CS246087B2 - Herbicide and method of efficient substances production - Google Patents

Abstract

Herbicides of formula: <IMAGE> R and R1 being an alkyl radical.l

Description

(54) Herbicidal composition and process for the manufacture of active substances

The present invention relates to herbicidal compositions which contain as active ingredient novel compounds belonging to the chemical group of sulfonimides containing an aminomethylphosphonic acid residue. Furthermore, the present invention relates to a process for the production of these new active ingredients as well as intermediates for their production and to the use of these new herbicides in agriculture.

A number of compounds are known which contain an aminomethylphosphonic acid residue and which have herbicidal properties, in particular from French Patent Nos. 2,129,327, 2,281,375, 2,251,569,

413 398, 2 463 149, from European Patent Nos. 53,871, 54,382, 73,574, and U.S. Patent Nos. 3,160,632,

455,675, 3,868,407, 4,388,103, 4,397,676, British Patent Specification No. 2,090,596, World Patent Publication No. WO 83/03608, and Belgian Patent Specifications No. 894,244, 894,245, · 894,590, . 894,591, 894,592, 894,593, 894,594 and 894,595.

A number of intermediates for the preparation of such compounds are also known, in particular from European Patent Specifications 81 459, 97 522, 55 695, French Patent Specification 2,193,830 and U.S. Pat. U.S. Patent Nos. 3,835,000 and 4,422,982.

Nevertheless, it is still desirable to extend the range of useful herbicides to better meet the constant needs of farmers, as well as the range of intermediates suitable for obtaining herbicides and useful for new synthetic routes. Some amides containing an aminomethylphosphonic acid residue are well known, but these are either ineffective or of little activity.

New compounds of formula I have now been found

OR ²

О = P-CH2-NH-CH2-CO-N-SO 2 R ¹

OR ³ R (I) wherein

R ¹ represents an alkyl group having 1 to 12 carbon atoms, a cyclopropyl group or a phenyl group, these groups being optionally substituted by alkyl groups or chlorine or fluorine atoms and containing in total not more than 12 carbon atoms,

R is hydrogen or is as defined for the substituent R ¹ ,

R ² and R ³ are hydrogen atoms, C 1 -C 6 alkyl or phenyl and salts thereof which are useful in agriculture.

These novel compounds have a high and sustained herbicidal effect. In addition, these novel compounds have low persistence and are readily biodegradable.

The herbicidally active compounds according to the invention are effective in post-emergence application and have a wide spectrum of effects, have a low systemic effect and are selective for certain crops if necessary.

The present invention therefore provides a herbicidal composition, characterized in that it contains at least one compound of the formula I as active ingredient.

OR ²

O = P-CH2-NH-CH2-CO-N-SO2-R ¹

I, I

OR ³ R (I) wherein

R ¹ represents an alkyl group having 1 to 12 carbon atoms, a cyclopropyl group or a phenyl group, these groups being optionally substituted by alkyl groups or chlorine or fluorine atoms and containing in total not more than 12 carbon atoms,

R is hydrogen or is as defined for R ¹ ,

R ² and R ³ are hydrogen atoms, C 1 -C 6 alkyl or phenyl, or an agriculturally useful salt thereof, together with at least one inert agricultural carrier.

Particularly preferred are herbicidal compositions which contain as active ingredient at least one compound of the formula I, in which R ¹ represents a C 1 -C 4 alkyl group and the other substituents have the meaning given above under the formula I.

According to the present invention, the novel herbicidally active compounds of the formula I are prepared by reacting the sulfonamides of the formula

R ° —NH — SO2 — R ”wherein

R 0 has the same meaning as R, except for a hydrogen atom,

R 1 has the same meaning as R ¹ except for the hydrogen atom, with the mixed anhydride of formula

OR ²¹ CH2-Ph

O = P — CH2 — N — CH2 — CO — O — CO — O — R “‘

AND

OR ³¹ in which

R ²¹ has the same meaning as R ² with the exception of hydrogen,

R ³¹ has the same meaning as R ³ except for the hydrogen atom and

R “‘ represents an alkyl group, after which the benzyl group was cleaved from the obtained compound by hydrogenolysis.

Reaction of the mixed anhydride of the above formula with the sulfonamide of the formula

R ° —NH — SO2 — R “in which R ° and R" are as defined above, is preferably carried out in a two-phase medium of an aqueous organic solvent in the presence of an alkaline agent and a phase transfer catalyst. The temperature is generally between 0 and 50 ° C. A quaternary ammonium salt of a strong acid such as tetraalkylammonium or trialkylammonium halide or sulfate may be used as the phase transfer catalyst (generally used in a concentration of 0.1 to 10% by weight relative to the mixed anhydride). As the alkali, preferably an alkali metal hydroxide or carbonate or an alkaline earth metal hydroxide or carbonate, preferably an alkali metal hydroxide, is used.

As mentioned above, 246087 compounds of formula I may also be present in the form of salts which are useful in agriculture. These salts may optionally form ingredients of compositions or formulations containing the active ingredient of the invention, the nature of the compositions used in practice will be explained later.

In addition to the above process for the preparation of the compounds of the formula I, they can also be obtained by preparing from the compounds of the formula III

OR ² R ⁴

O = P-CH2-N-CH2-CO-NH-SO2-R ¹

OR ³ (III) in which

R 1, R 2 and R ³ have the above meanings and

R ⁴ is a hydrogen atom or is a hydrogenolyzable group R ⁸ , wherein

R ⁸ is especially a group of the formula Ar (R ⁵ ) (R b) C - in which Ar is an aromatic group, preferably a phenyl group, and

R 5 and R ⁶ represent hydrogen atoms or an Ar group or an alkyl group containing up to 6 carbon atoms by reaction with an ester of the general formula

X — R wherein

R is as defined above for Formula I except for the hydrogen atom and

HX is a protonic acid (inorganic or organic acid), preferably a strong inorganic acid;

X is preferably chlorine, bromine or iodine or a sulfate group, whereupon the hydrogenolyzable group R ⁴ is cleaved from the compound obtained by hydrogenolysis and replaced with hydrogen.

The compound X-R is preferably an alkyl halide.

This reaction is preferably carried out in a solvent, in the presence of an alkaline reagent, at a temperature between -10 ° C and +100 ° C.

Reactants employed of the formula III are preferably those in which R 2, R ³ and R ⁴ are other than hydrogen. It may also be desirable to use compounds of formula III wherein R 2 and R 3 are hydrogen, but in this case a substantial part of compound X-R is consumed to esterify the hydroxyl groups of the compound of formula III.

Compounds of formula (III) wherein:

R 2, R 3 and R ⁴ are other than hydrogen, are generally prepared by reaction of compounds of Formula II

OR2 r8

O = P-CH 2 OH 2-N-CO-O-R ⁷

I 3

OR ³ (II) in which

R2 and R3 have the meanings already given in formula I except for the hydrogen atom, i.e. the groups OR2 and OR3 are hydrolyzable groups, preferably denoting alkyl groups,

R 8 is as defined above and

R ⁷ represents a hydrogen atom with a sulfonyl isothiocyanate of the general formula

R1-SO2-N = C = S wherein

R1 is as defined above, preferably in a solvent and in the presence of an alkaline reagent, preferably a tertiary amine. This reaction is preferably carried out at temperatures between 10 and 120 ° C.

In the various preceding formulas, Ar is an aromatic group, preferably an aryl group, and especially a phenyl group; this Ar group optionally bears one or more substituents which do not adversely affect the course of the reaction (alkyl, alkoxy, nitro, halogen and others, preferably at most 6), although this is not a detailed listing of such preferred groups substituents.

R ⁸ includes:

benzyl, 1-phenylethyl, 1-phenylpropyl, naphthylmethyl, 1-naphthylethyl, 1-naphthylpropyl, diphenylmethyl and trityl, i.e. triphenylmethyl.

Compounds of formula II wherein R 2, R ³ and R 4 are other than hydrogen and R 7 is hydrogen are generally prepared by hydrolysis of compounds of formula II wherein R 2, R 3, r 4 and R 7 are all other than hydrogen .

In practice, this hydrolysis is a saponification for which a molar amount of an alkaline agent is generally used which is equal to the molar amount of the compound of formula II.

Compounds of formula (II) wherein .246087

R ² , R ³ , R ⁴ and R ⁷ are all other than hydrogen, are conveniently prepared by reaction of a phosphite (or phosphomic acid ester) of formula IV

O-R ²

O = P — H

O-R ³ (IV) wherein

R ² and R ³ have the abovementioned meanings, with formaldehyde and N-substituted glycine derivative wherein the substituent on the nitrogen is hydrogenolyzable substituent.

In practice, the N-substituted glycine derivative is a compound of formula

R ⁴ -NH-CH 2 -CO-O-R ⁷ in which

R ⁴ and R ⁷ have the same meanings as in formula II.

This reaction is generally carried out at temperatures between 0 and 100 ° C, preferably at temperatures between 20 and 90 ° C, by simply mixing the reactants. Although a small excess (3: 1 to 1: 3 in molar ratio) of one of the reactants relative to the other is suitable, in practice it is much more convenient to use the reactants in about stoichiometric amounts and the excess should not deviate from the stoichiometric ratio by more than 20%.

Indeed, the fact that an excess of one of the reactants is not required relative to the other belongs to one of the main advantages of the present invention. A further advantage of the present invention resides in the achievement of good yields obtained in the preparation of the compounds of formula II.

Formaldehyde is used in any of its commercially available forms. According to the most widespread method, formaldehyde is used in the form of an aqueous solution with a concentration between

1% and a saturation state, preferably at a concentration of 30 to 40%.

The reaction may be carried out in the presence of an inert solvent, but in general the presence of such a solvent is not necessary and is a further advantage of the present invention that for the preparation of compounds of formula

II, the presence of a solvent is not required (except for the water contained in formaldehyde according to the preferred method).

The reaction product is isolated by any known method.

The compounds of formula II can be converted to herbicidally active compounds (which may be known) of formula V

OR ²

O = P-CH2-NH-CH2-CO-O-R ⁷

I ₃

OR ³ (V) in which

R ² , R ³ and R ⁷ are as defined above, by simple hydrogenolysis of the group R ⁸ . In most cases it is debenzylacl. It is preferably carried out in an aqueous or alcoholic medium at room temperature or at elevated temperature, at atmospheric pressure or at higher pressure. The catalyst may be used in conventional catalytic hydrogenolysis R ^eighth Suitable catalysts include palladium, platinum and Raney nickel. These catalysts may optionally be used on an inert support. It is also desirable to use the aforementioned metals, in particular palladium and platinum, in the form of salts, hydroxides or oxides which are converted to the corresponding metal by the action of hydrogen.

Preferred catalysts for debenzylation are palladium-based catalysts such as palladium on charcoal or palladium on barium sulfate or palladium hydroxide on charcoal. At the end of the reaction, the catalyst can be separated by filtration and the filtrate is evaporated. The product of formula (V) is thus obtained in a practically pure state. A considerable advantage of the process according to the invention is that the reaction time required for debenzylation is relatively short, allowing the use of smaller amounts of catalyst appropriately.

If it is desired to prepare non-esterified forms of known herbicidally active compounds such as N-phosphonomethylglycine alone, complete or partial hydrolysis of the compounds of formula V in a known manner is suitable, for example by heating with an aqueous solution of an acidic or alkaline reagent, especially an alkali metal or alkaline metal hydroxide or carbonate or with a strong inorganic or organic acid, such as hydrochloric acid, sulfuric acid, phosphoric acid, perchloric acid or arylsulfonic acid. This hydrolysis may also be combined with the preparation of salts (i.e., the preparation of salts which are useful in agriculture) or by conversion to other herbicidally active compounds.

Compounds of the present invention of formula VI

OH

O = P-CH2-NH-CH2-CO-N-SO2-R ¹

OH R (VI) is most conveniently prepared by desalkylation (or transesterification) of compounds of formula I wherein R ² and R ³ are other than hydrogen. This desalkylation is preferably carried out by treatment with hydrogen halide in an aprotic polar organic solvent, for example in lower aliphatic carboxylic acids.

Compounds of general formula

OR ²¹ CH2 CeH5

O = P — CH2 — N — СНг — CO — O — CO — O — R “‘

OR ³¹ which are used as starting materials in the process of the invention are prepared by reacting a compound of formula IX

R ² OR ⁸

I I

O = P — CH2 — N — Nг — COOH

J

R ³ O (IX) (preferably in the form of a salt) with an alkyl chloroformate (Cl-CO-O-alkyl).

The compound of formula IX is preferably used in the form of an ammonium salt and particularly preferably in the form of a salt with a tertiary amine such as triethylamine. The reaction is preferably carried out at a temperature between -30 and -10 ^° C in the presence of a solvent. If a solvent is used in which the salt formed during the reaction is insoluble, the reaction product can be separated by filtration. In this case, it is suitable to use ethers and esters as solvents, in particular tetrahydrofuran and ethyl acetate.

The compound of formula (IX) may be prepared by hydrolyzing a compound of formula (II), preferably in the presence of an alkaline agent in an amount at least equal to the stoichiometric amount. R? is other than hydrogen.

The following examples illustrate the C2H5-O. . CH2 — C6H5

I I

O = P — CH2 — N — CH2 — CO—

AND

C2H5 - about it and show the possibilities of its use, but its scope in no way limit.

Examples 1 to 11 illustrate the process and the physical properties of the herbicidally active compounds and chemical intermediates of the invention. The melting points generally correspond to the decomposition melting state. When spectral characteristics are given, they express either infrared (IR) absorption bands in cm ^-1 or chemical shifts of protons in the nuclear magnetic resonance spectrum (NMR).

In the latter case, the shifts are expressed in ppm (parts per million) and measurements are made in deuterated chloroform in the presence of tetramethylsilane as standard.

Example 12 illustrates the use of the compounds of the invention in post-emergence treatment of plants.

Example 1

N-benzyl-N- (diethylphosphonomethyl) glycine of formula X

C2H5-O CH2-C6H5

I I

O = P — CH2 — N — CH2 — COOH

AND

The C2H5-O (X) used as starting material was prepared as described in Example 7.

56.3 g of the compound of formula X is dissolved in 200 ml of acetonitrile. 0.1 ml of triethylamine is added to the solution, and then 24.5 g of methylsulfonyl isothiocyanate of the formula N-SO2-NCS is added dropwise. The released COS binds in methanolic sodium hydroxide solution. The temperature of the reaction mixture rose from 20 ° C to 35 ° C. After the addition, the reaction mixture was refluxed for 1 hour and then concentrated under reduced pressure.

70.5 g of an oily product of the formula —SO2 — СНз (XI) are obtained.

Example 2

23.5 g of the compound of formula XI are dissolved in 100 ml of dimethylformamide. 1.8 g of sodium hydride (purity: 80%) are then added to the reactor, which is maintained at 25 ° C and under a nitrogen atmosphere. After this addition, the reaction is allowed to proceed for 30 minutes at 20 ° C and then 9.9 g of methyl iodide are added. The temperature rises from 21 ° C to 24 ° C. The reaction mixture was then heated at 70 ° C for 30 minutes.

The solvent was evaporated and 200 ml methylene chloride was added. The reaction mixture was washed with aqueous sodium carbonate solution and then with water, dried and concentrated. 16 g of an oily product of the formula XII are obtained

C2H5-O CH2-C6H5

I I

O = P — CH2 — N — CH2 — CO — N — SO2 — СНз

I I

C2H5 — о СНз (XII)

EXAMPLE 3 g of anhydrous hydrogen bromide is dissolved in 100 ml of acetic acid at 15 DEG C. and this temperature is then maintained with an ice-water bath. A solution containing 45 g of the compound of formula XII and 45 ml of acetic acid is then added to the solution. The reaction was allowed to proceed at 20 ° C for 30 hours. The reaction mixture is concentrated, the residue is dissolved in methanol, the solution is precipitated by the addition of propylene oxide, the product is filtered off, washed with methanol and dried. 36 g (93% of theory) of the compound of formula XIII are obtained

ОН CH2 — CeH5

I I

O = P-CH2-N-CH2-CO-N-SO2-CH3

ОН СНз (XIII)

This product is a white powder, m.p. 205 ° C.

EXAMPLE 4 g of palladium-on-carbon catalyst (10% palladium) are mixed with 20 ml of concentrated hydrochloric acid and 150 ml of methanol. Then 8.4 g of the compound of formula XIII is dissolved. A stream of hydrogen was then passed through the solution, which was discontinued when the temperature returned from 24 ° C to 21 ° C. The mixture was filtered and the filtrate was concentrated. The concentrate was dissolved in 50 ml of methanol. 2 ml of propylene oxide are added to this solution to saline out. The precipitate was filtered off and washed with acetone. 4.8 g of the compound of formula XIV are obtained

OH

O = P — CH2 — NH — CH2 — CO — N — SO2 — СНз

I I

ОН СНз (xiv)

Example 5

1.466 g (14.66 mol) of a 30% (by weight) aqueous solution of formaldehyde was added to a mixture of 2830 g (14.66 mol) of N-benzyl glyclate and 2028 g (14, 17 mol) diethylphosphate [(C 2 H 5 O) 2 P (O) H]. The temperature rose to 41 ° C during the addition of the solution. The reaction mixture was then heated at 90 ° C for 1.5 hours and then cooled.

In order to extract the reaction product, 7 liters of methylene chloride are added to the mixture, and the mixture is then washed three times with 6 liters of water each. Remove the solvent. 4647 g of a light brown oil are obtained with a refractive index of n _D ^{20 of} 1.491. The yield was 92.4%.

The compound thus obtained corresponds to formula XV

C2H5O CH2-C6H5

I I

O = P — CH2 — N — CH2 — COOC2 H5

AND

C2H5 (XV)

Example 6

The procedure is the same as in Example 5, except that diethyl phosphite is replaced by dimethyl phosphite (also referred to as methyl phosphonate) of formula (СНзО) 2Р (О) Н.

Compound (XVI) is obtained in 87% yield

СНзО CH2 — СбН5

I I

О = P — CH2 — N — CH2 — COOC2H5

AND

(XVI)

Refractive index n _D ²⁰ = 1.499.

Example 7

An aqueous solution of 5% (w / w) sodium hydroxide (6.8 liters) was poured into 40% of the compound of formula XV over 1 během hour at 40 ° C. The mixture was then heated at 80 ° C for 12 hours, cooled and washed with 4 L of methylene chloride. The aqueous solution was acidified by addition of 800 ml of 10 N hydrochloric acid solution to pH 2. The product separated from the aqueous layer as an oil was extracted with 5 liters of methylene chloride. The methylene chloride solution was washed with water (2.times.5 L) and evaporated to dryness to give 2022 g (75% yield) of the compound of formula (X) which crystallized on storage (m.p. 37 DEG C.).

Example 8

The procedure is as in Example 7, but instead of a compound of formula XV a compound of formula XVI is used as starting material.

СНзО CH2-C6H6

I I

O = P — CH2 — N — CH2 — COOH

AND

СНзО (XVII) melting at 73.8 ° C. Yield 36%.

Example 9

A 500 ml reactor was charged with a solution of 68.6 g of the compound of formula XV in 150 ml of methanol. Then 9 g of a catalyst consisting of a paste containing 10% by weight of palladium on activated carbon are added. 4 6 0 8 7 charcoal and 10 ml of water. The atmosphere in the reactor was replaced with nitrogen and hydrogen was introduced at 20 ° C for 5 hours. The mixture was filtered, the filtrate was evaporated to give 49 g of the compound of formula XVIII

C2H5O

AND.

O = P — CH2 — NH — CH2 — COOC2 H5

AND

C2H5 (XVIII) as a liquid having a refractive index Ud ² 0 = 1.541. Yield 97 0/0.

12.7 g of this compound of formula XVIII are dissolved in 50 ml of an aqueous solution containing 20% by weight of hydrochloric acid. The solution was then heated to reflux for 20 hours. The reaction mixture was then concentrated under reduced pressure and the residue was washed with methanol. After drying, 6.5 g (yield 77%) of N- (phosphonomethyl) glycine are obtained.

Example 10

In a 250 ml reactor, 10 g of the compound of formula X is dissolved in 50 ml of methanol. 0.3 g of the paste catalyst used in Example 9 is then added to the solution. The atmosphere in the reactor is then replaced with nitrogen and hydrogen is introduced for 2 h at room temperature (20-25 ° C). The reaction mixture was then filtered, the filtrate was evaporated to give 7.5 grams (100% yield) of the compound of formula

C2H5O

O = P — CH2 — NH — CH2 — COOH

AND

C2HSO

After recrystallization, the title compound melts at 115 ° C.

Example 11

189 g of N-benzyl-N- (diethylphosphonomethyl) glycine X is dissolved in 600 ml of anhydrous tetrahydrofuran. To this solution was gradually added 60.6 grams of triethylamine at room temperature. After 15 minutes the temperature was lowered from room temperature to -10 ° C and 66 g of ethyl chloroformate was gradually added over 20 minutes. The temperature was then allowed to rise to + 10 ° C and the mixture. is filtered. The precipitate was washed with tetrahydrofuran. The combined filtrates were evaporated. Thus 225 g of a compound of formula XIX are obtained

C2H5O CH2- · CHIs

I I

O = P — CH2 — N — CH2 — CO — O — CO — O — C2HI

AND

C2H5 (XIX)

This mixed anhydride was dissolved in 500 mL of methylene chloride. 3 g of triethylbenzylammonium chloride and 72 g of N-methylmethanesulfonamide are then added to the solution. The mixture was cooled to + 10 ° C. 51 g of an aqueous solution containing 50% by weight of sodium hydroxide are then added dropwise. Stirring is then continued for 1 hour at 20 ° C and 300 ml of water are added.

The layers were separated, the organic layer was washed with water, dried and concentrated. 202 g (83% yield) with a refractive index of nD22 of 1.507 are obtained.

Compounds of general interest. of the formula I shown in the following Table I was prepared as described in Examples 3, 4 and 11.

.246 087

Table I

Compound number R R ¹ R ² and R ³ Physical properties (melting point) 1 СНз— СНз— н 213 ° C 2 СНз— С2Н5— н 219 ° C 3 СНз— (СНз) гСН— н 232 DEG 4 СНз— o-СНз — СбН4— н 217 ° C 5 СНз— p-СНз — СбН4— н 225 [deg.] C 6 C2H5 СНз— Н 322 ° C 7 П-СЗН7— СНз— Н 230 DEG 8 П-С4Н9— СНз— Н 231 ° C 9 СНз— С1 — СН2— н 190 ° C 10 cyclopropyl СНз— н 235 ° C 11 СНз— П-С4Н9— н 236 ° C 12 СНз— П-СЗН7— н 230 DEG 13 СНз— СбН13— н Mp 240 ° C 14 СНз- CF3- н Mp 180 ° C 15 Dec СНз— С12Н25— н 230 DEG 16 СНз— С1— (СНг) з— н 213 ° C 17 СвН5— СНз— н 234 ° C 18 СвН13— СНз— н 237 ° C

The following Table Ia lists the physical properties of the starting materials or intermediates of formula (Ia) useful for the preparation of the compounds of formula (I):

OR ² R ⁴

O = P-CH2-N-CH2-CO-N-SO2-R ¹

OR ³ R (laj

Compound No. R R ¹ R ² and R ³ R ⁴ Physical properties la СНз— СНз— С2Н5— benzyl n _D ²⁰ 1.507 2a СНз— С2Н5— С2Н5— benzyl n _D ²⁰ 1.506 3a СНз- (СНз) гСН— С2Н5- benzyl ID: 1700 NMR: 3.30-3.92 11.5 4a СНз— o-СНз — СвН4— С2Н5— benzyl mp 146 ° C 5 a СНз— p-СНз — СбН4— С2Н5— benzyl n _o ²⁰ 1.507 6a С2Н5— СНз— С2Н5— benzyl 7a П-СЗН7— СНз— С2Н5— benzyl IC: 1,696 8a П-С4Н9— СНз— С2Н5— benzyl n _n ²⁰ 1,494 9a СНз- С1-СН2- С2Н5— benzyl n _D ²⁰ 1.514 10a cyclopropyl СНз— С2Н5— benzyl no ²⁰ 1,505 11a СНз— П-С4Н9— С2Н5— benzyl По ²⁰ 1,491 12a СНз— П-СЗН7— С2Н5— benzyl no ²⁰ 1,499 13a СНз— п-СбН1з— С2Н5— benzyl По ²⁰ 1,496 14a СНз— CF3- С2Н5- benzyl n _D ²⁰ 1,477 15 a СНз— П-С12Н25— С2Н5— benzyl n _D ²⁰ 1,496 16a СНз— С1- (СН2) 3- С2Н5— benzyl n _o ²⁰ 1.512 17a from _{6 to 5} - СНз— С2Н5— benzyl mp 95 ° С 18a п-СбН13— СНз— С2Н5- benzyl IC: 1700 19a СНз— СНз— Н benzyl mp 205 ° C 20a СНз— С2Н5— н benzyl mp 212 ° C 21a СНз— (СНз) гСН— н benzyl mp 220 ° C 22 a СНз— o-СНз — СбН4— н benzyl mp 205 ° C 23a СНз— р-СНз — СвН4— н benzyl mp 224 ° C 24a С2Н5— СНз— н benzyl NMR: 3.74-4.72 13.2 25a Ц-СзН7— СНз- н benzyl IC: 1,696

. 4 6 9 8 9

Compound No. R R ¹ R ² and R ³ R4 Physical properties 26a n-C4H9— CH3— H benzyl NMR: 3.70-4.74 13 27a CH3— CI-CHh— H benzyl mp 155 ° C 28a cyclopropyl CH3— H benzyl mp 222 ° C 29a CH3— n-C4H9— H benzyl mp 218 ° C 30a CH3— n-C3H7— H benzyl mp 217 ° C 31a CH3— C6H13— H benzyl mp 206 ° C 32a CH3— CF3— H benzyl mp 150 ° C 33a CH3— C12H25— H benzyl mp 185 ° C 34a CH3— C1- (CH2) 3 - H benzyl mp 202 ° C 35a C6H5— CH3— H benzyl mp 204 ° C 36a C6H13— CH3— H benzyl mp 221 ° C

Example 12

Herbicidal effect in post-emergence treatment of various plant species

The seeds of the test plants are sewn into the pots of dimensions 9 X 9 X 9 cm filled with light agricultural soil, always in a number depending on the type of plant and the size of the seed.

The seeds are then covered with a layer of soil approximately 3 mm high and germinated until the emergence of germinate plants of a suitable stage of development. A suitable stage for treating monocotyledonous plants is to form a second leaf. A suitable stage for treating dicotyledonous plants is when the uterine leaf is opened and the first true leaf is developed.

The pots are then sprayed with a spray mixture in an amount corresponding to an applied volume of 500 liters per ha and containing the active ingredient at the desired concentration.

The spray mixture used for treatment is an aqueous suspension or solution of the active ingredient containing 0.1% by weight of Cemulsol NP 10 surfactant consisting of a polycondensation product of ethylene oxide and an alkylphenol, in particular a polycondensation product of ethylene oxide with nonylphenol) and 0.04% by weight of Tween 20 (surfactant consisting of oleate polycondensation product of sorbitol-derived ethylene oxide).

The application rate of the active ingredient is 4 kg / ha.

After treatment, the pots are placed in troughs filled with water and intended for bottom irrigation and maintained for 28 days at ambient temperature and 70% relative humidity.

After 28 days, the number of live plants in pots treated with the spray mixture containing the test drug and the number of live plants in the control pot were treated under the same conditions but using the spray mixture without the drug. The percentage of destruction effect of the treated plants compared to the untreated control is then determined. A percent destruction equal to 100% indicates complete destruction of the respective plant species and a value of 0% indicates that the number of live plants in the treated pot is the same as the number of live plants in the control pot.

The following plant species were used in the tests:

Name hedgehog corns leg rye multicolored broad beans mustard white goosefoot

Latin name

Abbreviation

Echinochloa crus-galli Phaseolus vulgaris Sinapis alba Chenopodium album

PA RG

BE MU

GO.? 4 S Й S 7

The results are summarized in Table IJ below.

Table II

Compound number BYE Type of plant GO RG BE HIM 1 100 ALIGN! 98 100 ALIGN! 100 ALIGN! 100 ALIGN! 2 98 95 100 ALIGN! 100 ALIGN! 100 ALIGN! 3 98 95 100 ALIGN! 100 ALIGN! 100 ALIGN! 4 20 May 30 0 100 ALIGN! 30 5 0 20 May 100 ALIGN! 98 80 6 80 70 100 ALIGN! 100 ALIGN! 100 ALIGN! 7 60 20 May 100 ALIGN! 95 80 8 0 0 0 80 80 9 40 70 100 ALIGN! 100 ALIGN! 98 10 0 10 100 ALIGN! 90 50 11 20 May 10 100 ALIGN! 100 ALIGN! 60 12 80 80 100 ALIGN! 100 ALIGN! 80 14 100 ALIGN! 100 ALIGN! 100 ALIGN! 100 ALIGN! 100 ALIGN! 16 30 0 100 ALIGN! 100 ALIGN! 20 May 17 10 0 0 80 20 May

The compounds listed in Table II were also used in an amount of 1 kg / ha and showed a good effect even at this substantially lower amount. These compounds also have a good effect on a large number of other plants. Some of these are listed in Table III below:

Table III

Czech name Latin name Kindweed bent Amaranthus retroflexus abutilon Abutilon theophrasti Sida spinosa beet Xanthium pennsylvanicum Bidens rdesno Polygonům convolvulus mustard Zea mays chickweed frog Stellaria media daisy Chrysanthemum rosička krevavá Digitaria sanguinalis bér Setaria faberi aubergine black Solanum nigrum šáchor Cyperus esculentus

The tests carried out show remarkably advantageous properties of the compounds of the present invention as herbicides with a broad spectrum of action and postemergence activity. Said compounds are generally ineffective in pre-emergence application.

In practice, the compounds of the invention are rarely used alone, but most often form part of suitable compositions. These compositions which can be used as herbicides contain as active ingredient the compound of the invention described above, in combination with solid or liquid carriers useful in agriculture and with surfactants also useful in agriculture. In particular, inert carriers and customary surfactants can be used for this purpose. The above compositions are also an object of the present invention.

These compositions may also contain all possible types of other ingredients, such as protective colloids, adhesives, thickeners, thixotropic agents, penetrating agents, stabilizers, complexing agents and the like, as well as other known active substances having pesticidal properties (in particular insecticidal, fungicidal or antifungal agents). herbicidal properties) or substances with the ability to control the growth of plants. More generally, the compounds of the invention may be combined with any solid or liquid additive, as appropriate to conventional techniques for making such compositions.

The dosage of the compounds according to the invention used may vary within wide limits, in particular depending on the nature of the undesirable plants to be removed and the usual degree of infestation of the crops with these undesirable plants.

In general, the compositions of the invention comprise from about 0.05 to 95% by weight of one or more active ingredients of the invention, from about 1 to 95% by weight of one or more solid or liquid carriers, and optionally from about 0.1 to 50% by weight of one or more surfactants.

Thus, in accordance with what has already been said herein, the compounds used in the sense of the invention are generally combined with carriers and optionally surfactants.

As used herein, the term "carrier" refers to an organic or inorganic, natural or synthetic material with which the active ingredient is combined to facilitate its application to the plant, its seeds or soil. Thus, this carrier is generally inert and must be useful in agriculture - in particular, it must be acceptable for the plant to be treated.

The carrier can be solid (clays, natural or synthetic silicates, diatomaceous earth, resins, waxes, solid fertilizers, etc.) or liquid (water, alcohols, especially butanol), esters, especially methylglycol acetate, ketones, especially cyclohexanone and isophorone, petroleum fractions, paraffinic or aromatic hydrocarbons, especially xylenes, aliphatic chlorinated hydrocarbons, especially trichloroethane, or aromatic chlorinated hydrocarbons, especially chlorobenzenes; water-soluble solvents such as dimethylformamide, dimethylsulfoxide or N-methylpyrrolidone, liquefied gases, etc.).

The surfactant may be an emulsifier, dispersant or wetting agent of the ionic or non-ionic type or a mixture of such surfactants. Examples include polyacrylic acid salts, lignosulfonic acid salts, phenolsulfonic or naphthalenesulfonic acid salts, polycondensation products of ethylene oxide with fatty alcohols, fatty acids or fatty series amines, substituted phenols (especially alkylphenols or arylphenols), sulfosuccinic acid ester salts, derivatives taurine (especially alkyltaurates), phosphoric acid esters with condensation products of ethylene oxide with alcohols or phenols, fatty acid esters of polyols, and sulfates, sulfonates and phosphates of functional derivatives of the above compounds.

The presence of at least one surfactant is generally necessary if the active ingredient and / or the inert carrier are only slightly soluble in water or not soluble in water, and the water serves as a medium for preparing the dosage form.

Thus, for application, the compounds of formula I are generally used in the form of compositions. Thus, the compositions of the present invention can exist in a very wide variety of solid or liquid forms.

Solid forms of these compositions include dusts (in which the content of the active compound of the formula I can range up to 80%) and granules, in particular granules obtained by extrusion, compression, impregnation of a granular carrier or powder preparation (content of the compound of formula I) in these granulates may range between 0.5 and 80% for the latter cases).

Liquid compositions or compositions which are converted to liquid preparations upon application include solutions, in particular emulsifiable concentrates, emulsions, suspension concentrates, aerosols, wettable powders, dry free-flowing preparations and pastes.

Emulsifiable or soluble concentrates usually contain 5 to 80% of active ingredient, while emulsions or solutions for direct application in this case contain 0.01 to 20% of active ingredient. In addition to the solvent, the emulsifiable concentrates may optionally contain 2 to 50% of suitable additives such as stabilizers, surfactants, penetration agents, corrosion inhibitors, dyes or adhesives.

Emulsions of any desired concentration which are particularly suitable for application to

plants, can be obtained from these concentrates by dilution with water. An example is the composition of several emulsifiable concentrates: active ingredient 100 ALIGN! G polycondensation product of ethylene oxide and alkylphenol 100 ALIGN! G ethylene glycol methyl ether 400 G Aromatic petroleum fraction distilling between 160 and 185 ° C 400 G

As another example, the emulsifiable composition

The following concentrate can be mentioned: active ingredient 50 epoxidized vegetable oil 25 mixture of alkylarylsulfonate and poly- glycol ether and fatty of alcohols 100 ALIGN! dimethylformamide 250 xylene 575

Sprayable suspension concentrates are formulated to form a liquid, stable, non-deposited product, and typically contain from about 10% to about 75% of the active ingredient, from about 0.5% to about 15% of surfactants, from about 0.1% to about 0.1%. up to 10% of thixotropic agents, from 0 to 10% of suitable additives, as antifoams, corrosion inhibitors, stabilizers, penetration agents and adhesives, and as a carrier a water or organic liquid in which the active ingredient is only slightly soluble or insoluble. Certain organic solids or inorganic salts 2 <3 β β δ 7 li may be dissolved in the carrier to aid in the prevention of the wettable powder composition.

sedimentation or act as

anti-freeze agents. active substance 400 g The following section provides an example of sodium lignosulfonate 50 G suspension suspension concentrate: sodium dibutylnaphthalenesulfonate 10 G silica 540 G active substance 500.0 g phosphate of the polycondensation product Example of 25% wettable powder composition: tristyrylphenol ethylene oxide polycondensation product ethylene- 50,0 g active substance 250 G oxide and alkylphenol 50,0 g isooctylphenoxypolyoxyethylene- sodium polycarboxylate 20,0 g ethanol 25 G ethylene glycol 50,0 g mixture of chalk (provenance Cham- organopolysiloxane oil pagne) and hydroxyethylcellulose (anti-foaming agent) 1.0 g (1: 1) 17 G polysaccharide 1.5 g sodium aluminum silicate 543 G water 316.5 g kieselguhr 165 G

Example of 10% wettable powder composition:

Wettable powders are generally formulated to contain 10 to 80% active ingredient, and generally contain 0 to 5% wetting agent, 3 to 10% dispersant and optionally 0 to 80% of one or more stabilizers and / or other additives, in addition to a solid carrier. penetration agents, adhesives or anti-caking agents, dyes, and the like.

The following are some examples of wettable powder compositions:

Active ingredient 50% calcium lignosulfonate (deflocculating agent) 5% isopropyl naphthalenesulfonate (anionic surfactant) 1% silica anti-caking 5% kaolin (filler) 39%

Another example of a wettable powder composition containing 25% active ingredient:

Active ingredient 25% polycondensation product of ethylene oxide and aliphatic amine (C10-18) 10% polycondensation product of ethylene oxide and aliphatic alcohol of 8 to 18 carbon atoms 10% silica anti-caking 25% kaolin 30%

Example composition 50% wettable powder: active ingredient 50% sodium alkylnaphthalenesulfonate 2% methylcellulose low viscosity 2% diatomite 46%

Example of composition 90% wettable powder: active ingredient 90.0% dioctylsulfosuccinic acid sodium salt 0.2% synthetic silica 9.8% active ingredient100 g mixture of saturated sodium sulfated fatty acids 30g condensation product of naphthalenesulfonic acid and formaldehyde 50g kaolin 820g

To produce these wettable powders, the active compound (s) is thoroughly mixed in suitable devices for mixing with additives which can be impregnated on the porous filler and the mixture is ground in mills or other suitable crushers. In this way, wettable powders are obtained with preferred wettability, nose and suspendability. These powders may be suspended in water to give a suspension of any desired concentration. This suspension can be used very advantageously in particular for application to plant leaves.

The water dispersible granules have a composition substantially the same as wettable powders. They can be prepared by granulating the compositions described for wettable powders, either by wet (by mixing the finely dispersed active ingredient with an inert filler and a small amount of water, for example 1 to 20%, or with an aqueous dispersant or binder solution, drying and sieving), or dry. by way (pressing, subsequent crushing and sieving).

Example of composition of water dispersible granules:

active ingredient 800g sodium alkylnaphthalene sulfonate 20g sodium methylene to (naphthalene) sulfonate 80g kaolin 100g

As already mentioned, aqueous dispersions and emulsions, for example formulations obtained by diluting wettable powders or emulsifiable concentrates of the invention with water, fall within the general range of compositions that can be used in the present invention. The emulsions may be of the water-in-oil or oil-in-water type and may have a thick consistency, such as mayonnaise.

All of these aqueous dispersions or emulsions or spray mixtures can be applied to the plants to be controlled in any suitable amount, mainly by spraying, in an amount which generally ranges from 100 to 1200 liters of spray mixture per hectare.

The compounds and compositions of the invention are suitably applied to plants and especially to weeds to be controlled when the weeds have green leaves. Their persistence is low and it is therefore advisable to carry out the treatment by sowing the crop before or after treatment, but coming to the surface shortly after treatment (2 to 3 weeks), i.e. after decomposition of the compounds of the invention.

The application rate of active compound is generally between 0.1 and 10 kg / ha, preferably between 0.5 and 8 kg / ha.

The basic function of the various additives or auxiliaries mentioned above is generally to facilitate the handling and dispersion of the compounds of the invention. In some cases, they may also promote the penetration of the active ingredient into the plant and thus may increase the normal effect of the active ingredients of the invention.

Claims (6)

SUBJECT L A herbicidal composition comprising as active ingredient at least one compound of formula (I) OR ² O = P-CH2-NH-CH2-CO-N-SO2-R ¹ I _s I OR 3 R (I) wherein R1 represents an alkyl group having 1 to 12 carbon atoms, a cyclopropyl group or a phenyl group, these groups being optionally substituted by alkyl groups or chlorine or fluorine atoms and containing a total of at most 12 carbon atoms, R is hydrogen or is as defined for R ¹ , R 2 and R 3 are hydrogen atoms, C 1 -C 6 alkyl or phenyl, or an agriculturally useful salt thereof together with at least one inert agricultural carrier. 2. A composition according to claim 1, wherein the active ingredient comprises at least one compound of formula (I) wherein: R ¹ and R ¹ are independently C 1 -C 12 alkyl, and R 2 and R 3 are hydrogen atoms together with an agricultural carrier. 3. A composition according to claim 1, characterized in that it contains as active ingredient at least one compound of formula I in which R ¹ represents an alkyl group having 1 to 4 carbon atoms and R, R ² and R ³ are as defined in point 1. 4. A composition according to any one of Claims 1 to 3 comprising from 0.5 to 95% by weight of the active ingredient. 5. A composition according to claim 4 comprising from about 5% to about 40% by weight of a surfactant. 6. A process for the preparation of an active ingredient according to claim 1, which comprises reacting a sulfonamide derivative of the formula: