CH631965A5 - 2-Trifluoromethylalkanesulphonanilides substituted in the p position, and agents and methods for modifying plant growth - Google Patents

Description

The invention relates to compounds of the general formula

HNS0oR1

C.

3rd

in which R1 and R2 each represent an alkyl group having 1 to 4 carbon atoms and n is 0 or 1 or 2, with the proviso that R1 and R2 do not simultaneously mean the methyl group, and salts of these compounds.

The new compounds act as modifiers for the plant growth of higher plants and are also herbicidally active. A particularly valuable property of these compounds lies in their ability to destroy rhizomatous wild black millet and sorghum halepense (L. Pers.), Often at doses tolerated by certain crops that are usually contaminated with this weed, for example cotton. The compounds of quite similar structure known from US Pat. No. 3,996,277, in which, according to the above formulas R1 and R2 simultaneously represent the methyl group, also selectively destroy rhizomatous millet in cotton, but do not have the further properties of the compounds according to the invention, For example, a selective activity towards the wild millet in other crops and / or particularly strongly specific, modifying plant growth or also a herbicidal activity.

The invention further relates to an agent for modifying the growth of higher plants, which is characterized in that it contains, as at least one active ingredient component, a new compound of the formula I and salts thereof which are acceptable for agriculture. The compound of formula I mentioned can be present on average in dispersed form and the agent can contain the usual stretching media.

The invention also relates to a method for modifying the growth of higher plants, which is characterized in that a compound of the formula I and salts which are acceptable for agriculture are applied to the plant

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Applies connections. The modification of the growth of higher plants relates in particular to the regulation of plant growth, to its control or to the extermination of plants.

Compounds of general formula I can form salts, i.e. Compounds of the above formula in which H by cation, e.g. an agriculturally compatible cation is replaced. These salts are preferably metal salts, ammonium salts and salts of organic amines and can be prepared by treating the compounds mentioned in their acid form with an appropriate base under mild conditions. The metal salts mentioned include in particular the alkali metal salts, such as lithium, sodium and potassium salts, the alkaline earth metal salts, such as barium, calcium and magnesium salts, and also the heavy metal salts, such as zinc and iron salts, and also other metal salts, such as aluminum salts. Suitable bases for the production of the metal salts are the metal oxides, hydroxides, carbonates, bicarbonates and alkoxides or alcoholates. Some salts can also be prepared by a cation exchange reaction by reacting a salt with an organic or inorganic salt in a cation exchange reaction. The salts of organic amines are primarily salts of aliphatic (for example alkyl), aromatic and heterocyclic amines and the corresponding mixed compounds. Primary, secondary or tertiary amines can be used to prepare these salts; preferably they contain no more than 20 carbon atoms. Such amines are, for example, morpholine, methylcyclohexylamine, glucosamine, amines derived from fatty acids, etc. The amine and ammonium salts can be prepared by reacting the acid form of the compound of the formula I with the corresponding organic base or with ammonium hydroxide. All salts of the type described are useful for agriculture; the specific selection depends on the particular intended use and the economic circumstances. The alkali, alkaline earth, ammonium and amine salts are particularly useful.

The salts of the compounds according to the invention are often prepared by reacting 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 is more convenient to work in a non-aqueous solvent such as an alcohol, acetone, or the like. The solvent is then usually removed from the solution obtained, for example by evaporation under reduced pressure.

The compounds according to the invention can be prepared by the reaction stages described below. The compound (or compound class) specified after each of the numbered stages represents the product of that stage (and, if applicable, the starting product for the next stage).

Method 1

Starting compound: 5-chloro-2-nitrobenzotrifluoride

1) 2-nitro-5-alkylthiobenzotrifluoride (contains the R2 group)

2) 4-alkylthio-2-trifluoromethylaniline

3) N-alkylsulfonyl-4-alkylthio-2-trifluoromethylalkanesulfonanide (contains the grouping —N (S02R1) 2)

4) Compound of the general formula I with n = 0

5) Compound of the general formula I with n = 1 or 2

Method 2

Starting compound: 2-aminobenzotrifluoride

1) 4-Thiocyano-2-trif! Uomethylaniline. This compound can be converted directly into the step 2) compound of method 1

2) N-alkylsulfonyl-4-thiocyano-2-trifluoromethylalkanesulfonani-lid (contains the grouping - N ^ OìR1 ^)

3) Compound of the general formula I with n = 0

Method 3

Starting compound: 2-aminobenzotrifluoride

1) 2-trifluoromethylalkanesulfonanilide (contains R1)

2) 4-bromo-2-trifluoromethylalkanesulfonanilide

3) Compound of the general formula I with n = 0.

The end product of methods 2 and 3, as shown, is of course the same as the product of step 4) according to method 1 and can be converted into the product of step 5) according to method 1.

Step 1) of method 1 is preferably carried out by heating 5-chloro-2-nitrobenzotrifluoride together with an alkanethiol or alkyl mercaptan in a slight excess in a suitable solvent in the presence of the appropriate amount of base. The solvent in which the reactants are soluble is, for example, a lower alcohol such as ethanol. The base is a strong organic or inorganic base. Suitable organic bases are tertiary amines such as N, N-dimethylaniline, triethylamine, pyridine, alkoxides or alcoholates such as sodium ethyl alcoholate and others. Suitable inorganic bases are alkali hydroxides such as sodium hydroxide and potassium hydroxide, calcium hydroxide and others. The product or the compound is isolated using customary methods.

Alternatively, step 1) can be carried out by stirring a solution of 5-chloro-2-nitrobenzotrifluoride and a phase transfer catalyst in methylene chloride with an aqueous basic solution of the alkanethiol. Other solvents such as benzene and dichlorobenzene as well as various catalysts such as organic ammonium salts can also be used. The alkanethiol is usually reacted in dilute (about 4% strength) aqueous base with 0.5 equivalent of 5-chloro-2-nitrobenzotrifluoride, dissolved in methylene chloride, in the presence of triethylbenzylammonium chloride (phase transfer catalyst). However, if a branched thiol, such as 2-propanethiol or 2-methyl-2-butanethiol, is used, additional amounts of base and thiol are required in order to achieve the best possible yields, since side reactions with the methylene chloride occur. This phase transfer reaction is usually preferred when mercaptans other than methanethiol are used, due to substantial amounts of by-products such as occur in the first described process and are often difficult to separate from the desired product.

The reaction in stage 2) is a reduction in the nitro group of the intermediate 2-nitro-5-alkylthiobenzotrif! Uorid. Well-known chemical or catalytic methods are successfully used for this. Raney nickel is a suitable catalyst for the reduction. The product is isolated using standard methods.

In step 3) of method 1, the bis-alkylsulfonylation is obtained by using two or more equivalents of alkanesulfonyl chloride and base in excess. In stage 4) the partial hydrolysis of the bis (alkylsulfonyl) intermediates takes place. This hydrolysis reaction gives high yields when working with strong bases such as potassium hydroxide in methanol.

Alternatively, the precursor compound of stage 3) can also be converted directly into the compound of stage 4) by means of a monoalkyl sulfonation reaction using one equivalent of alkanesulfonyl chloride and one equivalent of base. However, the two-stage process is usually more convenient to carry out and is therefore preferred. Suitable bases for stage 3) and for the monoalkylsulfonylation are organic or inorganic bases such as pyridine, triethylamine, dimethylcyclohexylamine and substituted pyridines.

Step 5) of method 1 is carried out using customary oxidation methods, for example with hydrogen peroxide in acetic acid, with sodium metaperiodate etc. The sulfoxide compound (n = 1) is formed when equimolar amounts of oxidizing agent and reactants are used, while working with 2 mol (or a small excess) of oxidizing agent per mole of reactant immediately receives the sulfone (n = 2).

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In stage 1) of method 2, 2-aminobenzotrifluoride is reacted with hydrogen cyanide (acid) or a salt thereof to form 4-thiocyano-2-trifluoromethylaniline. Suitable salts are alkali salts (sodium or potassium salt), copper (I) and ammonium thiocyanates. The reaction is carried out in the presence of bromine or chlorine and usually also in the presence of an alkali bromide or chloride and a suitable solvent such as methanol. Furthermore, 2-aminobenzotrifluoride can be reacted electrolytically with the thiocyanate in a simple manner.

In stage 2), the product in stage 1) is reacted with an alkane sulfonyl chloride (R1SOzCl) to form the corresponding 4-thio-cyano-2-trifluoromethylalkanesulfonanilide or with an excess of the alkanesulfonyl chloride to form N-alkylsulfonyl-4-thiocyano- 2-trifluoromethylalkanesulfonanilide implemented using the general procedure and the reaction conditions of stage 3) of method 1.

In step 3) the thiocyano group of the product of the previous step is alkylated in the presence of a strong base and the alcohol R2OH. If the preceding product is the N-alkylsulfonyl-4-thiocyano-2-trifluoromethylalkanesulfonanilide, the bis (alkylsulfonyl) group is partially hydrolyzed at the same time. This reaction is carried out under conditions analogous to the hydrolysis in stage 4) of method 1.

It can be seen from the preceding reaction scheme that 4-alkylthio-2-trifluoromethylaniline can be prepared directly from the corresponding 4-thiocyano-2-trifluoromethylaniline, which in turn is formed by step 1) of method 2. This reaction can be carried out using various common procedures. For example, the thiocyano grouping can be alkylated in alcoholic sodium cyanide solution. In this reaction, the alcohol determines the alkyl group. As an alternative, a sodium mercaptide is first formed from the thiocyano group and then alkylated using an alkylating agent such as an alkyl iodide (methyl iodide). The compound obtained is the same as the product of stage 2) according to method 1 and can of course be processed further using the method of method 1.

Stage 1) of method 3 is carried out using the same procedures as in stages 3) and 4) of method 1. Alternatively, this implementation can be carried out in a single stage, as previously stated in the discussion of stages 3) and 4) of method 1. The bromination of the 4-position of the ring and the reaction in which the 4-bromine atom is replaced by the 4-alkylthio group (steps 2) and 3) of method 3) are carried out using known methods. For example, bromine is added to a solution of 2-trifluoromethylalkanesulfonanilide in a water-alcohol solvent with stirring and the thioalkylation step is carried out by heating a mixture of copper-I-thioalcoholate, the 4-bromo compound, pyridine and quinoline in one A mixture of 12N hydrochloric acid and ice water is poured out and the desired compound is isolated therefrom, for example by means of extraction, distillation and / or recrystallization.

The various stages of the production process, as described above, are usually carried out at temperatures from about 0 to 50 ° C., with the exception of the oxidation stages for the preparation of the compounds of the general formula I with n = 1 or 2; the latter are expediently carried out at the reflux temperature. Atmospheric pressure (normal pressure) is usually maintained in all stages.

As mentioned above, the compounds of the general formula I according to the invention have a plant growth-modifying, including herbicidal activity, which is expediently determined using the greenhouse test methods described in US Pat. No. 3,996,277. By modifying plant growth, all deviations from the natural development of the plant, for example defoliation, stimulation, stunting or inhibition, delay, drying out,

Straw shooting, dwarfism regulation or control, etc., understood. This activity which modifies plant growth is generally observed when the compounds according to the invention intervene in certain processes within the plant. If these processes are essential or life-determining, the plant dies if it is treated with a sufficient dose of the new active compound.

The type of activity observed that modifies plant growth is highly dependent on the plant species or cultivars. The most important activities include the following: selective control or eradication of rhizomatous black millet in crops that are usually contaminated with it, for example cotton; Increasing the cane sugar yield with cane sugar. In this application, the active compound is usually applied in an amount of 0.122 to 2.244 kg / ha and about 3 to 12 weeks before the sugar cane is harvested; Delaying grass growth - this is important because the grass has to be cut less frequently; in this case, activity is achieved with doses as low as 0.037 kg / ha applied to growing grass. The maximum application dose for grass depends on the sensitivity of the respective grass under the special conditions. The lowest effective dose is chosen for reasons of economy, usually about 0.112 to 3.366 kg / ha.

The compounds of general formula I, in which R1 is the methyl group and R2 is the ethyl group, and those compounds in which R1 is methyl or ethyl group and R2 is the tert-butyl group, are preferred classes of compounds because of their very high activity.

The compounds of general formula I, in which R1 is the ethyl group and R2 is the methyl group, are a preferred class of compounds because of their ability to selectively destroy rhizomatous millet in cereal or maize fields.

The compounds of general formula I, in which R1 and R2 each represent the ethyl group, are preferred because of their ability to selectively destroy rhizomatous millet in cereal or maize fields and / or in soybean fields.

The compounds of general formula I in which R1 represents the methyl group and R2 represents the isopropyl group are also preferred because of their ability to selectively destroy rhizomatous millet in soybean fields.

The following examples serve to explain the invention in more detail. All parts are by weight unless otherwise stated.

Production Example I 2-nitro-5-ethylthiobenzotrifluorid

A solution of 5-chloro-2-nitrobenzotrifluoride (150 g, 0.67 mol) and benzyltriethylammonium chloride (15 g, 0.067 mol), phase transfer catalyst in methylene chloride (1500 ml) was stirred to a 0 to 5 ° C cold solution from sodium hydroxide (53.2 g,

1.33 mol) and ethanethiol (97.47 g, 1.57 mol) were added to water (1200 ml) in the course of 1 V% to 2 h. The reaction temperature was raised to room temperature and stirred for a further 17 h. By thin layer chromatography on silica gel with 10% ether / 90% petroleum ether (bp 30 to 60 ° C) as a diluent, it was shown that all 5-chloro-2-nitrobenzotrifluoride had reacted. The methylene chloride layer was separated from the aqueous layer and washed with water. The methylene chloride was then evaporated, leaving 2-nitro-5-ethylthiobenzotrifluoride as an oil.

This compound was also obtained using the general method of Example 1 of U.S. Patent No. 3,996,277.

Further compounds which were prepared according to the general process described above are: 2-nitro-5-isopropylthio-benzotrifluoride as an oil, 2-nitro-5-tert.butylthiobenzotrifluorid as an oil.

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Production Example 2

4-ethylthio-2-trifluoromethylaniline

A solution of 64% aqueous hydrazine (48.4 g, 1.5 mol) was added dropwise with stirring to a 50 ° C solution of 2-nitro-5-ethyl-thiobenzotrifluoride in 95% ethanol (1200 ml). After the addition was complete, the mixture was heated under reflux overnight. Thin layer chromatography indicated that all of the nitro compound had been reduced. The reaction mixture was then filtered and concentrated under reduced pressure. The remaining gold-colored liquid was taken up with methylene chloride and washed with water. After the methylene chloride had been evaporated off, the desired compound 4-ethylthio-2-trifluoromethylaniline remained.

This compound was also obtained using the general procedure of Example 2 of U.S. Patent No. 3,996,277. Other compounds which were prepared in the manner just described are: 4-isopropylthio-2-trifluoromethylaniline as an oil, 4-tert-butylthio-2-trifluoromethylaniline, mp. 68 to 70 ° C.

Production Example 3

N-ethylsulfonyl-4-methylthio-2-trifluoromethylethanesulfonanilide

Ethanesulfonyl chloride (16.1 g, 0.125 mol) was added dropwise with stirring to a cold (0.5 ° C) solution of 4-methylthio-2-trifluoromethylaniline (10.4 g, 0.05 mol) in pyridine (31.6 g, 0.4 mol). The solution was stirred at room temperature overnight and then poured into ice water and 12N hydrochloric acid (100 ml) with stirring, whereupon N-ethylsulfonyl-4-methylthio-2-trifluoromethylethanesulfonanilide separated as an oil.

The following connections were made in the same way:

N-methylsulfonyl-4-ethylthio-2-trifluoromethylmethanesulfonanide, mp. 130 to 135 ° C,

N-methylsulfonyl-4-n-propylthio-2-trifluoromethyl methanesulfone anilide as a solid,

N-methylsulfonyl-4-tert-butylthio-2-trifluoromethylmethanesulfonanilide, mp. 91 to 93 ° C.,

N-ethylsulfonyl-4-ethylthio-2-trifluoromethylethanesulfonanilide as a solid,

N-ethylsulfonyl-4-isopropylthio-2-trifluoromethylethanesulfonilide as an oil,

N-n-propylsulfonyl-4-methylthio-2-trifhiormethylpropanesulfone anilide as an oil,

N-n-butylsulfonyl-4-methylthio-2-trifluoromethylbutanesulfonanide as an oil.

Production Example 4

4-methylthio-2-trifluoromethylethanesulfonanilide

A solution of N-ethylsulfonyl-4-methylthio-2-trifluoromethyl-ethanesulfonanilide and 85% potassium hydroxide (10 g, 0.15 mol) in methanol (300 ml) was stirred at room temperature for about 2½ days. Then the solvent was removed under reduced pressure and the residue was taken up in hot water, filtered and the filtrate acidified with 12N hydrochloric acid. The precipitated product was taken up in methylene chloride and dried.

After removal of the drying agent and solvent, an oil was obtained which crystallized on treatment with hexane. Recrystallization from methylene chloride / hexane gave a gold-colored solid with mp 52 to 55 ° C.

Analysis for C, 0H12F3NO2S2:

Calculated: C40, l H 4.0 N4.7%

Found: C39.9 H 4.0 N4.6%

Other compounds prepared in this way: 4-n-propylthio-2-trifluoromethylmethanesulfonanilide, bp 150-156 ° C / 5 mm,

4-ethylthio-2-trifluoromethyl methanesulfonanilide, mp. 50 to 51 ° C,

4-tert-butylthio-2-trifluoromethyl methanesulfonanilide, bp 98 to 101 ° C,

4-ethylthio-2-trifluoromethylethanesulfonanilide as oil, 4-isopropylthio-2-trifluoromethylethanesulfonanilide, mp. 51 to 53 ° C,

4-methylthio-2-trifluoromethylpropanesulfonanilide, mp. 67 to 70 ° C,

4-methylthio-2-trifluoromethylbutanesulfonanilide, mp. 46 to 55 ° C, 4-t-butylthio-2-trifluoromethylethanesulfonanilide, mp. 67 to 69 ° C.

Production Example 5

4-methylsulfinyl-2-trifluoromethylethanesulfonanilide

To a solution of 4-methylthio-2-trifluoromethylethanesulfonanilide (3 g, 0.01 mol) in glacial acetic acid (25 ml) was added 30% hydrogen peroxide (1.13 g, 0.01 mol) with stirring. The solution was stirred at room temperature overnight, just heated to reflux and then treated with water. The aqueous mixture was extracted with methylene chloride, the extract was washed with water and dried. After removing the drying agent and the solvent, a yellow oil was obtained and after recrystallization from methylene chloride / hexane, a white solid.

Analysis for QoH ^ FaNC ^ Sj:

Calculated: C38.0 H 3.8 N4.4%

Found: C38.0 H 3.8 N4.4%

Other compounds prepared in this way: 4-ethylsulfinyl-2-trifluoromethyl methanesulfonanilide as an oil, 4-tert-butylsulfinyl-2-trifluoromethylethanesulfonanilide, mp. 133 to 135 ° C.,

4-ethylsulfinyl-2-trifluoromethylethanesulfonanilide, yellow paste. Production Example 6

4-methylsulfonyl-2-trifluoromethylethanesulfonanilide

To a solution of 4-methylthio-2-trifluoromethylethanesulfonanilide (1.5 g, 0.005 mol) in glacial acetic acid (15 ml) was added 30% hydrogen peroxide (2.3 g, 0.02 mol) with stirring. The solution was heated under reflux for 2 Vi h, water was added and the mixture was cooled. The precipitate obtained was filtered off, washed with water and dried; a white solid with mp 156 to 159 ° C. was obtained.

Analysis for C10Hi2F3NO2S2:

Calculated: C36.2 H 3.6 N4.2%

Found: C36.2 H 3.6 N4, l%

Other compounds prepared in this way: 4-ethylsulfonyl-2-trifluoromethylmethanesulfonanilide, mp. 141 to 144 ° C,

4-propylsulfonyl-2-trifluoromethylmethanesulfonanilide, mp. 155 to 158 ° C,

4-tert-butylsulfonyl-2-trifluoromethylethanesulfonanilide, mp. 143 to 147 ° C,

4-isopropylsulfonyl-2-trifluoromethylmethanesulfonanilide, mp. 134 to 143 ° C,

4-tert-butylsulfonyl-2-trifluoromethylmethanesulfonanilide, mp. 195 to 200 ° C,

4-ethylsulfonyl-2-trifluoromethylethanesulfonanilide, mp. 82 to 86 ° C,

4-methylsulfonyl-2-trifluoromethylpropanesulfonanilide, mp. 152 to 157 ° C,

4-methylsulfonyl-2-trifluoromethylbutanesulfonanilide, mp 93-113 ° C.

Production Example 7

4-thiocyano-2-trifluoromethylaniline

With stirring, became a cold (0 to 5 ° C) solution of 2-aminobenzotrifluoride (6.44 g, 0.04 mol) and sodium thiocyanate

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(9.72 g, 0.12 mol) in methanol (100 ml), a solution of bromine (6.6 g, 0.42 mol) in methanol (25 ml) saturated with sodium bromide was added dropwise. After the addition of the bromine was complete, the solution was stirred for a further 20 min and then poured into water (750 ml) and neutralized with sodium carbonate. The oil obtained was taken up in methylene chloride and dried. After the drying agent and solvent had been separated off, 4-thiocyano-2-trifluoromethylaniline was obtained as an oil which solidified on standing (yield 8.4 g, 96%). A cleaned sample melted at 52 to 55 ° C.

Analysis for C8HsF3N2S:

Calculated: C44.0 H 2.3 N12.8%

Found: C43.7 H 2.3 N 12.9%

Production Example 8 4-methylthio-2-trifluoromethylaniline

A solution of 4-thiocyano-2-trifluoromethylaniline (1.09 g, 0.005 mol) and sodium cyanide (0.125 g, 0.0025 mol) in methanol (50 ml) was refluxed for about 16 h. Methanol was removed from the cold reaction mixture by evaporation under reduced pressure; the residue was taken up in methylene chloride, washed with water and dried. After removing the drying agent and the solvent, the desired compound was obtained as a yellow oil, yield 1 g, 91%.

Other compounds prepared in this way: 4-isopropylthio-2-trifluoromethylaniline as an oil, 4-n-propylthio-2-trifluoromethylaniline as an oil.

Production Example 9

4-methylthio-2-trifluoromethylaniline

A solution of 4-thiocyano-2-trifluoromethylaniline (2.1 g, 0.1 mol) in ethanol (25 ml) was stirred with a solution of sodium sulfide nonahydrate (2.4 g, 0.01 mol) in water (5 ml) and the mixture was heated to 50 ° C. for 40 min. Then methyl iodide (1.55 g, 0.011 mol) was added all at once and the warm mixture was stirred for a further 2 h. Thin layer chromatography on silica gel with 50% hexane / 50% methylene chloride as a diluent alongside an authentic sample showed that all of the thiocyano compound had reacted to form the desired compound.

Production Example 10

4-bromo-2-trifluoromethyl methanesulfonanilide

Bromine (6.7 g, 0.042 mol) was added dropwise with stirring to a solution of 2-trifluoromethyl methanesulfonanilide (prepared from 2-aminobenzotrifluoride analogously to Examples 3 and 4 above) in a mixture of 40 ml of water and 150 ml of ethanol. The reaction mixture was heated under reflux and kept under reflux for 2 h. The mixture was then cooled and the major part of the solvent was stripped off in vacuo. The remaining oil was taken up with methylene chloride (100 ml); Any water still present was separated off in the separating funnel. Then the methylene chloride solution was dried. Removal of the drying agent and methylene chloride gave an oil which solidified on treatment with hexane. The solid was recrystallized from hexane / methylene chloride, mp 62 to 66 ° C.

Analysis for C8H7BrF3N02S:

Calculated: C30.2 H 2.2 N4.4%

Found: C30.5 H 2.2 N4.4%

Production Example 11

4-isopropylthio-2-trifluoromethyl methanesulfonanilide

Copper I-thioisopropylate was prepared by mixing a mixture of isopropyl mercaptan (15.2 g, 0.2 mol), copper I-oxide (14.3 g, 0.1 mol) and ethanol (250 ml) overnight Reflux was stirred. After evaporation of the solvent, the remaining solid was washed with ethanol; Yield 26.6 g.

A mixture of copper I-thioisopropylate (3.1 g, 0.022 mol), 4-bromo-2-trifluoromethyl methanesulfonanilide (6.3 g, 0.0198 mol), pyridine (30 ml) and quinoline (30 ml) became 2 h heated to 190 ° C; then everything had dissolved. The reaction solution was cooled to 100 ° C. and poured out into a mixture of 12N hydrochloric acid and ice water; this mixture was extracted with chloroform. After the chloroform had been evaporated off, an oil remained which was heated for 2 hours with 5% sodium hydroxide solution (300 ml). The basic medium was clarified by treating with coal, washed with methylene chloride and then acidified to give an oil. The oil was extracted with methylene chloride; the combined extracts were dried and stripped to give 4.5 g of product. Distillation gave 2.3 g of product, which passed at 130 to 150 ° C / 5 mmHg and was further purified by recrystallization from hexane / methylene chloride. The desired compound 4-isopropylthio-2-tri-fluoromethyl methanesulfonanilide melted at 56 to 66 ° C.

Analysis for CnH14F3N02S2:

Calculated: C42.2 H 4.5 N4.5%

Found: C41.6 H 4.4 N4.4%

4-n-Propylthio-2-trifluoromethyl methanesulfonanilide, bp. 150 to 156 ° C / 5 mmHg was prepared in the same way.

Production Example 12

4-ethylthio-2-trifluoromethyl methanesulfonanilide

N-methylsulfonyl-4-thiocyano-2-trifluoromethyl methanesulfonanilide (4.5 g, 0.012 mol) made from 4-thiocyano-2-trifluoromethyl anilide (Example 7) using a procedure analogous to Example 3 above, became a solution of 85 % Potassium hydroxide (2.4 g, 0.036 mol) placed in ethanol (100 ml). This solution was stirred at room temperature overnight; then ethanol was evaporated and the residue heated with water. The aqueous mixture was filtered and the filtrate acidified to give an oil. The oil was extracted with methylene chloride and the extract dried and washed with water; after evaporation of the methylene chloride, the desired product was obtained as an oil. In the same way, 4-isopropylthio-2-trifluoromethyl methanesulfonic anilide was prepared and obtained as an oil.

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Claims (4)

631 965 1. A compound of the general formula in which R1 and R2 each represent an alkyl group with 1 to 4 carbon atoms and n is 0 or 1 or 2, with the proviso that R1 and R2 are not simultaneously the methyl group, and their salts. 2. A compound according to claim 1, wherein n is 0. 3. A compound according to claim 1, wherein n is 1. 4. A compound according to claim 1, wherein n is 2. 5. A compound according to claim 1, wherein R1 is the methyl group and R2 is the ethyl group. 6. A compound according to claim 1, wherein R1 is the ethyl group and R2 is the methyl group. 7. A compound according to claim 1, wherein R1 is the ethyl group and R2 is the ethyl group. 8. A compound according to claim 1, wherein R1 is the methyl group and R2 is the isopropyl group. 9. A compound according to claim 1, wherein R1 is the methyl group and R2 is the tert-butyl group. 10. A compound according to claim 1, wherein R1 is the ethyl group and R2 is the tert-butyl group. 11. 4-ethylthio-2-trifluoromethyl methanesulfonanilide according to claim 5. 12. 4-ethylsulfinyl-2-trifluoromethylmethanesulfonanilide according to claim 5. 13. 4-ethylsulfonyl-2-trifluoromethyl methanesulfonanilide according to claim 5. 14. 4-methylthio-2-trifluoromethylethanesulfonanilide according to claim 6. 15. 4-Methylisulfinyl-2-trifluoromethylethanesulfonanilide according to claim 6. 16. 4-methylsulfonyl-2-trifluoromethylethanesulfonanilide according to claim 6. 17. 4-isopropylthio-2-trifluoromethyl methanesulfonanilide according to claim 8. 18. 4-isopropylsulfonyl-2-trifluoromethyl methanesulfonanilide according to claim 8. 19. Agent for modifying the growth of higher plants, characterized in that the agent as at least one active ingredient component, a new compound of formula c 3rd S (0) nR ' in which R1 and R2 each represent an alkyl group with 1 to 4 carbon atoms and n is 0 or 1 or 2, with the proviso that R1 and R2 are not simultaneously the methyl group, and contains their agriculturally acceptable salts. 20. Process for modifying the growth of higher plants, characterized in that a new compound of the formula c. Is applied to the plants 3rd in which R1 and R2 each have an alkyl group with 1 to 4 carbon atoms and n is 0 or 1 or 2, with the proviso that R1 and R2 are not simultaneously the methyl group, and applies their agriculturally acceptable salts.