NL8000487A - SUBSTITUTED 4-ALKYLTHIOALCANE SULFONANILIDS AND THEIR DERIVATIVES. - Google Patents

Description

*

Substituted 4-alkylthioalkanesulfonanilides and derivatives thereof.

The invention relates to halogen-substituted methane and chloromethane sulfonanilides, substituted in the para-position by alkylthio, alkylsulfinyloyl alkylsulfonyl groups, and optionally substituted by trifluoromethyl, and salts thereof acceptable in agriculture or horticulture. The compounds of the invention are active herbicides and plant growth modifiers. The invention also relates to herbicidal compositions containing the said compounds and to the use of the compounds to control and control the growth of higher plants.

The invention more particularly relates to compounds of the general formula I, wherein R represents an alkyl group with 1-4 (preferably 1-2) carbon atoms or monohalomethyl (chloromethyl, bromomethyl, iodomethyl or fluoromethyl), R 'represents a alkyl group of 1-4 carbon atoms, A represents halogen or CF ^, B represents hydrogen or halogen and n represents 0-2, where when A represents CF ^ B is halogen, and salts thereof acceptable in agriculture or horticulture, on preparations for killing and modifying the growth of higher plants, which composition consists essentially of a compound of the invention dispersed in a diluent medium, using the compounds of the invention to modify the growth of higher plants and for killing higher plants and for methods of preparing the compounds of the invention. The invention is particularly useful in the field of selective herbicides to control special 8000487 2 weed species in the presence of specific crops (with little or no damage to the crops), for example to control weeds, such as rhizomatous Johnson grass, annual grasses, yellow nut sedge and / or red nut sedge, in crop-5 crops, such as cotton or soybeans.

The compounds of the formula I wherein R represents -C 1 Cl and A represents chlorine or bromine are a preferred group of compounds and the compounds of formula 1 wherein R represents -CH 1 and A represents chlorine or bromine a second preferred group of compounds, in both cases because of the highly useful activity.

The compounds of the formula I can form salts, ie compounds of the above formula, in which H is replaced by a cation acceptable in agriculture or horticulture. These are generally metal, ammonium and organic amine salts and can be prepared by treating the acid form of the compound with a suitable base under mild conditions. These metal salts of the invention include alkali metal (eg lithium, sodium and potassium), alkaline earth metal (eg barium, calcium and magnesium) and heavy metal (eg zinc and iron) salts as well as other metal salts such as aluminum. Suitable bases for use in the preparation of the metal salts include metal oxides, hydroxides, carbonates, hydrogen carbonates and alkoxides. Some salts can also be prepared by a cation exchange reaction (by reaction of a salt of the invention with an organic or inorganic salt in a cation exchange reaction). The organic amine salts include the salts of aliphatic (eg, alkyl), aromatic and heterocyclic amines, as well as those with a mixture of these types of amines. The amines useful in the preparation of the salts of the invention can be primary, secondary or tertiary and preferably contain no more than 20 carbon atoms. Such amines include, for example, morpholine, methylcyclohexylamine, glucosamine, amines derived from fatty acids, etc. The amine and ammonium salts can be prepared by reacting the acid form with the appropriate organic base or ammonium hydroxide. All salts of the types indicated above are acceptable in agriculture or horticulture, with the salt being selected depending on the special intended application and the economy of the situation. Of special interest 5. are the alkali metal, alkaline earth metal, ammonium and amine salts.

The salts of the invention are frequently formed by reaction of the precursors in aqueous solution. This solution can be evaporated to give the salt of the compound, usually as a dry powder. In some cases, it may be easier to use a non-aqueous solvent, such as an alcohol, acetone, etc. The resulting solution is then treated to remove the solvent, for example, by evaporation under reduced pressure.

The compounds of the invention can be prepared according to the reaction scheme indicated on Irt formula sheet.

The reaction of step (1) involves the formation of the substituted 4-thiocyanoanilines from the corresponding substituted anilines (known or for which the preparation methods are well known), generally using conventional means.

The reaction of step (2) involves the direct formation of the substituted 4-alkylthioanilines from the corresponding 4-thiocyanoanilines. This reaction can be performed using a variety of conventional techniques. For example, the thiocyano portion can be alkylated in an alcoholic sodium cyanide solution. Preferably, the alcohol contains the same hydrocarbon residue as the desired alkyl group. On the other hand, a sodium capcide may first be formed from the thiocyano portion and then alkylated using an alkylating agent such as an alkyl halide (methyl iodide).

Step (2) can also be performed by first converting the sodium mercaptide to the free mercaptan by acidification. The mercaptan is then reacted with an alkylating agent such as an alkyl halide (methyl iodide) in the presence of an organic base. Suitable organic bases are tertiary amines such as triethylamine, dimethyl cyclohexylamine, pyridines and the like. This reaction is usually preferred when the alkyl halide is a tert-butyl halide (tert-butyl bromide).

The reaction of step (3) is the methanesulfonylation or chloromethanesulfonylation of the product of step (2) with two or more equivalents of methanesulfonyl chloride or chloromethanes-sulfonyl chloride in the presence of a base. If 1-2 equivalents of the sulfonyl chloride are used, a mixture of mono- and bis (sulfonylated) product can be obtained, which can be used in step (4). If two or more equivalents of the chloride are reacted, the formation of the 15 bis (sulfonylated) product is favored. Suitable bases for the reaction of step (3) are organic or inorganic bases, such as pyridine, triethylamine, N.N-dimethylaniline and substituted pyridine and the like. Liquid bases in excess can be used to eliminate the need for the use of a solvent. Stronger bases promote the formation of bis (sulfonylated) product over the mono (sulfonylated) product.

Step (4) is the partial hydrolysis of the intermediate bis compounds. This is a high yield basic hydrolysis reaction using a strong base such as potassium hydroxide in methanol. Alternatively, the precursor of step (3) can be directly converted to the product of step (4) by a mono (sulfonylation) reaction using one or more equivalents of base. This reaction is favored by a base weaker than pyridine, such as 3-bromopyridine.

Step (5) is performed using conventional oxidation methods such as hydrogen peroxide in acetic acid, sodium meta periodate and the like. The sulfoxide-35 compound (n = 1) is formed when equimolar amounts of the oxidizing agent and the reactant are used, while the sulfone (n = 2) is prepared directly using two mill (or a small excess) of the oxidizing agent per mole of the reactant.

The herbicidal activity of the compounds according to the invention was determined by means of comparative tests on greenhouse plants. The application activities before and after the emergence of the plants were determined in a direct comparative test on selected weed species. The following weeds are examples of weeds used for these tests.

Grasses:

Giant foxtail (Setaria faberi)

Cinnabar (Echinochloa crus-galli)

Blood millet (Digitaria ischaemum) 15 Cultivated grass (Agropyron repens)

Yellow nut sedge (Cyperus esculentus)

Broad-leaved plants:

Red goosefoot (Amaranthus retroflexus)

Purslane (Portulaca oleracea) 20 Wild mustard (brassica kaber)

Field bindweed (Convolvulus arvensis)

The chemicals to be tested are dissolved in a small amount of acetone or other suitable solvent and then diluted with water to give a concentration of 2000 ppm. Samples are diluted from this concentrate to obtain a final concentration of 500 ppm. 80 ml of this solution are added to a 15 cm jar containing the weed seeds to obtain a concentration equivalent to 20 pounds / acre. The use of 20 ml of this solution gives a concentration equal to 5 pounds / acre. All subsequent watering is done from the bottom.

Two pots per treatment are used. The observations are made 2-3 weeks after treatment and recorded as the percent mortality at application of the emergence of the plants for each species compared to the untreated control plants.

8000487 6

In order to determine the post-emergence activity of the plants, the same weed mixtures were grown for 2-3 weeks until the grassy crops were about 2.5-7.5 cm in length and the broad-leaved crops were about 2 in length. Possessed 5-3.8 cm. They are sprayed with a 2000 ppm solution as described above for about 10 seconds or until good wetting of the blade surfaces is achieved.

The observations are made 2-3 weeks after the treatment and recorded as the percent mortality for each species compared to the untreated control plants.

The compounds of the invention are generally active as herbicides. The mechanism or mechanisms by which this herbicidal activity is mediated are currently unknown. However, the compounds of the invention also exhibit varying types of plant growth modifying activity. The plant growth modification as defined herein consists of all deviations from natural development, eg defoliation, stimulation, growth inhibition, growth retardation, dehydration, sedation, dwarfism (withering away), regulation and the like. This plant growth modifying activity is generally observed when the compounds of the invention begin to interfere with certain processes within the plant. If these processes are essential, the plant will die if treated with a sufficient amount of the compound. However, the observed type of the growth-modifying activity varies with the types of the plants.

Before application to plants, the compounds can be finely divided and suspended in any conventional aqueous media. In addition, spreaders, wetting agents, adhesives or other additives can be added if desired. Dry powders, as such or diluted with inert materials, such as diatomaceous earth, can also be used as dust materials (sputtering materials) 8000487! yr 7 for this purpose. The formulations are applied to the plants or the soil is covered when plant emergence control is desirable. The application amounts are generally 0.5-20 pounds / acre, but these amounts can be increased or decreased according to the individual conditions of use.

The compounds of the invention may advantageously be combined with other known herbicides to broaden or maximize the weed spectrum that can be controlled by the herbicidal compositions of the invention or to control a weed which is not well controlled better control with the specific compounds according to the invention. These other known herbicides include phenoxy herbicides, for example 2.4-D, 2.4.5-T, silvex and the like, carbamate herbicides, thiocarbamate and dithiocarbamate herbicides, substituted urea herbicides, for example diuron, monuron, and the like, triazine herbicides, for example simazine and atrazine, chloroacetamide and chlorinated aliphatic acid herbicides, chlorinated benzoic and phenylacetic acid herbicides, such as chloro-20 amben, and other herbicides, such as trifluraline, paraquat, nitraline and the like. Furthermore, herbicidal compositions containing the compounds of the invention may additionally contain nematocides, fungicides, insecticides, fertilizers, spore metals, soil conditioners, other plant growth control agents and the like. Such combinations are within the scope of the invention.

The invention is further illustrated but not limited by the following examples, wherein, unless otherwise indicated, the parts are parts by weight.

Example I

2-Chloro-6-trifluoromethylnitrobenzene.

A mixture of 3-chloro-2-nitrobenzoic acid (25 g, 0.12 mol) and sulfur tetrafluoride (42.1 g, 0.389 mol) is heated at 130 ° C in a Hastelloy B reaction vessel for 16 hours. The unreacted sulfur tetrafluoride is vented through a washer and the remaining material is poured 8000487 8 into a solution of sodium fluoride (6.2 g) and water (200 ml). Sodium carbonate is added to a pH of 8 and the basic mixture is extracted with ether. The combined ether extracts are washed with water and dried. By removing the drying agent and ether, a product is obtained, which is purified by chromatography on silica gel with petroleum ether (bp 30-60 ° C) ether as eluent.

Analysis:

Calculated for 0 ^ 20 ^ 02: C 37.37, H 1.34, N 6.21%. Found: C 36.8, H 1.2, N 5.9%.

The following compound is prepared using the same general procedure: S-chloro-2-trifluoromethylnitrobenzene, a liquid.

Example II

5-chloro-2-trifluoromethylaniline.

Aqueous ammonium sulfide (60 g, 52-60%) is added dropwise to a warm (75 ° C) stirred ethanol solution of 5-chloro-2-trifluoromethylnitrobenzene (22.6 g, 0.1 mol) and the resulting mixture is heated at a heating bath temperature of 97 ° C for 4 hours, then allowed to cool to room temperature. The reaction mixture is poured into water and the organic product extracted with diethyl ether. After washing and drying the ether solution, the ether is removed by evaporation to yield the desired product.

The following compound can be prepared according to the same general procedure: 2-chloro-6-trifluoromethylaniline.

Example III

2-Bromo-4-thiocyanoaniline.

30 To a cold (0-5 ° C) stirred solution of o-bromoaniline (20.6 g, 0.12 mol) and sodium thiocyanate (29.2 g, 0.36 mol) in methanol (300 ml) is added dropwise a solution of bromine (19.5 g, 0.122 mol) in methanol (75 ml), saturated with sodium bromide. The solution is stirred for 1 hour after the addition of the bromine, then poured into water (2 liters) and neutralized with sodium carbonate. The resultant 8000487 solid waste is collected, washed with water and dried; melting point = 74-79 ° C.

The following compounds are prepared using the same general procedure: 5 2-chloro-4-thiocyanoaniline, mp. 63-65 ° C, 2-fluoro-4-thiocyanoaniline, mp. 34-35 ° C, 2.5-dichloro-4-thiocyanoaniline, mp. 11 ° -1,5 ° C, 2,3-dichloro-4-thiocyanoaniline, mp. 132-137 ° C, 2-iodo-4-thiocyanoaniline, mp. 92-93 ° C.

Example IV

2-bromo-4-methylthioaniline.

A solution of 2-bromo-4-thiocyanoaniline (11.5 g, 0.05 mol) and sodium cyanide (1.23 g, 0.025 mol) in methanol (100 ml) is stirred at room temperature overnight.

Sodium cyanide (0.025 mol) is then added and the reaction mixture is refluxed for 2 hours and then cooled (0-5 ° C). Methyl iodide is added and stirring is continued. Thin layer chromatography shows the presence of one product stain. The product is recovered by extraction with methylene chloride; 8.4 g.

The following further compounds are prepared by the same general method: 2-chloro-4-methylthioaniline, an oil, 2,3-dichloro-4-methylthioaniline, a solid.

Example V

2-Chloro-4-ethylthioaniline

A solution of 2-chloro-4-thiocyanoaniline (40 g, 0.22 mol) in ethanol (250 ml) is added to a stirred solution of sodium sulfide nonahydrate (58.5 g, 0.22 mol) in water ( 110 ml) and the mixture is heated (50 ° C) for 45 minutes. Ethyl iodide (36.6 g, 0.22 mol) is added and stirring is continued for 2 hours at 50 ° C and then at room temperature overnight. The reaction mixture is poured into water (3 liters) and the product extracted with ether.

The combined extracts are washed with water and dried (CaSO4). Removal of the desiccant and solvent gives 8000487

I.Q

2-chloro-4-ethylthioaniline, an oil.

The following other compounds are prepared by the same general method: 2-bromo-4-ethylthioaniline, an oil, 2-fluoro-4-ethylthioaniline, an oil, 2-chloro-4-isopropylthioaniline, an oil, 2,5-dichloro-4 -ethylthioaniline, an oil, 2,3-dichloro-4-methylthioaniline, an oil, 2-iodo-4-ethylthioaniline, an oil.

Example VI

2-Chloro-4-tert-butylthioaniline.

A solution of 2-chloro-4-thiocyanoaniline (36.9 g, 0.20 mol) in ethanol (100-200 ml) is added to a stirred solution of sodium sulfide nonahydrate (48.04 g, 15.0 g). 20 mol) in water (100 ml) and the mixture is heated (50 ° C) for 90 minutes. The cooled reaction mixture is poured into water (1 liter) and dilute hydrochloric acid is added to bring the pH to 6-6.5. The product is extracted with ether, the ether extract is washed with water and then dried. Removal of the desiccant and the ether gives 2-chloro-4-mercaptoaniline as a yellow oil.

Dimethylcyclohexylamine (22.86 g, 0.18 mol) in methylene chloride (125 ml) is added dropwise to a stirred solution of 2-chloro-4-mercaptoaniline (27 g, 0.17 mol) and tert-butyl bromide ( 22.86 g, 0.18 mol) in methylene chloride (125 ml) and the mixture is stirred at room temperature for about 68 hours. A further amount of dimethylcyclohexylamine (2.3 g) and tert-butyl bromide (2.5 g, 0.018 mol) is added and stirring is continued overnight. The reaction mixture is poured into water and the product is extracted with methylene chloride. The combined extracts are washed with dilute hydrochloric acid, water and dried. After removal of the desiccant and methylene chloride, crude 2-chloro-4-tert-butylthioaniline is obtained as a beige solid.

35 8000487 v. -r 11

Example VII

2-Bromo-4-methylthiochloromethanesulfonanilide.

Chloromethanesulfonyl chloride (0.03 mol) is added dropwise to a cold (0-5 ° C) stirred solution of 2-brocm-4-methylthioaniline (6.2 g, 0.028 mol) in pyridine (20 ml). The solution is stirred at room temperature overnight, poured into ice water and 12N. hydrochloric acid with stirring to give 2-bromo-4-methylthiochloromethane sulfonanilide as an oil. A methylene chloride-10 solution of the oil is washed with water and dried. A red oil is obtained by removing the desiccant and methylene chloride. Crystallization from methylene chloride-hexane gives a red-yellow-brown solid; melting point = 72-85 ° C.

Analysis: Calculated for CgHgBrClN02S2i C 29.0, H 2.7, N 4.2%

Found: C 29.6, H 2.8, N 4.3%.

The following compounds are prepared using the same general method: 2-chloro-4-methylthiochloromethanesulfonanilide, m.p. 79-82 ° C, 2-chloro-4-methylthiomethanesulfonanilide, mp. 128-133 ° C, 2,3-dichloro-4-methylthiochloromethanesulfonanilide, mp. 119-123 ° C, 2,3-dichloro-4-methylthiomethanesulfonanilide, mp. 165-170 ° C, 4-methylthiomethanesulfonanilide, mp. 107.5-110 ° C.

Example VIII

2-Bromo-4-methylthiomethanesulfonanilide.

To a stirred mixture of 4-methylthio-methanesulfonanilide (7.6 g, 0.035 mol) iron filings (0.35 g) and glacial acetic acid (50 ml) is added dropwise bromine (5.6 g, 0.035 mol). The reaction mixture is then heated at 110 ° C for 2 hours, cooled and poured into water (300 ml). The oily product is extracted with methylene chloride, the combined extracts are washed with water and dried. By removing the desiccant and solvent, the product is obtained in the form of an oil. The oil is crystallized from hexane and the yellow-brown solid recrystallized from hexane-methylene chloride to give a brown solid; 8000487 12 melting point = 100-110 ° C.

Analysis:

Calculated for CgHjgBrN02S2: C 32.4, H 3.4, N 4.7%

Found: C 33.1, H 3.4, N 4.7%.

Example IX

2-Chloro-4-ethylthiochloromethanesulfonanilide.

Chloromethanesulfonyl chloride (4.0 g, 0.027 mol) is added dropwise to a stirred solution of 2-chloro-4-ethylthioaniline (5.0 g, 0.027 mol) in 3-bromopyridine-10 (6.4 g, 0.041 mol) ) and the mixture is stirred at room temperature overnight. The reaction mixture is taken up in methylene chloride (200ml) and dilute hydrochloric acid (20%, 200ml), the layers are separated and the methylene chloride solution is washed three times with dilute hydrochloric acid (10%, 200ml) and then dried ( CaSO ^). By removing the desiccant and solvent, the product is obtained as a reddish oil. This oil is taken up in hexane and cooled to yield the product, 2-chloro-4-ethylthiochloromethane-sulfonanilide, m.p. 70-72 ° C.

20 Analysis:

Calculated for C ^ HjJCI2NO2S2: C 36.0, H 3.7, N 4.7%

Found: C 36.3, H 3.5, N 4.7%.

The following compounds were prepared using the same general method: 2-Bromo-4-ethylthiochloromethanesulfonanilide, m.p. = 63-65 ° C, 2-chloro-4-isopropylthiochloromethanesulfonanilide, mp. 50-53 ° C, 2-fluoro-4-ethylthiochloromethanesulfonanilide, mp. 78-8 ° C, 2-chloro-4-ethylthiomethanesulfonanilide, m.p. 101-103 ° C, 2-chloro-4-isopropylthiomethanesulfonanilide, mp. 78-80 ° C, 2-chloro-4-ethylthioethanesulfonanilide, mp. 64-66 ° C, 2-chloro-4-isopropylthioethanesulfonanilide, m.p. 52-53 ° C, 2-bromo-4-ethylthiomethanesulfonanilide, mp. 83-85 ° C, 2-fluoro-4-ethylthiomethanesulfonanilide, mp. 89-91 ° C, 2.5-dichloro-4-ethylthiomethanesulfonanilide, mp. 143-144 ° C, 35 2-fluoro-4-ethylthioethanesulfonanilide, mp. 77-79 ° C, 2-fluoro-4-methylthioethanesulfonanilide, mp. = 69-71 ° C, 8000487 * 13 2-fluoro-4-methylthiomethanesulfonanilide, m.p. 133-135 ° C, 2-fluoro-4-methylthiochloromethanesulfonanilide, mp. 88-90 ° C, 2-bromo-4-isopropythiomethane ulfonanide, m.p. 82-84 ° C, 2-bromo-4-isopropylthioethanesulfonanilide, mp. 62-64 ° C, 2-bromo-4-ethylthioethanesulfonanilide, mp. 77.5-79.5 ° C, 2-fluoro-4-isopropylthiochloromethanesulfonanilide, an oil, 2-bromo-4-tert-butylthiochloromethanesulfonanilide, m.p. 100-102 ° C, 2-iodo-4-ethylthiochloromethanesulfonanilide, mp. = 74-76 ° C, 2.5-dichloro-4-ethylthiochloromethanesulfonanilide, mp. = 132.5-134 ° C, 2.5-dibromo-4-ethylthiochloromethanesulfonanilide, mp. 189-195 ° C, 2.5-dibromo-4-isopropylthiochloromethanesulfonanilide, 15 mp. 132-133 ° C, 2,3-dichloro-4-ethylthiochloromethanesulfonanilide, mp. = 92-94 ° C,

2-bromo-4-isopropylthiochloromethanesulfonanilide, m.p. 56-59 ° C. Example X.

N-chloromethylsulfonyl-chloro-ethylthiochloromethanesulfon anilide.

Chloromethanesulfonyl chloride (60 g, 0.4 mol) is added dropwise to a cold (0-5 ° C) stirred solution of 2-chloro-4-ethylthioaniline (15.1 g, 0.081 mol) in pyridine (104 ml). The solution is stirred at room temperature and poured into ice water and 12N. Stir hydrochloric acid powder. The product is extracted into CKCl2C, washed with water and dried. Removal of the desiccant and solvent gives the crude product. The silica product is obtained as an oil by chromatography on silica gel using methylene chloride as an eluent.

Example XI

2-Chloro-4-ethylthiochloromethanesulfonanilide.

A solution of N-chloromethylsulfonyl-2-35 chloro-4-ethylthiochloromethanesulfonanilide (7.2 g, 0.017 mol) and 85% potassium hydroxide (2.9 g) in methanol is stirred at room temperature for about 800048714. The solvent is removed by evaporation, the residue taken up in hot water, filtered and the filtrate acidified with 12N. hydrochloric acid. The product is collected by filtration and air dried.

Example XII

2-Chloro-4-methanesulfinylchloromethanesulfonanilide.

To a stirred solution of 2-chloro-4-methylthiochloromethanesulfonanilide (1.8 g, 0.0061 mol) in ice vinegar (20 ml) is added 30% Ts hydrogen peroxide (0.0061 mol). The solution is stirred at room temperature overnight, just refluxed and then treated with water. The aqueous mixture is extracted with methylene chloride, washed with water and dried. A yellow oil is obtained by removing the desiccant and solvent. Crystallization from hexane gives a white solid; mp. 99-110 ° C.

Analysis:

Calculated for CgH ^ C ^ NO ^: c 31.8, H 3.0, N 4.6%

Found: C 31.8, H 3.0, N 4.7%.

The following compounds are prepared using the same general method: 2-bromo-4-methanesulfinylchloromethanesulfonanilide, m.p. 108-116 ° C, 2-bromo-4-ethanesulfinylchloromethanesulfonanilide, mp. 157-159 ° C, 2,3-dichloro-4-methanesulfinylchloromethanesulfonanilide, m.p. 153-163 ° C, 2-chloro-4-methanesulfinylmethanesulfonanilide, m.p. 162-165 ° C, 2-chloro-4-ethanesulfinylmethanesulfonanilide, mp. 121-123 ° C, 2-chloro-4-ethanesulfinylethanesulfonanilide, mp. 109-112 ° C, 2-bromo-4-ethanesulfinylmethanesulfonanilide, mp. 119 DEG-121 DEG C., 2-fluoro-4-ethanesulfinylmethanesulfonanilide, m.p. 122-124 ° C, 2-fluoro-4-ethanesulfinylethanesulfonanilide, mp. 128-130 ° C, 2-fluoro-4-methanesulfinylethanesulfonanilide, mp. Mp 111-133 ° C, 2-bromo-4-isopropylsulfinylmethanesulfonanilide, mp. 104-106 ° C, 35 2-bromo-4-isopropylsulfinylethanesulfonanilide, m.p. 118-120 ° C, 2-fluoro-4-methanesulfinylmethanesulfonanilide, mp. = 149-150 ° C, 8000487 15 2-bromo-4-ethanesuX-inyXethanesuXfonaniXide, m.p. 113-115 ° C, 2-fluoro-4-methanesulfinyl chloromethanesulfonaniide, m.p. 118 DEG-122 DEG C., 2-fluoro-4-isopropylsuXfinyXchloromethane, suXfonanilide, 5 mp. 118 DEG-121 DEG C. 2-bromo-4-tert.-butylisyl ethyl chloromethane sulfonamide, snip. 112-115 ° C, 2-iodo-4-ethanesulfinyl chloromethanesulfonanilide, m.p. = 165-167 ° C, 2.5-dichloro-4-ethanesuXfinyXmethanesuXfonaniXide, mp. = 149-150 ° C, 10 2.5 "dichloro-4-ethanesulfonylxxmethanesulfonaniide, m.p. 151-154 ° C, 2,3-dichloro-4-ethanesulfinichloromethanesuiylanide, m.p. 118 DEG-121 DEG C., 2-chloro-4-tert-butyl-thiochloro-methanesulfonamide, 15 m.p. = 89-90 ° C,

Example XIII

2-Chloro-4-methane oxi onyXchXoor methane oxononiXide.

30% hydrogen peroxide (0.0405 moX) is added to a stirred solution of 2-chloro-4-methyXthiochXoromethane sulfonanide (3.0 g, 0.0101 moX) in glacial acetic acid (30 mX). The solution is heated under reflux for 2.5 hours, water is added and the mixture is cooled. The residual precipitate is collected by filtration, washed with water and dried to obtain a white solid; 25 mp. 172-180 ° C.

AnaXyse:

Calculated for CgHgCX ^ O ^: C 30.2, H 2.8, N 4.4%

Found: C 30.2, H 2.8, N 4.4%.

The susceptible compounds were also prepared using this general method: 2-bromo-4-methanesulfonic methyl methanesulfonaniide, m.p. 156-168 ° C, 2-bromo-4-ethanesulfonyl Chloromethanesulfonaniide, m.p. = 120-122 ° C, 35 2-chloro-4-ethanesuXfonyXchXoormethanesuXfonaniXide, mp. * 146-148 ° C,

o f \ O.. r? T

16 2-chloro-4-isopropylsulfonylchloromethanesulfonanilide, m.p. 146-149 ° C, 2-fluoro-4-ethanesulfonylchloromethanesulfonanilide, mp. 143-144 ° C, 5 2-chloro-4-methanesulfonylmethanesulfonanilide, m.p. 167-169 ° C, 2-chloro-4-isopropylsulfonylmethanesulfonanilide, mp. 142-144 ° C, 2-chloro-4-ethanesulfonylethanesulfonanilide, mp. 92-94 ° C, 2-chloro-4-isopropylsulfonylethanesulfonanilide, mp. 115-117 ° C, 2-bromo-4-methanesulfonylmethanesulfonanilide, mp. 170-171.5 ° C, 10 2-bromo-4-ethanesulfonylmethanesulfonanilide, mp. 122-125 ° C, 2-fluoro-4-ethanesulfonylmethanesulfonanilide, mp. 165-167 ° C, 2,3-dichloro-4-methanesulfonylmethanesulfonanilide, m.p. 167-180 ° C, 2-bromo-4-isopropylsulfonyl methanesulfonanilide, m.p. 133-135 ° C, 2-bromo-4-isopropylsulfonylethanesulfonanilide, mp. 110-112 ° C, 2-fluoro-4-methanesulfonylchloromethanesulfonanilide, m.p. 153-155 ° C, 2-fluoro-4-isopropylsulfonylchloromethanesulfonanilide, m.p. 140-142 ° C, 2-bromo-4-tert-butylsulfonylchloromethanesulfonanilide, 20 mp. 169-170 ° C, 2.5-dichloro-4-ethanesulfonylmethanesulfonanilide, mp. 171-174 ° C, 2.5-dichloro-4-ethanesulfonylchloromethanesulfonanilide, mp. 182-183 ° C, 2,3-dichloro-4-ethanesulfonylchloromethanesulfonanilide, mp 164-166 ° C, 2-fluoro-4-methanesulfonylmethanesulfonanilide, mp. 181-183 ° C, 2-bromo-4-ethanesulfonylethanesulfonanilide, mp. 88-91 ° C, 2-iodo-4-ethanesulfonylchloromethanesulfonanilide, m.p. 130-132 ° C. 30 4 8000487

Claims (7)

1. Compounds of the general formula 1, wherein R represents an alkyl group of 1-4 carbon atoms or mono-halomethyl, RT represents an alkyl group of 1-4 carbon atoms, 5. represents halogen or -CF ^, B represents hydrogen or halogen and n represents 0-2, where, when A represents CF 1, B is halogen, as well as salts thereof acceptable in agriculture and horticulture. Compounds according to claim 1, characterized in that R 1 contains a carbon atom. Compounds according to claim 1, characterized in that n is 0. Compounds according to claim 1, characterized in that η is 1. Compounds according to claim 1, characterized in that n is 2. 6. 2-Bromo-4-ethanesulfinylchloromethanesulfonanilide. 7. 2-Bromo-4-ethanesulfonylchloromethanesulfonanilide. 8. 8-Chloro-4-methanesulfinylchloromethanesulfonanilide. 9. 2-Chloro-4-methanesulfonylchloromethanesulfonanilide. 10. 2-Chloro-4-ethanesulfinylchloromethanesulfonanilide. 11. 2-Chloro-4-ethanesulfonylchloromethanesulfonanilide. 12. A method of modifying the growth of plants, characterized in that use is made of one or more compounds as defined in claims 1-11. Preparation for modifying the growth of higher plants, characterized in that it contains one or more compounds as defined in claims 1-11 dispersed in a diluent medium acceptable for agriculture or horticulture. 14. Compounds, preparations and methods as described in the description and / or examples. 8000487 NHSC ^ R "-Ó I s (o) /« Reaction scheme HHZ. NH2 a 8 ~ 0 oi- * i »- '^ SCN SR' (3) T NHSO? R NHSO ^ RN (SOz.R ) t Av ^ ανΛ \ AB "Y (5) (<) Y s (o) -,> rI sr 'sr' Minnesota Mining and Manufacturing Company, Saint Paul, Minnesota, Ver. St. v. America. 8000487