of suitable aromatic intermediates (F. Muth, ibid:, page 572) or by oxidative chlorination of Iow-valence sulfur intermediates (mercap-tan$,'diaryl disulfides or S-benzylmercaptansj (F. Muth, iba.d., page 580, S. Pawlenko, Ioc. cit., page 1073).
The sulfonyl carbamates of the formula IV were prepared by conventional reactions or'similarly to such reactions (for example EP-A 120 814'. However, the sulfvnyZisocyanates of the formula II, i.n an inert solvent, such as ether or:dichloromethane, can also be donverted with phenol into;the carbamates,of the formula IV.
Carbamates of'the formula VI are obtainable by known reactions or similarly to such reactions (for exampl~ EP-A 101 670), but can also be prepared from the .corresponding isocyanates VII by reaction with phenol.
The isocyanates of the formula VII are obtained ( N
~~< ~~~~
- 13 - O.Z. 0050/43041 from the amines of the formula~III by treatment with oxalyl chloride or phosgene (similarly to Angew. Chem. 83 (1971), 407 or EP-A 388 873).
The synthesis of 2-amino-4-fluoro-6-methoxy pyrimidine and 2-amino-4-ethoxy-6-fluoropyrimidine is disclosed in DE-A-39 00 471.
2-Amino-4-chloro-6-trifluromethylpyra.midine is known from the literature (J. Heterocycl. Chem. 20 (1983), 219). The 4-alkoxy-2lamino-6-trifluoromethyl-pyri.midines III (Rl ~ methyl or ethyl; Rs - Vii) can be obtained from this intermediate by reaction with corres-a ponding alcoholates (cf. process examples).
. 4-Methoxy-2-methylmercapto-6-trifluoropyrimidine (J. Heterocycl. Chem: 20 (1983), 219) can be converted with HzO2 into the 2°methylsulfone, which is reacted with amines and hydroxylamines to give the starting materials of the general formula III (cf. process examples).
The salts of the compounds I are obtainable in a conventional manner (EP-A-304 282 or US-A 4,599,412).
They are obtained by deprotonation of the corresponding sulfonylureas I in water or i~ an inert organic solvent at from -80 to 120°C, preferably from 0 to 60°C, in the presence of a tease: .
Examples of suitable bases are alkali metal or alkaline earth,metal hydroacides, hydrides, oxides or alcoholates,.such as sodium hydroxide, patassium hydrox ide, lithium hydroxide, sodium methylate, sodium ethylate, sbdium tert-butylat~, sodium hydride, calcium hyd~:ide or calcium.-oxide.
,. ,.
..~, ..
.r :. ,. ,; ,. - ....' . ; .~:., z . ,:,;_.... ..' , . , '; r., ",,~.... ..._r..r:.. .. ..:.,,..:.~. ~.:~~....:,.... ...,.~..~ ~ ,. . ~
.,:.:,,.,.,., f , ., ~~.~~J~c~
~eZe ~~50/43041 -..Lxamples of suitable solvents in addition to .~tx. ' water are alcohols, such as methanol, ethanol and tent-butanols, ethers, such as tetrahydrofuran and dioxane, acetonitrile, dimethylformamide, ketones, such as acetone and methyl ethyl ketone, and halahydrocarbonse The deprotonation can be carried out at atmos-pheric pressure or at up to 50 bar, preferably at from atmospheric pressure to 5 bar gage pressure.
The compounds I or tie herbicides containing them, and their environmentally compatible salts of alkali metals and alkaline earth metals, can very readily control weeds in crops such as wheat, rice and corn,, without damaging the crops, an effect which occurs in particular at low application rates. They can be used, for example, in the form of directly sprayable solutions, powders, suspensions, including concentrated aqueous, oily or other suspensions or dispersions, emulsions, oil .
dispersions, pahtes, dusts, broadcasting agents or granules, by spraying, nebulizing, dusting, broadcasting or pouring. The application forms depend on the ~.ntend~d uses; they should in'any'case ensure vei°y fine distribu-tion of the nswel activ~'ingredients:
The compounds' I are suitable in general for the preparation of directly sprayable s~lutions, emulsions, pastes or' oil dispersions. Suitable inert additives include mineral oil fractions having s medium to high bailing p~int, such as kerosene or diesel oil, and coal tar oils and oils of vegetable or animal origin, alipha-tic, cyclic and aromatic hydrocarbons, eg. toluene, x~tlene, paraffan, tetrahydronaphthalene, alkylated naphthalenes or derivatives thereof, methanol, ethanol, propanol; butanol, cyclohexanol, cyclohexanone, chloro benxene, isophorone ~r strong polar solvents, such as N, I~i-dimethylf ormamide, diethyl sulfoxid~, N-methyl pyrr~lidone or wai:~r:
l~queous application forms can be prepared from emulsion concentrates, dispersions, pastes, wettable _ ___ ..... _. ...... _._. ..... ... .. . , . .. . .. . , .. ... . .. . ... ..
.:.~....... :~..,..-..,.f:..,. ~ .~....,.~~ .. ... .. , .~.,.._. . ..

- 15 - p.Z. 0050!43041 .. ~rnwa~e~g ~r,r ~r~atcexwdi~cpers~in:~e g~ca~x~u:~e~ ri~r a,dd~.r~g w~:x~;e~
.six. ~.
For the. preparation of emulsions, pastes or oil diaper-s~.ons, the substances, as such or dissolved in an oil or solvent, can be homogenized in water by means of Wetting agents, adherents, dispersants or emulsifiers. Sowever, concentrates which consist of active ingredient, wetting agents', adherents, dispersants or emulsifier"s and pos-sibly solvents or oil and which are suitable far dilution with water can also be prepared.
lU Suitable surfactants are the alkali metal, alkaline earth metal, amacnonium salts of aromatic sulfonic acids, for example lignin-, phenol-, naphthalene- and dibutylnaphthalenesulfonic acid, and of fatty acids, alkyl- and alkylarylsulfonates, alkylsulfates, laur~rl ether sulfates and fatty alcohol sulfates, and salts of sulfated hexa-, hepta- and octadecanols, and of fatty alcohol glycol ethers, condensates of sulfonated naph-thalene and its derivates with formaldehyde, condensates of naphthalene and of naphthalenasulfnnic acids with phenol and formaldehyde, polyoxyethyle~ne oetylphenol ether, ethoxylated isc~octyl~, octyl- os nonylphenol, alkylphenol polyglycol-ether, tributglphenyl polyglycol eth~r, alkylaryl polyether alcohols, isotridecyl alcohol, fatty alcohollethylene oxide condensates, sthoxylated castor oil, polyoxyethylene alkyl ether or polyoxy-propylene, lauryl- alcohol polyglycol ether acetal, sarbit~1esters, lignineulfite v~aste liquors or methyl.dellulose.
Powders, broadcasting agents and dusts can be 30- p~egared by mixing or milling the active ingredients together with a s~lid Barrier.
Granules, for example coated, impregnated and hog~geneous granules can be prepared by binding the active ingredients to solid carrier. Solid carriers are ~u:neral acids, such as silicas, silica gels, silicates, talc, kaolin, limestone, lime, chalk, bole, loess, clay, do~.omite, kieselguhr, calcium sulfate, magnesium sulfate, magnesium oxide, milled plastics, fertilizers, such as ammonium sulfate, ammonium phosphate, ammonium nitrate and ureas, and vegetable products, such as grain flour, bark meal, wood meal and nutshell meal, cellulosic powders or other solid carriers.
The formulations contain in general from 0.01 to 95, preferably from 0.5 to 90, °s by weight of active ingredient.
It is worth mentioning that a definition of each chemical compound identified by a specific compound number hereinbelow (i.e. compound N° 1) can be found in Table 1 on pages 26 to 28 of the present specification.
Examples of formulations are:
I. 90 parts by weight of compound No. 1 are mixed with 10 parts by weight of N-methyl-a-pyrrolidone, and a solution which is suitable for use in the form of small drops is obtained.
II. 20 parts by weight of compound No. 2 are dis-solved in a mixture of 80 parts by weight of xylene, 10 parts by weight of the adduct of from 2 0 8 to 10 mol of ethylene oxide with 1 mol of N-monoethanololeamide, 5 parts by weight of the calcium salt of dodecylbenzenesulfonic acid and 5 parts by weight of the adduct of 40 mol of ethylene oxide with 1 mol of castor oil. By pouring the solution into 100, 000 parts by weight of water and finely distributing it therein, an aqueous dispersion which contains 0 . 02 % by weight of the active ingredient is obtained.
III. 20 parts by weight of compound No. 7 are dissolved in a mixture Which consists of 40 parts by weight of cyclohexanone, 30 parts by weight of isobutanol, 20 parts by weight of the adduct of 7 mol of ethylene oxide with 1 mol of isooctylphenol and 10 parts by weight of the adduct of 40 mol of 16a ethylene oxide with 1 mol of castor oil. By pouring the solution into 100,000 parts by weight of water and finely distributing it therein, an aqueous dispersion which contains 0.02% by weight of the active ingredient is obtained.
IV. 20 parts by weight of active ingredient No. 8 are 2~.~~~~8 . _ ~,7 _ l7. Z . 005 ~ .. dissolved in a mixture which consists of 25 pasts ~'g~ x ~ ~
. by weight of cyclohexanone, 65 parts by weight of a mineral oil fraction boiling within a range from 230 to 280~C and 10 parts by weight of the adduct of 40 mol of ethylene oxide with 3 mol of castor oil. ~y pouring the solution into 300,000 parts by weight of water and finely, distributing it therein, an aqueous dispersion which contains 0.02% by weight of the active ingredient is 30 obtained.
V. 20 parts by weight of active ingredient ~to. 34 are thoroughly mixed with 3 parts by weight of ' the sodium salt of diisobutylnaphthalene-a--sulfonic acid, 37 parts by weight of the sodium 35 salt of a ligninsulfonic acid obtained from a sulfite waste liquor and 60 parts by weight of silica gel powder, and the mixture is milled in a ha~uner x.11: ~y finely distributing the ~.xture in 20,000 paste by weight of water, a 20 spray liqu~~ which contains 0.3~ by wea.ght of the active ingredgert i~ obtained.
VI. 3 parts by 'aei~ht of active ingredient ~Io. 27 are mixed with 97 parts by weight of finely divided ka~lin. pr dust which contains 3~ by weight of 25 the active ingredi~n~ is obtained in this manner.
Y~~. 30 p.$rts by weight of active ingredient No. Z0 ire tlaor~ughly ~t3.xed pith a anixtnre ~f 92 parts ~
~y soaeight of sil~.ca gel powder and 8 parts by weight of liquid paraffin, which was sprayed onto 30 the surface of the silica gel. A preparation of the active ingred~.ent having good adhesion is ~btained in this manner.
Vf~.T. 20 parts by weight of active ingredient No. 3 are thoroughly ynixed with 2 parts by weight of the 35 calcium salt of dodecylbenzenesulfonic acid, 8 parts by wegght of a fatty alcohol polyglycol ether, 2 parts by Weight of the sodium salt of a ~1~~~~t~
1g ~ O.Z. 0050/43041 ~~x--.~.,,phenol/urea/formaldehyde condensate and ~g parts by weight of a garaffinic mineral oil. A stable oily dispersion is obtained.
Application may be effected by the preemergence or postemergence meth~d. If the active ingredients are less well tolerated by certain crops, it is possible to use application methods in which the herbicides are sprayed with the aid of the sprayers in such a way that the leaves of the sensitive craps are as far as gossible not affected, whereas the active ingredients reach the leaves of undesirable plants growing underneath or the uncovered soil, surface (post-directed, lay-by).
The app~.ication rates of active ingredient are from 0.001 to 3, preferably from 0.01 to l, kg/ha of active ingredient, depending on the aim of control, the season, the target plants and the stage of growth.
In view of the versatility of the application methods, the novel compounds or agents containing them may also be used in a further number of crops for eli.min~
sting undesirable plants. For example, the followa.ng crops ass suitablet Botanical name Com~.non name Allium ceps onions Ananas comosus pineapples , Arachis hypogaea peanuts (groundnuts) Asparagus offic~inalis . asparagus Beta vt~lgaris spP, altissima ~ sugarbeets Beta vulgaris sppraga fodder beets Hrassica magus var. napus: rapeseed Hrassica napus var. napobrassica swedes Brassica raga var. silvestris beets Camelli.a~sinensis tea plants Carthamus tinctorius safflower Citrus limon lemons Citrus sinensis orange trees Coffee arabica (Coffee canephora, Coffee liberica) coffee plants P

19 _ O.Z. 0050/43041 Hc~ta~xxca:l name Cc~~ia~un trauae-- -"jpx. ' Cucumis.~sativus cucumbers Cynodon dactylon Bermudagrass in turf and lawns Oaucus carota carrots Elaeis guineensis . oil palms Fragaria vesca strawberr.~.es Glycine max soy beans Gossypium hirsutum (Gossypium arboreum cotton Gossypium herbaceum Gossypium vitifolium) Helianthus annuus sunflowers Hevea brasiliensis rubber plants , Hordeum vulgate barley Humulus lupulus hops Ipomoea batatas sweet potatoes Juglans regia walnut trees L~ns culinaris lentils Linum usitatiseimum' flax Lycopersicon lycopersicum tomatoes Males sPP aPPle trees -~nihot esculenta- cassava Medic:~go sativa alfalfa ( lucerne ~

Musa spp. banana plants Nicotiana abacum tobacco (N ~sticaj Olea europaea olive trees Oryza sativa rice Phaseolus lunatus limabeans Phaseolus vulgaris , ; snapbeans, green ~, beans, dry beans .

Picea abies Norway spruce Pines'sPP pine trees Pisum sativum gnglish peas Prunes avium cherry trees - Prunes persica peach trees Gd eJ v W l _ ~.Z. 0050/43041 I~otani:cal name - ~'°mu~on name ----T~yrus communis pear trees Ribes sylvestre redcurrants Ribes uva-crisps gooseberries Ricinus communis castor-oil plants Saccharum officinarum sugar cane Secale cereals rYe . ...
Solanum tuberosum Trish gotatoes Sorghum bicolor (S. vulgare) ' sorghum Theobroma cacao cacao plants Trifolium pretense red clover Triticum aestivum wheat Triticum durum durum wheat Vicia faba tick beans Vitis vinifera grapes Zea ways Indian corn, sweet corn, mal2e In order to broaden the action spectrum to achieve synergistic effects, the pyrimidinyl-substituted sulfonylureas of the fonaula I can be mixed and applied together with many members of other herbicidal or growth-regulating groups of active ingredients. For example, dia2inee, 4H-3,1-benzoxaza.ne derivatives, ben2othia-diazinones, 2,6-dinitsoanilines, N-phenylcarbamates, thiocarbamates, halocarboxylic acids, triazines, amides, ureas, diphenyl.ethers, triazinones, uracils, ben2ofuran derivatives, cyclohexane-1,3-dune derivatives, cyuinolinecarboxylic acid derivatives, phenoxy- and hetaryloxyphenylpropionic acids and their salts, esters and amides, and ~thers, are suitable as components of the mixture .
It may also be useful to apply the compounds of the formula I, alone or in combination with other herbi-cides, also as a mixture together with further crop protection agent, for example with pesticides or agents for controlling phytopathogenic fungi or bacteria. The mi.sc~.bility with mineral salt solutions which are used ~1~.~:~
- 21 - O. Z . 0050/43041 for ~ liminating nutrient and trace element deficiencies is also, of interest. Nonphytotoxic oils and oil con-centrates may also be added.
Typical examples of the preparation of the intermediates II-VII are given below.
1. 2-Amino-4-methoxy-6-trifluoromethylpyrimidine 28.1 g of a 30% strength by weight ..,solution of sodium methylate (O. x6 mol) in methanol (internal tem-perature below 40°C) were added'dropwise to a solution of 25.? g of 2-amino-4-chloro-b-trifluoromethylpyrimidine (0.13 mot) in 200 ml of methanol. Stirring was carried out for one hour at 20-25°C, the volatile components were ' removed under reduced pressure from a water pump at 65°C, the residue was taken up in l 1 of dichloromethane, the.
solution was washed with water, the dichloromethane phase was dried over NaZSO, and the solvent was removed under seduced pressure from a water pump. 23.4 g of the product (93% of theory) were obtained as colorless crystals of melting point 208-109°C.
2-Amino-4--ethoxy-6-trifluosomethylpyrimidine of melting point 114-116°C was obtained in a similar manner by reacting 2-amino-4-chloro=6-trifluorontethylpyrimidine with sodium methylate im ethanol.
2. 4-~Iethoxy-2-methylsulfonyl-6-trifluoromethyl-Pyr~dirne ? .1 g of a 30% strength by we~.ght solution of $z02 (63 mmol) a.n water were added dropwise to ~ solution of 5.0 g of 2,4-methoxy°2-methylsulfonyl-S-trifluoromethyl-pysimidine (22 'mmol) in 50 ml of glacial acetic acid.
The mixture was heated slawly to an internal temperature of 90°C and stirred for 1 hour at ,this temperature, and, the reaction batch was cooled to 25°C and then .introduced into 2 1 of glacial acetic acid. The product was ex-traced with 200 ml of dichloromethane, the organic phase wa.~ we.shed With a dilute sodium thiosulfate solution and then with water, the solution of the product was dried over NazSO, and the solvent was removed under reduced ~~r.~~
22 - O. Z . 0050/43041 pres~ur~ from a water pump. 5. ~. g of the product ( ~0% of .~x~ ' . ' theory'. were obtained as colorless crystals of melting point 88-90°C.
3. 2-(~I-Methoxyamino)-4-methoxy-6-trifluoromethyl-pyrimidine 66.6 g of a 1.6 molar solution of n-butyllithium ( 0 .156 mol j in n-hexane were added dropwise to a solution of 6.5 g of O-methylhydroxylammonium chloride (?8 mmolj in 200 ml of tetrahydrofuran ~at -ZO°C. Stirring was carried out for I0 minutes at -10°C, and 20 g of 4-methaxy-2-methylsulfonyl-6-trifluoromethylgyrimidine (?8 mmol) were added to the cloudy solution. Stirring ' was carried out for 1 hour at 25°C, the reaction batch was introduced into 200 n1. o~ water, and the organic ghase was separated off, washed with water and dried.
Removal of the solvent gave an oily, slightly impure product, which could be crystallized in pentane at -78°C.
7;,5 g of the product (43% of theory) were obtained as colorless crystals of melting point 44-46°C.

4. 2-Iaocyanato-4-methoxy-6-~rifluoromethylpyrimidine 38. 3 g of oxalyl chloride ( 0. 3 mol' were added dropwise to a suspension of 2-amino-4-methoxy-6-tri fluoramethylpyrimidine (78 mmol) in 1d0 ml of toluene.
The refluxing mixture was stirred for 4 hours, after which the homogeneous solution obtained was subjected to fractional distillation: The-title compound (9.9 g; 58%
of theory) was obtaihed as an oil of boiling point 44 ,~OoC ~~~5 mbar).

5. 4-Methoxy-2-[(phenoxycarbonyljamino~-6-trifluoro-methylpyrimidine 4.2 g of phenol (45 mmoly were added at 25°C to a solution of 9.~9'~g of 2-isocyanato-4-methoxy-6-tri-floor~methylpyrimidine ( 45 m~nol j in 50 ml caf methylene chloride. Stirring was carried out for 16 hours at 25°G, the pnethylene chloride was distilled off under reduced pressure and the residue was stirred vigorously with a00 ml of a dii opr~pyl ether/hexane mix~c~ure (v/v 2~.~~~~8 23 _ O.Z. 0050/43041 , 1 : ~l(1 j., ~,rhereupon crystallization occurred. ~'he product was filtered off with suction and dried under reduced pressure from a water pump at 50°C. The title compound (12.2 g; 87% of theory] was obtained as colorless crys-tale of melting point 85-88°C.

6. 2-(Methylsulfinyl)benzenesulfonamide 14.8 g of hydrogen perox~.de (0.13.. mol), 30%
strength in HTO, were added dropwise at from 25 to 30°C
to a suspension of 26.5 g of 2-(methylthiojbenzene-sulfonamide ( 0.13 mol ) and 2.1 g of NaTWO~ ~ 2Hz0 in 88 ml of glacial acetic acid. Stirring was carried out for 45 minutes at 25'°C, the reaction mixture was poured onto 400 ml of water and the precipitate was filtered off with suction. Tt was washed with water and dried under reduced pressure from a water pump at 40°C. 24.3 g (85%
of theory] of the title compound Were thus obtained.
1H-1NMR spectrum ( 250 MHz, CD3SOCD3, int. TMS ) : 8 .16 d (1H), 7.82-8.0 m (2H), 7.77 b= (2S), 7.63-7.85 m (2Hj, 2.76 s (3H), ? : lei- ( n-Hutylaa:ino ) carbonyl-2~methylsulfinylbenzene-sulf onamide 10.2 g of n-Butyl isocyanate (0.10 molj Were added drogwise at 25°C to a suspension of 20.1 g of 2-(methylsulfinyl ) benzenesulfonamide ( 0:09 anol j in 250 ml of acetonitrile. 13.9 g of potassium carbonate (0:10 mol) were'added, after which the refluxing mixture was stirred fo= 4 hours. After cooling to 0°C, the mixture ~aa poured onto 400 ml ice/water, brought to a pH
of ~, by adding concentrated hydrochloric acid and ex-tracted with methylene chloride. The organic extracts were washed neutral with water and dried. After removal of the solvent, 25~ g of the title compound (85% of th~oryj were obtained as a gale brown oil.
I~-NI~R spectrum (250 MHz, CDCl~, int. TMSj: 8.28 d (1B), gWaO d (lHj, 7.89 t (2Hj, 7.?3 t (1H), 6.03 t (IH), 3.13 m (2H), 2.95 s (3H), 1.38 m (2Hj, 1.24 m (2Hj, w 85 t ( 3H j .

. 212~j~8 r 24 _ O.Z. 0050!43041 ii . ' l-._( l~et~yylsu~.finyl ) be.uzenesulfonyl . ~-gocy~.ri~ate ,Phosgene was slowly passed into a refluxing solution (cooled with solid carbon dioxide) of 25 g of N
[(n-butylamino)carbonyl-2-methylsulfinyl]benzenesulfon amide and 0.4 g of 1,4-diazabicyclo[2.2.2]octane in 400 ml of xylene, until an internal temperature of 110°C
was reached. The Cooling was removed and the volatile components were distilled off under reduced pressure from a water pump at 80°C. The remaining sulfonyl isocyanate was reacted without further purification.
9. N-[(n-Butylamino)carbony!-2-(N,N-dimethylamino-sulfonyl)]benzenesulfonamide .
18.6 g of n-butyl isocyanate (0.18 mol) were added dropwise at 25°C to a suspension of 44.2 g of 2 [N,N-dimethylaminosulfonyl]benzenesulfonamide (0.17 mol) (prepared similarly to 2-[N,N-diethylamino)-sulfonyl]
benzenesulfonamide in US-B-4,310,346) in 450 ml of acetonitrile: A-fter the addition of 25.4 g of potassium carbonate (0:18 mol), the refluxing mixture was stirred for 3 hours. After cooling to 0°C, the reaction mixture was pou=ed onto 400 ml of ice/~ater andvbrought to a pH
of I by adding concentrated hydrochloric acid, and the precipitate-formed was filtered off with suction, washed neutral with water and dried under reduced pressure from a water pump at 44°C. 60 g of the title compound (99% of theory) were obtained in this manner:
1H-NMR spectrum (250 MHz, CDCl~ int. TMS): 8.55 br (1H), ~ . 30 d ( 1H ) , 8 . 05 d ( 1H ) , 7 : 7-7 . 9 m ( 1H ) , 6 . 52 t ( 1H ) , 3.17 qua (28), 2.94 s '(6H), 1.43 qui (2H), 1.25 sext (2Hj, 0:85 t (3H).
10. 2-[N,:N-(,Dimethylam~.no)sulfonyl]benzenesulfonyl isocyanate The sulfonylurea obtained in Example 9. was converted into the corresponding sulfonyl isocyanate, similarly to the preparation of 2-(methylsulfinyl) benzenesulfonyl isocyanate.
Typical examples of the synthesis of the 21~~~~~
-- 25 - O.Z. 0050143041 su~.fr~nylureas ~ and their salts are described below.
~~a'-11. 2-Nitro-1-N-[4-methoxy-6-trifluoromethylpyrimidine-2-yl)aminocarbonyl]benzenesulfonamide g of 2-nitrobenzenesulfonyl isocyanate (35 mmol) in 10 m1 of 1,2-dichloroethane were added at 25°C to a mixture of 6.7 g of 2-amino-4-methoxy-6-tri-fluoromethylpyrimidine (35 mmol) in 10 ml, ~f dichloro-methane. Stirring was carded out for 14 hours at 25°C, after which the solvent was removed under reduced pres-sure from a water pump at 40°C and the residue was stirred vigorously for 2 hours with 50 m1 of diethyl ether. The product was filtered off with suction and dried under reduced pressure from a water pump at 40°C.
3 g of the title compound (20% of theory] were obtained as colorless crystals of melting point 204-205°C. ~ v 12: Sodium 2-nitro-1-N-[(4-methoxy-6-trifluoromethyl-pyrimidin-2-yl)aminocs,rbonyl]benzenesulfonami.de 0.65 g (36 mmol) of a solution of sodium meth=
ylate (30% by weight) in methanol was added at 25°C to a ZO susgension ref 1.5 g of 2-vitro-I-N-[(4-a~eethoxy-6-tri fluoromethylpyri~nidin-2-yl)aminocarbonyl]benzn~nesulfon-amide (3:6 Col) in 20' ml of methanol. Shirring was carried nut for '10 minutes at 25 °C after which the homogeneous solution was evaporated down under reduced pressure from a water gump at 50°C: The title compound was obtained in~duantitative yield as colorless crystals having a decomposition temperature of 1.64-166°C.
13 , 2-[ [ (;~~Fluor~-6-a~ethoxyPYrimidin~2-yl ) amir~o carbonyl]aaninosulfonyl]benzenesulfonic acid N,N
dir~thygamide ~ .1 g of ~- ( diu~ethylami.no ) sulfonylbenzenesulf on~rl ;
isc~cyanate (2S mmol) ~ae~re added at 25°C to~a suspension of 4:0 g of 2-amino-4-fluoro-6-methoxypyrimidine (2~ mmol)-in 30 ml of ethylene chloride. Stirring was carried'out for 16 hours at 25°C and the precipitated product was filtered -off with suction. To eliminate unconverted pyrimidine, the precipitate was stirred ~1 ~~r~3 28 ~ O.Z. 0050/43041 wigp,~ously With diisopropyl~ether. The product was filtered off with suction, washed with n-hexane and dried at 40°C under reduced pressure from a water pump.

7.2 g (59%) of the title compound (decomposition temperature 138°C) were obtained in this manner. Further product could be isolated from the mother liquor.
1H--NMR spectrum (Z50 MHz, CD3COCD" int. TMS,.. E (gpm) ) 2.91 s (6H), 4.17 s (6H), 6.24 s (1H), 7.8-8.0 m (2H), 8.04 m (1H), 8.50 m (1H), 9.63 br (1H), 12.25 br (1H).
14. [(4-Fluoro-6-methoxypygimidine-2-yl)aminocarbonyl]-2-methylsulfonylbenzenesulfonamide 4.7 g of 2-(methylsulfinyl)benzenesulfonyl isocyanate (19 mmol) were added at 25°C to a solution of 2.7 g of 2-amino-4-fluoro-6-methoxypyrimidine (19 mmol) in 30 ml of methylene chloride. Htirring was carried out for 16 hours at 25°C, after which the precipitated product was filtered off, with suction, washed with a little ether and dried under reduced pressure from a v~rater Bump at 50°C. 0.9 g ~f the title ct~mpound ( 10% of theory) at melting 'pointc 161-176°~ was obtained in this manner: Further product could be isolated from the mother liquor.
The active ingredients stated in Table 1 below were obtained by a sinni.lar separation method.
.25 TABLE 1 R3 R~

N
SO--~~1-~6 ' ~
RZ

N
_ 2? _ 0.~. 0050/43041 AcAll~ ~1 R~ Rd r .
' ~
~n~rEd!!at Na 1 CH3 S02NICH3?ZH F 198 2 CH3 S02N(CH3j2H F 161-168"

3 CH3 S02NtCH3)2H F 184-I92"' 4 CHI OCFzCFZH H F 135-139 CH3 (~F3 H F 181-182 6 CH3 t7CF3 H . F 140146' ? CH3 N02 H F 159-16?

8 CH3 N02 H F 214"

9 CH3 SOZICZH5~2H F 206 CH; S02~C2Hg)2H F 200"

11 CHg CF3 . H F 181 12 CH3 CF3 H F 178' 13 CH3 CH3 H F 185-193 due.

14 CH3 CH3 H F 166' 1~ CH3 OCH3 H F 20?-209 16 CH3 ~H3 , H g 1?0'' Z7 CHI cF3 6-CH3 F 206=209 air.

lg CH3 CF; 6-CH3 F ~ 250*

19 CH3 N02 H CF3 204_ZOS

22 CH3 CFA H CF3 1?4-179' 23 CH3 CF3 H CF3 156-160..

24 CFi3 SOzCH3- H CF3 202-204 CH3 OSOZCH3 H CF3 19?-200 26 CND OCFZCF2H H F I64t 2? CHI SCH3 H F 192-193 28 CH3 SCH3 H F 120-135*

Na alt oo~,) (~ oomP.) a w K
alt (de ~1~~~~8 2g _ O.Z. 0050/43041 ,~,~ . R3 R4 RS trc.P. [ ~C
" _ R1 1 ~

io~dime Na "

2 9 CH; SCH; H F 2 0 5--210' 30 CH; CH~OCH3 H F 167-169 31 CH; SCH3 H CF; 163-166 32 CH3 SCH; H CF; 146-151*

33 C~HS SCH3 H CF; 172=173 34 CH; CH20CH3 H CF3 165 35 CH3 OCF; H CF; 153-154 36 CH; OCF3 H CF3 107*

37 CH; SCH; 6-SCH; CF3 190-192 , 38 CH; SCH3 6-SCH; CF; 1?4' 39 CH; SCH; 6=SCH; F 191-193 40 CH; SCH; 6-SCH~ F 186*

4I CH; OCH2CF3 5-OCHZCF; F 189-190 42 CH; f7CHZCF3 5-OCHZCF3 F 152* ~w 43 CH3 Sp2C2H5 5-Cl F 205-209 ' Na tit (dip,) a r ~d) K ~

The compounds shown can below also be obtained in a similar .
manner:

~~ o _ CF3 , N

' S0--C~-~/

NOZ F
O

R~

SOZ--NH-C-NH-~/ ~

or'the Na is salts hydrogen, thereof, 3-methyl, where R' i - 29 - a.Z. 0050!43041 4-~r~~ ~,t~y~.. W-~athy~., 6-a~~tl~yl., :i-ethyl, 4-ethyl, 5~att~y~., .,~ ~' 6-ethyl, 3-fluoro, 4-fluoro, 5-fluoro, 6-fluoro, 3-ch~.oro, 4-chloro, 5-chloro, 6-chloro, 3-~thoxy, 4-~ethoxy, 5-anethoxy, 6-anethoxy, 3-ethoxy, 4-ethoxy, S-ethoxy, 6-ethoxy or 6-methylthioP
0CH3 ~ Cg3 ...
N
s0~-~-~--C~TH
-N , ,-.
OCFi3 s OCH3 ~ g N
S02-.-NH-C-~.~!
N°
~CH~
or the Ira salts there~~, where ~' is hyc~rnge~a, 3-ynethyl, 4-methyl. p 5-nctethyl, 6-methyl, 3-ethyl, 4-~thyl, 5-ethyl, 6-ethyl, 3-fluoro, 4-fl.txoro, 5-fl~orci, 6-fluoro, 3-chloro, 4~chloro, S-chloro, 6-chloro, 3-~ethoxy, 4-m~t~oxy~ 5~~nethoxy, 6~~ethoxy, 3-ethoxy, 4-ethoxy, 5-etho~cy, 6-ethoxy or 6~~~thylthio;
~~,3 ~ ~
~g N
~~~NH~.-c~---~!
~~3 OCF'3 ~ CFA
R9 ~~ N
1 S02-,-.NH--~~~/

~lw~~~~
V s i1 0 ~~~
or tYa~ Vila ~a~.t~ thereof, where ~4 ~.~ hyc~ogen~o v ~-methyl., ~~la-4-methyl, 5-methyl, S-methyl, 3-ethyl, 4~ethyl, ~-ethyl, 6--ethyl, 3~fluoro, 4r~fl.uoro, 5~fluoro, 6~fluoro, 3°
chlaro, 4-~chlaro, a-chl.oro, 6-chloro, 3°m~thox~', ~-methoxy, 5-methaxy, 6-methoxy, 3-ethaxy, 4-ethaxy, 5-ethaxy, 6~ethoxy or 6-methylthio;
CF3 0 CF3 . ...
\ 502.x--c~-_(/ \
N-aC~i3 ~4 S02-~TFi--~CC~1I3~
I3_ ar the Ira pelts thereof, where Vita ,~.s hydrogen, 3-methyl, 4-methyl, 5-methyl, 6-methyl, 3-ethyl, 4--etk~yl, ~°-ethyl, 6-ethyl, 3-fluoro, ~-fluoro, 5-flu~ro, 6-fluosa, 3-chloro, 4-~hloro, 5-chloro, 6-chloro, 3-aaethaxy, methoxy, 5~methoxy, s-methoxy, 3-ethoxy, ~-ethoxy, ~-ethoxy, ~-ethaxy or g-~ethylthlo;
~FZCF~H 0 CFg N
\ sod--c-~~l \
OCFZCFzH ~ g soy-~x..~~--~_ - 31 - ~~ ~ ~ 0050/43041 dr iG~~~-- Na ~~s:1'~~- 't~~~e~ewcrof o va'he~'~-.-R~ .is .h~.~~',~rt~exa, 3~~ote'~f~~'1, .~ ~ _ ~' 4-methyl, 5-methyl, 6-methyl, 3-ethyl, 4-ethyl, 5-ethyl, .
6-ethyl, 3-fluoro, 4-fluoro, 5-fluo~ro, 6-fluoro, 3-chloro, 4-chloro, 5-chloro, ~-chloro, 3-methoxy, 4 methoxy, 5-methoxy, 6-methoxy, 3-ethoxy, 4-ethoxy, 5 ethoxy, 6-ethoxy or 6-methylthio;
CH3 O ~~,3 ...

N
S~z~--~~~/ a N_ OCH~
CH3 ~ F
H~ .
N
S0--C~--.~l N_ ~C~I3 or tlae Na salts thereof, where R' is hydxogee, 3-methyl, 4-methyl, 5-methyl, 5--methyl, 3-ethyl, 4-ethyl, 5-ethyl, 6-ethyl, 3-fluoro, 4~fluoro, 5-fluoro, 6--fluoro, 3-chloro, 4-~chlo~o, 5-chloro, 6-chloxo, 3-methoxy, 4-methox~r, 5~methoxy, 6-methoxy, 3-ethoxy, 4-ethoxy, 5-ethoxy, 6-ethoxy ~r 6-methylthio;
or the Na salts thereof, ' where R3 is hy~lrog~n, 3-methyl, 4s~~,~h~l, 5-methyl, ~-methyl, 3~ethyl~ 4-ethyl, 5-ethyl, .15 6-ethyl:, 3-fluoro, 4-~f~.u~ro, 5-fluoro, s-fluoro, 3- .
ch~:o~o, 4°chloro, 5-chl~ro, 6-ehloro, 3-methoxy~ 4-~e.~hoxy, 5-methoxy, 6-anethoxy, 3-ethoxy, 4-ethoxy, 5-~thoxy, 5-sthoxy or 6-methylthio;

~~~~ ~%r~
- ~2 - OoZ. ~05~D1~3041 CFIaOCH~ ~ Cg3 N
SO~~,--C.~,pgi--N~ , .

CHZ0CH3 g Ft9 ,I . N
S02--~~c[ -.-~--(!
o~ N -or the Na salts thereof, where R' is hydrog~r~, 3-methyl, ~-methylo 5-methyl, 6-methyl, 3-ethyl, ~-ethyl, 5-ethyl, 6-ethyl, 3-fluoro, 4-fluoro, 5-fluoro, 6-fluoro, 3-chloro, ~-chloro, 5-~hloro, 6-chloro, 3-~tethoxy, 4- :::;
me~hoxy, 5-methcxy, s-methoxy, 3-ethoxy, 4-ethoxy, 5-ethoxy, 6~ethoxy or 6-~etkaylthio;
SCF~ ~ 0 CF3 Rq (~ N
~ SOa-----r~e-C

. SCF3 ~ F
~I i sox-c-~H-or the Na silts thereof, v~here I~° is h~rlroc~en, 3-methyl, 4-me~.hyl, 5-methyl, ~-methyl, 3-ethyl, ~-ethyl, 5-ethyl, 5-~~hyl, 3-fluoro, 4-fluoro, 5-fluoro, 6-fluoro, 3-1Q . ~hloro, 4-chloro~ 5-chloro, 5-chioro, 3-methoxy, methoxy, 5-methoxy, 6-methoxy, 3-ethoxy, 4-ethoxy, 5-2~.~,~~w~
~lr ._, 3~ .~ VoZo ~~ .
eth~x~,~;, 6-ethoxy or 6-anetlaylthio~
OSOaCHC3 0 Cg~

N
!i soy--c.~--~e ~

N_ t~S02CIi3 O . ~

ii ~ ~
~~.--~-.~--~--.~

--or the Ids salts thereof, where R4 is hydrogen, 3-methyl, 4-methyl, 5-methyl, 6~m~thyl, 3-ethyl, ~-ethyl, 5-ethyl, 6-ethyl, 3-fl~oro, ~~-fluoro, 5-fluoro, 6-fl~aoro, ch3.oro, 4-chloro, 5-chhro, 6-chloro, 3-a~etlaoxy, 4- .

methoa~y, 5a~tethc~xy, 6~methoxy, 3-ethoxy, 4-~thoxy, eth~~y, s.~~t~~~y ~r s~~~thy~ah~.~;

OSO~t:F3 ~ CF3 R~

ii N

sod--.c-~-(e' ~-O~OZCF3 R~

ii N
S~~-~~1H~~TH--~e :

_.. N ~ :.. '.::
..

or the Na salts thereof, where R' is hydrogen, 3mme~hy3., ~4-metlhyl, 5~a~aethyl, 6-methyl, 3-ethyl, 4-ethyl;, 5-~thy3l, 6-ethyl, 3-fluoro, ~-fluoro, 5-fluoro~ 6-flaasaro~

ohloro, 4-chloro, 5-chloro, 6-chloro, 3~metho~cy, . 4-methc~xy, 5-methoxy, 6-methoxy, 3-ethoxy, ~-ethoxy, 5-~'a' ~r - ' ethoxy, 6-ethoxy o= C-methylthio.
Use Examples The herbicidal action of the N-[(pyrimidin-2 yljaminocarbonyl~benzenesulfonamide of the formula f on the growth of the test plants is demonstrated by the following greenhouse experiments. '°
The culture vessels used are plastic flower pots having a capacity of 300 cm$ and containing loamy sand with about 3.0% of humus as a substrate. The seeds of the test plants are sown shallow and separately according to species.
For the purpose of the postemergence treatment, the plants which are e~.ther directly sown or grown in the same vessehs are selected, or they are first grown segarately as seedlings and transplanted into the test vessels a few days laefore the treatment.
The test plants, at a height of growth of from 3 to 15 cm, depending on the form of growth, are then treated with the active'ingredients which are suspended or emulsified in water as a distributing' medium and which aye sprayed through finely distributing nozzles. The ' application rate for the postemergence treatment is 0.06 and 0:03 kg/ha a.i. (acti~re 3.ngredient,.
The test vessels are placed in a~ greenhouse, w~rm~s areas (from 20 ~~ 35°C~' being g~referred fos sr~armth-loving species and fgom 10 to 20°C being preferred fir those of temperate climates: The test period extends over fr~m 2 t~ ~ weekso During this time, the plants are tended and their r~act~on to the individual treatments is evaluated.
Evaluation i~ based~on a scale of from 0 to 100:
100 means no e~aergence of the plants or complete destruc-tio~t of at least the above-ground pa$-ts, and 0 means no ~5 damage or normal course of growth.
The plants used in the greenhouse experiments consisted of the following species:

. ~~.29~~~
35 _ ~.Z. 0050/43041 ~otarW xJL xiarne ~:ommori ndjotte .~,r-Alopecurus myosuroides slender foxtail Echinochloa crus-galli barnyard grass Setaria italics foxtail millet Zea mat's corn When used at a rate of 0.06 and 0.03 kg/ha a.i.
by the postemergence method, Example No.,,.ll controls u:adesirable plants very well while at the same time being compatible with the example crap corn.
1~ Compound No. 11 was compared with the comparative substance J disclosed in EP-A 101 308. The results, ,..~.. .
which are listed in Table I, demonstrate the substantial- .
ly better herbicidal activity in conjunction with high selectivity in the example crop corn.
Co~gounds No.' 23, 25 'and 19 were compared with the comparative substances N and O disclosed in DE--A
27 15 786 (US 4,120,691)° The results listed in Tables I:I to IV demonstrate the better herbicidal act%vity in conjunction with high selectivity in the example crop minter wheat ;(Triticum aestivum):
Table I: Herbicidal activity in postemergence applica-ti.on in the greenhouse SQz-NIiCON~i--~~ ~

r"
r~ ..i - 36 O.Z.

Exle No. I1 J

Cz$s n-CaH7 ~rpplication rate (kg/ha a.i.) 0.06 0.03 0.06 0.03 Test plants (damage in %) F.lopecurus myosuraides 95 . 80 55 0 Echinochloa crux-galli 100 98 30 10 Setaria italics 85 85 20 15 Zea ways 15 15 ZO 0 Table II: Herbicidal.activity in postemergence applies-tion in the greenhouse SOZ-I~THC~IE~i--~~

C Ex~a~le No.~~~ 25 .":"'~...~r.,o _,N ~.......,.~..~..~...

, ' OSO2CH3 Cl I R

Application rate (kg/ha a.i.) (0.06 ~U.03 10.06 0.03 Test plants damage in % ) ~
' Triticum sestivum 20 0 1~l 5 Echinochloa crux-galli 85 70 40 30 Amaranthus retroflexus 100 100 98 98 Sinapis alba 100 100 90 80 Solanum nigrum 100 100 40 30 Veronica spp. 85 T5 40 30-Table III: applica-Herbicidal activity in postemergence tion in greenhouse the $pZ---NHCONH-~~

21~~a?~
- 38 - O.Z. 0050/43041 _'af x .' Example Nos 23 N

?ti, CF3 C1 Application rate (kg/ha a.i.) 0.06 0.03 0.06 0.03 Test plants (damage in %) Echinoehloa crus-galli 88 60 40 30 Abutilon theoprasti 95 95 50 40 Chenopodium album 100 100 95 90 Chrysanthemum corinarium 100 100 75 65 Galium aparine 90 90 40 20 ' Solanum nigrum 100 100 40 30 Polygonum persicaria 100 95 80 50 Table'IV. activity postemergen~e applica-Herbicidal in tion greenhouse in the g pZ
~.
NFICONFi--~/

. - . N_ CH3 ' OCH3 a - , . ... ,,.
. , .. _ . .. , ..,.,a:
.,. .. .
:.r,..:..
..
.,.
..
..
.
..
..
"
............,vn >.....,..., ....
.
,., , .
,..
,.
..c ..
,..
.
.,....
..
.
....
n...
.
.

N

" Os4.
~~ 00 -adx '~ .:..
.

Example No. 19 O

C . . ..;;
.. .:

Application rate (kg/ha a.i.j 0.06 0.03 0.06 0.03 Test plants (damage in %) Triticum aestivum 10 10 50 40 Echinochloa crux-galli 75 65 80 80 Amaranthus retroflexus 100 100 100 I00 Sinapis albs 75 75 90 90 Solanum nigrum 100 95 98 90

Claims (15)

WHAT IS CLAIMED IS:

1. An N-[(pyrimidin-2-yl)aminocarbonyl]-benzenesulfonamide of the formula I

where R1 is methyl or ethyl;
R2 is hydrogen or methyl;
R3 is C1-C4-alkyl which may carry from one to three methoxy groups or fluorine atoms;
or R3 is a group ER6 in which E is O or S, R6 being C1-C2-alkyl, which may carry from 1 to 3 or 1 to 5 fluorine atoms, with the exception of difluoromethoxy, and, if E is O and at the same time R5 is trifluoromethyl, R6 may furthermore be methylsulfonyl, ethylsulfonyl, trifluoro-methylsulfonyl, allylsulfonyl or propargylsulfonyl;
NO2 or OH;
or R3 is di-C1-C3-alkylaminosulfonyl if R5 is fluorine;
or R3 is C1- or C2-alkylsulfonyl which may carry 1-3 halogen atoms;

R4 is hydrogen, methyl, ethyl, methoxy, ethoxy, fluorine, chlorine, methylthio, ethylthio or C1-C2-haloalkoxy;
and R5 is fluorine or trifluoromethyl, and its environmentally compatible salts, with the exception of compounds I with R3 = methyl and R4 =
hydrogen or methyl, if R5 is trifluoromethyl.

2. An N-[(pyrimidin-2-yl)aminocarbonyl]benzene-sulfonamide of the formula I as claimed in claim 1, where R1 is methyl, R2 and R4 are hydrogen, R3 is methyl-sulfonyloxy (E = O, R6 = methylsulfonyl) and R5 is trifluoromethyl .

3. An N-[(pyrimidin-2-yl)aminocarbonyl]benzene-sulfonamide of the formula I as claimed in claim 1, where R1 is methyl, R2 and R4 are hydrogen, R3 is trifluoromethyl and R5 is trifluoromethyl or fluorine.

4. An N-[(pyrimidin-2-yl)aminocarbonyl]benzenesulfonamide of the formula I as claimed in claim 1, where R1 is methyl, R2 and R4 are hydrogen, R3 is trifluoromethoxy and R5 is trifluoromethyl or fluorine.

5. An N-[(pyrimidin-2-yl)aminocarbonyl]benzenesulfonamide of the formula I as claimed in claim 1, where R1 is methyl, R2 is hydrogen, R3 is thiomethyl or methoxy, R4 is 6-methylthio and R5 is trifluoromethyl or fluorine.

6. An N-[(pyrimidin-2-yl)aminocarbonyl]benzenesulfonamide of the formula I as claimed in claim 1, where R1 is methyl, R2 and R4 are hydrogen, R3 is methoxymethyl and R5 is trifluoromethyl or fluorine.

7. An N-[(pyrimidin-2-yl)aminocarbonyl]benzenesulfonamide of the formula I as claimed in claim 1, where R1 is methyl, R2 and R4 are hydrogen, R3 is nitro and R5 is trifluoromethyl or fluorine.

8. An N-[(pyrimidin-2-yl)aminocarbonyl]benzenesulfonamide of the formula I as claimed in claim 1, where R1 is methyl, R2 and R4 are hydrogen, R3 is methylsulfonyl or ethylsulfonyl and R5 is trifluoromethyl or fluorine.

9. An N-[(pyrimidin-2-yl)aminocarbonyl]benzenesulfonamide of the formula I as claimed in claim 1, where R1 is methyl, R2 and R4 are hydrogen, R3 is N,N-dimethylsulfamoyl and R5 is fluorine.

10. A process for the preparation of an N-[(pyrimidin-2-yl)aminocarbonyl]benzenesulfonamide of the formula I as claimed in claim 1, wherein a sulfonyl isocyanate of the formula II:

wherein R3 and R4 are as claimed in claim 1, and is reacted in an inert organic solvent, with about a stoichiometric amount of a 2-aminopyrimidine derivative of the formula III:

wherein R1, R2 and R5 are as claimed in claim 1.

11. A process for the preparation of an N-[(pyrimidin-2-yl)aminocarbonyl]benzenesulfonamide of the formula I as claimed in clam 1, wherein a carbamate of the formula IV:
wherein R3 and R4 are as defined in claim 1, is reacted in an inert organic solvent, at from 0 to 120°C, with about the stoichiometric amount of 2-aminopyrimidine of the formula III as claimed in claim 10.

12. A process for the preparation of an N-[(pyrimidin-2-yl)aminocarbonyl]benzenesulfonamide of the formula I as claimed in claim 1, wherein a corresponding sulfonamide of the formula V:
wherein R3 and R4 are as defined in claim 1, is reacted in an inert organic solvent, with a phenyl carbamate of the formula VI:
wherein R1, R2 and R5 are as defined in claim 1.

13. A process for the preparation of an N-[(pyrimidin-2-yl)aminocarbonyl]benzenesulfonamide of the formula I as claimed in claim 1, wherein a corresponding sulfonamide of the formula V:

wherein R3 and R4 are as defined in claim 1, is reacted in an inert organic solvent, with an isocyanate of the formula VII:

wherein R1 and R5 are as claimed in claim 1.

14. A herbicide containing an N-[(pyrimidin-2-yl)amino-carbonyl]benzenesulfonamide of the formula I as claimed in claim 1 or its salt and conventional carriers.

15. A method for controlling undesirable plant growth, wherein a herbicidal amount of an N-[(pyrimidin-2-yl)aminocarbonyl]benzenesulfonamide of the formula I as claimed in claim 1 or of one of its salts is allowed to act on the plants or their habitat.