CA1222752A - Sulfonylureas and sulfonylthioureas, the preparation thereof, and method of use thereof as herbicides and/or growth regulators - Google Patents
Sulfonylureas and sulfonylthioureas, the preparation thereof, and method of use thereof as herbicides and/or growth regulatorsInfo
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Abstract
Case 5-13938/=
Novel sulfonylureas and sulfonylthioureas, the preparation thereof, and method of use thereof as herbicides and/or growth regulators ABSTRACT
The invention relates to novel sulfonylureas of the formula I
(I) wherein R1 is hydrogen or C1-C5alkyl, R2 and R3, each independently of the other, are hydrogen, C1-C5alkyl, C1-C5alkoxy, C1-C5alkylthio, C1-C5haloalkyl,halogen,C1-C5haloalkyl-thio, C1-C4alkylamino, C1-C4dialkylamino, an alkoxyalkyl group or alkoxyalkoxy group, each containing not more than 6 carbon atoms, Z is oxygen or sulfur, E is -CH= or -N=, and Q is an unsubstituted or substituted 6-membered heterocyclic radical containing 2 to 3 nitrogen atoms and bound through a carbon atom, and the salts thereof.
A process for the preparation of the novel compounds and the use there-of are also described. The compounds of formula I can be used in the form of agriculturally useful compositions for controlling weeds and/
or for selectively influencing plant growth.
Novel sulfonylureas and sulfonylthioureas, the preparation thereof, and method of use thereof as herbicides and/or growth regulators ABSTRACT
The invention relates to novel sulfonylureas of the formula I
(I) wherein R1 is hydrogen or C1-C5alkyl, R2 and R3, each independently of the other, are hydrogen, C1-C5alkyl, C1-C5alkoxy, C1-C5alkylthio, C1-C5haloalkyl,halogen,C1-C5haloalkyl-thio, C1-C4alkylamino, C1-C4dialkylamino, an alkoxyalkyl group or alkoxyalkoxy group, each containing not more than 6 carbon atoms, Z is oxygen or sulfur, E is -CH= or -N=, and Q is an unsubstituted or substituted 6-membered heterocyclic radical containing 2 to 3 nitrogen atoms and bound through a carbon atom, and the salts thereof.
A process for the preparation of the novel compounds and the use there-of are also described. The compounds of formula I can be used in the form of agriculturally useful compositions for controlling weeds and/
or for selectively influencing plant growth.
Description
Case 5-13938/=
Novel sulfonylureas and sulfonylthioureas, the preparation thereof, and method of use thereof as herbicides and/or growth regulators .. . ~. , . . . .~
The present invention relates to a group of novel sulfonylureas and sulfonylthioureas which have valuable growth regulating properties and which are suitable for selectively-influencin~ Plant growthS
for the control of weeds e g. in crops of useful plants and/or for influencing the phytotoxic properties of other herbicidal compounds.
The invention also relates to the preparation of these sulfonylureas and sulfonylthioureas, and to agricultural compositions which con-tain them.
~ccordingly, the invention relates to compounds of the formula I
Q_SO2_NH_C_N_~
Rl 3 wherein Rl is hydrogen or Cl-C5alkyl, R2 and R3, each independently of the other, are hydrogen, Cl-C5alkyl, Cl-C5alkoxy, Cl-C5alkylthio, Cl-C5haloalkyl,halogen~clC5haloalkyl-thio, Cl~C4alkylamino, Cl-C4dialkylamino, an alkoxyalkyl group or alkoxyalkoxy group, each containing not more than 6 carbon atoms, Z is oxygen or sulfur, R is -CH= or -N=, and Q is an unsubstituted or substituted 6-membered heterocyclic radical containing 2 to 3 nitrogen atoms and bound through a carbon atom, and the salts thereof.
sæ
Depending on the indicated number of carbon atoms, alkyl by itself or as moiety of another substituent will be understood as meaning e.g.
the following groups: methyl, ethyl, propyl, butyl or pentyl and the isomers thereof such as isopropyl, isobutyl, tert-butyl, isopentyl etc.
Haloalkyl denotes a monohalogenated or perhalogenated alkyl radical, e-g. CF3, CH2Cl, CC13, CHC12, CH2I, C2H4Cl, C2H4Br, C~2~r etc. Through-out this specification, halogen denotes fluorine, chlorine, bromine or iodine, with fluorine, chlorine or bromine being preferred. Agri-culturally suitable salts are e.g. those which the compounds of formula I form with amines, alkaline metal bases or alkaline earth metal bases, or with quaternary ammonium bases. Suitable alkali metal or alkaline earth metal bases will be understood as meaning here in particular the hydroxides, such as lithium, sodium, potassium, magnesium or calcium hydroxide.
~xamples of suitable salt-forming amines are primary, secondary and tertiary aliphatic and aromatic amines such as methylamine, ethyl-amine, propylamine, isopropylamine, the four butylamine isomers, dimethylamine~ diethylamine, diethanolamine, dipropylamine, diiso-propylamine, di-n-butylamine, pyrrolidine, piperidine, morpholine, trimethylamine, triethylamine, tripropylamine, quinuclidine, pyridine, quinoline and isoquinoline. Preferred amines are ethylamine, propyl-amine, diethylamine or triethylamine, with isopropylamine and dieth-anolamine being most preferred.
Examples of quaternary ammonium bases are, in general, the cations of haloammonium salts, e.g. the tetramethylammonium cation, the tri-methylbenzylammonium cation, the triethylbenzylammonium cation, the tetraethylammonium cation, the trimethylethylammonium cation, and also the ammonium cation.
~ ~p~
Typical substituents of the radical Q in formula I are: halogen, pseudohalogen, nitro, alkyl, haloalkyl, alkoxy, alkylthio, haloalkoxy, haloalkylthio, amino, alkylamino, dialkylamino, alkylcarbonylamino~
alkylcarbonyl, alkoxycarbonyl, alkylthiocarbonyl, carbamoyl, alkyl-aminocarbonyl, dialkylaminocarbonyl, alkylsulfinyl, alkylsulfonyl, alkenyloxy, alkynyloxy, and the following groups such as phenyl, phenoxy or phenylthio, which are unsubstituted or substituted by halogen, nitro, cyano, alkyl, alkoxy, haloalkyl or haloalkoxy, and also benzyl or benzyl substituted by halogen and/or alkyl. Preferred substituents are those containing not more than 6, preferably not more than ~, carbon atoms in the aliphatic moiety.
The following 6-membered heterocyclic radicals Q are typical substi-tuents within the scope of this invention: pyrimidine, pyridazine, pyrazine and triazine, with pyrazine being preferred.
The heterocyclic radical Q may be unsubstituted or contain one or more substituents.
The compounds of formula I are biologically active oils, resins or solids which are stable at room temperature and have very valuable growth regulating, in particular, growth inhibiting, properties.
They can therefore be used in agriculture or related fields for selectively reducing the growth of monocot and dicot plants. Depending on the mode of application or on the rate of application, the com-pounds act as selective or total herbicides.
A preferred group of compounds of formula I comprises those compounds wherein Z is oxygen and Rl is hydrogen.
A particularly preferred group of compounds of formula I comprises those compounds wherein Rl is hydrogen, each of R2 and R3 independent-ly of the other is Cl-C3alkyl, Cl-C3alkoxy, Cl-C3haloalkyl, Cl-C3halo-alkoxy, halogen or C2-C4alkoxyalkyl, Z is oxygen, E is nitrogen or CH, Q is a heterocyclic radical as defined for formula I which is unsubstituted or substituted by a member selected Erom chlorine, bromine, fluorine, nitro, cyano, Cl-C4alkylcarbonyl, Cl-C4alkoxy-carbonyl, Cl-C3alkoxy, Cl-C3alkylthio, C3-C5alkoxyalalkoxy~Cl-C3-alky sulfinyl, Cl-C3alkylsulfonyl, Cl-C4alkyl, trifluoromethyl, trichloro-methyl, Cl-C4cyanoalkyl, C2-C~alkenyloxy, C3-C4alkynyloxy or N-Cl-C4alkylcarbonylamino.
Particularly preferred individual compounds are:
N-(2-methylpyrazin-3--yl~ulfonyl)-N'-t4-methoxy-6-methyl-1,3,5-triazin-
Novel sulfonylureas and sulfonylthioureas, the preparation thereof, and method of use thereof as herbicides and/or growth regulators .. . ~. , . . . .~
The present invention relates to a group of novel sulfonylureas and sulfonylthioureas which have valuable growth regulating properties and which are suitable for selectively-influencin~ Plant growthS
for the control of weeds e g. in crops of useful plants and/or for influencing the phytotoxic properties of other herbicidal compounds.
The invention also relates to the preparation of these sulfonylureas and sulfonylthioureas, and to agricultural compositions which con-tain them.
~ccordingly, the invention relates to compounds of the formula I
Q_SO2_NH_C_N_~
Rl 3 wherein Rl is hydrogen or Cl-C5alkyl, R2 and R3, each independently of the other, are hydrogen, Cl-C5alkyl, Cl-C5alkoxy, Cl-C5alkylthio, Cl-C5haloalkyl,halogen~clC5haloalkyl-thio, Cl~C4alkylamino, Cl-C4dialkylamino, an alkoxyalkyl group or alkoxyalkoxy group, each containing not more than 6 carbon atoms, Z is oxygen or sulfur, R is -CH= or -N=, and Q is an unsubstituted or substituted 6-membered heterocyclic radical containing 2 to 3 nitrogen atoms and bound through a carbon atom, and the salts thereof.
sæ
Depending on the indicated number of carbon atoms, alkyl by itself or as moiety of another substituent will be understood as meaning e.g.
the following groups: methyl, ethyl, propyl, butyl or pentyl and the isomers thereof such as isopropyl, isobutyl, tert-butyl, isopentyl etc.
Haloalkyl denotes a monohalogenated or perhalogenated alkyl radical, e-g. CF3, CH2Cl, CC13, CHC12, CH2I, C2H4Cl, C2H4Br, C~2~r etc. Through-out this specification, halogen denotes fluorine, chlorine, bromine or iodine, with fluorine, chlorine or bromine being preferred. Agri-culturally suitable salts are e.g. those which the compounds of formula I form with amines, alkaline metal bases or alkaline earth metal bases, or with quaternary ammonium bases. Suitable alkali metal or alkaline earth metal bases will be understood as meaning here in particular the hydroxides, such as lithium, sodium, potassium, magnesium or calcium hydroxide.
~xamples of suitable salt-forming amines are primary, secondary and tertiary aliphatic and aromatic amines such as methylamine, ethyl-amine, propylamine, isopropylamine, the four butylamine isomers, dimethylamine~ diethylamine, diethanolamine, dipropylamine, diiso-propylamine, di-n-butylamine, pyrrolidine, piperidine, morpholine, trimethylamine, triethylamine, tripropylamine, quinuclidine, pyridine, quinoline and isoquinoline. Preferred amines are ethylamine, propyl-amine, diethylamine or triethylamine, with isopropylamine and dieth-anolamine being most preferred.
Examples of quaternary ammonium bases are, in general, the cations of haloammonium salts, e.g. the tetramethylammonium cation, the tri-methylbenzylammonium cation, the triethylbenzylammonium cation, the tetraethylammonium cation, the trimethylethylammonium cation, and also the ammonium cation.
~ ~p~
Typical substituents of the radical Q in formula I are: halogen, pseudohalogen, nitro, alkyl, haloalkyl, alkoxy, alkylthio, haloalkoxy, haloalkylthio, amino, alkylamino, dialkylamino, alkylcarbonylamino~
alkylcarbonyl, alkoxycarbonyl, alkylthiocarbonyl, carbamoyl, alkyl-aminocarbonyl, dialkylaminocarbonyl, alkylsulfinyl, alkylsulfonyl, alkenyloxy, alkynyloxy, and the following groups such as phenyl, phenoxy or phenylthio, which are unsubstituted or substituted by halogen, nitro, cyano, alkyl, alkoxy, haloalkyl or haloalkoxy, and also benzyl or benzyl substituted by halogen and/or alkyl. Preferred substituents are those containing not more than 6, preferably not more than ~, carbon atoms in the aliphatic moiety.
The following 6-membered heterocyclic radicals Q are typical substi-tuents within the scope of this invention: pyrimidine, pyridazine, pyrazine and triazine, with pyrazine being preferred.
The heterocyclic radical Q may be unsubstituted or contain one or more substituents.
The compounds of formula I are biologically active oils, resins or solids which are stable at room temperature and have very valuable growth regulating, in particular, growth inhibiting, properties.
They can therefore be used in agriculture or related fields for selectively reducing the growth of monocot and dicot plants. Depending on the mode of application or on the rate of application, the com-pounds act as selective or total herbicides.
A preferred group of compounds of formula I comprises those compounds wherein Z is oxygen and Rl is hydrogen.
A particularly preferred group of compounds of formula I comprises those compounds wherein Rl is hydrogen, each of R2 and R3 independent-ly of the other is Cl-C3alkyl, Cl-C3alkoxy, Cl-C3haloalkyl, Cl-C3halo-alkoxy, halogen or C2-C4alkoxyalkyl, Z is oxygen, E is nitrogen or CH, Q is a heterocyclic radical as defined for formula I which is unsubstituted or substituted by a member selected Erom chlorine, bromine, fluorine, nitro, cyano, Cl-C4alkylcarbonyl, Cl-C4alkoxy-carbonyl, Cl-C3alkoxy, Cl-C3alkylthio, C3-C5alkoxyalalkoxy~Cl-C3-alky sulfinyl, Cl-C3alkylsulfonyl, Cl-C4alkyl, trifluoromethyl, trichloro-methyl, Cl-C4cyanoalkyl, C2-C~alkenyloxy, C3-C4alkynyloxy or N-Cl-C4alkylcarbonylamino.
Particularly preferred individual compounds are:
N-(2-methylpyrazin-3--yl~ulfonyl)-N'-t4-methoxy-6-methyl-1,3,5-triazin-
2-yl)urea and N-(2-methoxypyrazin-3-ylsulfonyl)-N'-(4-methoxy-6-methyl-1,3,5-triazin-2-yl)urea.
The compounds of formula I may be prepared in a manner known per se in an inert organic solvent or mixture of solvents.
The compounds of formula I may be prepared as follows in accordance with equation [1]
Q 2 X-~ (I) [l]
(II) (III) by reacting a phenylsulfonyl derivative of the formula II with a com-pound of the formula III, wherein X and W are -NH2, -N=C=Z or -NRl-CZ-OR groups, the substituents Rl, R2, R3, Q, Z and E are as defined for formula I, R is an aliphatic or atomatic radical, prefer-ably Cl-C4alkyl, phenyl or benzyl, with the proviso that the reac-tants of the formulae II and III are also so chosen that an amino function reacts either with an isocyanato or isothiocyanato function or with the [-NRl-CZ-OR] group.
The process is conveniently carried out in the presence of a base.
It can often be of advantage to carry out the reaction in an inert gas atmosphere, e.g. under nitrogen. The process for preparing the compounds of formula I is an object of the invention.
If desired, the compounds of formula I may be converted into basic, agriculturally suitable addition salts by reaction with amines, alkali metal hydroxides or alkaline earth metal hydroxides, or with quaternary ammonium bases. This is accomplished e.g. by reacting a compound of formula I with an equimolar amount of base and removing the solvent by evaporation. Such reactions, and also the preparation of individual starting materials of the formula III, are known and described e.g. in US patent specifications 3 384 757 and 3 410 887.
The starting compounds of the formula III are known or they are prepared by methods which are known per se.
Some of the compounds of formula II, wherein W is NH2, are known. The novel compounds of formula II have been specially developed for synthesising the compounds of formula I. They therefore constitute an object of the invention.
The starting compounds of formula II, wherein W is -NH-CZ-OR, are novel and have been specially developed for synthesising the compounds of formula I. They therefore also constitute an object of the inven~
tion. They are prepared by methods which are known per se.
The sulfonamides of the formula II can be prepared by reacting the corresponding sulfonyl chlorides or sulfonyl fluorides with ammonia or ammonium hydroxide solutions (seee.g. J.Chem. Soc. Perkin Trans. 1, 1972, 522).
~%2;~
The isocyanates of the formulae II and III can be prepared by phos-genating the corresponding amino compounds, in the presence of butyl-isocyanate and in a chlorinated hydrocarbon as solvent, at reflux temperature. Reference is made in this connection to "Neuere Methoden der praparativen organischen Chemie",Vol. VI, pp. 211-229; Verlag Chemie, Weinheim, 1970. When using thiophosgene9 isothiocyanates of the formulae II and III are obtained in corresponding manner.
:
The isothiocyanates of formula II are also prepared by treating the sulfonamides of formula II with carbon disulfide and potassium hydroxide and subsequently phosgenating the dipotassium salt [see Arch. Pharm. 299, 174 (1966)].
Compounds of the formulae II and III, wherein W and X are the -NRl-CZ-OR group, can be obtained from the corresponding amino com-pounds by reaction with a haloformate or halothioformate of the formula IV
z Hal- C- OR (IV) or with a dicarbonate or dithiocarbonate of the formula V
R- O- C- OR (V) wherein Hal is halogen, preferably chlorine or bromine, Z is oxygen or sulfur and R is an aliphatic or aromatic radical, preferably Cl-C4alkyl, phenyl or benzyl. This reaction is preferably conducted in the presence of a base.
The starting amines of the formula III are known or they can be prepared by per se known methods of synthesising heterocyclic amines (see "The Chemistry of Heterocyclic Compounds", Vol. XVI, Interscience Publishers, New York, London~ in which methods of synthesising2-amino-pyridines and of 2-amino-1,3,5-triazines may be found).
~2~
These reactions are conveniently carried out in aprotic, inert organic solvents such as methylene chloride, tetrahydroEuran, acetonitrile, dioxan, or toluene.
The reaction temperaturesare preferably in the range from -20 to +120C. The reactions are normally slightly exothermic and can be carried out at room temperature. To shorten the reaction time or also to initiate the reaction it is expedient to heat the reaction mixture brief]y to boiling point. The reaction times can also be shortened by addition of a few drops of a base or isocyanate as catalyst.
The compounds of formula I are stable compounds which are of low toxicity to man and animals.
When preparing the compounds of formula I in accordance with equation [1], isomeric reaction products of the formulae Ia and Ib 1 ~
N
Q-S02-NHC -- N~ ~--R2 (la) R3 . =Æ
. N
Q_SO2_NHC \ E/ 3 (Ib) can be isolated in certain cases by addition of a compound of formula Il to a ring nitrogen atom of a compound of formula III. In the formulae Ia and Ib above, Rl, R2, R3, Q, Z and E are as defined for formula I. These isomeric compounds Ia and Ib also influence plant growth. Accordingly, all agrochemically usef:ul compounds and compound mixtures which are obtained by reacting compounds of formula II with compounds of formula III also fall within the province of the present invention. Sulfonylureas containing two to three nitrogen atoms in the 6-membered heterocyclic radical Q are novel.
Surprisingly, it has been found that the novel compounds of formula I
have good selective herbicidal properties and are therefore suitable for use in crops of cultivated plants. Moreover, it can also be ob-served that some of the compounds even damage problem weeds which up to now have only been controlled with total herbicides.
A number of the compounds of formula I are translocatable, i.e. they are absorbed at the treated site of the plant (leaf, stem, root etc.) and transported to other sites where they exert their action. In doing so, they not only follow the path of nutrient transport from the roots to the leaves, but also conversely penetrate to the roots from the leaves. Thus with the aid of this translocatability, e.g.
by means of a surface treatment, it is possible to damage perennial weeds to their roots. Furthermore, compared with conventional herbi-cides, the compounds of formula I are effective even when used in very low rates of application.
In addition9 the compounds of formula I are able to potentiate the phytotoxic action of other herbicides against certain noxious plants and to reduce the toxicity of such herbicides to some cultivated plants. This can lead to a lowering of the total concentration of herbicide and consequently to a reduced environmental impact.
If the rates of application are further lowered, then the growth regulating properties of the compounds of formula I predominate. The compounds exert a selective action on the plant metabolism, which results in particular in a reduction of the vegetative growth often - 9 ~
in favour of the generative growth. This selective influence on the physiological processes of plant development makes the compound of formula I useful for different purposes, especially for those in connection with labour-saving in measures taken in crops of culti-vated plants or for increasing yield.
The compounds of formula I disclosed herein can be used as herbicides and/or as growth regulators. Previous experience with growth regula-tors has shown that the active ingredients are able to induce one or more different responses in the plants. These different responses depend largely on the time of application, i.e. on the development stage of the seed or plant, on the mode of application, and in partic-ular on the concentrations employed. Such responses differ in turn, however, depending on the species of plant. Accordingly, the appli-cation of compounds of formula I affords the possibility of in-fluencing the growth of plants in the desired manner.
Vegetative plant growth is inhibited with the novel compounds of the formula I or with the compositions containing them. By means of this growth inhibition the compounds of the invention are able to increase substantially the yield of plants. Thus the vegetative growth of e.g.
soybean plants and other leguminosae such as beans, peas or lentils is reduced in favour of the generative growth, whereby a direct in-crease in yield is achieved. The vegetative growth of other species of plants, e.g. of vines 9 cereals, grasses and ornamentals, is also inhibited in desired manner. In addition, a significant strengthening of the supporting tissue of the treated plants is ~bserved.
An interesting manner of influencing plant growth derives from the special property of the compounds of formula I of selectively in-fluencing the growth of specific plants, especially cereals. This selective growth inhibition substantially increases the breaking ~ z~q~
strength of the plants while the yield remains unchanged, thereby providing a very interesting method of protecting plant crops from lodging caused by storms or prolonged rainfall. Further, selective inhibition of the vegetative growth of many cultivated plants permits more plants to be grown per unit of crop area, resulting in a signif-icant increase in yield with the same fruit setting and in the same crop area. The use of growth inhibitors also brings about a more effective utilisation of nutrients which are then able increasingly to promote flower formation and fruiting. In this manner, higher yields are achieved while the amount of waste vegetative plant resi-dues ~e.g. straw, potato foliage, beet leaves) is simultaneously reduced.
To be singled out for special mention is also the possibility of in-hibiting the formation of shoots in different types of plants, especiall~ tobacco plants, whenever the main shoot has been pruned shortly before flowering with the object of increasing the growth of the leaves.
Accordingly, the present invention relates to the use of the compounds of formula I as herbicides and/or growth regulators. The invention also relates to a method of controlling weeds pre- and postemergence, of inhibiting the growth of monocot and dicot plants, especially of grasses, cereals and tobacco suckers, as well as of increasing the yield of leguminous plants.
The compounds of the formula I are used in unmodiEied form, or prefer-ably, together with the adjuvants conventionally employed in the art of formulation, and are therefore formulated in known manner to emulsifiable concentrates, coatable pastes, directly sprayable or dilut.lble solutions, dilute emulsiolls, wettable powdcrs, soluble powclcrs, dusts, ~rall~ t~s, ilnd also ~nc l)stJl:ltiolls in ~!.g. pOlylll(`r substallces. Like the nature of the compositions, the meLIIods of application, such as spraying, atomising, dusting, scattering or pouring, are chosen in accordance with the intended objectives and the prevailing circumstances.
The formulations, i.e. the compositions or preparations containing the compound (active ingredient~ of the formula I and, where appropriate, a solid or liquid adjuvant, are prepared in known manner, e.g. by homogeneously mixing and/or grinding the active ingredients with extenders, e.g. solvents, solid carriers and, where appropriate, surface-active compounds (surfactants).
Suitable solvents are: aromatic hydrocarbons, preferably the fractions containing 8 to 12 carbon atOms, e.g. xylene mixtures or substituted naphthalenes, phthalates such as dibutyl phthalate or dioctyl phthalate, aliphatic hydrocarbons such as cyclohexane or paraffins, alcohols and glycols and their ethers and esters, such as ethanol, ethylene glycol monomethyl or monoethyl ether, ketones such as cyclo-hexanone, strongly polar solvents such as N-methyl-2-pyrrolidone, dimethyl sulfoxide or dimethyl formamide, as well as epoxidised vege-table oils such as epoxidised coconut oil or soybean oil; or water.
Tlle solid carriers used e.g. for dusts and dispersible powders, are normally natural mineral fillers such as calcite, talcum, kaolin, montmorillonite or attapulgite. In order to improve the physical properties it is also possible to add highly dispersed silicic acid or highly dispersed absorbent polymers. Suitable granulated adsorptive carriers are porous types, for example pumice, broken brick, sepiolite or bentonite; and suitable nonsorbent carriers are materials r ~7~2 such as calcite or sallcl. In ~ddition, a gr~at nulllb~r of pregranlllated mnt~ri~ls of inorg;lllic or or~ ic n~ture c~\n be u;~cl. e.~. esl-ecially dolomite or pulverised plant residues.
Depending on the nature of the compound of the formula I to be formu-lated, suitable surface-active compounds are nonionic, cationic and/
or anionic surfactants having good emulsifying, dispersing and wetting properties. The term "surfactants" will also be understood as comprising mixtures of surfactants.
Suitable anionic surfactants can be both water-soluble soaps and water-soluble synthetie surface-aetive eompounds.
Suitable soaps are the alkali metal salts, alkaline earth metal salts or unsubstituted or substituted ammonium salts of higher fatty aeids tClO-C22), e.g. the sodium or potassium salts of oleie or stearic acid, or of natural fatty acid mixtures which can be obtained e.g. from coconut oil or tallow oil. Mention may also be made of fatty acid methyltaurin salts.
More frequently, however, so-called synthetic surfactants are used, espeeially fatty sulfonates, fatty sulfates, sulfonated benzimidazole derivatives or alkylarylsulfonates.
The fatty sulfonates or sulfates are usually in the form of alkali metal salts, alkaline earth metal salts or unsubstituted or substi-tuted ammoniums salts and contain a C8-C22alkyl radical which also includes the alkyl moiety of acyl raclicals, e.g. the sodium or calcium salt of lignonsulfonic acid, of dodecylsulfate or of a mixture of fatty alcohol sulfates obtained from natural fatty acids. These compounds also comprise the salts of sulfuric acid esters and sulfonic acids of fatty alcohoL/ethylene oxide adducts. The sulfonated benz-imidazole derivatives preferably contain 2 sulfonic acid groups and one fatty acid radical containing 8 to 22 carbon atoms. Examples ~L~d~752 - 13 ~
of alkylarylsulfonates are the sodium, calcium or tricthanolamine s~lts of do(lecyll)el)z~ sulfollic acid, dibutyl~ LIl~llene~slllfollic aeid,or of a naplltllalenesulfonic aci~/foL~naldehyde condensation product.
Also suitable are corresponding phosphates, e.g. salts of the phosphoric acid ester of an adduct of p-nonylphenol with 4 to 14 moles of ethylene oxide, or phospholipids.
Non-ionic surfactants are preferably polyglycol ether derivatives of aliphatic or cycloaliphatic alcohols, or saturated or unsaturated Eatty acids and alkylphenols, said derivatives containing 3 to 30 glycol ether groups and 8 to 20 carbon atoms in the (aliphatic) hydrocarbon moiety and 6 to 18 carbon atoms in the alkyl moiety of the alkylphenols.
Further suitable non-ionic surfactants are the water-soluble adducts of polyethylene oxide with polypropylene glycol, ethylenediamine propylene glycol and alkylpolypropylene glycol containing 1 to 10 carbon atoms in the alkyl chain, which adducts contain 20 to 250 ethylene glycol ether groups and 10 to 100 propylene glycol ether groups. These compounds usually contain 1 to 5 ethylene glycol units per propylene glycol unit.
Representative examples of non-ionic surfactants are nonylphenol-polyethoxyethanols, castor oil polyglycol ethers, polypropylene/poly-ethylene oxide adducts, tributylphenoxypolyethoxyethanol, polyethylene glycol and octylphenoxyethoxyethanol. Fatty acid esters of polyoxy-ethylene sorbitan and polyoxyethylene sorbitan trioleate are also suitable non-ionic surfactants.
Cationic surfactants are preferably quaternary ammonium salts which contain, as ~-substituent, at least one C8-C22alkyl radical and, as further substitucnts, lower unsubstituted or halogenated alkyl, benzyl or lower hydroxyalkyl radicals. The salts are preferably in the form of halides, metilylsulfates or ethylsulfates, e.g. stearyltrimethyl-ammonium chloride or benzyldi(2-chloroethyl)ethylamlllonium bromide.
~22~52 I`he surractal~ts custo~ari1y employed in the art oE formulation are descril)ed e.g. in "McCutcheon's Detergent~ and Imu1sifiers Annual", ~IC Publishing Corp. Ridgewood, New Jersey, 1979, and Sisley and Wood, "Encyclopedia of Surface Active Agents", Chemical Publishing Co., Inc.
New York, 1964.
The pesticidal compositions usually contain 0.1 to 95%, preferably 0.1 to 80%, of a compound of the formula I, 1 to 99.9% of a solid or liquid adjuvant, and 0 to 25%, preferably 0.1 to 25%9 of a surfactant.
Preferred formulations are composed in particular of the following constituents (% = percentage by weight):
Emulsifiable eoncentrates active ingredient:1 to 20%, preferably 5 to 10%
surfactant:5 to 30%, preferably 10 to 20%
liquid carrier:50 to 94%, preferably 70 to 85%
Dusts active ingredient:0.1 to 10%, preferably 0.1 to 1%
solid carrier:99.9 to 90%, preferably 99.9 to 99%
Suspension concentrates active ingredient:5 to 75%, preferably 10 to 50%
water:94 to 25%, preferably 90 to 30%
surfactant:l to 40%, preferably 2 to 30%
Wettable powders:
active ingredient:0.5 to 90%, preferably 10 to 80%
surfactant:0.5 to 20%, preferably l to 15%
solid carrier: 5 to 95%, preferably 15 to 90%
~'227~i~
~ 15 -Granulates act;ve ingred;ent:0.5 to 30%, preferably 3 to 15%
solid carrier:99.5 to 70~, preferably 97 to 85~.
Whereas commercial products will be preferably formulated as concen-trates, the end users will normally employ dilute formu]ations. The formulations can be diluted to a concentration as low as 0.001~. The rates of application are normally from 0.01 to 10 kg a.i./ha.
The compositions may also contain further ingredients, such as stabi-lisers, antifoams, viscosity regulators, binders, tackifiers as well as fertilisers or other active ingredients in order to obtain special effects.
The invention also relates to agriculturally suitable compositions which contain at least one compound of formula I as active ingredient.
Furthermore, the present invention relates to a process for the preparation of such compositions, which comprises intimately mixing the active ingredient with one or more substances or groups of sub-stances described herein. The invention also relates to a method of treating plants, which comprises applying thereto the compounds of formula I or the novel compositions containing them.
In the following Examples parts and percentages are by weight.
Preparatory Example _ample 1:
a) 3-Chloropyridazine-6-sulfonamide ~ I Ig~
A suspension of 20 g of 3-chloropyridazine-6-thiol and 54.4 g of potassium hydrogen fluoride in 200 ml of 50~ acetic acid is cooled to 0C. With v;gorous stirring, chlorine is then introduced into the suspension at 0-SC over 3 hours. The sulfonyl chloride is precipi-tated from the reaction mixture by addition of 300 ml of cold water, isolated by filtration~ and washed with cold water. In the meantime, a suLfonating flask is charged with an excess of ammonia. The sulfonyl chloride is then added, in portions, with stirring. The reaction mixture is stirred for several hours, diluted with 100 ml of cold water, and insoluble constituents are removed by filtration. The fil-trate is adjusted to pH 4 with dilute hydrochloric acid and then filtered, affording 11 g of the compound of the above formula with a melting point of 150-152C (decomposition).
b) N-(3-Chloropyridazine-6-suLfonyl)phenylcarbamate Cl-~ S02-NH-C-0-~
To a solution of 10.6 g of 3-chloropyridazine-6-sulfonamide in 50 ml of dimethylformamide are added, under nitrogen and at room temperature, 2.5 g of a 55~ dispersion of sodium hydride in oil in portions over 15 minutes. After a further 15 minutes at 35C, the reaction mixture is cooled to 25C and then 12.4 g of diphenyl carbonate are added to the solution. The reaction mixture is stirred for 2 hours at room temperature and then poured into a mixture of 500 ml of ice/water and 50 ml of hydrochloric acid. The precipitate is filtered with suction~ washed with cold water and dried in a vacuum cabinet, affording 14.4 g of the compound of the above formula with a melting point of 136C.
2~;2 c) N-(3-Chloropyridazine 6-sulfonyl)~N'-(4-methoxy-6-methyl-1,3,5-triazin-2-yl)urea Cl-~ SO -NH-C-NH~
A mixture of 14.2 g of N-(3-chloropyridazine-6-sulfonyl)phenylcarbamateand 6.3 g of 2-amino-~-methoxy-6-methyl-1,3,5-triazine are refluxed for 1 hour in 120 ml of absolute dioxan. When the reaction is complete, the mixture is concentrated in vacuo and the residue is taken up in a saturated aqueous solution of sodium bicarbonate and the insoluble constituents are extracted with methylene chloride. The aqueous phase is acidified with dilute hydrochloric acid and extracted with methylene chloride. The methylene chloride solu,tion is dried over sodium sulfate and concentrated, affording 7 g of the compound of the above formula with a melting point of 135C.
The intermediates and final products listed in the following tables can be prepared in corresponding manner:
dil ~
~A~
Table 1: Q S2 NH2 _ Compound . _ _ I .
_ QIAbbreviation Physi~al data ~ \ / 3 .
1.1 1~11_ Q 1 ~.p. 109-110C
i,2 ~ /OCH3 Q 2 m.p. 115-120~C
' 3 ; Q 3 L.5 ~1 ~ Q 5 1D6 ,H3C--l W~ ~ I Q 6 1.7 L:l-CO-CU3I Q 7 1.8 ~/il_ Q 8 Table 1: Q - S02 - NH2 (continuation) rCompound ¦ Q ¦ Abbreviation ~ Physical data _ _ . _ . ~
1.9 / ~
1.10 ~ l_ Q 10 Cl ~CH3 1.12 U3Co ~ l Q I
1.13 ~ Q 13 Cl o~ \~-Cl 1.14 Cl Q 14 1.15 ~ Q 15 Cl ~ ~9 Table 1: Q - SO - NH (continuation) Compound Q¦ Abbreviation j Physical data _ 3 1.16 b~oc~;;Q 16 1.17 ~ -OCH3Q 17 ~\
1.18 ~ ~Q 18 ~.19 33c~ 19 ~1.20 ~ -CF3 ~ . Q 20 !C2H5 1.21 1~b Q 21 1 22 I H3C-i~ ~ Q 22 \N''~ l l .~
1.23 H3C-II~ Q 23 Table 1: Q S2 NH2 (contin~lation Compound = --I Phys ical data 1. 24 \Il-OCH3 Q 24 _ Cl 1025 ~ I-Cl Q 25 . 1. 26 2~OCH Q 26 1.27 i~ CI I Q 27 1.20 . I ~ 2 5 Q 28 1029 1 ~ 11_ 3 7 Q 29 1.3û [ \11-OC3U7-i Q 30 1. 3l I ll-C4H9-n Q 31 1.32 ~ ~Ij_ 4 9 Q 32 2~52 Table 1: Q ~ S2 - NH2 (continuation) . .. ~
Compound Q ¦ Abbreviation ¦ Physical data _ _ 1.33 I\11-C4H9-s Q 33 _C~U Q 35 1.36 1~ 3 7 Q 36 1.37 1j-C3H7-i Q 37 1.38 \1;-C4H9-n ~ Q 38 1.39 ~ \--C4H -i . . I
~ 23 _ble 2- Q - S02 - W
..
Com~ound ¦ Q W Physical data 2.1 Q 1 ~NH-CO-OC~13 2.2 Q 2 -NH-CO-OCH3 2.3 Q 3 -NH-CO-OCH3 2.4 Q 4 -NH-CO-OCH3 2.5 Q 5 -NH-CO-OCH3 2.6 Q 6 -NH-CO-OCH3 2.7 Q 7 -NH-CO-OCH3 2.8 Q 8 -NH-CO-OCH3 2.9¦ Q 9 -NH-CO-OCH3 2.10Q 10 -NH-CO-OCH3 2.11Q 11 -NH-CO-OCH3 2.12Q 12 -NH-CO-OCH3 2.13Q 13 -NH-CO-OCH3 2.14Q 14 -NH-CO-OCH3 2.15Q 15 NH-CO-OCH3 2.16Q 16 -NH-CO-OCH3 2.17Q 17 -NH-CO-OCH3 2.18Q 18 -NH-CO-OCH3 2.19Q 19 -NH-CO-OCH3 2.20Q 20 -NH-CO-OCH3 2.21¦ Q 21 ~NH-CO-OCH3 2.22~ Q 22 -NH-CO-OCH
2.24Q 24 -NH-CO-OCH
2.25Q 25 -NH-CO-OCH
2.26Q 26 -NH-CO-OCH
2.27Q 27 -NH-CO-OCH3 ¦
2.28Q 1 -NH-CO-O-C6H ¦ m.p. 141-143C
2.29Q 2 -NH-CO-O-C H ~ m.p. 135-136C
Table2: Q-S02-W (continuation) . _ . . . - - ~
Compound¦ Q ¦ W Physica1data .. _ , ?..30 Q3 ~NH-CO-O-C6H
2.32 Q5 -NH-CO-O-C H
2.33 Q6 -~1-CO-O-C6H
2.34 Q7 -NH-CO-O-C6H
2~35 Q8 -NH-CO-O-C H
2.36 Q9 -NH-CO-O-C6H
2.37 Q10-NH-CO-O-C a 2.38 Q11-NH-CO-O-C H
2.39 Q12-NH-CO-O-C H
2.40 Q13-NH-CO-O-C6H
2~41 Q14-NH-CO-O-C H
2.42 Q15-NH-CO-O-C H
2.43 Q16-NH-CO-O-C H
2.45 Q18-NH-CO-O-C H
12.47 Q20-NH-CO-O-C H
~2.48 Q21-NH-CO-O-C H
l2.49 Q22-NH-CO-O-C H
! 2.50 Q23-NH-CO-O-C H
2.51 Q24 -NH-CO-O-C6 i2.52 Q25 -NH-CO-O-C H
2.53 Q26 -NH-CO-O-C H
! 2.54 Q27 -NH-CO-O-C
2.55 Q1 -NH-CO-OC2H
¦2.56 Q2 -NH-CO-OC2H
2.57 Q3 -NH-CO-OC2H
~2~
'ra~le 2:Q - S02 - W (continuation) Compound ¦ Q W ¦ Physlcal data ...._ ?.59 Q 5NH-C0-OC H
2.60 Q 6-NH~C0-OC H
2.61 Q 7-NH-C0-OC2H5 2.62 Q 8-NH-C0-OC2H5 2.63 Q 9-NH-C0-OC2H5 2.64 Q 10-NH-C0-OC2H5 2.65 Q-ll-NH-C0-OC H
2.66 Q 12-NH-C0-OC H
2.67 Q 13-NH-C0-OC2H5 2.68 Q 14-NH-C0-OC2H5 2.69 Q 15-NH-C0-OC2H5 2.70 Q ]6NH-C0 OC2H5 2.72 Q 18-NH-C0-OC2H5 2.73 Q 19~NH-C0 OC2H5 '2.74 Q 20-NH-C0-OC H
2.75 Q 21¦_NH_CO_OC2H5 ¦2.76 Q 22-NH-C0-OC2H5 2.77 ~ Q 23 -NH-C0-OC2H5 2.78 ¦ Q 24 -NH-C0-OC2H5 2.79 ~ Q 25 -NH-C0-OC2H5 2.80 I Q 26 I-NH-CO-OC2H5 2.81 ~ Q 27 ¦_NH_CO_OC2H5 2.82 ~ Q 28 I-NH-C0-OC2H5 2.83 ! Q 1-N=C=0 2.~4 ¦ Q 2-N=C=0 2.85 Q 3-N=C=0 2.86 Q 4-N=C=0 2.87 Q 5-N=C=0 2~752 ~26~
Ta~le2: Q-SO~-W (continuationj _.................. . . . _ ~
Compound Q W Physical data ___ ._ 2.88 Q 6 -N=C=0 ¦
2.89 Q 8 -N=C=0 2~90 Q 9 -N=C=0 2091 Q 10 -N=C=0 2D92 Qll -N=C=0 2.93 ~ Q 12 -N=C=0 2.94 Q 13 -N=C=0 2095 Q 14 -N=C=0 2.96 Q 15 -N=C=0 2.97 Q 16 -N=C=0 2O98 Q 17 -N=C=0 2.99 IQ 18 -N=C=0 20100 Q19 -N=C=0 20101 Q 20 -N=C=0 20102 Q21 -N=C=0 20103 Q 22 -N=C=0 2O104 Q.23 -N=C=0 2.105 Q 24 -N=C=0 2.106 Q 25 -N=C=0 2~107 Q 26 -N=C=0 20108 Q 27 ¦ -N=C=0 _ . .
~Z;~7~i~
~ble 3: Q-SO~-NU-C-N~ Z
. .~
¦ poundl Q Z E ¦ Rl R2 I R3 ¦ m.p. 1 C]
. . ~ ~ __ .
The compounds of formula I may be prepared in a manner known per se in an inert organic solvent or mixture of solvents.
The compounds of formula I may be prepared as follows in accordance with equation [1]
Q 2 X-~ (I) [l]
(II) (III) by reacting a phenylsulfonyl derivative of the formula II with a com-pound of the formula III, wherein X and W are -NH2, -N=C=Z or -NRl-CZ-OR groups, the substituents Rl, R2, R3, Q, Z and E are as defined for formula I, R is an aliphatic or atomatic radical, prefer-ably Cl-C4alkyl, phenyl or benzyl, with the proviso that the reac-tants of the formulae II and III are also so chosen that an amino function reacts either with an isocyanato or isothiocyanato function or with the [-NRl-CZ-OR] group.
The process is conveniently carried out in the presence of a base.
It can often be of advantage to carry out the reaction in an inert gas atmosphere, e.g. under nitrogen. The process for preparing the compounds of formula I is an object of the invention.
If desired, the compounds of formula I may be converted into basic, agriculturally suitable addition salts by reaction with amines, alkali metal hydroxides or alkaline earth metal hydroxides, or with quaternary ammonium bases. This is accomplished e.g. by reacting a compound of formula I with an equimolar amount of base and removing the solvent by evaporation. Such reactions, and also the preparation of individual starting materials of the formula III, are known and described e.g. in US patent specifications 3 384 757 and 3 410 887.
The starting compounds of the formula III are known or they are prepared by methods which are known per se.
Some of the compounds of formula II, wherein W is NH2, are known. The novel compounds of formula II have been specially developed for synthesising the compounds of formula I. They therefore constitute an object of the invention.
The starting compounds of formula II, wherein W is -NH-CZ-OR, are novel and have been specially developed for synthesising the compounds of formula I. They therefore also constitute an object of the inven~
tion. They are prepared by methods which are known per se.
The sulfonamides of the formula II can be prepared by reacting the corresponding sulfonyl chlorides or sulfonyl fluorides with ammonia or ammonium hydroxide solutions (seee.g. J.Chem. Soc. Perkin Trans. 1, 1972, 522).
~%2;~
The isocyanates of the formulae II and III can be prepared by phos-genating the corresponding amino compounds, in the presence of butyl-isocyanate and in a chlorinated hydrocarbon as solvent, at reflux temperature. Reference is made in this connection to "Neuere Methoden der praparativen organischen Chemie",Vol. VI, pp. 211-229; Verlag Chemie, Weinheim, 1970. When using thiophosgene9 isothiocyanates of the formulae II and III are obtained in corresponding manner.
:
The isothiocyanates of formula II are also prepared by treating the sulfonamides of formula II with carbon disulfide and potassium hydroxide and subsequently phosgenating the dipotassium salt [see Arch. Pharm. 299, 174 (1966)].
Compounds of the formulae II and III, wherein W and X are the -NRl-CZ-OR group, can be obtained from the corresponding amino com-pounds by reaction with a haloformate or halothioformate of the formula IV
z Hal- C- OR (IV) or with a dicarbonate or dithiocarbonate of the formula V
R- O- C- OR (V) wherein Hal is halogen, preferably chlorine or bromine, Z is oxygen or sulfur and R is an aliphatic or aromatic radical, preferably Cl-C4alkyl, phenyl or benzyl. This reaction is preferably conducted in the presence of a base.
The starting amines of the formula III are known or they can be prepared by per se known methods of synthesising heterocyclic amines (see "The Chemistry of Heterocyclic Compounds", Vol. XVI, Interscience Publishers, New York, London~ in which methods of synthesising2-amino-pyridines and of 2-amino-1,3,5-triazines may be found).
~2~
These reactions are conveniently carried out in aprotic, inert organic solvents such as methylene chloride, tetrahydroEuran, acetonitrile, dioxan, or toluene.
The reaction temperaturesare preferably in the range from -20 to +120C. The reactions are normally slightly exothermic and can be carried out at room temperature. To shorten the reaction time or also to initiate the reaction it is expedient to heat the reaction mixture brief]y to boiling point. The reaction times can also be shortened by addition of a few drops of a base or isocyanate as catalyst.
The compounds of formula I are stable compounds which are of low toxicity to man and animals.
When preparing the compounds of formula I in accordance with equation [1], isomeric reaction products of the formulae Ia and Ib 1 ~
N
Q-S02-NHC -- N~ ~--R2 (la) R3 . =Æ
. N
Q_SO2_NHC \ E/ 3 (Ib) can be isolated in certain cases by addition of a compound of formula Il to a ring nitrogen atom of a compound of formula III. In the formulae Ia and Ib above, Rl, R2, R3, Q, Z and E are as defined for formula I. These isomeric compounds Ia and Ib also influence plant growth. Accordingly, all agrochemically usef:ul compounds and compound mixtures which are obtained by reacting compounds of formula II with compounds of formula III also fall within the province of the present invention. Sulfonylureas containing two to three nitrogen atoms in the 6-membered heterocyclic radical Q are novel.
Surprisingly, it has been found that the novel compounds of formula I
have good selective herbicidal properties and are therefore suitable for use in crops of cultivated plants. Moreover, it can also be ob-served that some of the compounds even damage problem weeds which up to now have only been controlled with total herbicides.
A number of the compounds of formula I are translocatable, i.e. they are absorbed at the treated site of the plant (leaf, stem, root etc.) and transported to other sites where they exert their action. In doing so, they not only follow the path of nutrient transport from the roots to the leaves, but also conversely penetrate to the roots from the leaves. Thus with the aid of this translocatability, e.g.
by means of a surface treatment, it is possible to damage perennial weeds to their roots. Furthermore, compared with conventional herbi-cides, the compounds of formula I are effective even when used in very low rates of application.
In addition9 the compounds of formula I are able to potentiate the phytotoxic action of other herbicides against certain noxious plants and to reduce the toxicity of such herbicides to some cultivated plants. This can lead to a lowering of the total concentration of herbicide and consequently to a reduced environmental impact.
If the rates of application are further lowered, then the growth regulating properties of the compounds of formula I predominate. The compounds exert a selective action on the plant metabolism, which results in particular in a reduction of the vegetative growth often - 9 ~
in favour of the generative growth. This selective influence on the physiological processes of plant development makes the compound of formula I useful for different purposes, especially for those in connection with labour-saving in measures taken in crops of culti-vated plants or for increasing yield.
The compounds of formula I disclosed herein can be used as herbicides and/or as growth regulators. Previous experience with growth regula-tors has shown that the active ingredients are able to induce one or more different responses in the plants. These different responses depend largely on the time of application, i.e. on the development stage of the seed or plant, on the mode of application, and in partic-ular on the concentrations employed. Such responses differ in turn, however, depending on the species of plant. Accordingly, the appli-cation of compounds of formula I affords the possibility of in-fluencing the growth of plants in the desired manner.
Vegetative plant growth is inhibited with the novel compounds of the formula I or with the compositions containing them. By means of this growth inhibition the compounds of the invention are able to increase substantially the yield of plants. Thus the vegetative growth of e.g.
soybean plants and other leguminosae such as beans, peas or lentils is reduced in favour of the generative growth, whereby a direct in-crease in yield is achieved. The vegetative growth of other species of plants, e.g. of vines 9 cereals, grasses and ornamentals, is also inhibited in desired manner. In addition, a significant strengthening of the supporting tissue of the treated plants is ~bserved.
An interesting manner of influencing plant growth derives from the special property of the compounds of formula I of selectively in-fluencing the growth of specific plants, especially cereals. This selective growth inhibition substantially increases the breaking ~ z~q~
strength of the plants while the yield remains unchanged, thereby providing a very interesting method of protecting plant crops from lodging caused by storms or prolonged rainfall. Further, selective inhibition of the vegetative growth of many cultivated plants permits more plants to be grown per unit of crop area, resulting in a signif-icant increase in yield with the same fruit setting and in the same crop area. The use of growth inhibitors also brings about a more effective utilisation of nutrients which are then able increasingly to promote flower formation and fruiting. In this manner, higher yields are achieved while the amount of waste vegetative plant resi-dues ~e.g. straw, potato foliage, beet leaves) is simultaneously reduced.
To be singled out for special mention is also the possibility of in-hibiting the formation of shoots in different types of plants, especiall~ tobacco plants, whenever the main shoot has been pruned shortly before flowering with the object of increasing the growth of the leaves.
Accordingly, the present invention relates to the use of the compounds of formula I as herbicides and/or growth regulators. The invention also relates to a method of controlling weeds pre- and postemergence, of inhibiting the growth of monocot and dicot plants, especially of grasses, cereals and tobacco suckers, as well as of increasing the yield of leguminous plants.
The compounds of the formula I are used in unmodiEied form, or prefer-ably, together with the adjuvants conventionally employed in the art of formulation, and are therefore formulated in known manner to emulsifiable concentrates, coatable pastes, directly sprayable or dilut.lble solutions, dilute emulsiolls, wettable powdcrs, soluble powclcrs, dusts, ~rall~ t~s, ilnd also ~nc l)stJl:ltiolls in ~!.g. pOlylll(`r substallces. Like the nature of the compositions, the meLIIods of application, such as spraying, atomising, dusting, scattering or pouring, are chosen in accordance with the intended objectives and the prevailing circumstances.
The formulations, i.e. the compositions or preparations containing the compound (active ingredient~ of the formula I and, where appropriate, a solid or liquid adjuvant, are prepared in known manner, e.g. by homogeneously mixing and/or grinding the active ingredients with extenders, e.g. solvents, solid carriers and, where appropriate, surface-active compounds (surfactants).
Suitable solvents are: aromatic hydrocarbons, preferably the fractions containing 8 to 12 carbon atOms, e.g. xylene mixtures or substituted naphthalenes, phthalates such as dibutyl phthalate or dioctyl phthalate, aliphatic hydrocarbons such as cyclohexane or paraffins, alcohols and glycols and their ethers and esters, such as ethanol, ethylene glycol monomethyl or monoethyl ether, ketones such as cyclo-hexanone, strongly polar solvents such as N-methyl-2-pyrrolidone, dimethyl sulfoxide or dimethyl formamide, as well as epoxidised vege-table oils such as epoxidised coconut oil or soybean oil; or water.
Tlle solid carriers used e.g. for dusts and dispersible powders, are normally natural mineral fillers such as calcite, talcum, kaolin, montmorillonite or attapulgite. In order to improve the physical properties it is also possible to add highly dispersed silicic acid or highly dispersed absorbent polymers. Suitable granulated adsorptive carriers are porous types, for example pumice, broken brick, sepiolite or bentonite; and suitable nonsorbent carriers are materials r ~7~2 such as calcite or sallcl. In ~ddition, a gr~at nulllb~r of pregranlllated mnt~ri~ls of inorg;lllic or or~ ic n~ture c~\n be u;~cl. e.~. esl-ecially dolomite or pulverised plant residues.
Depending on the nature of the compound of the formula I to be formu-lated, suitable surface-active compounds are nonionic, cationic and/
or anionic surfactants having good emulsifying, dispersing and wetting properties. The term "surfactants" will also be understood as comprising mixtures of surfactants.
Suitable anionic surfactants can be both water-soluble soaps and water-soluble synthetie surface-aetive eompounds.
Suitable soaps are the alkali metal salts, alkaline earth metal salts or unsubstituted or substituted ammonium salts of higher fatty aeids tClO-C22), e.g. the sodium or potassium salts of oleie or stearic acid, or of natural fatty acid mixtures which can be obtained e.g. from coconut oil or tallow oil. Mention may also be made of fatty acid methyltaurin salts.
More frequently, however, so-called synthetic surfactants are used, espeeially fatty sulfonates, fatty sulfates, sulfonated benzimidazole derivatives or alkylarylsulfonates.
The fatty sulfonates or sulfates are usually in the form of alkali metal salts, alkaline earth metal salts or unsubstituted or substi-tuted ammoniums salts and contain a C8-C22alkyl radical which also includes the alkyl moiety of acyl raclicals, e.g. the sodium or calcium salt of lignonsulfonic acid, of dodecylsulfate or of a mixture of fatty alcohol sulfates obtained from natural fatty acids. These compounds also comprise the salts of sulfuric acid esters and sulfonic acids of fatty alcohoL/ethylene oxide adducts. The sulfonated benz-imidazole derivatives preferably contain 2 sulfonic acid groups and one fatty acid radical containing 8 to 22 carbon atoms. Examples ~L~d~752 - 13 ~
of alkylarylsulfonates are the sodium, calcium or tricthanolamine s~lts of do(lecyll)el)z~ sulfollic acid, dibutyl~ LIl~llene~slllfollic aeid,or of a naplltllalenesulfonic aci~/foL~naldehyde condensation product.
Also suitable are corresponding phosphates, e.g. salts of the phosphoric acid ester of an adduct of p-nonylphenol with 4 to 14 moles of ethylene oxide, or phospholipids.
Non-ionic surfactants are preferably polyglycol ether derivatives of aliphatic or cycloaliphatic alcohols, or saturated or unsaturated Eatty acids and alkylphenols, said derivatives containing 3 to 30 glycol ether groups and 8 to 20 carbon atoms in the (aliphatic) hydrocarbon moiety and 6 to 18 carbon atoms in the alkyl moiety of the alkylphenols.
Further suitable non-ionic surfactants are the water-soluble adducts of polyethylene oxide with polypropylene glycol, ethylenediamine propylene glycol and alkylpolypropylene glycol containing 1 to 10 carbon atoms in the alkyl chain, which adducts contain 20 to 250 ethylene glycol ether groups and 10 to 100 propylene glycol ether groups. These compounds usually contain 1 to 5 ethylene glycol units per propylene glycol unit.
Representative examples of non-ionic surfactants are nonylphenol-polyethoxyethanols, castor oil polyglycol ethers, polypropylene/poly-ethylene oxide adducts, tributylphenoxypolyethoxyethanol, polyethylene glycol and octylphenoxyethoxyethanol. Fatty acid esters of polyoxy-ethylene sorbitan and polyoxyethylene sorbitan trioleate are also suitable non-ionic surfactants.
Cationic surfactants are preferably quaternary ammonium salts which contain, as ~-substituent, at least one C8-C22alkyl radical and, as further substitucnts, lower unsubstituted or halogenated alkyl, benzyl or lower hydroxyalkyl radicals. The salts are preferably in the form of halides, metilylsulfates or ethylsulfates, e.g. stearyltrimethyl-ammonium chloride or benzyldi(2-chloroethyl)ethylamlllonium bromide.
~22~52 I`he surractal~ts custo~ari1y employed in the art oE formulation are descril)ed e.g. in "McCutcheon's Detergent~ and Imu1sifiers Annual", ~IC Publishing Corp. Ridgewood, New Jersey, 1979, and Sisley and Wood, "Encyclopedia of Surface Active Agents", Chemical Publishing Co., Inc.
New York, 1964.
The pesticidal compositions usually contain 0.1 to 95%, preferably 0.1 to 80%, of a compound of the formula I, 1 to 99.9% of a solid or liquid adjuvant, and 0 to 25%, preferably 0.1 to 25%9 of a surfactant.
Preferred formulations are composed in particular of the following constituents (% = percentage by weight):
Emulsifiable eoncentrates active ingredient:1 to 20%, preferably 5 to 10%
surfactant:5 to 30%, preferably 10 to 20%
liquid carrier:50 to 94%, preferably 70 to 85%
Dusts active ingredient:0.1 to 10%, preferably 0.1 to 1%
solid carrier:99.9 to 90%, preferably 99.9 to 99%
Suspension concentrates active ingredient:5 to 75%, preferably 10 to 50%
water:94 to 25%, preferably 90 to 30%
surfactant:l to 40%, preferably 2 to 30%
Wettable powders:
active ingredient:0.5 to 90%, preferably 10 to 80%
surfactant:0.5 to 20%, preferably l to 15%
solid carrier: 5 to 95%, preferably 15 to 90%
~'227~i~
~ 15 -Granulates act;ve ingred;ent:0.5 to 30%, preferably 3 to 15%
solid carrier:99.5 to 70~, preferably 97 to 85~.
Whereas commercial products will be preferably formulated as concen-trates, the end users will normally employ dilute formu]ations. The formulations can be diluted to a concentration as low as 0.001~. The rates of application are normally from 0.01 to 10 kg a.i./ha.
The compositions may also contain further ingredients, such as stabi-lisers, antifoams, viscosity regulators, binders, tackifiers as well as fertilisers or other active ingredients in order to obtain special effects.
The invention also relates to agriculturally suitable compositions which contain at least one compound of formula I as active ingredient.
Furthermore, the present invention relates to a process for the preparation of such compositions, which comprises intimately mixing the active ingredient with one or more substances or groups of sub-stances described herein. The invention also relates to a method of treating plants, which comprises applying thereto the compounds of formula I or the novel compositions containing them.
In the following Examples parts and percentages are by weight.
Preparatory Example _ample 1:
a) 3-Chloropyridazine-6-sulfonamide ~ I Ig~
A suspension of 20 g of 3-chloropyridazine-6-thiol and 54.4 g of potassium hydrogen fluoride in 200 ml of 50~ acetic acid is cooled to 0C. With v;gorous stirring, chlorine is then introduced into the suspension at 0-SC over 3 hours. The sulfonyl chloride is precipi-tated from the reaction mixture by addition of 300 ml of cold water, isolated by filtration~ and washed with cold water. In the meantime, a suLfonating flask is charged with an excess of ammonia. The sulfonyl chloride is then added, in portions, with stirring. The reaction mixture is stirred for several hours, diluted with 100 ml of cold water, and insoluble constituents are removed by filtration. The fil-trate is adjusted to pH 4 with dilute hydrochloric acid and then filtered, affording 11 g of the compound of the above formula with a melting point of 150-152C (decomposition).
b) N-(3-Chloropyridazine-6-suLfonyl)phenylcarbamate Cl-~ S02-NH-C-0-~
To a solution of 10.6 g of 3-chloropyridazine-6-sulfonamide in 50 ml of dimethylformamide are added, under nitrogen and at room temperature, 2.5 g of a 55~ dispersion of sodium hydride in oil in portions over 15 minutes. After a further 15 minutes at 35C, the reaction mixture is cooled to 25C and then 12.4 g of diphenyl carbonate are added to the solution. The reaction mixture is stirred for 2 hours at room temperature and then poured into a mixture of 500 ml of ice/water and 50 ml of hydrochloric acid. The precipitate is filtered with suction~ washed with cold water and dried in a vacuum cabinet, affording 14.4 g of the compound of the above formula with a melting point of 136C.
2~;2 c) N-(3-Chloropyridazine 6-sulfonyl)~N'-(4-methoxy-6-methyl-1,3,5-triazin-2-yl)urea Cl-~ SO -NH-C-NH~
A mixture of 14.2 g of N-(3-chloropyridazine-6-sulfonyl)phenylcarbamateand 6.3 g of 2-amino-~-methoxy-6-methyl-1,3,5-triazine are refluxed for 1 hour in 120 ml of absolute dioxan. When the reaction is complete, the mixture is concentrated in vacuo and the residue is taken up in a saturated aqueous solution of sodium bicarbonate and the insoluble constituents are extracted with methylene chloride. The aqueous phase is acidified with dilute hydrochloric acid and extracted with methylene chloride. The methylene chloride solu,tion is dried over sodium sulfate and concentrated, affording 7 g of the compound of the above formula with a melting point of 135C.
The intermediates and final products listed in the following tables can be prepared in corresponding manner:
dil ~
~A~
Table 1: Q S2 NH2 _ Compound . _ _ I .
_ QIAbbreviation Physi~al data ~ \ / 3 .
1.1 1~11_ Q 1 ~.p. 109-110C
i,2 ~ /OCH3 Q 2 m.p. 115-120~C
' 3 ; Q 3 L.5 ~1 ~ Q 5 1D6 ,H3C--l W~ ~ I Q 6 1.7 L:l-CO-CU3I Q 7 1.8 ~/il_ Q 8 Table 1: Q - S02 - NH2 (continuation) rCompound ¦ Q ¦ Abbreviation ~ Physical data _ _ . _ . ~
1.9 / ~
1.10 ~ l_ Q 10 Cl ~CH3 1.12 U3Co ~ l Q I
1.13 ~ Q 13 Cl o~ \~-Cl 1.14 Cl Q 14 1.15 ~ Q 15 Cl ~ ~9 Table 1: Q - SO - NH (continuation) Compound Q¦ Abbreviation j Physical data _ 3 1.16 b~oc~;;Q 16 1.17 ~ -OCH3Q 17 ~\
1.18 ~ ~Q 18 ~.19 33c~ 19 ~1.20 ~ -CF3 ~ . Q 20 !C2H5 1.21 1~b Q 21 1 22 I H3C-i~ ~ Q 22 \N''~ l l .~
1.23 H3C-II~ Q 23 Table 1: Q S2 NH2 (contin~lation Compound = --I Phys ical data 1. 24 \Il-OCH3 Q 24 _ Cl 1025 ~ I-Cl Q 25 . 1. 26 2~OCH Q 26 1.27 i~ CI I Q 27 1.20 . I ~ 2 5 Q 28 1029 1 ~ 11_ 3 7 Q 29 1.3û [ \11-OC3U7-i Q 30 1. 3l I ll-C4H9-n Q 31 1.32 ~ ~Ij_ 4 9 Q 32 2~52 Table 1: Q ~ S2 - NH2 (continuation) . .. ~
Compound Q ¦ Abbreviation ¦ Physical data _ _ 1.33 I\11-C4H9-s Q 33 _C~U Q 35 1.36 1~ 3 7 Q 36 1.37 1j-C3H7-i Q 37 1.38 \1;-C4H9-n ~ Q 38 1.39 ~ \--C4H -i . . I
~ 23 _ble 2- Q - S02 - W
..
Com~ound ¦ Q W Physical data 2.1 Q 1 ~NH-CO-OC~13 2.2 Q 2 -NH-CO-OCH3 2.3 Q 3 -NH-CO-OCH3 2.4 Q 4 -NH-CO-OCH3 2.5 Q 5 -NH-CO-OCH3 2.6 Q 6 -NH-CO-OCH3 2.7 Q 7 -NH-CO-OCH3 2.8 Q 8 -NH-CO-OCH3 2.9¦ Q 9 -NH-CO-OCH3 2.10Q 10 -NH-CO-OCH3 2.11Q 11 -NH-CO-OCH3 2.12Q 12 -NH-CO-OCH3 2.13Q 13 -NH-CO-OCH3 2.14Q 14 -NH-CO-OCH3 2.15Q 15 NH-CO-OCH3 2.16Q 16 -NH-CO-OCH3 2.17Q 17 -NH-CO-OCH3 2.18Q 18 -NH-CO-OCH3 2.19Q 19 -NH-CO-OCH3 2.20Q 20 -NH-CO-OCH3 2.21¦ Q 21 ~NH-CO-OCH3 2.22~ Q 22 -NH-CO-OCH
2.24Q 24 -NH-CO-OCH
2.25Q 25 -NH-CO-OCH
2.26Q 26 -NH-CO-OCH
2.27Q 27 -NH-CO-OCH3 ¦
2.28Q 1 -NH-CO-O-C6H ¦ m.p. 141-143C
2.29Q 2 -NH-CO-O-C H ~ m.p. 135-136C
Table2: Q-S02-W (continuation) . _ . . . - - ~
Compound¦ Q ¦ W Physica1data .. _ , ?..30 Q3 ~NH-CO-O-C6H
2.32 Q5 -NH-CO-O-C H
2.33 Q6 -~1-CO-O-C6H
2.34 Q7 -NH-CO-O-C6H
2~35 Q8 -NH-CO-O-C H
2.36 Q9 -NH-CO-O-C6H
2.37 Q10-NH-CO-O-C a 2.38 Q11-NH-CO-O-C H
2.39 Q12-NH-CO-O-C H
2.40 Q13-NH-CO-O-C6H
2~41 Q14-NH-CO-O-C H
2.42 Q15-NH-CO-O-C H
2.43 Q16-NH-CO-O-C H
2.45 Q18-NH-CO-O-C H
12.47 Q20-NH-CO-O-C H
~2.48 Q21-NH-CO-O-C H
l2.49 Q22-NH-CO-O-C H
! 2.50 Q23-NH-CO-O-C H
2.51 Q24 -NH-CO-O-C6 i2.52 Q25 -NH-CO-O-C H
2.53 Q26 -NH-CO-O-C H
! 2.54 Q27 -NH-CO-O-C
2.55 Q1 -NH-CO-OC2H
¦2.56 Q2 -NH-CO-OC2H
2.57 Q3 -NH-CO-OC2H
~2~
'ra~le 2:Q - S02 - W (continuation) Compound ¦ Q W ¦ Physlcal data ...._ ?.59 Q 5NH-C0-OC H
2.60 Q 6-NH~C0-OC H
2.61 Q 7-NH-C0-OC2H5 2.62 Q 8-NH-C0-OC2H5 2.63 Q 9-NH-C0-OC2H5 2.64 Q 10-NH-C0-OC2H5 2.65 Q-ll-NH-C0-OC H
2.66 Q 12-NH-C0-OC H
2.67 Q 13-NH-C0-OC2H5 2.68 Q 14-NH-C0-OC2H5 2.69 Q 15-NH-C0-OC2H5 2.70 Q ]6NH-C0 OC2H5 2.72 Q 18-NH-C0-OC2H5 2.73 Q 19~NH-C0 OC2H5 '2.74 Q 20-NH-C0-OC H
2.75 Q 21¦_NH_CO_OC2H5 ¦2.76 Q 22-NH-C0-OC2H5 2.77 ~ Q 23 -NH-C0-OC2H5 2.78 ¦ Q 24 -NH-C0-OC2H5 2.79 ~ Q 25 -NH-C0-OC2H5 2.80 I Q 26 I-NH-CO-OC2H5 2.81 ~ Q 27 ¦_NH_CO_OC2H5 2.82 ~ Q 28 I-NH-C0-OC2H5 2.83 ! Q 1-N=C=0 2.~4 ¦ Q 2-N=C=0 2.85 Q 3-N=C=0 2.86 Q 4-N=C=0 2.87 Q 5-N=C=0 2~752 ~26~
Ta~le2: Q-SO~-W (continuationj _.................. . . . _ ~
Compound Q W Physical data ___ ._ 2.88 Q 6 -N=C=0 ¦
2.89 Q 8 -N=C=0 2~90 Q 9 -N=C=0 2091 Q 10 -N=C=0 2D92 Qll -N=C=0 2.93 ~ Q 12 -N=C=0 2.94 Q 13 -N=C=0 2095 Q 14 -N=C=0 2.96 Q 15 -N=C=0 2.97 Q 16 -N=C=0 2O98 Q 17 -N=C=0 2.99 IQ 18 -N=C=0 20100 Q19 -N=C=0 20101 Q 20 -N=C=0 20102 Q21 -N=C=0 20103 Q 22 -N=C=0 2O104 Q.23 -N=C=0 2.105 Q 24 -N=C=0 2.106 Q 25 -N=C=0 2~107 Q 26 -N=C=0 20108 Q 27 ¦ -N=C=0 _ . .
~Z;~7~i~
~ble 3: Q-SO~-NU-C-N~ Z
. .~
¦ poundl Q Z E ¦ Rl R2 I R3 ¦ m.p. 1 C]
. . ~ ~ __ .
3.1 Q 3 O N H CH3 OCH3 3.2 Q 3 O CH 11 CH3 OCH3 3.4 Q 5 S N CH3 CH3 CH3 3~5 Q 7 O N H CH3 OCH3 306 Q 6 O N H ~ CH3 OCH3 3.7 Q 8 O N H CH3 OCH3 3.8 Q 8 O CH H CH3 OCH3 3.10 Q 10O N H CH3 OCH3 3.12 Q 11O N H OCH3 OCH3 3.13 Q 11O CH H CH3 OCH3 3.14 Q 27O N H CH3 C~3 3.15 Q 27O CH H CH3 OCH3 3.16 Q 13S N H CH3 CH2 3.17 Q 13O CH H H I H
3.18 Q 18O N H 3 ¦ CH3 ~3.19 Q 19 1 0 N CH3 CH3 l CH3 3.20 Q 180 N H CH3 OCH3 ¦3.21 Q 3~ O CH H CH3 CH3 160-161 ¦3.22 Q 3O N H I CH3 OCH3 3.23 Q 5 O CH H l CH3 OCH3 3.24 Q 5 O N H I CH3 OCH3 3.25 Q 6 O CH H l CH3 OCH3 3.26 Q 17O N H I CH3 OCH3 3.27 Q 17i 0 N H OCH3 OCH3 3.28 Q 6 ¦ O N H CH3 OCH3 - 28 ~
Table 3: l ~ (continuation) . . ~
Com-pound Q Z E Rl _2 3 -m.p. [C]
3.29 Q 20 O N CH3 CH3 CH3 3.30 Q 7 S N H CH3 OC3H7-n 3.31 Q 21 O N H CH3 C2H5 3.32 Q 13 O N H CH3 OCH3 3.33 Q 13 O CH H CH3 OCH3 3.34 Q 22 S CH CH3 CH3 CH3 3.35 Q 23 O N H OCH3 OCH3 3.36 IQ 1 O N H CH3 OCH3 153-154 3.37 ¦Q1 O N H OCH3 N(CH3)2 154-155 3.38 IQ l O N H OCH3 C2H5 3 39 1` 1 O N H OCH3 OCH(CH3)2 3.40 IQ 1 O N H OCH3 CH2cF3 3.41 'Q 1 O N H C2H5 OCH3 139-141 3.42 ~Q 1 O N H C2H5 C2H5 3.43 ~Q 1 O N H SCH3 OCH3 3.44 IQ 1 O N H CH3 C2H5 143-144 3.45 ~Q 1 O CH H 3 3 165-167 3.46 IQ 1 O CH H ICH3 OCH3 138-141 3.47 ~Q 1 O CH H CH3 OCHF2 142-145 3.48 i Q 1 O CH H CH3 N(CH3)2 3.49 jQ 1 O CH H OCH3 OCH3 160-163 3.50 Q 1 O CH H OCHF2 OCHF2 3.51 IQ 1 O CH H OCH3 OCHF2 3.52 jQ 1 O CH H OCH3 Cl 3.53 jQ 1 O CH H OCH3 F
3.54 iQ 1 O CH H OCH3 N(CH3)2 3.55 IQ 1 O CH H CH2F OCH3 Table 3_ Q-S02-NH-C-N--~ ~ (continuation) Rl \2~ \R
Com~ ---r -----~ - -~pound Q Z I E 1 1 2 R3 i m-p- ~ C]
_ . ~ ._ _ . ..
3.56 Q 1O CH H OCHF2 N(CH3)2 3.57 Q 1O CH H OCH3 OCF2~CHF2 3.58 Q 1O CH H CH3 OCF2-CHF2 3.59 Q 2O N H CH3 OCH3 135-137 3.60 Q 2O N H OCH3 N(CH3)2 180-181 3.61 Q 2O N H OCH3 C2H5 3.62 Q 2O N H OCH3 OCH(CH3)2 3.63 Q 2O N H OCH3 0CH2CF3 3.64 Q 2O N H C2H5 OCH3 122-124 3.65 Q 20 N H C2H5 C2H5 3.66 Q 2 O N H SCH3 OCH3 3.67 Q 2O N H CH3 C2H5 123-125 3.68 Q 2O CH H 3 ¦ CH3 166-167 3.69 Q 2O CH H CH3 1 OCH3 139-141 3.70 Q 2O CH H CH3 ~ OCHF2 116-123 3.71 Q 2O CH H CH3 ¦N(CH3)2 3.72 Q 2O CH H OCH3 ~OCH3 143-147 3.73 Q 2 O CH H OCHF2 ¦ OCHF2 j3.75 Q 2O CH H ¦OCH3 Cl 3.76 Q 2 O CH H OCH3 F
3.77 IQ 2O CH H OCH3 N(CH3)~
3.78 IQ 2O CH H CH2F ¦OCH3 3~79 IQ 21 0 CH H OCHF2 jN(CH3)2 3.80 `Q 21 0 CH H OCH3 1 OCF2-CHF
3.81 IQ 21 0 CH H CH3 1OCF2-CllF2 ¦3.82 Q 14 i N H ICH3 OCH3 7 ~N_o~2 Table3: Q-SO NH-C-N- ~E (continuation) R =.
Com~
pound¦Q ¦7~ ¦ E ¦ Rl l R2 l R3 ¦ m.p. [ C~
. __ _ _ _ __ _ __ . . _. .
3.83Q14 O CH H CH3 OCH3 3.84Q 14 O CH H CH3 CH3 3.85Q14 O CH H OCH3 OCH3 3.86Q~4 O CH H CH3 OCHF2 3.87Q 24 O N H CH3 OCH3 3.88Q 24 O CH H l CH3 OCE~3 3.89Q 24 O CH H l CH3 OCHF2 3.90Q ?.5 O N H CH3 OCH3 3.91Q 25 O CH H CH3 OCH3 3.92Q 26 O N H CH3 OCH3 3.93Q 26 O CH H CH3 OCH3 3.94Q 15 O CH H CH3 OCH3 3.95Q 15 O N H CH3 OCH3 3.96Q 15 O CH H CH3 OCHF2 3.97I Q16 O N H ~ CH3 OCH3 3.90Q 16 O CH H ~ CH3 OCH3 3.99Q 17 O N H ¦ CH3 OCH
3.100 Q 17 O CH H l C~13 OCH3 3.101 Q 27 O N H OCH3 C2H5 3.102 IQ 27 O N H OCH3 bCH(CH3)2 3.103 Q 27 O N H CH3 OCH3 3.104 Q 27 O N H OCH3 N~CH3)2 3.105 IQ 27 O N H OCH3 0CH2CF3 3.106 IQ 27 O N H C2H5 OCH3 3.107 Q 27 O N H OCH3 OCH3 3.108 Q 27 O N H CH3 C2H5 3.109 Q 27 O CH H CH3 CH3 3.110 IQ 27 O CH H CH3 OCH3 ~L~7~
Ta~le 3: Q-SO -NH-C~N-~ ~R (continuation) I
I Com-~ T--- R ~ 3 -----T ~c pound Q Z + E 1 ¦----_2 3 m.p. ]
3.111 Q 27 O CH CH3 CH3 C2H5 3.112 Q 27 O CH H OCH3 OCH3 3.113 Q 27 O CH H OCHF2 OCHF2 3.114 Q 27 O CH H OCH3 OCHF2 3.]15 Q 30 O N H OCH3 C2H5 3.116 Q 30 O N H OCH3 l CH(CH3)2 3.117 Q 30 O N H CH3 OCH3 3.118 Q 30 O N H OCH3 N(CH3)2 3.1]9 Q 30 O N H OCH3 l CH2CF3 3.120 Q 30 O N H C2H5 OCH3 3.121 Q 30 O N H OCH3 OCH3 ¦3.122 Q 30 O N H CH3 C2H5 3.123 Q 30 O CH H CH3 CH3 3.124 Q 30 O j CH H CH3 OCH3 3.125 Q 30 O ¦ CH H CH3 OCHF2 ¦3.126 Q 30 O CH H OCH3 OCH3 ~3.127 Q 30 O CH H OCHF2 OCHF2 3.128 Q 30 O CH H OCH3 OCHF2 13.l29 Q 32 O N H OCH3 C2H5 3.130 I Q 32 O N H OCH3 IOCH(CH3)2 3.131 ¦ Q 32 1 0 ¦ N H CH33 ¦ OCH3 3.132 ~ Q 32 j O N ¦ H
3.133 I Q 32 O N H OCH3 CH2cF3 ~3.134 ~ Q 32 O N H C2H5 OCH3 3.135 Q 32 O N H - OCH3 OCH3 3.136 Q 32 O N H CH3 C2H5 3.137 Q 32 O CH H CH3 CH3 ,3.138 Q 32 O CH H CH3 OCH3 ., ' _ ~ 32 ~
Tab le 3: Q-so -NH- 3-N~ (continuation) R \N~~\R
cO~ ~ ------- ~-- r ~ 3 - -I ~ - --pound Q Z ¦ 1 R~ R3 ¦ m-p- [ C]
... _ ~_. _ . __ 3.139 Q 32 O CH H CH3 OCHF2 3.140 Q 32 O CH H OCH3 OCH3 3.141 Q 32 O CH H OCHF2 OCHF2 3.142 Q 32 O CH H OCH3 OCHF2 3.143 Q 33 O N H OCH3 C2HS
3.144 Q 33 O N H OCH3 OCH(CH3)2 3~145 Q 33 O N H CH3 ¦ OCH3 3.146 Q 33 O N H OCH3 ¦ N(CH3)2 3.147 Q 33 O N H OCH3 0CH2CF3 3.148 Q 33 O N H C2H5 OCH3 ¦3.149 Q 33 O N H OCH3 OCH3 ~3.150 Q 33 O N H CH3 C2H5 3.151 Q 33 O CH H CH3 CH3 3.152 Q 33 O CH H CH3 OCH3 3.153 Q 33 O CH H CH3 OCHF2 3.154 Q 33 O CH H OCH3 OCH3 3.155 Q 33 O CH H OCHF2 OCHF2 3.156 Q 33 O CH H OCH3 OCHF2 3.157 Q 34 ! H OCH3 C2H5 3.158 Q 34 O ~ N H OCH3 OCH(CH3)2 3.159 Q 34 i i N H CH3 OCH3 3.160 Q 34 ¦ O N H OCH3 N(CH3)2 3.161 ¦ Q 34 O N H OCH3 0CH2CF3 3.162 ¦ Q 34 O N H C2H5 OCH3 3.163 ¦ Q 34 ~ O ¦ N H OCH3 OCH3 3.164 ¦ Q 34 ¦ O I N H CH3 C2H5 13.165 ¦ Q 34 1 0 ¦ CH H CH3 CH3 ¦3.166 ¦ Q 34 ~ O ~ CH U CH3 ¦ OCH
I~J~
Z N~2 Table 3: Q-SO NH~ N~ (continuation) \N~
I pound ~ _ _ _ E Rl 2 ~ ~ ~ P [C]
1~ -~- --- ~ ~
3c167Q 34 O CH H CH3 OCHF2 3.168Q 34 O CH H OCH3 OCH3 3.169Q 34 O CH H OCHF2 OCHF2 3.170Q 34 O CH H OCH3 OCHF2 3.171Q 37 O N H OCH3 2 5 3.172Q 37 O N .~ OCH3 OCH(CH3)2 3~173Q 37 O N H CH3 OCH3 3 r 1/4 Q 37 O N H OCH3 N(CH3)2 3.175Q 37 O N H OCH3 0CH2CF3 3.176Q 37 O N H C2H5 OCH3 3.177Q 37 O N H OCH3 OCH3 3.178Q 37 O N H CH3 C2H5 3.179Q 37 O CH H CH3 CH3 3.1$0Q 37 O CH H CH3 OCH3 3.181¦ Q 37 O CH H CH3 OCHF2 3.182I Q 37 O CH H OCH3 OCH3 3.183¦ Q 37 O CH H OCHF2 OCHF2 3.184~ Q 37 O CH H OCH3 OCHF2 l3.185 ! Q 38 o N H OCH3 2 5 ¦3.186 I Q 38 O N H OCH3 OCH(CH3)2 3.187! Q 38 O ¦ N H CH3 OCH3 3.188¦ Q 38 O ¦ N H OCH3 N(CH3)2 3.189j Q 38 O N H OCH3 2 3 3.190Q 38 O N H C2H5 OCH3 3.191Q 38 O N H OCH3 OCH3 3.192Q 38 O N H CH3 C2HS
3.193Q 38 O CH H CH3 CH3 3.194Q 38 O , CH H CH3 OCH3 . . . ~. _ ~L22Z75ii2 Table 3: Q-SO -NH-C-N-~ ~. (continuation) R '=-__ ~ .. _ .
pCound Q Z E Rl R2 R3 ~-P- r C]
_ _ G _ _ . ._ .~ .
3.195 Q 38 O CH H CH3 OCHF2 3.196 Q 38 O CH H OCH3 OCH3 3~197 Q 38 O CH H OCHF2 OCHF2 3.199 Q 39 O N H OCH3 ¦ C2H5 3.200Q 39 O N H OCH3 l CH(CH3)2 3.201Q 39 O N H CH3 OCH3 3~202Q 39 O N H OCH3 N(CH3)2 3-203Q 39 O N H OCH3 OCH~CF3 3~205Q 39 O N H OCH3 OCH~
3.206Q 39 O N H CH3 C2H5 ¦3.207 Q 39 O CH H CH3 CH3 l3.208 Q 39 O CH H CH3 OCH3 ¦2.209IQ 39 CH H CH3 OCHF2 l3.210 Q 39 O CH H OCH3 OCH3 ¦3.211 Q 39 O CH H OCHF~ OCHF2 j3.212 Q 39 O CH H OCH3 OCHF2 3.213Q 28 O N H CH3 OCH3 3.214Q 28¦ O N I H OCH3 N(CH3)2 3.215Q 28 O I ~T H OCH3 C2H5 3.216Q 28 O j N H OCH3 OCH(CH3)2 3.217Q 28 O N H OCH3 0CH2CF3 3.218Q 28~ O N H C2H5 OCH3 3.219Q 28¦ O N H C2H5 C2H5 3.220Q 281 0 N H SCH3 OCH3 3.221Q 28¦ O N H CH3 C2H5 - 35 ~
Z ~ (continuation) Table 3: Q~SO -NH-C-N-_ 2 1 ~ =0 1 ~ 3 _. . _ .____ . _ _. .
poumnd Q Z E 1 1 2 R3 ¦ m.p. [C]
__ . l -._ _ .
3~222Q 28 O CH H CH3 CH3 3.223Q 28 O CH H CH3 1OCH3 3.225Q 28 O CH H CH3 IN(CH3)2 2.227Q 28 O CH H OCHF2 1OCHF2 3~228Q 28 O CH H OCH3 OCHF2 j3.229 Q 28 O CH H OCH3 C1 3.230IQ 28 O CH H OCH3 F
¦3~231 Q 28 O CH H OCH3 N(CH3)2 ~3.232 Q 28 O CH H CH2F OCH3 13.233 Q 28 O CH H OCHF2 N(CH3)2 j30234 Q 28 O CH H OCH3 OCF2-CHF2 3.235Q 281 0 CH H CH3 OCF2-CHF2 ~3.236 Q 29 1 0N H CH3 OCH3 j30237 Q 29 O N H OCH3 N(CH3)2 3.238~Q 29j O N H OCH3 C2H5 ~30239 IQ 29 ¦ ON H OCH3 jOCH(CH3,2 j3.240 IQ 29 j ON H OCH3 ¦OCH2cF3 3.241jQ 29~ O N¦ H OC H ~0 3.242! Q 291 0 N H 2 5 1 2 5 3.244~Q 291 0 N H CH3 10C2H5 3.245IQ 29¦ CH H 3 1 3 3.246IQ 291 0 CH H CH3 ~OCH3 3-247IQ 29 j CH H CH3 ~OCHF2 13-248¦Q 291 0 CH H CH3 ,N~CH3)2 3.249IQ 29~ O CH H ` OCH3 f OCH3 -, ¦ !
- 36 _ Table 3: 1 \2 (continuation) Com- _ l ~ __ .
pound Q Z E Rl R2 R3 m.p.[C]
_.... ___ _. _~ ...... , _ _ __ 3.250 Q 29 . O CH H I OCHF2 1 OCHF2 3. 251 Q 29 O CH H I OCH3 OCHF2 3.252 Q 29 O CH H OCH3 Cl 3.253 Q 29 O CH H OCH3 F
3.254 Q 29 O CH H OCH3 I N(CH3)2 3.255 Q 29 O CH H CH2F OCH3 30256 Q 29 O CH H OCHF2 N(CH3)2 3~257 Q 29 O CH H OCH3 OCF2-CHF2 3~258 Q 29 O CH H CH3 OCF2-CHF2 3.259 Q 31 O N H CH3 OCH3 3.260 Q 31 O N H OCH3 N(CH3)2 3.261 Q 31 O N H OCH3 C2H5 3~262 Q 31 O N H OCH3 OCH(CH3)2 3.263 Q 31 O N H OCH3 0CH2CF3 3.264 Q 31 O N H C2H5 OCH3 3.265 Q 31 O N H C2H5 C2H5 3.266 Q 31 O N H ~CH3 OCH3 3~267 Q 31 O N H CH3 C2H5 3.268 Q 31 O CH H l CH3 CH3 3.269 Q 31 O CH H CH3 OCH3 3.270 Q 31 O I CH H CH3 ! OCHF2 3.271 Q 31 O I CH H CH3 N(CH3)2 3.272 Q 31 O ~ CH H OCH3 OCH3 3.273 Q 31 O CH H OCHF2 OCHF2 13.274 Q 31 O CH H OCH3 OCHF2 13.275 Q 31 ¦ O CH H OCH3 Cl ¦3.276 Q 31 ¦ O CH H OCH3 F
13.277 Q 31 1 0 CH 3 OCH3 ( 3)2 7~%
Table 3: Q_SO2_NH_C_N_-~ ~ (continuation) I 2 ~r 3~278Q 31 O CH H CH2F OCH3 3~279Q 31 O CH H OCHF2 N(CH3)2 3~280Q 31 O CH H OCH3 OCF2-CHF2 3.28%Q 35 O N H CH3 OCH3 3.283Q 35 O N H OCH3 N(CH3)2 3.284Q 35 O N H OCH3 C2H5 3.285Q 35 O N M OC~3 OCH(CH3)2 3.286Q 35 O N H OCH3 0CH2CF3 3.287Q 35 O N H C2H5 OCH3 3.289Q 35 O N H SCH3 OCH3 3~2900 35 O N H CH3 C2H5 30292Q 35 O ¦ CH H CH3 OCH3 3.293Q 35 O ¦ CH H CH3 OCHF2 30294Q 35 O ¦ CH H l CH3 N(CH3)2 3.295Q 35 O ¦ CH H j OCH3 OCH3 j30296 Q 35 O I CH H L OCHF2 OCHF2 3~297IQ 35 I CH H ¦ OCH3 OCHF2 !3~298 IQ 35 O ¦ CH H j OCH3 Cl 30299IQ 35 j CH H ¦ OCH3 F
3.3 ~Q 35 ! CH H I OCH3 N(CH3)2 3.301IQ 35 O ¦ CH H CH2F `i OC~3 3 33iQ 35 CH H OCHF2 N(CH3)2 3.304IQ 35 O CH H OCH3 OCF2-CHF2 3.305IQ 35 O CH H CH3 OCF2-CHF2 3.306,Q 1 O N H I OCH3 OCH3 142-143 , . j . ~
7~
Table 3: Q-SO -~-C-N~ (continuation) ~N=
1 ~ 3 ~ound Q¦ Z _ }~ .-I ~ j 3.307 Q 2O N H OCH3 OCH3 124-126 3.308 Q 36 O N H CH3 C~3 3.309 Q 36 O N H OCH3 N(CH3)2 3.310 Q 36 O N H OCH3 C2H5 3.311 Q 36 O N H OCH3 OCH(CH3)2 3.312 Q 36 O N H OCH3 0CH2CF3 3.313 Q 36 O N H C2H5 OCH3 3.314 Q 36 O N H C2H5 C2H5 3.3L5 Q 36 O N H SCH3 OCH3 3,316 Q 36 O N H CH3 C2H5 3.317 Q 36 O CH H CH3 CH3 3.318 Q 36 O CH H CH3 OCH3 3.319 Q 36 O CH H CH3 OCHF2 3.320 Q 36 O CH H CH3 N(CH3)2 3.321 Q 36 O CH H OCH3 OCH3 3.322 Q 36 O CH H OCHF2 OCHF2 3.323 Q 36 O CH H OCH3 OCHF2 3.324 Q 36 O CH H OCH3 Cl 3.325 Q 36 O CH H OCH3 F
3.326 Q 36 O CH H OCH3 N(CH3)2 j 3.327 Q 36 O CH H CH2F OCH3 l3.328Q 36 O CH H OCHF2 N(CH3)2 j 3.329 Q 36 ¦ O CH H OCH3 OCF2-CHF
3.330 Q 36 1 0 CH H CH3 _ ~2~7~
For application9 the compounds of formula -L can be processed to the following formulations.
Formulation Examples Example 2:
Formulation examples for compounds of formula I
(percentages are by weight) a) Wettable powders a) b) c) .
compound of formula I 20% 60% 0.5%
sodium lignosulfonate 5% 5% 5%
sodium laurylsulfate 3% - -sodium diisobutylnaphthalenesulfonate - 6% 6%
octylphenol polyethylene glycol ether (7-8 moles of ethylene oxide) - 2% 2%
highly dispersed silicic acid 5% 27% 27%
kaolin 67%
sodium chloride - - 59.5%
The active ingredient is thoroughly mixed with the adjuvants and the mixture ;s thoroughly ground in a suitable mill, affording wettable powders which can be diluted with water to give suspensions of the desired concentration.
b) Emulsifiable concentrate a) b) compound of formula I 10% 1%
octylphenol polyethylene glycol ether (4-5 moles of ethylene oxide) 3% 3%
calcium dodecylbenzenesulfonate castoroil polyglycol ether (36moles of ethyleneoxide) 4% 4%
cyclohexanone 30% 10%
xylene mixture 50% 79%
~ 40 -Emulsions of any required concentration can be obtained from this concentrate by dilution with water.
c) Dusts a) b) compound of formula I 0.1% 1%
talcum 99 9%
kaGlin - 99%
Ready for use dusts are obtained by mixing the active ingredient with the carrlers, and grinding the mixture in a suitable mill.
d) Extruder granulate a) b) .. . . _ _ .
compound of formula I 10% 1%
sodium lignosulfonate 2% 2%
carboxymethylcellulose 1% 1%
kaolin 87% 96%
The active ingredient is mixed and ground with the adjuvants, and the mixture is subsequently moistened with water. The mixture is extruded and then dried in a stream of air.
e) Coated granulate compound of formula I 3%
polyethylene glycol 200 2%
kaolin 94%
The finely ground active ingredient is uniformly applied, in a mixer, to the kaolin moistened with polyethylene glycol. Non-dusty coated granulates are obtained in this manner.
~ 41 -f) Suspension concentrate a) b) compound of formula I 40% 5%
ethylene glycol 10% 10%
nc,nylphenol polyethylene glycol ether (15 moles of ethylene oxide) 6% 1%
sodium lignosulfonate 10% 5%
carboxymethylcellulose 1% 1%
37% aqueous formaldehyde solution 0.2% 0.2%
silicone oil in the form of a 75%
aqueous emulsion 0.8% 0.8%
water 32% 77%
The finely ground active ingredient is intimately mixed with the adjuvants, giving a suspension concentrate from which suspension of any desired concentration can be obtained by dilution with water.
g) Salt solution , _ compound of formula 5%
isopropylamine 1%
octylphenol polyethylene glycol ether (78 moles of ethylene oxide) 3%
water 91%
Emulsions of the desired concentration may be prepared from such con-centrates by dilution with water. These emulsions are particularly suitable for foliar application. In addition it is possible to prepare further wettable powders with other mixture ratios or other carriers and adjuvants customarily employed in formulation technology. The active ingredients are intimately mixed with the adjuvants in suitable mixers and ground in corresponding mills and rollers to give wettable powders of excellant wettability and suspension power which can in turn be diluted with water to give suspensions of the desired con-centration which are particularly suitable for foliar application.
The invention also relates to such compositions.
~2~7$~
Compositions which are formulated in the manner described above and which contain one of the compounds of Table 1 can be successfully used for growth regulation and/or for herbicidal application.
Biological Examples Example 3: Preemergence herbicidal action In a greenhouse, plant seeds are sown in flower pots of 12-15 cm diameter. Immediately after sowing, the surface of the soil is treated with an aqueous dispersion or solution of the compounds to be tested.
Concentrations of 4 kg a.i./ha are employed. The pots are then kept in the greenhouse at 22-25C and 50-70% relative humidity. The test is evaluated 3 weeks later. The compounds of formula I are very effective in this test, i.e. the test plants are irreversibly damaged so that they die or wither.
Example 4: Postemergence herbicidal action (contact action) .
large number of weeds and cultivated plants, both monocots and dicots, are sprayed postemergence in the 4- to 6-leaf stage with an aqueous dispersion of test compound at a rate of application of 4 kg a.i./ha, and then kept at 24-26DC and 45-60% relative humidity. The test is evaluated 15 days after treatment. The compounds of formula I
have good herbicidal action in this test.
Example 5: Growth inhibition of cereals ... .
Summar barley (Hordeum vulgare) and summer rye tSecale) are sown in sterilised soil in plastic beakers in a greenhouse and watered as required. The cereal shoots are treated about 21 days after sowing with an aqueous spray mixture of a compound of the formula I. The concentration corresponds to 0.5 and 2.5 kg respectively of active ingredient per hectare. Evaluation of the growth of the cereals is made 10 and 21 days after application. A comparisonwithuntreated controls shows that the growth of cereal plants treated with compounds of the formula I is significantly reduced.
i2 Example 6: Growth inhibition of grasses Seeds of the grasses Lolium perenne, Poa pratensis, Festuca ovina, and Cynodon dactylon are sown in plastic dishes filled with an earth/
peat/sand mixture (6:3:1), in a greenhouse, and watered as required.
The emergent grasses are cut back weekly to a heightof4cm, and about 50 days after sowing and 1 day after the last cut are sprayed with an aqueous spray mixture of a compound of the formula I. The con-centration of test compound corresponds to a rate of application of 2.5 kg per hectare. The growth of the grasses is evaluated 10 and 21 days after application. The evaluation shows that the compounds of Table 1 effect a significant reduction in growth.
3.18 Q 18O N H 3 ¦ CH3 ~3.19 Q 19 1 0 N CH3 CH3 l CH3 3.20 Q 180 N H CH3 OCH3 ¦3.21 Q 3~ O CH H CH3 CH3 160-161 ¦3.22 Q 3O N H I CH3 OCH3 3.23 Q 5 O CH H l CH3 OCH3 3.24 Q 5 O N H I CH3 OCH3 3.25 Q 6 O CH H l CH3 OCH3 3.26 Q 17O N H I CH3 OCH3 3.27 Q 17i 0 N H OCH3 OCH3 3.28 Q 6 ¦ O N H CH3 OCH3 - 28 ~
Table 3: l ~ (continuation) . . ~
Com-pound Q Z E Rl _2 3 -m.p. [C]
3.29 Q 20 O N CH3 CH3 CH3 3.30 Q 7 S N H CH3 OC3H7-n 3.31 Q 21 O N H CH3 C2H5 3.32 Q 13 O N H CH3 OCH3 3.33 Q 13 O CH H CH3 OCH3 3.34 Q 22 S CH CH3 CH3 CH3 3.35 Q 23 O N H OCH3 OCH3 3.36 IQ 1 O N H CH3 OCH3 153-154 3.37 ¦Q1 O N H OCH3 N(CH3)2 154-155 3.38 IQ l O N H OCH3 C2H5 3 39 1` 1 O N H OCH3 OCH(CH3)2 3.40 IQ 1 O N H OCH3 CH2cF3 3.41 'Q 1 O N H C2H5 OCH3 139-141 3.42 ~Q 1 O N H C2H5 C2H5 3.43 ~Q 1 O N H SCH3 OCH3 3.44 IQ 1 O N H CH3 C2H5 143-144 3.45 ~Q 1 O CH H 3 3 165-167 3.46 IQ 1 O CH H ICH3 OCH3 138-141 3.47 ~Q 1 O CH H CH3 OCHF2 142-145 3.48 i Q 1 O CH H CH3 N(CH3)2 3.49 jQ 1 O CH H OCH3 OCH3 160-163 3.50 Q 1 O CH H OCHF2 OCHF2 3.51 IQ 1 O CH H OCH3 OCHF2 3.52 jQ 1 O CH H OCH3 Cl 3.53 jQ 1 O CH H OCH3 F
3.54 iQ 1 O CH H OCH3 N(CH3)2 3.55 IQ 1 O CH H CH2F OCH3 Table 3_ Q-S02-NH-C-N--~ ~ (continuation) Rl \2~ \R
Com~ ---r -----~ - -~pound Q Z I E 1 1 2 R3 i m-p- ~ C]
_ . ~ ._ _ . ..
3.56 Q 1O CH H OCHF2 N(CH3)2 3.57 Q 1O CH H OCH3 OCF2~CHF2 3.58 Q 1O CH H CH3 OCF2-CHF2 3.59 Q 2O N H CH3 OCH3 135-137 3.60 Q 2O N H OCH3 N(CH3)2 180-181 3.61 Q 2O N H OCH3 C2H5 3.62 Q 2O N H OCH3 OCH(CH3)2 3.63 Q 2O N H OCH3 0CH2CF3 3.64 Q 2O N H C2H5 OCH3 122-124 3.65 Q 20 N H C2H5 C2H5 3.66 Q 2 O N H SCH3 OCH3 3.67 Q 2O N H CH3 C2H5 123-125 3.68 Q 2O CH H 3 ¦ CH3 166-167 3.69 Q 2O CH H CH3 1 OCH3 139-141 3.70 Q 2O CH H CH3 ~ OCHF2 116-123 3.71 Q 2O CH H CH3 ¦N(CH3)2 3.72 Q 2O CH H OCH3 ~OCH3 143-147 3.73 Q 2 O CH H OCHF2 ¦ OCHF2 j3.75 Q 2O CH H ¦OCH3 Cl 3.76 Q 2 O CH H OCH3 F
3.77 IQ 2O CH H OCH3 N(CH3)~
3.78 IQ 2O CH H CH2F ¦OCH3 3~79 IQ 21 0 CH H OCHF2 jN(CH3)2 3.80 `Q 21 0 CH H OCH3 1 OCF2-CHF
3.81 IQ 21 0 CH H CH3 1OCF2-CllF2 ¦3.82 Q 14 i N H ICH3 OCH3 7 ~N_o~2 Table3: Q-SO NH-C-N- ~E (continuation) R =.
Com~
pound¦Q ¦7~ ¦ E ¦ Rl l R2 l R3 ¦ m.p. [ C~
. __ _ _ _ __ _ __ . . _. .
3.83Q14 O CH H CH3 OCH3 3.84Q 14 O CH H CH3 CH3 3.85Q14 O CH H OCH3 OCH3 3.86Q~4 O CH H CH3 OCHF2 3.87Q 24 O N H CH3 OCH3 3.88Q 24 O CH H l CH3 OCE~3 3.89Q 24 O CH H l CH3 OCHF2 3.90Q ?.5 O N H CH3 OCH3 3.91Q 25 O CH H CH3 OCH3 3.92Q 26 O N H CH3 OCH3 3.93Q 26 O CH H CH3 OCH3 3.94Q 15 O CH H CH3 OCH3 3.95Q 15 O N H CH3 OCH3 3.96Q 15 O CH H CH3 OCHF2 3.97I Q16 O N H ~ CH3 OCH3 3.90Q 16 O CH H ~ CH3 OCH3 3.99Q 17 O N H ¦ CH3 OCH
3.100 Q 17 O CH H l C~13 OCH3 3.101 Q 27 O N H OCH3 C2H5 3.102 IQ 27 O N H OCH3 bCH(CH3)2 3.103 Q 27 O N H CH3 OCH3 3.104 Q 27 O N H OCH3 N~CH3)2 3.105 IQ 27 O N H OCH3 0CH2CF3 3.106 IQ 27 O N H C2H5 OCH3 3.107 Q 27 O N H OCH3 OCH3 3.108 Q 27 O N H CH3 C2H5 3.109 Q 27 O CH H CH3 CH3 3.110 IQ 27 O CH H CH3 OCH3 ~L~7~
Ta~le 3: Q-SO -NH-C~N-~ ~R (continuation) I
I Com-~ T--- R ~ 3 -----T ~c pound Q Z + E 1 ¦----_2 3 m.p. ]
3.111 Q 27 O CH CH3 CH3 C2H5 3.112 Q 27 O CH H OCH3 OCH3 3.113 Q 27 O CH H OCHF2 OCHF2 3.114 Q 27 O CH H OCH3 OCHF2 3.]15 Q 30 O N H OCH3 C2H5 3.116 Q 30 O N H OCH3 l CH(CH3)2 3.117 Q 30 O N H CH3 OCH3 3.118 Q 30 O N H OCH3 N(CH3)2 3.1]9 Q 30 O N H OCH3 l CH2CF3 3.120 Q 30 O N H C2H5 OCH3 3.121 Q 30 O N H OCH3 OCH3 ¦3.122 Q 30 O N H CH3 C2H5 3.123 Q 30 O CH H CH3 CH3 3.124 Q 30 O j CH H CH3 OCH3 3.125 Q 30 O ¦ CH H CH3 OCHF2 ¦3.126 Q 30 O CH H OCH3 OCH3 ~3.127 Q 30 O CH H OCHF2 OCHF2 3.128 Q 30 O CH H OCH3 OCHF2 13.l29 Q 32 O N H OCH3 C2H5 3.130 I Q 32 O N H OCH3 IOCH(CH3)2 3.131 ¦ Q 32 1 0 ¦ N H CH33 ¦ OCH3 3.132 ~ Q 32 j O N ¦ H
3.133 I Q 32 O N H OCH3 CH2cF3 ~3.134 ~ Q 32 O N H C2H5 OCH3 3.135 Q 32 O N H - OCH3 OCH3 3.136 Q 32 O N H CH3 C2H5 3.137 Q 32 O CH H CH3 CH3 ,3.138 Q 32 O CH H CH3 OCH3 ., ' _ ~ 32 ~
Tab le 3: Q-so -NH- 3-N~ (continuation) R \N~~\R
cO~ ~ ------- ~-- r ~ 3 - -I ~ - --pound Q Z ¦ 1 R~ R3 ¦ m-p- [ C]
... _ ~_. _ . __ 3.139 Q 32 O CH H CH3 OCHF2 3.140 Q 32 O CH H OCH3 OCH3 3.141 Q 32 O CH H OCHF2 OCHF2 3.142 Q 32 O CH H OCH3 OCHF2 3.143 Q 33 O N H OCH3 C2HS
3.144 Q 33 O N H OCH3 OCH(CH3)2 3~145 Q 33 O N H CH3 ¦ OCH3 3.146 Q 33 O N H OCH3 ¦ N(CH3)2 3.147 Q 33 O N H OCH3 0CH2CF3 3.148 Q 33 O N H C2H5 OCH3 ¦3.149 Q 33 O N H OCH3 OCH3 ~3.150 Q 33 O N H CH3 C2H5 3.151 Q 33 O CH H CH3 CH3 3.152 Q 33 O CH H CH3 OCH3 3.153 Q 33 O CH H CH3 OCHF2 3.154 Q 33 O CH H OCH3 OCH3 3.155 Q 33 O CH H OCHF2 OCHF2 3.156 Q 33 O CH H OCH3 OCHF2 3.157 Q 34 ! H OCH3 C2H5 3.158 Q 34 O ~ N H OCH3 OCH(CH3)2 3.159 Q 34 i i N H CH3 OCH3 3.160 Q 34 ¦ O N H OCH3 N(CH3)2 3.161 ¦ Q 34 O N H OCH3 0CH2CF3 3.162 ¦ Q 34 O N H C2H5 OCH3 3.163 ¦ Q 34 ~ O ¦ N H OCH3 OCH3 3.164 ¦ Q 34 ¦ O I N H CH3 C2H5 13.165 ¦ Q 34 1 0 ¦ CH H CH3 CH3 ¦3.166 ¦ Q 34 ~ O ~ CH U CH3 ¦ OCH
I~J~
Z N~2 Table 3: Q-SO NH~ N~ (continuation) \N~
I pound ~ _ _ _ E Rl 2 ~ ~ ~ P [C]
1~ -~- --- ~ ~
3c167Q 34 O CH H CH3 OCHF2 3.168Q 34 O CH H OCH3 OCH3 3.169Q 34 O CH H OCHF2 OCHF2 3.170Q 34 O CH H OCH3 OCHF2 3.171Q 37 O N H OCH3 2 5 3.172Q 37 O N .~ OCH3 OCH(CH3)2 3~173Q 37 O N H CH3 OCH3 3 r 1/4 Q 37 O N H OCH3 N(CH3)2 3.175Q 37 O N H OCH3 0CH2CF3 3.176Q 37 O N H C2H5 OCH3 3.177Q 37 O N H OCH3 OCH3 3.178Q 37 O N H CH3 C2H5 3.179Q 37 O CH H CH3 CH3 3.1$0Q 37 O CH H CH3 OCH3 3.181¦ Q 37 O CH H CH3 OCHF2 3.182I Q 37 O CH H OCH3 OCH3 3.183¦ Q 37 O CH H OCHF2 OCHF2 3.184~ Q 37 O CH H OCH3 OCHF2 l3.185 ! Q 38 o N H OCH3 2 5 ¦3.186 I Q 38 O N H OCH3 OCH(CH3)2 3.187! Q 38 O ¦ N H CH3 OCH3 3.188¦ Q 38 O ¦ N H OCH3 N(CH3)2 3.189j Q 38 O N H OCH3 2 3 3.190Q 38 O N H C2H5 OCH3 3.191Q 38 O N H OCH3 OCH3 3.192Q 38 O N H CH3 C2HS
3.193Q 38 O CH H CH3 CH3 3.194Q 38 O , CH H CH3 OCH3 . . . ~. _ ~L22Z75ii2 Table 3: Q-SO -NH-C-N-~ ~. (continuation) R '=-__ ~ .. _ .
pCound Q Z E Rl R2 R3 ~-P- r C]
_ _ G _ _ . ._ .~ .
3.195 Q 38 O CH H CH3 OCHF2 3.196 Q 38 O CH H OCH3 OCH3 3~197 Q 38 O CH H OCHF2 OCHF2 3.199 Q 39 O N H OCH3 ¦ C2H5 3.200Q 39 O N H OCH3 l CH(CH3)2 3.201Q 39 O N H CH3 OCH3 3~202Q 39 O N H OCH3 N(CH3)2 3-203Q 39 O N H OCH3 OCH~CF3 3~205Q 39 O N H OCH3 OCH~
3.206Q 39 O N H CH3 C2H5 ¦3.207 Q 39 O CH H CH3 CH3 l3.208 Q 39 O CH H CH3 OCH3 ¦2.209IQ 39 CH H CH3 OCHF2 l3.210 Q 39 O CH H OCH3 OCH3 ¦3.211 Q 39 O CH H OCHF~ OCHF2 j3.212 Q 39 O CH H OCH3 OCHF2 3.213Q 28 O N H CH3 OCH3 3.214Q 28¦ O N I H OCH3 N(CH3)2 3.215Q 28 O I ~T H OCH3 C2H5 3.216Q 28 O j N H OCH3 OCH(CH3)2 3.217Q 28 O N H OCH3 0CH2CF3 3.218Q 28~ O N H C2H5 OCH3 3.219Q 28¦ O N H C2H5 C2H5 3.220Q 281 0 N H SCH3 OCH3 3.221Q 28¦ O N H CH3 C2H5 - 35 ~
Z ~ (continuation) Table 3: Q~SO -NH-C-N-_ 2 1 ~ =0 1 ~ 3 _. . _ .____ . _ _. .
poumnd Q Z E 1 1 2 R3 ¦ m.p. [C]
__ . l -._ _ .
3~222Q 28 O CH H CH3 CH3 3.223Q 28 O CH H CH3 1OCH3 3.225Q 28 O CH H CH3 IN(CH3)2 2.227Q 28 O CH H OCHF2 1OCHF2 3~228Q 28 O CH H OCH3 OCHF2 j3.229 Q 28 O CH H OCH3 C1 3.230IQ 28 O CH H OCH3 F
¦3~231 Q 28 O CH H OCH3 N(CH3)2 ~3.232 Q 28 O CH H CH2F OCH3 13.233 Q 28 O CH H OCHF2 N(CH3)2 j30234 Q 28 O CH H OCH3 OCF2-CHF2 3.235Q 281 0 CH H CH3 OCF2-CHF2 ~3.236 Q 29 1 0N H CH3 OCH3 j30237 Q 29 O N H OCH3 N(CH3)2 3.238~Q 29j O N H OCH3 C2H5 ~30239 IQ 29 ¦ ON H OCH3 jOCH(CH3,2 j3.240 IQ 29 j ON H OCH3 ¦OCH2cF3 3.241jQ 29~ O N¦ H OC H ~0 3.242! Q 291 0 N H 2 5 1 2 5 3.244~Q 291 0 N H CH3 10C2H5 3.245IQ 29¦ CH H 3 1 3 3.246IQ 291 0 CH H CH3 ~OCH3 3-247IQ 29 j CH H CH3 ~OCHF2 13-248¦Q 291 0 CH H CH3 ,N~CH3)2 3.249IQ 29~ O CH H ` OCH3 f OCH3 -, ¦ !
- 36 _ Table 3: 1 \2 (continuation) Com- _ l ~ __ .
pound Q Z E Rl R2 R3 m.p.[C]
_.... ___ _. _~ ...... , _ _ __ 3.250 Q 29 . O CH H I OCHF2 1 OCHF2 3. 251 Q 29 O CH H I OCH3 OCHF2 3.252 Q 29 O CH H OCH3 Cl 3.253 Q 29 O CH H OCH3 F
3.254 Q 29 O CH H OCH3 I N(CH3)2 3.255 Q 29 O CH H CH2F OCH3 30256 Q 29 O CH H OCHF2 N(CH3)2 3~257 Q 29 O CH H OCH3 OCF2-CHF2 3~258 Q 29 O CH H CH3 OCF2-CHF2 3.259 Q 31 O N H CH3 OCH3 3.260 Q 31 O N H OCH3 N(CH3)2 3.261 Q 31 O N H OCH3 C2H5 3~262 Q 31 O N H OCH3 OCH(CH3)2 3.263 Q 31 O N H OCH3 0CH2CF3 3.264 Q 31 O N H C2H5 OCH3 3.265 Q 31 O N H C2H5 C2H5 3.266 Q 31 O N H ~CH3 OCH3 3~267 Q 31 O N H CH3 C2H5 3.268 Q 31 O CH H l CH3 CH3 3.269 Q 31 O CH H CH3 OCH3 3.270 Q 31 O I CH H CH3 ! OCHF2 3.271 Q 31 O I CH H CH3 N(CH3)2 3.272 Q 31 O ~ CH H OCH3 OCH3 3.273 Q 31 O CH H OCHF2 OCHF2 13.274 Q 31 O CH H OCH3 OCHF2 13.275 Q 31 ¦ O CH H OCH3 Cl ¦3.276 Q 31 ¦ O CH H OCH3 F
13.277 Q 31 1 0 CH 3 OCH3 ( 3)2 7~%
Table 3: Q_SO2_NH_C_N_-~ ~ (continuation) I 2 ~r 3~278Q 31 O CH H CH2F OCH3 3~279Q 31 O CH H OCHF2 N(CH3)2 3~280Q 31 O CH H OCH3 OCF2-CHF2 3.28%Q 35 O N H CH3 OCH3 3.283Q 35 O N H OCH3 N(CH3)2 3.284Q 35 O N H OCH3 C2H5 3.285Q 35 O N M OC~3 OCH(CH3)2 3.286Q 35 O N H OCH3 0CH2CF3 3.287Q 35 O N H C2H5 OCH3 3.289Q 35 O N H SCH3 OCH3 3~2900 35 O N H CH3 C2H5 30292Q 35 O ¦ CH H CH3 OCH3 3.293Q 35 O ¦ CH H CH3 OCHF2 30294Q 35 O ¦ CH H l CH3 N(CH3)2 3.295Q 35 O ¦ CH H j OCH3 OCH3 j30296 Q 35 O I CH H L OCHF2 OCHF2 3~297IQ 35 I CH H ¦ OCH3 OCHF2 !3~298 IQ 35 O ¦ CH H j OCH3 Cl 30299IQ 35 j CH H ¦ OCH3 F
3.3 ~Q 35 ! CH H I OCH3 N(CH3)2 3.301IQ 35 O ¦ CH H CH2F `i OC~3 3 33iQ 35 CH H OCHF2 N(CH3)2 3.304IQ 35 O CH H OCH3 OCF2-CHF2 3.305IQ 35 O CH H CH3 OCF2-CHF2 3.306,Q 1 O N H I OCH3 OCH3 142-143 , . j . ~
7~
Table 3: Q-SO -~-C-N~ (continuation) ~N=
1 ~ 3 ~ound Q¦ Z _ }~ .-I ~ j 3.307 Q 2O N H OCH3 OCH3 124-126 3.308 Q 36 O N H CH3 C~3 3.309 Q 36 O N H OCH3 N(CH3)2 3.310 Q 36 O N H OCH3 C2H5 3.311 Q 36 O N H OCH3 OCH(CH3)2 3.312 Q 36 O N H OCH3 0CH2CF3 3.313 Q 36 O N H C2H5 OCH3 3.314 Q 36 O N H C2H5 C2H5 3.3L5 Q 36 O N H SCH3 OCH3 3,316 Q 36 O N H CH3 C2H5 3.317 Q 36 O CH H CH3 CH3 3.318 Q 36 O CH H CH3 OCH3 3.319 Q 36 O CH H CH3 OCHF2 3.320 Q 36 O CH H CH3 N(CH3)2 3.321 Q 36 O CH H OCH3 OCH3 3.322 Q 36 O CH H OCHF2 OCHF2 3.323 Q 36 O CH H OCH3 OCHF2 3.324 Q 36 O CH H OCH3 Cl 3.325 Q 36 O CH H OCH3 F
3.326 Q 36 O CH H OCH3 N(CH3)2 j 3.327 Q 36 O CH H CH2F OCH3 l3.328Q 36 O CH H OCHF2 N(CH3)2 j 3.329 Q 36 ¦ O CH H OCH3 OCF2-CHF
3.330 Q 36 1 0 CH H CH3 _ ~2~7~
For application9 the compounds of formula -L can be processed to the following formulations.
Formulation Examples Example 2:
Formulation examples for compounds of formula I
(percentages are by weight) a) Wettable powders a) b) c) .
compound of formula I 20% 60% 0.5%
sodium lignosulfonate 5% 5% 5%
sodium laurylsulfate 3% - -sodium diisobutylnaphthalenesulfonate - 6% 6%
octylphenol polyethylene glycol ether (7-8 moles of ethylene oxide) - 2% 2%
highly dispersed silicic acid 5% 27% 27%
kaolin 67%
sodium chloride - - 59.5%
The active ingredient is thoroughly mixed with the adjuvants and the mixture ;s thoroughly ground in a suitable mill, affording wettable powders which can be diluted with water to give suspensions of the desired concentration.
b) Emulsifiable concentrate a) b) compound of formula I 10% 1%
octylphenol polyethylene glycol ether (4-5 moles of ethylene oxide) 3% 3%
calcium dodecylbenzenesulfonate castoroil polyglycol ether (36moles of ethyleneoxide) 4% 4%
cyclohexanone 30% 10%
xylene mixture 50% 79%
~ 40 -Emulsions of any required concentration can be obtained from this concentrate by dilution with water.
c) Dusts a) b) compound of formula I 0.1% 1%
talcum 99 9%
kaGlin - 99%
Ready for use dusts are obtained by mixing the active ingredient with the carrlers, and grinding the mixture in a suitable mill.
d) Extruder granulate a) b) .. . . _ _ .
compound of formula I 10% 1%
sodium lignosulfonate 2% 2%
carboxymethylcellulose 1% 1%
kaolin 87% 96%
The active ingredient is mixed and ground with the adjuvants, and the mixture is subsequently moistened with water. The mixture is extruded and then dried in a stream of air.
e) Coated granulate compound of formula I 3%
polyethylene glycol 200 2%
kaolin 94%
The finely ground active ingredient is uniformly applied, in a mixer, to the kaolin moistened with polyethylene glycol. Non-dusty coated granulates are obtained in this manner.
~ 41 -f) Suspension concentrate a) b) compound of formula I 40% 5%
ethylene glycol 10% 10%
nc,nylphenol polyethylene glycol ether (15 moles of ethylene oxide) 6% 1%
sodium lignosulfonate 10% 5%
carboxymethylcellulose 1% 1%
37% aqueous formaldehyde solution 0.2% 0.2%
silicone oil in the form of a 75%
aqueous emulsion 0.8% 0.8%
water 32% 77%
The finely ground active ingredient is intimately mixed with the adjuvants, giving a suspension concentrate from which suspension of any desired concentration can be obtained by dilution with water.
g) Salt solution , _ compound of formula 5%
isopropylamine 1%
octylphenol polyethylene glycol ether (78 moles of ethylene oxide) 3%
water 91%
Emulsions of the desired concentration may be prepared from such con-centrates by dilution with water. These emulsions are particularly suitable for foliar application. In addition it is possible to prepare further wettable powders with other mixture ratios or other carriers and adjuvants customarily employed in formulation technology. The active ingredients are intimately mixed with the adjuvants in suitable mixers and ground in corresponding mills and rollers to give wettable powders of excellant wettability and suspension power which can in turn be diluted with water to give suspensions of the desired con-centration which are particularly suitable for foliar application.
The invention also relates to such compositions.
~2~7$~
Compositions which are formulated in the manner described above and which contain one of the compounds of Table 1 can be successfully used for growth regulation and/or for herbicidal application.
Biological Examples Example 3: Preemergence herbicidal action In a greenhouse, plant seeds are sown in flower pots of 12-15 cm diameter. Immediately after sowing, the surface of the soil is treated with an aqueous dispersion or solution of the compounds to be tested.
Concentrations of 4 kg a.i./ha are employed. The pots are then kept in the greenhouse at 22-25C and 50-70% relative humidity. The test is evaluated 3 weeks later. The compounds of formula I are very effective in this test, i.e. the test plants are irreversibly damaged so that they die or wither.
Example 4: Postemergence herbicidal action (contact action) .
large number of weeds and cultivated plants, both monocots and dicots, are sprayed postemergence in the 4- to 6-leaf stage with an aqueous dispersion of test compound at a rate of application of 4 kg a.i./ha, and then kept at 24-26DC and 45-60% relative humidity. The test is evaluated 15 days after treatment. The compounds of formula I
have good herbicidal action in this test.
Example 5: Growth inhibition of cereals ... .
Summar barley (Hordeum vulgare) and summer rye tSecale) are sown in sterilised soil in plastic beakers in a greenhouse and watered as required. The cereal shoots are treated about 21 days after sowing with an aqueous spray mixture of a compound of the formula I. The concentration corresponds to 0.5 and 2.5 kg respectively of active ingredient per hectare. Evaluation of the growth of the cereals is made 10 and 21 days after application. A comparisonwithuntreated controls shows that the growth of cereal plants treated with compounds of the formula I is significantly reduced.
i2 Example 6: Growth inhibition of grasses Seeds of the grasses Lolium perenne, Poa pratensis, Festuca ovina, and Cynodon dactylon are sown in plastic dishes filled with an earth/
peat/sand mixture (6:3:1), in a greenhouse, and watered as required.
The emergent grasses are cut back weekly to a heightof4cm, and about 50 days after sowing and 1 day after the last cut are sprayed with an aqueous spray mixture of a compound of the formula I. The con-centration of test compound corresponds to a rate of application of 2.5 kg per hectare. The growth of the grasses is evaluated 10 and 21 days after application. The evaluation shows that the compounds of Table 1 effect a significant reduction in growth.
Claims (14)
1. A compound of the formula (I) wherein R1 is hydrogen or C1-C5alkyl, R2 and R3, each independently of the other, are hydrogen, C1-C5alkyl, C1-C5alkoxy, C1-C5alkylthio, C1-C5haloalkyl,halogen,C1-C5haloalkyl-thio, C1-C4alkylamino, C1-C4dialkylamino, an alkoxyalkyl group or alkoxyalkoxy group, each containing not more than 6 carbon atoms, Z is oxygen or sulfur, E is -CH= or -N=, and Q is an unsubstituted or substituted 6-membered heterocyclic radical containing 2 to 3 nitrogen atoms and bound through a carbon atom selected from the group pyrimidine, pyridazine, pyrazine and triazine, wherein the optimal substituents are selected from the group halogen, nitro, C1-C6-alkyl, C1-C6-haloalkyl, C1-C6-alkoxy, C1-C6-alkylthio, C1-C6-haloalkoxy, C1-C6-haloalkylthio, amino, C1-C6-alkylamino, di-C1-C6-alkylamino, C1-C6-alkylcarbonylamino, C1-C6-alkylcarbonyl, C1-C6-alkoxycarbonyl, C1-C6-alkylthiocarbonyl, carbamoyl, C1-C6-al-kylaminocarbonyl, di-C1-C6-alkylaminocarbonyl, C1-C6-alkylsulfinyl, C1-C6-alkylsulfonyl, C2-C6-alkenyloxy, C2-C6-alkynyloxy, or by phenyl, phenoxy or phenylthio, which are unsubstituted or substitu-ted by halogen, nitro, cyano, C1-C6-alkyl, C1-C6-alkoxy, C1-C6-haloalkyl or C1-C6-haloalkoxy, or by benzyl or benzyl substituted by halogen and/or C1-C6-alkyl, or a salt thereof.
2. A compound of the formula I according to claim 1, wherein Z is oxygen and R1 is hydrogen.
3. A compound of the formula I according to claim 1, wherein R1 is hydrogen, each of R2 and R3 independently of the other is C1-C3alkyl, C1-C3alkoxy, C1-C3haloalkyl, C1-C3haloalkoxy, halogen or C2-C4alkoxy-alkyl, Z is oxygen, E is nitrogen or CH, Q is a heterocyclic radical as defined for formula I, which is unsubstituted or substituted by a member selected from chlorine, bromine, fluorine, nitro, cyano, C1-C4alkylcarbonyl, C1-C4alkoxycarbonyl, C1-C3alkoxy, C1-C3alkylthio, C3-C5alkoxyalkoxy, C1-C3alkylsulfinyl, C1-C3alkylsulfonyl, C1-C4alkyl, trifluoromethyl, trichloromethyl, C1-C4cyanoalkyl, C2-C4alkenyloxy, C3-C4alkynyloxy or N-C1-C4alkylcarbonylamino.
4. A compound according to claim 3, wherein Q is a pyrazinyl radical.
5. A process for the preparation of a compound of the formula I as defined in claim 1, which comprises reacting a phenylsulfonyl derivative of the formula II
Q - S02W (II) with a compound of the formula III
(III) wherein X and W are one of the groups -NH2, -N=C=Z or -NR1CZ-OR, the sub-stituents R1, R2, R3, Q, Z and E are as defined for formula I, R is an ali-phatic or aromatic radical, with the proviso that the reactants of the formulae II and III are also so chosen that an amino function reacts either with an isocyanato or isothiocyanato function or with the [-NR1-CZ-OR] group.
Q - S02W (II) with a compound of the formula III
(III) wherein X and W are one of the groups -NH2, -N=C=Z or -NR1CZ-OR, the sub-stituents R1, R2, R3, Q, Z and E are as defined for formula I, R is an ali-phatic or aromatic radical, with the proviso that the reactants of the formulae II and III are also so chosen that an amino function reacts either with an isocyanato or isothiocyanato function or with the [-NR1-CZ-OR] group.
6. A process according to claim 5, wherein R is C1-C4alkyl, phenyl or benzyl.
7. A process according to claim 5, wherein the process is carried out in the presence of an inert solvent or of a mixture of solvents.
8. A process according to claim 9, wherein the reaction is carried out in the presence of a base.
9. N-(2-Methylpyrazin-3-ylsulfonyl)-N'-(4-methoxy-6-methyl-1,3,5-triazin-2-yl)urea according to claim 1.
10. N-(2-Methoxypyrazin-3-ylsulfonyl)-N'-(4-methoxy-6-methyl-1,3,5-triazin-2-yl)urea according to claim 1.
11. A method of controlling weeds pre- or postemergence and/or of influencing the growth of useful plants, which method comprises applying to noxious or useful plants, to parts of said plants or to the locus thereof, an effective amount of a compound of the formula I
according to claim 1.
according to claim 1.
12. A method according to claim 11 of selectively controlling weeds.
13. A method according to claim 11 of inhibiting plant growth.
14. A herbicidal composition which contains as active ingredient a compound of formula I according to claim 1, together with a carrier and/or inert adjuvants.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA000428445A CA1222752A (en) | 1983-05-18 | 1983-05-18 | Sulfonylureas and sulfonylthioureas, the preparation thereof, and method of use thereof as herbicides and/or growth regulators |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA000428445A CA1222752A (en) | 1983-05-18 | 1983-05-18 | Sulfonylureas and sulfonylthioureas, the preparation thereof, and method of use thereof as herbicides and/or growth regulators |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1222752A true CA1222752A (en) | 1987-06-09 |
Family
ID=4125273
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000428445A Expired CA1222752A (en) | 1983-05-18 | 1983-05-18 | Sulfonylureas and sulfonylthioureas, the preparation thereof, and method of use thereof as herbicides and/or growth regulators |
Country Status (1)
| Country | Link |
|---|---|
| CA (1) | CA1222752A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5232922A (en) * | 1990-02-10 | 1993-08-03 | Hoechst Aktiengesellschaft | Imidazole compounds, processes for their preparation, pharmaceuticals based on these compounds and some intermediates |
-
1983
- 1983-05-18 CA CA000428445A patent/CA1222752A/en not_active Expired
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5232922A (en) * | 1990-02-10 | 1993-08-03 | Hoechst Aktiengesellschaft | Imidazole compounds, processes for their preparation, pharmaceuticals based on these compounds and some intermediates |
| US5356922A (en) * | 1990-02-10 | 1994-10-18 | Hoechst Aktiengesellschaft | Imidazole compounds, processes for their preparation, pharmaceuticals based on these compounds and some intermediates |
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