CA1231948A - N-phenylsulfonyl-n'-pyrimidinyl- and -triazinyl-ureas - Google Patents

N-phenylsulfonyl-n'-pyrimidinyl- and -triazinyl-ureas

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CA1231948A
CA1231948A CA000408671A CA408671A CA1231948A CA 1231948 A CA1231948 A CA 1231948A CA 000408671 A CA000408671 A CA 000408671A CA 408671 A CA408671 A CA 408671A CA 1231948 A CA1231948 A CA 1231948A
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alkyl
compound
alkenyl
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Werner Fory
Willy Meyer
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Syngenta Participations AG
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Ciba Geigy Investments Ltd
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    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07DHETEROCYCLIC COMPOUNDS
    • C07D239/00Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings
    • C07D239/02Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings
    • C07D239/24Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members
    • C07D239/28Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, directly attached to ring carbon atoms
    • C07D239/32One oxygen, sulfur or nitrogen atom
    • C07D239/42One nitrogen atom
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07DHETEROCYCLIC COMPOUNDS
    • C07D239/00Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings
    • C07D239/02Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings
    • C07D239/24Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members
    • C07D239/28Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, directly attached to ring carbon atoms
    • C07D239/46Two or more oxygen, sulphur or nitrogen atoms
    • C07D239/47One nitrogen atom and one oxygen or sulfur atom, e.g. cytosine
    • AHUMAN NECESSITIES
    • A01AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01NPRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N47/00Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
    • A01N47/08Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having one or more single bonds to nitrogen atoms
    • A01N47/28Ureas or thioureas containing the groups >N—CO—N< or >N—CS—N<
    • A01N47/36Ureas or thioureas containing the groups >N—CO—N< or >N—CS—N< containing the group >N—CO—N< directly attached to at least one heterocyclic ring; Thio analogues thereof
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07DHETEROCYCLIC COMPOUNDS
    • C07D239/00Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings
    • C07D239/02Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings
    • C07D239/24Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members
    • C07D239/28Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, directly attached to ring carbon atoms
    • C07D239/46Two or more oxygen, sulphur or nitrogen atoms
    • C07D239/48Two nitrogen atoms
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07DHETEROCYCLIC COMPOUNDS
    • C07D239/00Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings
    • C07D239/02Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings
    • C07D239/24Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members
    • C07D239/28Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, directly attached to ring carbon atoms
    • C07D239/46Two or more oxygen, sulphur or nitrogen atoms
    • C07D239/52Two oxygen atoms
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07DHETEROCYCLIC COMPOUNDS
    • C07D239/00Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings
    • C07D239/02Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings
    • C07D239/24Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members
    • C07D239/28Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, directly attached to ring carbon atoms
    • C07D239/46Two or more oxygen, sulphur or nitrogen atoms
    • C07D239/56One oxygen atom and one sulfur atom
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07DHETEROCYCLIC COMPOUNDS
    • C07D251/00Heterocyclic compounds containing 1,3,5-triazine rings
    • C07D251/02Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings
    • C07D251/12Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
    • C07D251/26Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with only hetero atoms directly attached to ring carbon atoms
    • C07D251/40Nitrogen atoms
    • C07D251/42One nitrogen atom
    • C07D251/46One nitrogen atom with oxygen or sulfur atoms attached to the two other ring carbon atoms
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07DHETEROCYCLIC COMPOUNDS
    • C07D521/00Heterocyclic compounds containing unspecified hetero rings

Abstract

Case 5-13494/1+2/=

N-Phenylsulfonyl-N'-pyrimidinyl- and -triazinyl-ureas Abstract N-Phenylsulfonyl-N'-pyrimidinyl- and -triazinyl-ureas of the general formula and the salts of these compounds with amines, alkali metal or alkaline earth metal bases or quaternary ammonium bases have good pre-emergence and post-emergence selective herbi-cidal properties and growth-regulating properties.
In this formula, A is a C1-C6-alkyl radical which is substituted by halogen, C1-C4-alkoxy, C1-C4-alkylthio, C1-C4-alkylsulfinyl, C1-C4-alkylsulfonyl, C1-C4-halogenoalkoxy, C1-C4-halogenoalkylthio, C1-C4-halogeno-alkylsulfinyl or C1-C4-halogenoalkylsulfonyl, or is a C2-C6-alkenyl radical substituted by the above radicals, E is the methine group or nitrogen, X is oxygen, sulfur or a sul-finyl or sulfonyl bridge, Z is oxygen or sulfur, m is the number one or two, R1 is hydrogen, halogen, C1-C5-alkyl, C2-C5-alkenyl or a -Y-R5 radical, R2 is hydrogen, halogen, C1-C5-alkyl, C1-C5 alkenyl, C1-C4-halogeno-alkyl or a -Y-R5, -COOR6, -N02 or -CO-NR7-R8 radical, R3 is hydrogen, C1-C4-alkyl, C1-C4-alkoxy, C1-C4-alkylthio, C1-C4-halogenoalkyl, halogen, C1-C4-halogeno-alkoxy or alkoxyalkyl having not more than 4 carbon atoms, R4 is C1-C4-halogenoalkoxy or C1-C4-halogenoalkylthio, R5 and R6 are each C1-C5-alkyl, C2-C5-alkenyl or C2-C6-alkynyl, R7 and R8 independently of one another are hydrogen, C1-C5-alkyl, C2-C5-alkenyl or C2-C6-alkynyl and Y is oxygen, sulfur or a sulfinyl or sulfonyl bridge, and A can also be an unsubstituted C2-C6-alkenyl radical if X is simultaneously oxygen.

Description

4 '~1~ ~A ~a Case 5-1~494/1~2/-N-Phenylsulfonyl-N'-pyrimidinyl- and -tr;azinyl-ureas The present invention relates to novel herbicidally active and plant growth-regulating N-phenylsulfonyl-N'-pyrimidinyl- and -triazinyl ureas, processes for their preparat;on, composit;ons containing them as act;ve sub-stances, and their use for controlling weeds, in particular For selectively controll;ng weeds in crops of useful plants or for regulating and inhibiting plant gro~th~
The N-phenylsulfonyl-N'-pyrimid;nyl- and -tr;az;nyl-ureas according to the invent;on are those of the general ~ormula I

1 ZN ~3 (1) ~--S02-N~I-C-NH-~
2 (~-t~) \R~, m ;n wh;ch A ;s a c1-c6-alkyl rad;cal wh;ch ;s subst;tuted by halogen, C1 C~-alkoxy, C1-C4-alkyl~h;o, C1~C4-alkyl-sulfinyl, C1-C4-alkylsulfonyl, C1-C4-halogenoalkoxy, C1-C4-halogenoalkylthior C1-C4-halogenoalkylsulfinyl or C1-C4-halogenoalkylsulFonyl, or is a C2-C6-alkenyl radical substituted by the above rad;cals, E ;s the methine group or nitrogen, X is oxygen, sulfur or a sulfinyl or sul~Fonyl br;dge, Z is oxygen or sul~Fur, m ;s the number one or two, R1 ;s hydrogen, halogen, C1-C~-alkyl, C2-C5-alkenyl or a Y-Rs rad;cal~ R2 is hydrogen, halogen, C1-C5-alkyl, C2-C5-alkenyl~ C1-C4-halogenoalkyl or a -Y-R5, COOR6, -N02 or -CO-~R7-R~ radical~ R3 is hydrogen, C1-C~- $~

~L~3~

alky~, C1-C4-alkoxy, C1-C4-alkylthio, c1-c4-halo9eno-alkyl, C1-C4-halogenoalkoxy, halogen or alkoxyalkyl having not more than 4 carbon atoms, R4 is C1-C4-halogenoaLkoxy or C1-C~-halogenoalkylthio, R~ and R6 are each C1-C5-alkyl~ C2-C5-alkenyl or C2-CO-alkynyl~ R7 and R8 independently of one another are hydrogen, C1 C5-alkyl, C2-C5-alkenyl or C2-C6-alkynyl and Y is oxygen, sulfur or a sulfinyl or sulfonyl brid~e, and in which A can also be an unsubstituted c2-c6-alkenYl radical if X ;s simultane-ously oxy~en, and the salts of these compounds.
- Urea compounds, triazine compounds and pyrimidine compounds having a herbicidal action are generally known.
Arylsulfamoyl-heterocyclyl-anlinocarbamoyl compounds having a herbicidal and plant growth regulatin~ action have recently been disclosed, for example in Dutch Patent 121r7~8, European Patent Publications rlos. 9,419 and 23,422, U.S.
Patent No. 4,127,405, German Offenlegungsschrift 2,715,786 and French Patent Specificat;on 1,468,747.
In the definitions, alkyl is to be understood as mean;ng stra;ght-cha;n or branched alkyl, for example methyl, ethyl, n-propyl, ;-propyl, the four isomeric butyl radicals, n~amyl, i-amyl, 2-amyl, 3-amyl, n-hexyl and ;-hexyl.
Alkoxy is to be understood as 0ean;ng methoxy, ethoxy, n-propoxy, i-propoxy and the four isomeric butoxy rad;cals, but especially methoxy, ethoxy or i-propoxy.
Examples of alkylthio are methylthio, ethylthio, n-propylthio, i-propylth;o and n-butylth;o~ but especially methylth;o and ethylthio.
ixamples of alkenyl radicals are v;nyl, allyl, iso-propenyl, prop-1-enyl, but-1-enyl, but-2-enyl, ~ut-3-enyl, isobut-1-enyl, ;sobut-2-enyl, pent-1-enyl, pent-2-enyl, pent-3-enyl and pent-4-enyl, but especially vinyl, allyl and pent-4-enyl~
Examples of alkylsulfinyl are methylsulf;nyl, ethyl-sulfinyl, n-propylsulf;nyl and n-butylsulfinyl, but especi-ally methylsulfinyl and ethylsulf;nyl.

~LZ3~3f~f3 Examples of alkylsulfonyl are methylsul~onyl, ethyl-sulfonyl, n-propylsulfonyl and n-butylsulfonyl, but espec;-ally methylsulfonyl and ethylsul~onyl.
Halogen in the definitions and in halogeno-alkyl, -alkoxy, -alkylsulfinyl, -alkylsulfonyl and -al'~ylthio is to be understood as mean;ng fluorine, chlorine or bromine, but preferably fluorine or chlorine.
Preferred halogenoalkyl radicals, which may also be constituents of larger substituent groups, for example of a halogenoalkoxy or halogenoalkylthio radical, are difluoro-methyl, trifluoromethyl~ perfluoroethyl, 2,~,2-tri-Fluoro ethyl, chloro~luoromethyl, bromofluoromethyl, 2-chloroethyl, 1,1,2,2-tetrafluoroethyl, 2-fluoroethyl, 2,~,2-trichloro-ethyl, bromod;fluoromethyl, chlorod;~luoromethyl, 1,1,2-tri-fluoro-2-chloroethyl, 1,1,2-tr;~luoro-2-bromoethyl and ~,1, 2,3,3,3-hexafluoropropyl, but esoecially d;fluoromethyl, ~,2,2-trifluoroethyl and perfluoroethylO
Alkynyl radicals in the def;nitions of the above symbols are as a rule propargyl, but-2-ynyl, but-~-ynyl and the isomeric pentynyl and hexynyl radicals, but the alkynyl radical is preferably propargyl or but-2- or -3-ynyl.
The ;nvent;on also relates to the salts which the compounds of the formula I can form with amines, alkali metal and alkal;ne earth metal bases and quaternary ammon;um bases.
of the alkali metal and alkal;ne earth metal hydrox-;des, the hydroxides of lithium, sodium, potassium, magnes-;um and calc;um, but espec;ally those of sod;um and potas s;um, are pre~erred salt-~orming agents.
Examples of amines suitable for salt formation are primary, secondary and ~ert;ary aliphatic and aromatic amines, such as methylamine, ethylam;ne, propylamine, i-propylamine, the four ;someric butylam;nes, d;methylam;ne, d;ethylamine~ diethanolam;ne, dipropylam;ne, d;isopropyl-amine, d;-n-butylamine, pyrrolidine, piperidine, morpholine, trimethylamine, trieth~lam;ne, tr;propylam;ne, qu;nucl;dine, pyr;dine, quinoline and i-quinolineO but especially ethyl-~L23~9~3 amine, propylamine, diethylamine and triethylamine, and inpart;cular iso-propylamine and diethanolam;ne.
Examples of quatern3ry ammonium bases are, in ~eneral, the cations of ammonium hal;de salts, for example the tetramethylammonium cation, the trimethylbenzylammonium cation, the triethylbenzylammon;um cation, the tetraethyl-ammon;um cation, the trimethylethylammon;um cat;on and the ammon;um cation~
Preferred compounds of the formula I according to the invention are those in ~hich a) X or b~ Z is oxygen or c) m is the number one and d) the radicals R3 and R4 to-gether contain not 00re than 4 carbon atoms.
Combination of the preferred features gives the following further preferred group of compounds of the formula I in which ~ and Z are oxygen, m is the number one and the rad;cal -X-A occupies the ortho-pos;tion relative to the sulfonyl group.
Within th;s group, preferred compounds are moreover those in wh;ch the radicals R3 and R4 together contain not more than 4 carbon atoms.
Particularly preferred compounds within th;s sub-group are those in which R~ is halogenoethoxy or halogeno-methoxy Of these, those in which R4 is the 2,2,Z-tri-fluoroethoxy radical or the difluoromethoxy radical are in turn preferred.
Specific preferred compounds are N-(2-difluoro-methoxyphenyl-sulfonyl)-N'-[4-methoxy-6~-(2,2,2-trifluoro-ethoxy) 1,3,5-triazin-2-yl~-urea, N-~2-(2-chloroethoxy)~
phenylsulfonyl~-N'-C~-methoxy-6-~2,2,2-trifluoroethoxy)-1,3,5-tr;az;n-2-yl]-urea, N-(2-trifluoromethoxyphenyl-sulfonyl)-N'-(~-difluoromethoxy-6-methyl-pyrimidin-2-yl)-urea and N-~2-difluoromethoxyphenyl-sulfonyl)-N'-(4-di-fluoromethoxy-6-methyl-pyrimidin-2-yl)-urea.
The compounds of the formula r are prepared in an inert organ;c solvent.
In a first process, the compounds of the formula I
are obtained by a procedure which comprises reacting a , , , 3L'~3~9~

phenylsuLfonam;de of the formula II
S02~ 2 R -i 11 1 ~ ~ (II) R (X-A) 2 m ;n which A, R1, R2, X and m are as defined under formula I, with an N-pyr;m;dinyl- or ~.r;az;nyl-carbamate of the formula III

Rl lt l! \N ~E ( I I I ) in ~hich E, R3, R4 and Z are as defined under formula I
and R11 is hydrogen, halogen~ nitro or C1-C3-alkyl~ in the presence of a base.
In a second process, compounds of the formula I are obtained by a procedure which comprises react;ng a phenyl-sulfonyl isocyanate or isothiocyanate of the formula IV

11-~2~ Z
~ ~.X(~_A~ (IV~

in ~hich A, R1, R2, m, X and Z are as defined under formula I, with an amine of the formula V

N-.~3 (V) ~4 in which E, R3 and R~ are as defined under formula I, in the presence or absence of a base.
In a further process, the compounds of the formula I are preparad by a procedure which comprises react;ng a sul~onamide of the formula II given above with an isocyan-~;23~

ate or isothiocyanate of the -formula VI
~3 ~ tVI) in which E, R3, ~ and Z are as defined under formula I, in the presence or absence of a base.
Finally, the comPounds of the formula I can also be obta;ned by a procedure which comprlses reacting an N-phenylsulfonylcarbamate of the formula VII
o ~ \--SO -~ C-O- ~ ~
R (~ ) (VII) ;n wh;ch A, R1, R2~ m and X are as defined under formula I and R11 ;s hydrogenr halogen, n;tro or C1-C3-alkyl, with an amine of the formula V defined above.
I-f des;red, the result;ng ureas of the formula I can be converted ;nto add;t;on salts by means of arnines, alkali metal or alkal;ne earth metal hydroxides or quaternary arnmon;um bases. Th;s ;s efFected, for example, by react;on w;th an equ;molar amount of base and evaporat;on of the solvent.
The starting materials of the formulae II, IV and ~III and the ortho-substituted hydroxyphenyl- or subs-t;tuted ortho-hydroxypllenyl-sulfonamides of the formula VIII
S02~ 2 iI

2 ~ " ~VIII) ;n which R1 and R2 are as defined under formula I and X' ;s oxygen or sulfur, as starting materials of certain sulfon-amide representat;ves of the -formula II, have been d;sclosed ;n European Patent Application 44,~7.

~23~L9f~

Some of the starting materials oF the formulae III, V and VI are known~ Novel compounds of the formulae III and VI can be obtained by conventional methods from correspond-;ng compounds of the formula '1.
~ lovel fluoroalkoxy-amino-pyrimidines and -triazines of the formula V, the;r preparation and the preparation of corresponding compounds of the formulae III and VI therefrom have been disclosed in Swiss Patent Application 3527/82-8~
The reactions to give compounds oF the formula I are advantageousLy carried out in aprotic, inert, organic sol-vents~ such as methylene chloride, tetrahydroFuran, aceto-nitrile, dioxane and toluene. Bases which can be used are inorganic bases, such as amines, for example triethylamine, quinuclidine~ quinoline, pyridine and the like~ and inor-ganic bases, such as hydrides, for example sodium hydride or calcium hydride, hydroxides, for example sod;um hydroxide and potassium hydroxide, carbonates, for example sodium carbonate and potassium carbonate, and bicarbonates, ~or example potassium bicarbonate and sodium bicarbonate.
Ti1e reaction temperatures are preferably between ~20 and +120C. The reactions ~enerally proceed slightly exotherm;cally, and can be carried out at room temperature.
For the purpose of shortening the reaction time or for initi3ting the reaction, the mixture is appropriately warmed to its boiling point for a short time.
The end products can he isolated by concentrating the mixture and/or evaporating off the solvent and can be purified by recrystallisation or trituration of the solid residue in solvents in ~hich they are no-t readily soluble, such as ethers, aromatic hydrocarhons and chlor;nated hydro-carbons.
The act;ve substances of the formula I are stable compounds. Their handLing requires no precautionar~
measures~
~ hen used in relatively small amounts, the compounds of the formula I have good selectively growth-inh;b;ting and selectively herbicida( properties which make them excellent for use in crops of use~ul plants, in ~articular cereals, cotton, soybean, maize and rice. In some cases, weeds which have hitherto been affected only by total herbicides are also damaged.
The mode of action of these active substances is unusual. Many of them are translocatable, i.e. they are taken up by the plant and transported to other po;nts, where they then act~ It is thus possible, for example, to damage perenn;al weeds as far as the roots by surface treatment.
In contrast to other herb;cides and grow-th regulators, the novel compounds of the formula I already act when appl;ed in very small amounts.
The compounds o-f the formula I also have powerful plant growth regulating propert;es, wh;ch can result in an increase in the yield of crops or harvest. Moreover, many compounds of the formula I exh;bit a concentration-dependent plant growth inhibiting act;on. The growth of both mono-cotyledons and d;cotyledons ;s impa;red.
Thus, for example, the growth of Legum;nosae fre-quently planted as cover crops ;n agr;culture in trop;cal regions can be selectively inhibited by the compounds of the formula I, so that although so;l eros;on between crops ;s prevented, the cover crops cannot compete with the crop.
Inh;b;tion of the vegetative growth enables many crop plants to be planted closer together, so that an ;ncreased y;eld in relat;on to soil area can be ach;eved.
A further mechanism of increasing yield with growth ;nh;bitors ;s based on the fact that a greater amount of nutrients ;s available for flower and fruit formation, whilst vegetat;ve growth is restr;c-ted~
The compounds of the formula I can also be used to prevent stored potatoes from sprout;ng. '~hen potatoes are stored over winter~ sprouts -frequently develop, resulting ;n shrinkage, loss of we;ght and rott;ng.
When relatively large amounts are applied, the development of all the tested plants is damaged to the extent that the plants die.

~L2~ 8 The invention also relates to herbicidal and piant growth regulating compositions containing a novel active substance of the formula I, and to methods of pre-emergence and post-emergence control of weeds, of inhibiting the plant growth of monocotyledons and dicotyledons, especially -grasses, tropical cover crops and tobacco side-shoots, and of regulating plant growth~ especially of leguminosae.
The compounds of the formula I are used in unmodi-fied form or, preferably, as compositions together with the ass;stants convent;onally used in the art of formulation, and are therefore processed in a kno~n manner to, for example, emulsion concentrates, solutions which can be sprayed directly or diluted, dilute enuls;ons, wettable powders, soluble powders, dusts, granules or compositions encapsulated in, for example, polymeric substances. ~he methods of application, such as spraying, misting, dusting, scattering or uatering, like the type of composition, are chosen according to the intended a;ms and the ~i~en circum-stances.
The formulations, i.e~ the compositions, prepara-tions or combinations containing the active substance of the formula I and, where relevant, a solid or liquid adjuvant are prepared in a known manner, for example by intinate mixing and/or grinding of the active substances w;th exten-ders~ for example with solvents, solid carriers and, uhere appropriate, surface-active compounds ~surfactants).
Suitable solvents include aromatic hydrocarbons, preferably C8-c12-fractions~ fcr example xylene mixtures or substituted naphthalenes, phthalates, such as dibutyl phthalate or dioctyl phthalate, aliphatic hydrocarbons~ such as cyclohexane or para-f-f;ns, alcohols and glycols and ethers and esters thereof, such as ethanol, ethylene glycol, ethylene glycol monomethyl ether or ethylene glycol mono-ethyl ether, ketones, such as cyclohexanone, highly polar solvents, such as N methyl-2-pyrrolidone, dimethylsulfoxide or dimethylforlnamide~ vegetable o;ls, wh;ch may be epox;-dised, such as epoxidised coconut oil or soybean oil, and water.
Solid carriers used, for example for dusts and dispersible powders, are as a rule ground natural minerals, such as calcite, talc, kaolin, montmorillonite or attapulgiteu Highly disperse silica or highly disperse absorben-t polymers can also be added to improve the physical properties. Suitable granular, adsorbent carriers include porous materials, for example pumice, brick dust, sepiolite or bentonite, and examples of non-absorptive carriers include calcite and sand. In addition, a large number of pre-granulated materials of inorganic or organic nature, such as, in particular, dolomite or comminuted plant residues, can be used.
Suitable slJrface-active compounds depend on the nature of the act;ve substance of the formula I to be formu-lated and include non-ionic, cationic and/or anionic sur-factants with good emulsifying~ dispersing and wetting properties. ~urfactants are also to be understood as meaning surfactant mixtures.
Suitable anionic surfactants can be either so-called water-soluble soaps or water-soluble synthetic surface-active compounds.
Soaps are the alkali metal, alkaline ear-th metal or substituted or unsubstituted ammon;um salts of i1;gher fatty ac;ds (C10-C22), for example the Na or ~ salts of oleic ac;d or stearic acid, or of naturally occurring fatty acid mixtures, which can be isolated, for example, from coconut oil or tallow oil~ ;atty acid methyl-taurine salts can also be used.
~ owever, so-called synthetic sur-factants are more frequently used, especially fatty sulfonatesO fatty sulfates, sulfonated benzimidazole derivatives or alkylaryl sulfonates.
The fatty sulfonates and sulfates are as a rule in the form of alkali metal, alkaline earth metal or substituted or unsubstituted ammonium salts and contain an alkyl radical having ~ to 22 C atoms, alkyl also including the alkyl moiety o-f acyl radicals, for example the Na or Ca salt of ~3~

l;gnin-sulfonic acid, o-f dodecyl-sulfuric acid ester or of a fatty alcohol sulfate mixture prepared from naturally occurring -Fatty acids~ These also include the salts of sulfuric acid esters and sulfonic acids of fatty alcoholt ethylene oxide adducts. The sulfonated benzi~idazole derivat;ves preferably con~ain 2 sulfonic acid groups and a fatty acid radical having 8-22 C atoms. Examples of alkylaryl sulfonates are the ~a, Ca or triethanolamine salts of dodecylbenzenesulfonic acid, d;butylnaphthalenesulfonic acid or a naphthalenesulfonic acid/formaldehyde condensate.
Corresponding pnosphates~ for example salts of the phosphoric acid ester of a p-nonylphenol/ethylene oxide 4:14 adduct, can also be used.
Suitahle non-ionic surfactants include, in particu-lar, polyglycol ether derivatives of aliphatic or cyclo-aliphtic alcohols, saturated or ur,saturated fatty acids and alkylphenols, ~hich can conta;n 3 to 30 glycol ether groups and ~ to 20 carbon atoms in the ~aliphatic) hydrocarbon radical and 6 to 1~ carbon atoms in the alkyl radical of the alkylphenols.
Other suitable non-ionic surfactants are the water-soluble adducts, containing 20 to 250 ethylene glycol ether groups and 10 to 100 propylene glycol ether groups, of poly-ethylene oxide and polypropylene glycol, ethylenediarnino-polypropylene glycol and an alkylpolypropylene glycol having 1 to 10 carbon atolns in the alkyl chain. The a'oove con~
pounds usually contain 1 to 5 e-thylene glycol units per propylene glycol unit.
Examples of non-ionic sur-factants include nonyl-phenol-polyethoxyethanols, castor oil polyglycol ethers, polypropylene/polyethylene oxide adducts, tr;butylphenoxy-polyethanol, polyethylene glycol and octylphenoxypolyethoxy-ethanol.
Fatty acid esters of polyoxyethylene sorbitan, such as polyoxyethylene sorbitan tr;oleate~ can also be used.
The cationic sur-factants are, in particular, quater-nary amlnonium salts wh;ch contain at least one alkyl radical ~L~3~

having 8 to 22 C atoms as an N-subst;tuent and, as further substituents, lower alkyl radicals, which may be halogenated~
benzyl or lower hydroxyalkyl radicals. The salts are pre-ferably in the form oF halides, methyl-sulFates or ethyl-sulfates, for examp~e s-tearyltrimethylammonium chloride and ben2yldi-(2-chloroethyl)-ethylam~onium brornide.
The surfactants customary in the art of formulation are described in, inter alia, the following publications:
"McCutcheon's Detergents and Emulsifiers Annual" MC Publish-ing Corp., Ridgewood~ New Jersey, 1979 and S;sley and ~ood, "Encyclopedia of Surface Active Agents". Chemical Publishing Co., Inc. New York, 1964.
The pesticidal preparations as a rule contain 0.1 to 95X, in p3rticular 0.1 to 80%, of active substance of the formula I, 1 to 99.9X of a solid or liquid adjuvant and 0 to 25%, in particular 0.1 to 25%, of a surfactant.
In part;cular9 preferred formulat;ons have the following compositions~ (X = per cent by wei~ht) Emulsifiable concentrates ~ .
Active substance- 1 to 20%, preferahly 5 to 10X
Surfactant: 5 to 30X, preferahly 10 to 20%
Liquid carrier: 50 to 94YO~ preferably 70 to 85-~.
Dusts Active substance: n.1 to 10X, preferably 0.1 to 1%
Solid carrier: 99~9 to 90%~ preferably 99.9 to 99X.
Suspension concentrates Active substance: ~ to 75%, preferably 10 to 50%
Water: 94 to 25X, preferably 90 to 30X
SurFactant: 1 to 40~, preferably 2 to 30Y,.
Wettable powders Active subs~ance: O.S to 90%, preferably 1 to 80X
Surfactant: 0.5 to 20X, preferably 1 to 15X
Solid carrier: 5 to 9S%, preferably 15 to 92~.
Granules . . .
Active substance: ~.5 to 30X, preferably 3 to 15X
Solid carrier: 99.5 to 70X, preferably 97 to ~5X.
Ilhilst concentrated compositions are preferred as ~23~

commercial products, -the end consumer as a rule uses dilute compos;t;ons. The use forms can be d;luted down to 0.001~
of active substancea The amounts applied are as a rule 0.01 to 10 kg of active substance/ha, preferably 0.025 to 5 kg of active substance/ha.
The compositions can also conta;n other additives such as stabilisers, antifoams, viscosity regulators, binders, tackifiers and fertilisers or other active substances to achieve special effects.
In the following examples, the temperatures are given in degrees centigrade C and the pressures are given in millibars mb.
Preparation Examples Example 1: N-t2-Difluoromethoxyphenyl-sulfonyl)-N'-~4-methoxy-6-(2,2,2-trifluoroethoxy)-1,3,5-triazin~2-yl]-urea.
a) 124.6 9 o-f 2-difluoromethoxyphenyl-sulfonyl isocyan-ate in 100 ml of dioxane are added dropwise to a suspension of ao.3 9 of 2-amino-4-chloro-6~methoxy-1,3,5-triazine in 400 ml o~f absolute dioxane in the course of 1û minutes. The reaction mixture is warmed to 9G-100 for 3 hours, and the solution is then cooled and concentrated to give 180 g of N-(Z-difluoromethoxyphenyl-sulfonyl)-N'-(4-chloro-6-methoxy-1,3,5-triazin-2-yl~-urea of meLting point 167 16~.
b~ A mixture of 8.2 9 of N-(2-difluoromethoxyphenyl-sulfonyl)-N'-t4-chloro-6 methoxy-1,3,5-tr;azin-2-yl)-urea, oO ml of dioxane, 20 ml of 2,2,2-trifluoroethanol and 5.5 9 of potass;um carbonate is stirred at 55-60 for 12 hours and then taken up in 300 ml of water and filtered over active charcoal~ After the mixture has been acid;fied with 2 N hydrochloric ac;d, the product precipitates and is separated off by filtration. ~ield: 7.7 9 of N-t2-di~
fluoromethoxyphenyl-sulfonyl)-N'-~4-methoxy-6-(2,2,2-tri-fluoroethoxy)-1,3,5--triazin-2-yl~-urea of melting point 155-157.
Example 2: N-t2-Difluorolnethoxyphenyl-sulfonyl)-N'-(/t-di-fluoromethoxy-6-methyl-pyrimidin-2-yl)-urea. __ a) Gaseous difluorochloromethane is passed into a solu-
3~ i8 tion of 62.5 g oF 2-am;no-4-hydroxy-5-methyl-pyrim;dine ;n 500 ml of water, 100 ml of 40~ sod;um hydroxide solution and 100 ml of dioxane at a tempera-ture of 70-75C over a period of 1Z hours. During this period, at hourly intervals, a total of 160 9 of solid sod;um hydroxide is added in equal port;ons. The organic phase ;s separated off and concentra-ted to about 1/10 of its volume~ the residue is poured into water and the solid which has precipitated is separated off to give 39.9 g of 2 amino-4-difluoromethoxy-6-methyl-pyr;mi-d;ne of melt;ng point 136-137C.
b) A mixture of 2.5 9 of 2-difluoromethoxyphenyl-sulfonyl isocyanate~ 1.75 9 of 2-amino-4-difluoromethoxy-6-methyl-pyrimidine and 30 ml of absolute d;oxane ;s stirred at a temperature of 70-75C for 2 hours. The solut;on is evaporated and the residue is crystallised from ether to give 4cO g of N-(2-difluoromethoxyphenyl-sulfonyl)-N'-(4-d;fluoromethoxy-6-methyl-pyrim;din-2-yl)-urea of melting point 163-164C7 Example 3: N-f;2-~2-Ethoxy-ethoxy)-phenyl-sulfonyl~-N'-(4-difluoromethoxy-6-methyl-pyr;midin-2-yl-)-urea.
a) 3.9 9 (0.025 mol) of phenyl chloroformate and O.f~5 9 of 4-dimethylam;no-pyridine are added ;n succession to a solution of 9.0 g (0.05 ¢ol) of Z-am;no-4-difluoromethoxy-6-methyl-pyrimidine in 30 ml of absolute tetrahydrofuran. The solution is stirred at Z0-25C for 24 hours and the reac-t;on mixture is then diluted ~ith 250 ml of ethyl acetate and the precipitate is separated off. 3.1 9 of 2-am;no-4-d;fluoromethoxy-6-methyl-pyrimidine hydrochlor;de of melting point 204-2~5C (decomposition) are thus obtained. To remove the res;dual starting material, the filtrate is eluted over a column containing the ion exchan~er ~ (MERCK), and the eluate ;s dried over sod;um sulfate and evaporated. 4.0 9 of 2-phenoxycarbonylam;no-4-d;fluoromethoxy-S-methyl-pyr;mi-dine are obtained as the crude product in the form of a viscous oil. ~fter crystallisation, the product has a melt-ing point of 56-5~C~
1H-NMR ~CDCl3~ : ~ = 2.5 ~s,CH3), 6.45 (s,1H~, ~.0-7.5 (5H), g~

7.56 (t,J=70 H~ CHF2) and 9.0 tNH~ ppm.
b) 1.8 g (O.n12 mol) of 1~5-diazabicyclo(5.4.0)undec-5-ene are added to a solution o-P 3.5 g (0~012 mol) of 2-phenoxycarbonylamino-4-difluoromethoxy-6-metnyl-pyrimidine, ;n the form of tlle crude product, and 2.9 9 (0.012 mol) of 2-(2-ethoxy~ethoxy)-benzenesulfonam;de ;n 100 ml of absolute acetonitr;le and the mixture is stirred at Z0-25C for 1 hour and then diluted with 500 ml of water and acidified with hydrochlor;c acid. The oil which separates out is takén up in 200 ml oF ethyl acetate and the mixture ;s dried over sod;um sulfate and evaporated. The o;ly residue is crystal-l;sed from diethyl ether and acetone to give N-C2-(2-ethoxy-ethoxy)-phenyl-sulfonyl~-N'-(4-d;fluoromethoxy-o-methyl-pyrimidin-2-yl)-urea of melting po;nt 90-95C ~decomposit;on) as colourless crystals in a y;eld of 2~7 9.
Example 4: 2-Am;no-4-difluoromethylthio-6-methoxy-1,3,5-tr;az;ne.
10.0 g of gaseous difluorochloromethane are passed ;nto a suspens;on of S.0 9 of 2-amino-4-mercapto-6-methoxy-1,3,5-triaz;ne and 4.8 9 of potass;um carbonate ;n 100 ml of d;methylformam;de at a temperature of 70-75C over a per;od of 9~ minu-tes. The react;on m;xture is evaporated, the residue is stirred w;th water and the solid precipitate ;s separated off to give 1.6 g of 2-amino-4-d;fluoromethyl-th;o-6-methoxy-1~3,5-triazine of melting point 146-150C.
Example 5: 2-Amino-4-chloro-6-difluoromethoxy-pyrim;d;ne A suspens;on of 16.4 9 o-f ~-amino-4,6-d;chloro-pyr;m;d;ne ;n 100 ml o-f 40'~ sodium hydroxide solut;on is stirred at a temperature of 95~100C -Por 1 hour. 200 ml of dioxane are added, and 20 9 of gaseous di-fluorochloromethane are passed ;n at a temperature of 70-7SC ;n the course of 1 hour. The organic phase is separated off and concentrated to about 1t5 of ;ts volume, the res;due is poured into ~ater and the sol;d precipitate is separated off to give 6 g of 2-amino-4-c'nloro-6-difluoromethoxy-pyrimidine of melting point 118-119C.

~23~

~ 16 -Example 6: 2-Amino-~-difluoromethoxY-6 methoxy-pyrimidine 19.2 9 of 2-amino-4~b-dimethoxy-pyr;midine hydro-chloride are heated at 150C ~or 2 hours, during which methyl chloride is detached to give 2-amino- 4-hydroxy-6-methoxy-pyrimidine. 80 ml of 40~ sodium hydroxide solution and 100 ml of d;oxane are added, and 22 9 of difluorochloro-methane are passed in at 70-75 ;n the course of 3t4 of an hour. The organic phase is separated off and concentrated to about 1/5 of its volume, the residue is poured into water and the solid precipitate is separated off to give 2.4 9 of 2-amino-4-difluoromethoxy-6-methoxy-pyrimidine of melting point 10~-107C.
Example 7: Z-Amino-4-methyl-6-C1,1,2-trifluoro-2-chloro-ethoxy~-pyrim;dine 25 9 of 2-amino-4-hydroxy-6-methyl-pyrimidine, 25.6 9 of chlorotrifluoroethylene, 13.8 9 of potassium hydroxide and ~00 ml of dimethylformamide are stirred together at bO in an autoclave for Z hours. The mixture is diluted with water and extracted with ethyl acetate and the extract is evaporated to give a dark oil. A little methylene chloride is added and the crystalline precipitate formed is separated off to give 8.7 g of 2-amino-4-methyl-6-(1,1~2~
trifluoro-2-chloro-ethoxy~-pyrimidine of melting point 73-74C.
The end products listed in the following table are obta;ned ;n a sim;lar manner~

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X ¦ A IE ! 3 I R4 M e l t 1 n 9 p o i n t 701 C~F2 ¦CH ¦ OCH3 OCHF2 145-149 702 CHF2 jCH CH3 OCHF2 704 C~F2 CH CH3 ~O-CH2-CF I

706 O ¦ -CF2-CHF~ CH OCtl3 1 OC~IF2 710 O -CF -CHF N OC~-3 2 F3 ~;~3~f~

Formulation Examples Example 8: Formulat;on examples for active substances of the formula I (% per cent by weight) a) Wettable powder a) b) c) active substance 20X bO% 0.5 Na lign;n-sulfonate 5% 5% 5%
Na lauryl-sulfate 3~ - -r~a diisobutylnaphthalene-sulfonate - 6% 6%
octylphenol-polyethylene glycol ether ~7-8 mols of ethylene oxide) - 2% 2%
h;ghly d;sperse s;lica 5% 27% 27%
kaolin ~7%
sod;um chloride - - 5~,5%
The active substance is mixed thoroughly with the adjuvants and the mixture is ground well in a suitable mill.
Wettable powders are obtained which can be diluted w;th water to give suspensions of any desired concentration.
b) Emulsion concentrate a) b~
active substance 10X 1%
octylphenol-polyethylene glycol ether (4-5 mols of ethylene oxide~ 3X 3%
Ca dodecylbenzenesulfonate 3% 3%
castor oil polyglycol ether (36 mols of ethylene oxide) 4% 4~
cyclohexanone 30% 10%
xylene mixture 50~ 79~
Emulsions of any desired concentra-t;on can be pre-pared from -this concentrate by dilut;on w;th ~later.
c) Dusts a) b) active substance 0.1~ 1X
talc 99.9%
kaol;n - 99%
Ready-to-use dusts are obtained by mixing the active substance w;th the carr;er and gr;nd;ng t'ne mixture on a suitable m;ll.
d) Extruded granules a) b) act;ve substance 10~ 1 B

Na lignin-sulfonate 2~o 2%
carboxymethylcellulose 1% 1%
kaolin 87~ 96%
The act;ve substance ;s m;xed with the adjuvants, and the mixture is ground and moistened with water. This mixture is extruded and the extruded mater;al is then dried in a stream of air.
e) Coated granules act;ve substance 3X
polyethylene glycol (molecular weight 200) 3%
kaolin 94%
The f;nely ground active substance is uniformly applied to the kaolin, moistened with polyethylene glycol, in a mixer. This gives dust-free coated granulesO
f) Suspension concentrate a) b) active substance 40% 5%
ethylene glycol 10X 10 nonylphenol-polyethylene glycol ether (15 mols of ethylene oxide) 6% 1X
Na lignin-sulfonate 10% 5%
carboxymethylcellulose 1X 1X
37Y aqueous formaldehyde solution 0.2% 0.2X
silicone oil in the form of a 75% aqueous emulsion 0.8% 0.8X
water 32% 77%
The finely ground active substance is intimately mixed with the adjuvants to give a suspension concentrate from which suspensions of any desired concentrat;on can be prepared by dilut;on with water.
g) Salt solution active substance SX
isopropylamine 1%
octylphenol-polyethylene glycol ether (78 mols of ethylene oxide) 3%
water 91%

~L23~

~ 5~ -B;ological Examples Example 9: Demonstration of the herbicidal action before emergence of the plants Plant seeds are sown in flowerpots 12-15 cm in dia-meter in a greenhouse. Immediately thereafter, the 50i l surface is treated w;th an aqueous dispersion or solution of the active substances. Concentrations of 4 k~ of active substance per hectare are used. The pots are then kept at a temperature of 22-25C and at 50-70~ relative atmospheric hum;dity ;n the greenhouse. The experiment is evaluated after 3 weeks, and the action on the experimental plants is rated accord;ng to the following scale:
1: Plants have not germinated or have been totally destroyed 2-3: Very powerful action
4-6: Moderate action 7-~: Weak action 9: No act;on (as untreated control).
Pre-emergence action Amount used: 4 kg of act;ve substance/hectare _ Compound No. Avena Setaria Sinapis Stellaria 3~ 2 ~ ~ 2 Example 10: Demonstration of the selectivity in pre-emergence use In the same experimental design as in Example 9, a larger number of plant seeds are treated with various amounts of active substance. The experiment was evaluated according to the same scale.

~L2~9L9f~

Pre-emergence action:
~ . . .
Action Compound Compound Compound _No. 1 No. 6 No. Z5 kg of active substance . û.06 0.03 0.06 0.03 0.06 0.03 applied/ha of test plants Wheat 9 9 7 9 9 9 Maize 2 6 6 7 9 9 Alopecurus myos. 2 2 4 6 6 6 Cyperus escul. 5 6 2 2 4 4 Abutilon 3 3 2 3 3 3 Chenopod;um sp. 3 3 2 2 3 3 Ipomoea 4 8 2 2 8 9 S;napis 2 2 2 2 2 2 Galium 4 4 2 2 2 3 _ ola tr;color 2 2 1 1 2 3 Example 11: Demonstration of the herbicidal action after emergence of the plants (contact action) A number of both monocotyledonous and d;cotyledonous weeds and crop plants are sprayed, after emergence, ;n the 4- to 6~leaf stage w;th an aqueous active substance disper-sion in dosages of 4 kg o-f active substance~ha, and are then kept at 24 to 26C and at 4~-60% relative atmospheric hurnidity. The experiment is evaluated 15 days a-fter the treatment and the plants are rated accord;ng to the same scale as in the pre-emergence experiment.
Post-emergence action Amount applied: 4 kg of active substance/hectare __ __ _ , , , , Com-p urd Avena Setaria Loli~m~Solanum¦Sinapis~Stellaria Phaseolus 2 2 2 3 ¦ 2 L 2 ¦ 2 3 Example 12: Demonstration of the selectivity in post-emergence use In the same exoerimental des;gn as in Example 11, a larger number of plants are treated ~ith various amounts of ~LZ~
- 5~ -active substance. The evaluation was carried out according to the scale given in Example 9.
Post-emergence action Action Compound Compound . __ No. 6 No. 25 kg of active substance 0.06 0.03 0~06 0O03 applied/ha of test plants Wheat ~ 9 9 9 Ma;ze 9 9 9 9 Dry rice 7 9 9 9 Cyperus escul. 3 4 4 4 Cotton 9 9 9 9 Xanth;um sp. 2 2 1 1 Chenopodium sp. 3 3 9 9 Sinapis 2 3 3 4 Galium aparine 1 2 6 7 Viola tr;color 3 ~ 3 4 Example 13: Demonstration of the ;nhibition of sprouting of stored potatoes _ _ A number of commercially available potatoes of the "Urgenta" variety without sprouts are washed and dried. The po-tatoes are then immersed in active substance emulsions of various concentrations~ in each case for one minute, and are then laid out on filter paper in plastic dishes and kept at temperatures of 14 and 21~ in -the dark at 50% relative atmospheric humidity. Evaluation was ef-fected 34 days after the application. At the same time, the weight loss of the tubers and the weight of sprouts were determined~ in compari-son with the untreated control. In this experiment, the compounds according to the invention showed complete preven-tion of sprouting. At the same time~ the weight loss of the potatoes was less than 10X of the weight loss of the control potatoes.
Example 14: Demonstration of the inhibition of growth in tropical leguminosae cover crops .. . ..
Test plants of the Psophocarpus palustris and ~2~f-~

_ 59 _ Centrosema pubescens var;ety are grown, from cuttings, ;n plast;c d;shes containing a soil/oeat/sand mixture (1:101).
After the small plants have taken root, they are repotted in 9 cm pots and watered as required. Further cult;vation of the plants takes place ;n a greenhouse at a daytime tempera-ture of 27C and a n;ghttime temperature of 21C, with a mean period of light of 14 hours (6000 lux) and at an atmos-pheric humidity of 70X. The test plants are cut back to a he;ght of about 15 cm and, 7 days thereafter, are sprayed w;th a spray l;quor of the act;ve substance (calculated as 0.3 or ~ kg of act;ve substance per hectare). 4 weeks after the appl;cat;on~ the growth of t'ne treated plants is corn-pared w;th that of control plants wh;ch have been pruned but not treated. In this experiment, the plants treated ~ith the act;ve substances of the formula I show a dist;nct reduct;on in new add;tional growth (less than 2r~o~ of the new additional growth cf untreated control plants) without the experimental plants thereby be;ng damaged.
Example 15: Demonstration of Dre-emergence selectiv;ty in soybe n crops The experimental plants are sown in sandy/loamy arable soil in plastic containers having a capacity of 3~ l (60x30x25 cm), and are covered with a layer of soil 1-Z cm deep and watered with water. After one day, the active sub-stance ;s a?plied in the form of an aqueous spray liquor in an amount corresponding -to 500 l/ha and in concentrations corresponding to 60 g/ha and 30 g/ha. The containers are then kept in a greenhouse at temperatures of 20-~5C and are watered as required. After 33 days, the experiment is evaluated and the plants are rated according to the sarne scale as in Exarnple 9.

Pre-emergence action ;n soybean crops Active substance No~ 31 Experimental plants Amount applied .
___ 0.06 kg/ha 0.03 kg/ha Soybean 7 8 Amaranthus ret. 2 3 Ipomoea p. 3 4 Portulaca o. 1 2 arachiaria pl. 3 4 Xanthium can. 3 3 _xample 16: Growth regulation of soybeans Soybeans of the "Hark" var;ety are sown in a soil/peat/sand m;xture in the ratio o:3:1 ;n plastic con-tainers and are placed in a cl;matically controlled chamber.
As a result of optimum selection of the temperature, ;llumina-tionr addition of fertiliser and water;ng, the plants have developed as far as the 5-6 trifoliate-leaf stage after about 5 weeks~ At this point in time, the plants are sprayed with the aqueous liquor of an active substance of the formula I until thoroughly wetu The concentration is up to 100 9 of active substance/ha. The evaluation is effected about 5 weeks after application of the active substance.
The active substances of the formula I according to the invention cause a noticeable increase in the number and weight of silicles on the main stem in comparison with the untreated control plants.

~Z3~

Growth-regulating action in soybean crops _ Active substance No. 31 _ Amount Height of plants Number of si~icles¦ Weight of silicles applied in X relative on the main stem on the main stem g/hato the control in ~ relative in % relative to the control to the control .. ~ . __ . ._

Claims (31)

WHAT IS CLAIMED IS:
1. An N-phenylsulfonyl-N'-pyrimidinyl- or -triazinyl-urea of the formula I

(I) in which A is a C1-C6-alkyl radical which is substituted by halogen, C1-C4-alkoxy, C1-C4-alkylthio, C1-C4-alkyl-sulfinyl, C1-C4-alkylsulfonyl, C1-C4-halogenoalkoxy, C1-C4-halogenoalkylthio, C1-C4-halogenoalkylsulfinyl or C1-C4-halogenoalkylsulfonyl, or is a C2-C6-alkenyl radical substituted by the above radicals, E is the methine group or nitrogen, X is oxygen, sulfur or a sulfinyl or sulfonyl bridge, Z is oxygen or sulfur, m is the number one or two, R1 is hydrogen, halogen, C1-C5-alkyl, C2-C5-alkenyl or a -Y-R5 radical, R2 is hydrogen, halogen, C1-C5-alkyl, C2-C5-alkenyl, C1-C4-halogenoalkyl or a -Y-R5, -COOR6, -N02 or -CO-NR7-R8 radical, R3 is hydrogen, C1-C4-alkyl, C1-C4-alkoxy, C1-C4-alkylthio, C1-C4-halogeno-alkyl, halogen or C1-C4-halogenoalkoxy, or alkoxyalkyl having not more than 4 carbon atoms, R4 is C1-C4-halogenoalkoxy or C1-C4-halogenoalkylthio, R5 and R6 are each C1-C5-alkyl, C2-C5-alkenyl or C2-C6-alkynyl, R7 and R8 independently of one another are hydrogen, C1-C5-alkyl, C2-C5-alkenyl or C2-C6-alkynyl and Y is oxygen, sulfur or a sulfinyl or sulfonyl bridge, and in which A can also be an unsubstituted C2-C6-alkenyl radical if X is simultaneously oxygen, and the salts of this compound.
2. A compound according to claim 1, in which A is a C1-C6-alkyl radical which is substituted by halogen, C1-C4-alkoxy, C1-C4-alkylthio, C1-C4-alkylsulfinyl, C1-C4-alkylsulfonyl, C1-C4-halogenoalkoxy, C1-C4-halogenoalkyl-thio, C1-C4-halogenoalkylsulfinyl or C1-C4-halogenoalkyl-sulfonyl, or is a C2-C6-alkenyl radical substituted by the above radicals, E is the methine group or nitrogen, X is oxygen, sulfur or a sulfinyl or sulfonyl bridge, Z is oxygen or sulfur, m is the number one or two, R1 is hydrogen, halogen, C1-C5-alkyl, C2-C5-alkenyl or a -Y-R5 radical, R2 is hydrogen, halogen, C1-C5-alkyl, C2-C5-alkenyl, C1-C4-halogenoalkyl or a -Y-R5, -COOR6, -NO2 or -C0-NR7-R8 radical, R3 is hydrogen, C1-C4-alkyl, C1-C4-alkoxy, C1-C4 alkylthio, C1-C4 halogenoalkyl, halogen or alkoxyalkyl having not more than 4 carbon atoms, R4 is C1-C4-halogenoalkoxy, R5 and R6 are each C1-C5-alkyl, C2-C5-alkenyl or C2-C6-alkynyl, R7 and R8 independently of one another are hydrogen, C1-C5-alkyl, C2-C5-alkenyl or C2-C6-alkynyl and Y is oxygen, sulfur or a sulfinyl or sulfonyl bridge, and in which A can also be an unsubstituted C2-C6-alkenyl radical if X is simultaneously oxygen, and the salts of this compound.
3. A compound according to claim 1, in which Z is oxygen.
4. A compound according to claim 1, in which X is oxygen.
5. A compound according to claim 1, in which the radi-cals R3 and R4 together contain not more than 4 carbon atoms.
6. A compound according to claim 1, in which m is the number one.
7. A compound according to claim 1, in which X and Z
are oxygen, m is the number one and the radical -X-A is in the 2-position relative to the sulfonyl group.
8. A compound according to claim 7, in which the radi-cals R3 and R4 together contain not more than 4 carbon atoms.
9. A compound according to claim 8, in which R4 is halogenoethoxy.
10. A compound according to claim 8, in which R4 is halogenomethoxy.
11. A compound according to claim 9, in which R4 is the 2,2,2-trifluoroethoxy radical.
12. A compound according to claim 10, in which R4 is the difluoromethoxy radical.
13. N-(2-Difluoromethoxyphenyl-sulfonyl)-N'-[4-methoxy-6-(2,2,2-trifluoroethoxy)-1,3,5-triazin-2-yl]-urea according to claim 1.
14. N-(2-Difluoromethoxyphenyl-sulfonyl)-N'-(4-difluoro-methoxy-6-methylpyrimidin-2-yl)-urea according to claim 1.
15. A process for the preparation of a compound of the formula I according to claim 1, which comprises a) reacting a phenylsulfonamide of the formula II

(II) in which A, R1, R2, X and m are as defined under formula I, with an N-pyrimidinyl- or -triazinyl-carbarnate of the formula III

(III) in which E, R3, R4 and Z are as defined under formula I and R11 is hydrogen, halogen, nitro or C1-C3-alkyl, in the presence of a base, or b) reacting a phenylsulfonyl isocyan-ate or isothiocyanate of the formula IV

(IV) in which A, R1, R2, m, X and Z are as defined under formula I, with an amine of the formula V

(V) in which E R3 and R4, are as defined under formula I, in the presence or absence of a base, or c) reacting a sulfonamide of the above formula II with an isocyanate or isothiocyanate of the formula VI

(VI) in which E, R3, R4 and Z are as defined under formula I, in the presence or absence of a base, or d) reacting an N-phenylsulfonyl-carbamate of the formula VII

(VII) in which A, R1, R2, m and X are as def;ned under formula I
and R11 ;s hydrogen, halogen, nitro or C1-C3-alkyl, with an amine of the above formula V and, if appropriate, con-verting the sulfonylurea of the formula into a salt by reacting it with an amine, an alkali metal or alkaline earth metal hydroxide or a quaternary ammonium base.
16. A process for the preparation of a compound of the formula I according to claim 1, which comprises reacting a phenylsulfonamide of the formula II

(II) in which A, R1, R2, X and m are as defined under formula I, with an N-pyrimidinyl- or -triazinyl-carbamate of the formula III

(III) in which E, R3, R4 and Z are as defined under formula I
and R11 is hydrogen, halogen, nitro or C1-C3-alkyl, in the presence of a base and, if appropriate, converting the sulfonylurea of the formula I into a salt by reacting it with an amine, an alkali metal or alkaline earth metal hydroxide or a quaternary ammonium base.
17. A process for the preparation of a compound of the formula I according to claim 1, which comprises re-acting a phenylsulfonyl isocyanate or isothiacyanate of the formula IV

(IV) in which A, R1, R2, m, X and Z are as defined under formula I, with an amino of the formula V

(V) in which E, R3 and R4 are as defined under formula I, in the presence or absence of a base, and, if appropriate, con-verting the sulfonylurea of the formula I into a salt by reacting it with an amine, an alkali metal or alkaline earth metal hydroxide or a quaternary ammonium base.
18. A process for the preparation of a compound of the formula I according to claim 1, which comprises reacting a sulfonylamide of the above formula II as defined in claim 16 with an isocyanate or isothiocyanate of the formula VI

(VI) in which E, R3, R4 and Z are as defined under formula I, in the presence of absence of a base, and, if appropriate, converting the sulfonylurea of the formula I into a salt by reacting it with an amine, an alkali metal or alkaline earth metal hydroxide or a cluaternary ammonium base.
19. A process for the preparation of a compound of the formula I according to claim 1, which comprises reacting an N-phenylsulfonyl-carbamate of the formula VII

(VII) in which A, R1, R2, m and X are as defined under formula I and R11 is hydrogen, halogen, nitro or C1-C3-alkyl, with an amine of the formula V as defined in claim 17, and, if appropriate convert-ing the sulfonylurea of the formula I into a salt by reacting it with an amine, an alkali metal or alkaline earth metal hydroxide or a quaternary ammonium base.
20. A method of controlling undesired plant growth, which method comprises applying thereto or to the locus thereof a herbi-cidally effective amount of a compound according to claim 1, or of an agriculturally acceptable composition containing a compound of the formula I as defined in claim 1.
21. A method of suppressing plant growth, which method comprises applying thereto or to the locus thereof an effective amount of a compound according to claim 1, or of an agriculturally acceptable composition containing a compound of the formula I as defined in claim 1.
22. A method according to claim 20 for selectively control-ling weeds in crops of cultivated plants, which method comprises applying the compound or composition premergence or post-emergence.
23. A method according to claim 22 for controlling weeds in crops of cereals, maize, rice and cotton.
24. A method according to claim 22 for controlling weeds in crops of soybeans.
25. A method according to claim 21 for suppressing plant growth further than the two-leaf stage, which method comprises applying the compound or composition pre-emergence.
26. A method of regulating plant growth in order to achieve greater yields, which method comprises applying thereto or the locus thereof an effective amount of a compound according to claim 1, or of an agriculturally acceptable composition containing a compound of the formula I as defined in claim 1.
27. A method according to claim 26 for regulating plant growth in crops of soybeans.
28. A method according to claim 21 for suppressing the growth of cover crop leguminosae.
29. N-[2-(2-Chloroethoxy)-phenyl-sulfonyl]-N'-[4-methoxy-6-(2,2,2-trifluoroethoxy)-1,3,5-triazin-2-yl]-urea according to claim 1.
30. N-(2-Trifluoromethoxyphenyl-sulfonyl)-N'-(4-difluoro-methoxy-6-methyl-pyrimidin-2-yl)-urea according to claim 1.
31. A herbicidal composition containing an agriculturally acceptable carrier and, as effective ingredient, a compound of the formula I as defined in claim 1.
CA000408671A 1981-08-06 1982-08-04 N-phenylsulfonyl-n'-pyrimidinyl- and -triazinyl-ureas Expired CA1231948A (en)

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KR840001149A (en) 1984-03-28

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