CS238643B2 - Herbicide agent and production method of effective compound - Google Patents

Abstract

Verbindungen der Formel worin A einen (substituierten) aliphatischen, cycloaliphatischen oder Phenylrest, R₁ H oder Alkyl, R₂ H, Alkyl oder (substituiertes) Phenyl, X O oder S, R₃ H, Halogen, N0₂, CN, (Di)al- kylamino, (subst.) Alkyl, (subst.) Alkoxy, (subst.) Alkylthio oder Alkoxycarbonyl, B eine einfache chemische Bindung oder eine (subst.) Methylen- oder Ethylengruppe, R₄ eine Carbonylgruppe oder eine davon abgeleitete funktionelle Gruppe, Z Stickstoff oder eine Methin-Gruppe und m 0 oder 1 bedeutet, sind wirksame Herbizide und Wachstumsregulatoren.

Description

wherein the general symbols are as defined below, or a physiologically acceptable base salt or acid salt thereof.

Further, a process for preparing the active ingredient is described.

The present invention relates to a herbicidal composition comprising, as an active ingredient, the novel heterocyclically substituted sulfonylureas of the following general formula (I).

It is already known that heterocyclically substituted phenylsulfonylureas, such as N- (2-chlorophenylsulfonyl) -N- (4-methoxy-6-methyl-1,3,5-triazin-2-yl) urea, have herbicidal properties. and further have the ability to control plant growth (cf. Dutch Patent Specification 121 788, DE-OS 27 15 786, EP 1 485, EP 1 514, EP 1 515, EP 4 163, EP 7 687, EP 9 419, EP 10 560 , EP 23,140, EP 23,141, EP 23,422, EP 35,893).

It has now been found that heterocyclically substituted phenyl, phenoxy, (halo) alkyl (haloalkoxysulfonylureas) containing a pyrimidine or s-triazine ring which is substituted with a carbonyl function or functional derivatives derived therefrom (e.g. acetals, semiacetals) as heterocyclic component , dioxolanes, mercaptals, dithiolanes, aminals, azomethines, oximes, oximethers and hydrazones) are suitable as herbicides.

The present invention relates to a herbicidal composition which is characterized in that it contains, in addition to the carriers and / or other additives normally used for this purpose, at least one compound of the formula I as active ingredient.

A-10O-SO2, -NH-C-NH2-; and (1) wherein

A is optionally C1-C4alkyl or C2-C4alkenyl or is a formula of formula

m is 0 or 1,

R3 represents a hydrogen atom, a chlorine atom, a nitro group, a dimethylamino group, a methyl group which is optionally substituted by a methoxy group, furthermore an alkoxy group having 1 to 2 carbon atoms which is optionally substituted by an alkoxy group having 1 to 2 carbon atoms,

B and D are each independently a single chemical bond or B is a methylene group or an ethylene group,

R 4 represents a group of the formula -CO-R 7, a group of the formula

 % G i X ^y - i f R * 8

τ or a group of the formula —c = N — R10

R7 where

Y is oxygen or sulfur,

R _s each represent an alkyl group having 1 to 4 carbon atoms, or both radicals R ₈ together form an ethylene or propylene bridge, and

Rjo is hydroxy or methoxy;

R 5 represents halogen, nitro, OCHF 2, methyl, C 1 -C 3 alkylsulfonyl, -SO ₂ N (alkyl) ₂ in which "C 1 -C 4 alkyl" or C 1 -C 4 alkoxycarbonyl in the alkoxy moiety, and

R 7 represents a hydrogen atom or a methyl group, and

Z represents a nitrogen atom or a methine group, or a physiologically acceptable salt thereof, or a salt thereof with an acid.

The novel compounds of the formula I can be synthesized from starting materials known per se or starting materials which can be prepared by known methods.

According to the invention, the compounds of formula (I) are prepared by treating the compounds of formula (II)

A - (O) _{m -} SO 2 - N = C = O (II) in which

A and m are as defined above or for compounds of formula III

A - (O) _m --SO 2 - NH - C = O (III), wherein Y

A and m are as defined above and

Y is chloro, (C1-C6) alkoxy or phenoxy, acts by compounds of formula (IV)

(IV) in which:

R ₃ , R _{Z (} , W and Z) have the meanings given above, and optionally the compounds of formula I obtained are converted by hydrogen halide cleavage, addition of halogen to the present multiple bonds or salt formation to other compounds of formula I as defined above.

The reaction of the compounds of formulas II and III and IV is preferably carried out in inert aprotic solvents such as acetonitrile, dichloromethane, toluene, tetrahydrofuran or dioxane at temperatures between 0 ° and the boiling point of the solvent. The starting materials of the formula (III) are optionally employed in the presence of an acid binding agent such as potassium carbonate, pyridine or triethylamine.

The possible subsequent cleavage of hydrogen chloride from the chloroalkyl residues A may be carried out in a known manner, for example by treatment with an alkali metal alkoxide, an alcoholic solution of sodium or potassium hydroxide, triethylamine or other acid-cleaving agents, optionally in the presence of another inert solvent or diluent such as toluene. between room temperature and boiling point.

The possible or additionally formed double bond in the residue A can also be added in a known manner by chlorine or hydrogen chloride, and thus, optionally, new compounds of the formula I can be obtained.

The chlorination is carried out in inert organic solvents such as dichloromethane or chloroform under illumination, for example with ultraviolet light, or in the presence of compounds which decompose into radicals, such as azodiisobutyronitrile, at temperatures between 0 ° C and the boiling point of the solvent. The addition of hydrogen chloride is carried out in the presence of inert solvents, for example toluene, by treatment with gaseous hydrogen chloride at lower temperatures, optionally in the presence of peroxide as a catalyst.

The compounds of formula I may form salts, wherein the hydrogen atom is replaced by a physiologically compatible cation. These are preferably alkali metal salts, alkaline earth metal salts, ammonium salts or organic amine salts.

Suitable bases for forming the salts of the invention are, for example, potassium carbonate, ammonia or ethanolamine. It is likewise possible to convert into salts the compounds which contain, in the substituent position R ₃ or R ₄ or in the substituent position V of the NH group, by treatment with strong acids such as hydrochloric acid, hydrobromic acid or sulfuric acid.

The starting compounds of formula IV in which Z is nitrogen are novel compounds which, by virtue of their bifunctional structure, are interesting intermediates which, in addition to being suitable for the preparation of the compounds of the formula I according to the invention, are also suitable for the manufacture of pharmaceuticals. To date, examples of s-triazines which are substituted by formyl function or ketofunction, or functional derivatives thereof, cannot be mentioned. Mouoamino-s-triazines which, in addition to any R ₃ radical, contain a formyl function or a ketofunction or functional derivatives thereof as a further substituent are first described in the present invention.

2-amino-s-triazines of the formula IV wherein Z is nitrogen and R _3, and - N-R ₄ have the abovementioned meanings, are therefore novel compounds.

Compounds of formula IV in which Z is nitrogen can be prepared according to methods which are principally known for the synthesis of monofunctional amino-s-triazines. Such methods are described, for example, in J. Org. Chem. 28, 1816 (1963); in s-Triazines and Derivatives 217 (New York, 1959); Chem. Pharm. Bull. 16, 474 (1968), Ber. 100, 1874 (1967) and Agric. Biol. Chem. 35, 1572 (1971). Instead of the starting materials used therein, the corresponding bifunctional compounds of formula VIII are used

X — B — R ₄ (VIII) wherein

X represents radicals of the formula CN, SO2, COCl or COO-alkyl, in which the alkyl contains 1 to 4 carbon atoms.

Examples of such compounds include glyoxalic acid esters, β-formylacetic acid esters, pyruvic acid esters, acetic acid esters, or functional derivatives derived therefrom, such as dialkoxy-2-acetic acid esters, dialkoxyacetonitriles, dialkoxypropionic acid esters or esters 1. 3-dioxolane-2-carboxylic acids, 1,3-dithiolane-2-carboxylic acid esters, 1,3-dioxolane-2-acetic acid esters or 2-methyl-1,3-dioxolane-2-acetic acid esters.

It was not to be expected that these bifunctional compounds would be cyclized to the triazines of the invention, rather a number of possible reaction products had to be envisaged. It is therefore surprising that the bifunctional compounds of formula VIII lead to the bifunctional triazines of formula IV in a simple manner and in good yields using the ipetodes known for monofunctional amino-s-triazines.

The preparation of the compounds of formula (IV) is illustrated in the following section using 2-amino-4-diethoxymethyl-6-methoxy-s-triazine, which is obtained from diethoxyacetic acid ethyl ester and guanidino-O-methylurea according to the following equation:

(C-Η'Ο LCHWOOCr * CHjO-C-NH- ^ C-NH-f 2 ^ 2 2 5 5 и Ц c

NH NH

OCHt

00 (0 <0Ο

These reactions are preferably carried out in polar solvents such as alcohols such as methanol or ethanol or aprotic polar solvents such as acetonitrile, dimethylformamide, tetrahydrofuran and dioxane at reaction temperatures between 0 ° C and the boiling point of the solvent. Since biguanide derivatives which are used as reactants of compounds of the formula VIIa, such as Ν, Ν-dimethylbiguanide or guanidino-O-methylisourea or amidines derivatives, such as O-methylisourea, are generally present in the form of insufficient stability. salts, they must first be converted to the free base.

For this purpose, strong bases or their solutions such as sodium methoxide, sodium ethoxide, potassium tert-butoxide or their alcoholic solutions are used; sodium hydride, alkali metal or alkaline earth metal carbonates or carbonates or tertiary amines such as ^1- triethylamine, ethyldiisopropylamine and pyridine.

The starting materials of formula VIII are known or can be prepared by known methods [JACS 4580 (1954); JACS 2661 (1947); Beilstein 3, III 1139; 3 Apr, 1494; 19 III / IV, 3450 et al.].

The amino-s-triazines of formula IV (with Z = nitrogen) can be converted to other amino-s-triazines of formula IV, depending on the radicals R ₃ and B-R 4. They are thus obtained by reacting compounds in which R is chlorine with alcohols, mercaptans, and amines with the addition of bases of a compound of formula IV in which R3 is O alkyl, S-alkyl, NH-alkyl or -N- (alkyl) ₂ -group.

If the compounds of formula IV Z have the meaning of nitrogen and the radical —B — R4 represents, for example, a carbonyl function or a ketal (acetal) function, further new compounds are obtained by reaction with alcohols, glycols, mercaptans, amines, hydroxylamines, anilines, hydrazines or semicarbazides. s-triazines of formula IV. This conversion is carried out according to the methods known in principle, which are collectively described in Houben-Weyl, Vol. VII, (1), pp. 413-488 or Vol. VI (3), pp. 204-270.

For this reaction sequence known per se, inert protic or aprotic solvents such as ketones, alcohols, halogenated hydrocarbons, aromatic hydrocarbons, ether or acetonitrile are used and are operated at temperatures between 0 DEG C. and the boiling point of the solvent. In general, acidic or basic catalysis is carried out. The reaction water resulting from these reactions is removed either azeotropically or with water-binding agents.

The starting materials of formula IV wherein Z is a methine group, are known or can be prepared in principle according to known methods, for example by cyclization of the corresponding guanidine derivatives with appropriately substituted 1 _t 3 - ^^ I ^] ^ (^^ ton [see. E.g. "The Chemistry of Heterocyclic Compounds", Vol. XVI (1962) and Supplements I (1970)] Compounds of formula IV wherein R 4 is a radical of formula COR 7 can also be converted to other compounds of formula IV by the method described below.

The sulfonyl isocyanates of the formula II are largely known or can be prepared in a simple manner by methods known in principle (cf. EP 15 683, DE-AS 1211165, DE-AS 1 226 565, DE-AS 1 230 016, DE-AS 1 568 640 and Chem Ber., 105, 2791, 2800 (1972)].

The sulfonylcarbamoyl- or -thiocarbam-o-yl chlorides of formula III can be prepared by conventional methods from the corresponding alkali metal salts of the corresponding sulfonamides of formula V known from the literature by reaction with phosgene or thiophosgene.

The sulfonylureas of the formula I which contain one or more asymmetric carbon atoms in the aliphatic residue A are present in enantiomeric or diastereomeric forms. In general, the corresponding compounds of the invention are obtained as racemates or as mixtures of diastereomers. If desired, conventional methods can be used to separate these mixtures into spherically uniform components. The preparation of the compounds in pure form is also possible using spherically uniform starting materials. Thus, for example, in the reaction of the aminoheterocycles of formula IV with threo- or erythro-1,2-dihaloalkylsulfonyl isocyanates, the corresponding threo- or ery-2,364,63 thro-1,2-dihaloalkylsulfonylureas are formed.

Further, the sulfonylureas of the formula I which contain one or more multiple bonds in the aliphatic residue A can be present as E- or as Z-isomers in the respective olefinic substitution. of which the preparation of the pure form or separation is also possible. For example, unsaturated sulfonyl isocyanates of the formula I are used in sterically uniform form. The invention therefore also relates to uniform enantiomeric and diastereomeric forms of the compounds of formula I.

The compounds of formula I have excellent herbicidal activity and have very good selectivity in important crop plants. It is suitable for the selective control of dicotyledonous and grassy weeds, both perennial and perennial in agriculturally important crop plants such as wheat, barley, rye, rice, corn, sugar beet, cotton and soya in pre-emergence and post-emergence treatments.

In addition, these compounds have an excellent ability to control the growth of crop plants at low doses. These substances interfere with the metabolism of plants and can therefore be used to deliberately influence the storage substances contained in plants and to facilitate harvesting, for example by inducing desiccation and arresting growth. Furthermore, the compounds are suitable for general regulation and suppression of undesirable vegetative growth without dying plants. Growth retardation plays a large role in numerous monocotyledonous and dicotyledonous crop plants, as it can reduce or prevent lodging altogether.

If the compounds are applied before germination of the weeds to the soil surface during pre-emergence or post-emergence treatment, the emergence of germs is not prevented. The weeds grow until the cotyledon stage, their growth is then adjusted and finally die after 3 to 5 weeks. When the active substances are applied to the green part of the plants in a post-emergence process, the growth is also drastically stopped after treatment and the weeds remain in the growth stage in which they were at the time of application or die completely, so it is possible to remove weed competition very quickly and permanently · harmful to crop plants.

Although the compounds of the present invention exhibit excellent herbicidal activity against monocotyledonous and dicotyledonous weeds, crop plants of economically important crops such as wheat, barley, rye, rice, corn, sugarbeet, cotton and soybean only damage insignificantly or do not harm them at all.

For this reason, the compounds according to the invention are excellent in combating undesirable plant growth in agricultural crops.

The compositions according to the invention contain the active compounds of the formula I in general in an amount of from 2 to 95% by weight. They can be used in the form of wettable powders, emulsifiable concentrates, sprayable solutions, dusts or granules in the form of conventional preparations.

Wettable powders are included; water uniformly dispersible formulations which · besides the active substance, also comprise diluents or inert substance, wetting agents, for example polyoxyethylated alkylphenols, polyoxyethylene hylované fatty alcohols, alkylsulfonates or alkylphenylsulfonates and dispersing agents, for example sodium ligninsulfonate, sodium 2,2 ^{<-dinaftylmethan} -6,6'-disulfonic acids, dibutylnaphthalenesulfonic acid sodium or oleylmethyltaurine sodium.

Emulsifiable concentrates are prepared by dissolving the active ingredient in an organic solvent, for example butanol, cyclohexanone, dimethylformamide, xylene, or else in high boiling aromatics or hydrocarbons, with the addition of one or more emulsifiers. The emulsifiers which may be used are, for example: calcium salts of alkylarylsulfonic acids, such as calcium salts of dodecylbenzenesulfonic acid, or non-ionic emulsifiers, such as polyglycol esters of fatty acids, alkylaryl polyglycol ethers, polyglycol ethers of fatty alcohols, condensation products. alcohols, propylene oxide and ethylene oxide, alkyl polyethers, sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters, or sorbitan polyoxyethylene esters.

Dusts are obtained by grinding the active ingredient with finely dispersed solids, for example talc, natural clays such as kaolin, bentonite, pyrophyllite or diatomite.

Granules can be produced either by spraying the active ingredient on an adsorptive, granulated inert material or by applying the active ingredient concentrates with adhesives such as polyvinyl alcohol, sodium polyacrylic acid, or also mineral oils onto the surface of carriers such as sand, kaolinite or granular inert ingredients. material. Using suitable active ingredients, granules can be prepared in the manner customary for the production of fertilizer granules, optionally in admixture with fertilizer.

The concentrations of the active compounds in the commercially available herbicidal compositions can vary.

In wettable powders, the concentration of active ingredient is, for example, between about 10 and 80%, the remainder consisting of the above-mentioned additives to these compositions. In emulsifiable concentrates, the active compound concentration may also be about 10 to 80 why. Powder formulations contain about 2 to 20% of active ingredient. In the case of granules, the active substance content depends in part on whether the active compound is liquid or solid and which granulating auxiliaries, fillers and the like are used.

For application as herbicides, the commercially available concentrates are optionally diluted in the customary manner, for example, with wettable powders and emulsifiable concentrates with water. Powder and granular compositions as well as sprayable solutions are no longer diluted with other inert substances prior to application. The required application rate varies depending on external conditions such as temperature, humidity, etc. In general, it is 0.005 to 10 kg / ha, preferably about 0.01 to 5.0 kg of active ingredient per ha.

For some areas of application, it may be expedient to use the new herbicides with one or more herbicides together, for example in the form of a mixture prepared in a tankmix or in the form of a finished composition, to achieve other advantageous effects.

The active compounds according to the invention can be combined with other herbicides, insecticides and fungicides.

Examples illustrating the method of production of active ingredients:

Example 1

N- (2-chlorophenylsulfonyl) -N‘- (4-diethoxymethyl-6-methylpyrimidin-2-yl) urea

To 10.55 g (0.05 mol) of 2-amino-4-ethoxy-6-methylpyrimidine in 50 ml of dichloromethane is added dropwise a solution of 11 g (0.05 mol) of 2-chlorophenylsulfonyl isocyanate in 20 ml at 0-5 ° C. ml of dichloromethane. The reaction mixture is stirred for 18 hours at room temperature, then n-hexane is added and the precipitated reaction product is filtered off. 19.8 g (93% of theory) of N- (2-chlorophenylsulfonyl) -N- (4-diethoxymethyl-O-methylpyrimidin-2-yl) urea, m.p.

Example 2

N- (4-diethoxymethyl-6-methylpyrimidin-2-yl) -N- (2-methoxycarbonylphenylsulfonyl) urea

To 10.55 g (0.05 mol) of 2-amino-4-diethoxymethyl-6-methylpyrimidine in 50 ml of dichloromethane is added dropwise a solution of 12 g (0.05 mol) of 2-methoxycarbonylphenylsulfonylisocyanate in 20 ml at 0-5 ° C. dichloromethane. The reaction mixture was stirred at room temperature for 12 hours, then added. The n-hexane and the precipitated reaction product are filtered off.

There was obtained 19 g (84% of theory) of N- (4-diethoxymethyl-6-methylpyrimidin-2-yl) -N- (2-methoxycarbonylphenylsulfonyl) urea, m.p. 170 [deg.] C.

Example 3

N- (2-chlorophenylsulfonyl) -N- (4-formyl-6-methylpyrimidin-2-yl) urea

34.3 g (00-8 molar) of N- (2-chlorophenylsulphonyl) -N '- (4-dipethoxymethyl-6-methylpyrimidin-2-yl) urea (cf. Example 1) are suspended in 350 ml of dioxane to this suspension was added 20 mL of dilute hydrochloric acid (1: 1) and the reaction mixture was further stirred at room temperature for 18 hours, then the precipitated product was filtered off and the precipitate was washed with dichloromethane to give 28 g (98%). - (2-chloro) -4- (4-formyl-6-methylpyrrolidin-2-yl) (urea, m.p. 142 ° C).

Example 4

N- (4-diethoxymethyl-6-methylpyrimidin-2-yl) -N- (1-methylpropen-1-ylsulfonyl) urea

To 6.18 g (0.03 mol) of 2-amino-4-diethoxymethyl-6-methylpyrimidine in 50 ml of dichloromethane was added dropwise a solution of 5.15 g (0.032 mol) of 1-methylpropen-1 at 0-5 ° C. -ylsulfonyl isocyanate in 20 ml of dichloromethane. The reaction mixture is stirred for a further 12 hours at room temperature, then n-hexane is added and the precipitated reaction product is filtered off. 9.7 g (88% of theory) of N- (4-diethoxymethyl-6-methylpyrimidin-2-yl) -N- (1-methylpropin-1-ylsulfonyl) urea, m.p. 100 DEG-102 DEG C., are obtained.

Example 5

N- (4-dimethoxymethyl-6-methylpyrimidin-2-yl) -N- (onylurea)

To 5.5 g (0.03 mol) of 2-amino-4-dimethoxymethyl-6-methylpyrimidine in 50 ml of dichloromethane was added dropwise a solution of 5.15 g (0.032 mol) of 1-methyl-propene at 0-5 ° C. Of 1-ylsulfonyl isocyanate in 20 ml of dichloromethane. The reaction mixture is further stirred at room temperature for 12 hours, then n-hexane is added and the precipitated product is filtered off. 9 g (87% of theory) of N- (4-dimethoxymethyl-6-methylpyrimidin-2-yl) -N- (1-methylpropen-1-ylsulphinyl) urea are obtained, m.p. 115 DEG-117 DEG.

In an analogous manner to the procedures described in Examples 1 to 5, using the corresponding starting materials, the following compounds of formula I are summarized in Table I, wherein Z is each a methine group:

example number

R3

B-R4 melting point (° C)

Ct

Cl

CH3

CH3

CH ₃

CH3

CH3

CH3

CH3

CH3

CH3

CH ₃

CH3

CH3

CH3 — СН (ОСНз) 2

150—151

-cwí o

162—163

-C 1 H (OC 2 H ₅ ) 2

-CH (OC2H5) ₂ —СН (ОСНз) 2 —СН (ОСНз) 2

- СН (ОС ₂ Н ₃ ) _{2 -} СН (ОС ₂ Н ₃ ) ₂

-СН (ОС ₂ Н ->) 2 —СНО

-CHO

-GHO

76—78

141—142

167—168

132—134

158—159

126—127 resin

92—95

140—142

158—159

172—173 m R ₃

B — R ₄ melting point (° C)

CH ₃

Cl

Whose

OCH ₃

Cl

0CH

0CH

0CH

0CH

OCH

OCH — CHO — CH (OC ₂ H ₅ ) ₂

-CH (OC ₂ H ₅ ) ₂ —CH (OC ₂ H ₃ ) ₂

CH ₃

I — C (OC ₂ H ₃ ) ₂ —CO — CH ₃ —CH = NOCH ₃ —CH = NOH s — ¹ —CH (OCH ₃ ) ₂

Cl

CH ₃

CH ₃ CHBrCHBr-Cl

0CH

OCH

OCH

OCH — CH (SC ₂ H ₃ ) ₂ —CH (OC ₂ H ₅ ) ₂ —CH (OC ₂ H ₃ ) ₂

145—148

121—122

106—107

144—145

167—168

194—195

190 (decomposition)

195 (decomposition)

165—166

144—145

133—134 resin

43—46

158

В — R4 melting point (° С) example

СНз —C (OC ₂ H ₅ ) ₂ I СНз

159—160

Cl

СНз

100 ALIGN!

101

О

О

О

О

О

О

СНз

СНз

СНз

СНз

СНз

СНз

СНз

СНз

104

141

СНз

СНз so ьиснрг.

000¾

СНз —С (ОСН ₃ )

СНз —С (ОС ₂ Н ₅ ) ₂

AND

СНз —С (ОС ₂ Н ₅ ) ₂

AND

СНз —СЩОСНзЪ —СН (ОС ₂ Н ₅ ) ₂ —С (ОС ₂ Н ₅ ) ₂ I СНз

—ССН _3. (ОСНз) ₂ —ССНз (ОСНз) 2

168—169

130—131

142-143

99—100

157—158

153—154

150—151

128—129

176-177

173—174

153

146—147

142 melting point (° C)

A m R ₃

B — R4

COOCHi

COOGHi

Я sonícc ^

CH2-O

H3C

CH ₃

CH3

CH 3 - CH 3 OC 1 H -h

Ο-Ί • s116—117

133—134

158

120—122

CH 3 -CH (SCH ₃ ) 2

Cl Cl <2 ^

CH 3 - CH 2 CH (OCH ₃ ) ₂ oil

CH 3 -CH 2 CH (OCH 3) 2

CH 3 - CH 2 CH (OCH ₃ ) ₂

CH 3 - CH 2 CH [OCH 3) ₂

OCH ₃ —CH ₂ CH (OCH ₃ ) ₂ oil oil

64—66 oil

OCH ₃ —CH ₂ CH (OCH ₃ ) ₂

CH ₃ —CH ₂ CH (OCH ₃ ) ₂

CH ₃

O oil oil oil

A m R ₃

BR _ó melting point (° C)

OOGH ₅

O

COOCH (CHj.

OOGHj

QCF _and h

CH ₃

CH ₃

CH ₃

CH ₃

OCH ₃

CH ₃

OCH3

OCH ₃

OCH ₃

CH ₃

OCH ₃

OCH ₃

OCH3

—CH ₂ CH (OCH ₃ ) ₂ —CH ₂ CH (OCH.i) ₂ —СН ₂ СН (ОСНз) ₂ —CH ₂ CH (OCH ₃ ) ₂

O oil oil oil oil oil oil

127—128 oil oil oil

143–146 oil melting point (° C) example А number m R ₃

BR ₄

353

oil

Example 148

N- (2-chlorophenylsulfonyl) -N- (4-diethoxymethyl-6-methoxy-s-triazin-2-yl) urea

To 11.4 g (0.05 mol) of 2-amino-4-diethoxymethyl-6-methoxy-s-triazine in 50 ml of dichloromethane at 0-5 ° C is added dropwise a solution of 11 g (0.05 mol) of 2-chlorophenylsulfonylisocyanate in 20 ml of dichloromethane. The reaction mixture is further stirred at room temperature for 18 hours, then n-hexane is added and the precipitated reaction product is filtered off. There were obtained 18.3 g (82%) of N- [2-chlorophenylsulfonyl) -N '- (4-diethoxymethyl-6-methoxy-s-triazin-2-yl) urea, m.p. 126-127 ° C. .

In an analogous manner, using the corresponding starting materials, the compounds of the formula I shown in Table II are obtained, Z being nitrogen in each case:

Table II

154 Cl 0 155 <(5 R - _Z NO 0 156 ^N ° W 0 161 OCHF _Z 0 162 Q- OCHF ^ 0 164 Я COOCH. Q

OCH ₃

OCH ₃

OCH ₃

OCH ₃

OCH ₃

OCH ₃ —CH (OCH ₃ ) ₂ 137–138 —CH (OG ₂ H ₅ ) ₂ 141–142 —CH (OCH _{; t} ) ₂ 154–155

-CH (OC ₂ H ₅ ) ₃

-CH (OCH ₃ ) ₂ —CH (OCH ₃ ) ₂

95— 96

103—104

119—121

B — R ₄

238B43

A m R ₃

Cl

Ct

Cl

Cl

OCHF ^

Cl

Cl ct

OCH ₃

OCH ₃

ОСН ₃

OCH ₃

ОСН ₃

ОСН ₃

ОСН ₃

ОСН ₃

ОСН ₃

ОС ₂ Н ₅

N (CH ₃ hr

ОСН ос _{2 3 5} н

- С (ОС ₂ Н ₅ ) ₂

AND

СНз

О—] ч J о— ¹

- СН (ОС ₂ Н _{5) 2}

- СН (ОС ₂ Н _{5) 2}

- СН (ОС ₂ Н _{5] 2}

—СН (ОС ₂ Н ₅ ) ₂ melting point (° С)

154—155

148—149

156—157

147—149

84— 85

87— 88

120—121

159—160

131— 132

132— 133

151—152

137—139

129-130

A m R ₃

B-Ri melting point (° C) example number

194

195

199

200

201

202

204

205

210

211

212

213

214

COCCH3

CC

CC

CC

CC

CC

CC

CC CC

0 N _{(CH3) 2} -CH (OC ₂ H ₅ ) ₂ 99 0 N _{(CH3) 2} - CH (OCH ₃ ) ₂ On 162—163 0 OCH3 ч 1 s -> Ο-Ί / 152—153 0 OCH ₃ 4 SJ 133—135 0 OCH3 <2 > 135—136 0 OCH3 -CH2-CH (OC ₂ H 5) ₂ 110-112 0 OCH3 CH (SCH ₃₎ 2 129—130 0 N _{(CH3) 2} s- < with- ] 148—150 0 OCH3 1 140—141 0 O (CH ₂ ) ₂ OC ₂ H ₅ -CH (OCH ₃₎ 2 resin 0 O (CH ₂ J ₂ OC ₂ H ₅ -CH (OC2H.5 ° ^C M_ J2 resin 0 OCH3 % 137—138 0 OCH3 ^{, CR} ₃ W CH 117—118

218

219

220

221

222

225

226

228

229

232

234

ct

Cl

CC

Cl

CC

ОСН ₃

ОС ₂ Нв

N ‰12

ОСН3

ОСН3

OCH3

ОСН ₃

ЩСН3) 2

ЩСН.3) o

OCH3

OCH3

OC ₂ H5

155—156 —СН (ОСН3) ₂ —СН (ОСН ₃ ) ₂ —СН (5СН ₃ ) ₂ —СН ₂ —СН ₂ —СН (ОСН ₃ ] ₂ —СН ₂ —СН (ОСН3] ₂

-CHfSQjHsh —СЩЭСЩЬ —СН (ОСН3) ₂

148—149

150—151

148—149

138—139

154—155

132—135

126—127

165—166 oil oil resin

237 example number

238

239

240

241

243

245

246

261

273

275

283

284

285

СНз

CH ₃ —CH = C—

СН ₃

СН ₃ —СН = С—

СООСН ^

m R ₃ br ₄ melting point (° С) 0 ОСН _Э Г “° т 98— 99 0 О (СН ₂ ) ₂ ОС ₂ Н ₅ о— ¹ -СН (ОС. ₂ Н ₅ ) ₂ resin 0 О (СН ₂ ) ₂ ОС ₂ Н ₅ -СН (ОСН ₃ ) ₂ resin 0 осн ₃ О ~ | ^c w 121—124 0 ОСН ₃ сн ₅ '0—1 117—119 0 ОСН ₃ 0 · 132—133 0 ОСН ₃ % I 150—151 0 ОС ₂ Н ₅ сн ₃ —СН (ОС ₂ Н ₅ ) ₂ 64— 66 0 N _{(CH3) 2} -СН (ОС ₂ Н _{5) 2} 83— 86 0 ОСН ₃ -СН (ОСН ₃ ) ₂ oil

N (CH ₃ ) ₂

О ОН ₃

осн ₃

СН _{2 —} СН (ОСН ₃ ) ₂

127—128

Example 286 (Starting materials)

2-amino-4-diethoxymethyl-6-methoxy-s-triazine

To a solution of guanidino-O-methylisourea prepared from 15.25 g (0.1 mol) of guanidino-O-methylisourea hydrochloride, 80 ml of absolute methanol and a solution of 2.53 g (0.11 mol) of sodium in 40 ml of methanol, 17.6 grams (0.1 mol) of diethoxyacetic acid ethyl ester was added dropwise at 0 ° C. The reaction mixture is stirred at room temperature for 20 hours, then filtered, the filtrate is concentrated, the residue is taken up in 2N acetic acid solution, extracted with methylene chloride, the organic phase is washed with water, dried over sodium sulfate, filtered, the filtrate is concentrated and recrystallized from ether-n-hexane. 15.4 g (67.5% of theory) of 2-amino-4-diethoxymethyl-6-methoxy-s-triazine of melting point 82 DEG-83 DEG C. are obtained.

The following compounds of formula IV are obtained in an analogous manner in which Z is always nitrogen:

example number

287

288

289

295

296

297

298

299

304

306

307

312

313

314

315

316

317

R.í

OCH ₃

OCH ₃

OCH3 осн,

OCH3

OCH3

OCH3

O (CH 2).>OC.> H ₅

O (CH ₂ ) ₉ OC> H ₅

N _{(CH3) 2}

N _{(CH3) 2}

OC ₂ H ₅

OC2H5

OCI-I3

OCH3

OCH3

OCH3

B — r ₄

Ο-η

^J S CH _{(CH3) 2} C (OC ₂ H _{5) 2}

CH ₃ —СН (ОСНч) ·, —CH (OC ₉ H ₅ ) ₉ —CH (OC ₂ H ₅ ) ₂ —CH (OCH ₃ ) o —CH (OC ₉ H ₅ ) ₉ —CH (OCH.) ₂

WITH-,

CH _d

melting point (° C)

120—122

130—132

105—108

135—137

121

75— 79

110—111

96—98 77

117—118

176—177

84— 86

102—103 .111—115

162—164

118—122

88 - melting point (° C) example number br ₄

318 OCH ₃

319 OCH ₃

O- | ^c +

CHj

166—167

144—145

320

NfCHjh

321 N _{(CH3) 2}

322 N _{(CH3) 2}

323 N (CH ₃ ) ₂

324 OCH ₃

331

N [CH _{3) 2} CH (SCH ₃ b CH (SC ₂ H _{5) 3}

174—175

170

142—143

126—128

125—129

226—229

Examples illustrating the composition and preparation of formulations:

Example A

The emulsifiable concentrate is obtained from parts by weight of active ingredient, parts by weight of cyclohexane as solvent, parts by weight of oxethylated nonylphenol (10 moles of ethylene oxide) as emulsifier.

Example В

A wettable powder which is readily dispersible in water is obtained by mixing parts by weight of active ingredient, parts by weight of quartz containing kaolin as inert substance and part by weight of sodium oleylmethyltaurine as wetting agent and dispersing agent, and the mixture obtained is ground in a pin mill. .

Example 1 a d C

The dust is obtained by mixing parts by weight of active ingredient with parts by weight of talc and the mixture of serozemele in a mill.

Examples illustrating biological activity:

1. Pre-emergence applications:

Seeds or pieces of rhizomes of monocotyledonous and dicotyledonous weeds are placed in clay soil in pots (9 cm diameter) of plastic and covered with soil. The compounds of the invention formulated as wettable powders or emulsifiable concentrates are applied to the soil surface in the form of an aqueous suspension or emulsion. The amount of water used per flower pot corresponds to 600 to 800 liters per ha. After treatment, the test pots were placed in a greenhouse and the test plants were grown under good growth conditions (temperature: 23 + 1 ° C; relative air humidity 60-80%). After about 3 weeks, plant damage was assessed visually. Untreated control plants are used for comparison.

The weed damage and / or crop plant compatibility are evaluated according to the following key from 0 to 5:

It means:

without effect

0 to 20% effect

20 to 40% effect

40 to 60% effect and 4 60 to 80% inert effect

Table 1

Activity of the compounds of the invention against monocotyledonous and dicotyledonous weeds in pre-emergence application (as compared to untreated control).

compound dose herbicidal effect of example kg / ha STM AMR LOM ECG

1 2.5 5 5 5 5 2 2.5 5 5 5 5 3 2.5 5 5 5 5 4 2.5 5 5 5 5 6 2.5 5 5 5 5 7 2.5 5 5 5 5 8 2.5 5 5 5 5 9 2.5 5 5 5 5 10 2.5 5 5 5 5 12 2.5 5 5 5 4 13 2.5 5 5 5 5 14 2.5 5 5 5 5 17 2.5 2 3 1 1 18 2.5 1 2 1 1 19 Dec 2.5 4 5 5 4 20 May 2.5 5 5 5 5 22nd 2.5 5 5 5 5 23 2.5 5 5 5 4 24 2.5 5 5 5 5 26 2.5 4 5 5 5 29 2.5 5 5 5 5 30 2.5 0 5 4 4 31 2.5 5 5 5 5 32 2.5 4 5 4 4 33 2.5 4 5 4 3 42 2.5 5 ' 5 5 5 43 2.5 4 - 5 - 92 2.5 4 5 5 4 72 2.5 3 5 3 1 93 2.5 5 5 5 5 90 2.5 3 4 4 2 91 2.5 4 5 5 5 96 2.5 5 5 5 5 95 2.5 5 5 5 5 94 2.5 4 5 5 4 97 2.5 5 5 5 5 99 2.5 4 5 5 4 104 2.5 5 5 5 5 100 ALIGN! 2.5 5 5 5 5 101 2.5 5 5 5 5 146 2.5 5 5 5 5 147 2.5 4 - 5 - 141 2.5 5 5 5 5 142 2.5 5 5 5 5 143 2.5 3 4 4 4 144 2.5 5 5 5 4 145 2.5 4 5 5 5 148 2.5 5 5 5 5 154 2.5 5 5 5 5 155 2.5 5 5 5 5 156 2.5 5 5 5 5 161 2.5 5 5 5 5 162 2.5 5 5 5 5 150 2.5 5 5 5 5 164 2.5 5 5 5 5 149 2.5 5 5 5 5 165 2.5 5 5 3 4 166 2.5 5 5 5 5 171 2.5 5 5 5 5 172 2.5 4 5 3 5 177 2.5 5 5 5 5

Example compound dose kg / ha STM herbicidal effect of AMR LOM ECG 178 2.5 5 5 5 5 181 2.5 5 5 5 5 182 2.5 5 5 5 5 186 2.5 5 5 5 5 187 2.5 5 5 5 5 188 2.5 4 2 3 3 193 2.5 5 5 5 5 194 2.5 5 5 4 4 195 2.5 5 5 4 3 199 2.5 5 5 5 5 200 2.5 5 5 5 5 201 2.5 5 5 5 5 202 2.5 5 5 5 5 204 2.5 5 5 5 5 205 2.5 2 1 1 1 210 2.5 5 5 5 5 211 2.5 3 4 3 3 212 2.5 2 2 2 3 213 2.5 5 5 5 5 214 2.5 5 5 5 5 215 2.5 5 5 5 5 218 2.5 5 5 5 5 219 2.5 5 5 5 5 220 2.5 5 5 5 5 226 2.5 5 5 5 5 232 2.5 5 5 5 5 234 2.5 5 5 5 5 237 2.5 5 5 4 5 238 2.5 5 5 5 5 239 2.5 5 5 4 4 240 2.5 5 5 4 5 221 2.5 5 5 5 5 228 2.5 5 - 3 - 230 2.5 2 - 2 - 229 2.5 4 - 0 - 192 2.5 5 5 5 5 283 2.5 1 - 0 - 246 2.5 5 5 5 5 245 2.5 5 5 5 5 284 2.5 5 5 5 5 202 2.5 5 5 5 5 210 2.5 5 5 5 5 225 2.5 5 5 5 5 222 2.5 5 - 5 5 332 2.5 5 5 5 5 333 2.5 5 5 5 5 334 2.5 5 5 5 4 335 2.5 5 5 5 5 336 2.5 5 5 5 5 337 2.5 5 5 5 5 338 2.5 5 5 5 5 339 2.5 5 5 5 5 340 2.5 5 5 5 5 341 2.5 5 5 5 5 342 2.5 5 4 5 5 343 2.5 5 5 5 5 344 2.5 5 5 5 5 345 2.5 5 5 5 5 346 2.5 5 5 5 5 347 2.5 5 5 5 5 348 2.5 5 5 5 5 349 2.5 5 5 5 5 340 2.5 5 5 5 5 351 2.5 5 5 5 5 352 2.5 5 5 5 5 353 2.5 5 5 5 5

at

2. Post-emergence applications:

Monocotyledon and dicotyledon weed seeds are planted in pots and grown in a greenhouse under good growth conditions. 3 weeks after sowing, the test plants are treated at the 3 leaf stage. The compounds according to the invention, which are processed into wettable powders or emulsion concentrates, are sprayed on the green part of the plant in various doses. After about 3 weeks of staying in the greenhouse under optimal growth conditions, the effect of the compounds of the invention is visually evaluated in comparison to untreated control plants.

Table 2

Effect of the compounds of the invention on monocotyledonous and dicotyledonous weeds in post-emergence application (comparison with untreated control).

Example compound dose kg / ha herbicidal effect STM AMR QUARRY ECG 1 2.5 5 5 5 5 14 2.5 4 5 4 4 18 2.5 2 19 Dec 2.5 4 5 4 3 3 2.5 4 5 5 4 4 2.5 5 5 4 5 17 2.5 2 2 2 2 2.5 5 5 5 5 6 2.5 5 5 5 5 8 2.5 4 5 5 3 9 2.5 5 5 5 5 20 May 2.5 5 5 5 5 72 2.5 2 3 2 1 22nd 2.5 5 5 5 5 31 2.5 3 4 5 4 32 2.5 2 4 5 2 23 2.5 2 4 5 2 12 2.5 5 5 5 5 26 2.5 3 5 5 2 30 2.5 5 5 5 3 29 2.5 0 5 2 2 24 2.5 5 5 5 5 10 2.5 5 5 5 5 93 2.5 3 5 5 5 91 2.5 3 5 5 5 96 2.5 3 5 5 4 95 2.5 3 5 5 5 94 2.5 2 5 3 4 42 2.5 4 5 5 5 97 2.5 3 5 4 5 141 2.5 3 5 3 5 142 2.5 4 5 5 5 92 2.5 4 5 4 4 33 2.5 3 5 4 4 143 2.5 3 5 4 3 144 2.5 5 5 5 4 90 2.5 4 5 4 3 145 2.5 5 5 5 5 104 2.5 5 5 5 5 7 2.5 5 5 5 5 100 ALIGN! 2.5 5 5 5 5 13 2.5 5 5 5 5 101 2.5 5 5 5 5 146 2.5 5 5 5 5 99 2.5 3 4 5 3 147 2.5 5 5 5 5 43 2.5 5 5 5 5 148 2.5 5 5 5 5 154 2.5 5 5 5 5 155 2.5 5 5 5 5 156 2.5 5 5 5 5

ECG compound dose of Example kg / ha STM herbicidal effect of AMR LOM

161 2.5 5 5 162 2.5 5 5 150 2.5 3 5 164 2.5 5 5 149 2.5 5 5 165 2.5 5 5 166 2.5 5 5 171 2.5 5 5 172 2.5 4 5 177 2.5 5 5 178 2.5 5 5 181 2.5 5 5 182 2.5 5 5 186 2.5 5 5 187 2.5 4 5 188 2.5 0 2 193 2.5 5 5 194 2.5 4 5 195 2.5 3 3 199 2.5 5 5 200 2.5 5 5 201 2.5 5 5 204 2.5 5 5 205 2.5 3 1 211 2.5 3 3 212 2.5 3 2 213 2.5 5 3 214 2.5 5 3 215 2.5 5 1 218 2.5 5 4 219 2.5 5 5 220 2.5 5 4 237 2.5 5 4 238 2.5 5 5 239 2.5 5 5 240 2.5 4 4 221 2.5 5 5 228 2.5 5 3 230 2.5 2 1 229 2.5 2 1 192 2.5 5 5 283 2.5 0 0 246 2.5 5 5 245 2.5 5 5 284 2.5 5 5 202 2.5 5 5 210 2.5 5 5 225 2.5 5 5 222 2.5 5 -

Abbreviations:

STM = Stellaria media

AMR = Amaranthus retroflexus LOM = Lolium multiflorum

ECG = Echinochloa crus galii

Comparative example:

In the same manner as described in the previous Example 1 (pre-emergence application) and Example 2 (post-emergence application), the following compounds A, B and C (A) were tested for comparison with the effect of the compounds of the invention

(C)

O

II

CO-NH

CH _S

The teachings of U.S. Pat.

of Tables 1a and 2a. Of these

Table la

Pre-emergence treatment

Comparative compound dose kg / ha herbicidal effect STM AMR QUARRY ECG AND 2.5 1 1 0 0 (B) 2.5 0 0 0 0 C 2.5 3 2 0 0

Table 2a

Post-emergence treatment:

Comparative compound dose kg / ha herbicidal effect STM AMR QUARRY ECG AND 2.5 3 0 0 1 (B) 2.5 0 0 0 0 C 2.5 4 0 0 0

The evaluation of the herbicidal effect is carried out on the same scale as in Examples 1 and 2. The weed abbreviations also have the same meaning as in Examples 1 and 2.

Claims (6)

OBJECT OF THE INVENTION Herbicidal composition, characterized in that it contains at least one compound of the formula I-J as active ingredient. N-O 2 SO 4 H-C-NH 4 z (i) in which A is optionally C1-C4alkyl or C2-C4alkenyl or is ¹ ; R 11 ₎ is hydroxy or methoxy, R ₃ is halogen, nitro, OCHF-j, methyl, C 1 -C 3 alkylsulfonyl, -SO ₂ -N (alkyl) ₂ wherein "alkyl" is C 1 -C 4 alkyl , or represents a (C 1 -C 4) alkoxycarbonyl group, and R ₇ represents a hydrogen atom or a methyl group and Z is a nitrogen atom or a methine group, or a physiologically acceptable salt thereof, or a salt thereof with an acid. 2. A composition according to claim 1, wherein the active ingredient comprises at least one compound of formula (Ia) and m is zero or 1; R ₃ is hydrogen, Cl, nitro, dimethylamino, methyl, which is optionally substituted by methoxy, furthermore represents alkoxy having 1 to 2 carbon atoms, optionally substituted alkoxy having 1 to 2 carbon atoms, V and D are each independently a single chemical bond or V is a methylene group or an ethylene group, R ₄ represents a group of the formula -CO- R ₇ , a group of the formula wherein A, m, B, R ₃ and R ₄ are as defined in 1, or a physiologically acceptable base salt or acid salt thereof. 3. A composition according to claim 1, characterized in that it contains as active ingredient at least one compound of formula Ib, ^X l Y R / 'i? ⁶ or represents a group of formula -C = NR ₁₀ , R? where Y is oxygen or sulfur, R ₈ is each C 1 -C 4 alkyl or both R ₈ are taken together to form an ethylene or propylene bridge ar / 6J wherein: A, m, B, R ₃ and R ₄ are as defined in 1, or a physiologically acceptable base salt or acid salt thereof. 4. A process for the preparation of the active ingredient of the formula I as well as the physiologically usable salts of these compounds with a base or with an acid, characterized in that the compounds of the formula II A- (O) _m -SO ₂ -N = C = O (Π) wherein A and m are as defined in 1 or for compounds of formula III (III) wherein: A and m are as defined in 1 a Y represents chlorine, an alkoxy group having 1 to 5 carbon atoms; 4 carbon atoms or phenoxy, act by compounds of the general formula IV (IV) in which: R 1, R 1, V 1 and Z are as defined in 1, and optionally the compounds of formula I obtained are converted by cleavage of hydrogen halide, addition of halogen to the present multiple bonds or salt formation to other compounds of formula I as defined above. 5. A process according to claim 4 for the preparation of an active ingredient according to claim 2 as well as physiologically acceptable salts of these compounds with a base or an acid, characterized in that the compounds of the formulas II or III in which A and m have and Y is as defined in 4, acting with compounds of formula IVa B, R ₃ and R ₄ are as defined in 1, and optionally the compounds of formula (Ia) obtained are converted by hydrogen halide cleavage, halogen addition to the present multiple bonds or salt formation to other compounds of formula (Ia) as defined above. 6. A process according to claim 4 for the preparation of an active ingredient according to general formula 1b as well as physiologically acceptable salts of these compounds with a base or with an acid, characterized in that the compounds of the formulas II or III in which A and m have and Y is as defined in 4, acting with compounds of formula IVb Wherein ⁴ B, R ₃ and R ₄ are as defined in 1, and optionally the compounds of formula 1b obtained are converted by cleavage of hydrogen halide, addition of halogen to the present multiple bonds or salt formation to other compounds of formula Jb as defined above.