SE443559B - PLANT GROWTH MODIFICATING 4-ALKYLTIO-2-TRIFLUORMETHYLALKANSULPHONANILIDES AND DERIVATIVES THEREOF AND THE USE OF THESE - Google Patents

Description

7803954-4 2 The compounds of formula I above may form salts, i.e. compounds of the above formula wherein H is replaced by an agriculturally acceptable cation. These salts are metal, ammonium and organic amine salts and can prepared by treating the acid form of the compound with a suitable base under mild conditions. Mix metal hall the compounds of the invention may be mentioned alkali metal (eg lithium, sodium and potassium), the alkaline earth the species metal salts (eg barium, calcium and magnesium) and the heavy metal salts (eg zinc and iron), as well as of other metals, such as aluminum. Suitable bases for use in the preparation of the metal salts grips metal oxides, hydroxides, carbonates, bicarbonates and alkoxides. Some salts are also produced by cation exchange reaction (by reacting a salt according to the invention with an organic or non-organic salt in a cation exchange reaction). The organic amine salts include means the salts of aliphatic (eg alkyl), aromatic and heterocyclic amines, as well as those with a mixture of these types of structures. The amines that are useful in the preparation of the salts according to the invention, can be primary, secondary or tertiary and contain preferably no more than 20 carbon atoms. Such amines include examples morpholine, methylcyclohexylamine, glucosamine, amines derived from fatty acids, etc. The amine and ammonium salts can be prepared by reacting the acid form with the suitable organic base or ammonium hydroxide. All of them the above salts are agriculturally acceptable and the salt chosen depends on the particular use and on economic considerations. Particularly useful are the alkali metal salts, the alkaline earth metal salts, the ammonium salts and the amine salts.

The salts of the invention are often formed by react the precursors in aqueous solution. This solution can evaporated to give the salt of the compound, usually as a dry powder. In some cases it may be more appropriate to use a non-aqueous solvent, such as alcohols, acetones, etc. The resulting solution is treated 7803934-4 in 3 then to remove the solvent, for example by evaporation at reduced pressure.

The compounds of the invention may be prepared by following reaction sequences. The compound (or class of associations), which are indicated after each numbered step, constitutes the product of this step (and the starting material for the next step, if any).

Method l Starting compound: 5-chloro-2-nitrobenzotrifluoride (1) 2-Nitro-5-alkylthiobenzotrifluoride (containing R2 group) (2) 4-alkylthio-2-trifluoromethylaniline (3) N-alkylsulfonyl-4-alkylthio-2-trifluoromethylalkane sulfonanilide (containing part -N (SO 2 R 1) 2) (4) the compound of formula I, wherein n is 0 (5) the compound of formula I, wherein n is 1 or 2.

Method 2 Starting compound: 2-aminobenzotrifluoride (l) 4-Thiocyano-2-trifluoromethylaniline Note: this compound can be converted directly to the product in step (2) according to method 1. (2) N-alkylsulfonyl-4-thiocyano-2-trifluoromethylalkane euifenaniiia (containing part -N (so2n1) 2) (3) the compound of formula I where n is 0.

Method 3 Starting compound: 2-aminobenzotrifluoride (1) 2-Trifluoromethylalkanesulfonanilide (containing RI Group) (2) 4-bromo-2-trifluoromethylalkanesulfonanilide (3) the compound of formula I where n is 0.

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

Step (1) according to method 1 is performed by heating -chloro-2-nitrobenzotrifluoride together with a small excess of an alkanethiol in a suitable solvent in presence of the applicable amount of base. The solvent is a solvent in which the reactants are soluble, such as 7803934-4 ' 4 a lower alkanol, eg ethanol. The base is a strong organic or inorganic base. Suitable organic bases are tertiary amines such as N, N-dimethylaniline, triethylamine, pyridine, alkoxides such as sodium ethoxide and the like. Suitable o- ' organic bases are alkali metal hydroxides, such as sodium and potassium hydroxides, calcium hydride and the like. Product isolated by conventional methods.

Alternatively, step (1) can be performed by stirring one methylene chloride solution of 5-chloro-2-nitro-benzotrifluoride and a phase transfer catalyst with an aqueous base solution of the alkanethiol. Other solvents, such as benzene and dichlorobenzene, and various catalysts, such as organic ammonium salts, can also be used. Usually react the alkanethiol is diluted in a dilute (about 4%) aqueous base with 0.5 equivalents of 5-chloro-2-nitrobenzotrifluoride dissolved in methylene chloride in the presence of triethylbenzylammonium chloride. (phase transfer catalyst). When a branched thiol, such as 2-propanethiol or 2-methyl-2-butanethiol, used is required however, additional amounts of base and thiol for best replacement due to side reaction with the methylene chloride. This phase transfer reaction is usually preferred when other captans other than methanethiol are used due to significant by-products formed during the first-described process late (which are often difficult to separate from the desired one the product). _ The reaction in step (2) is a reduction of the nitrogroup. pen of the intermediate 2-nitro-S-alkylthiobenzotrifluoride.

Chemical or catalytic methods known in the art niken, are successful. Raney nickel is a suitable lysator for the reduction. The product is isolated by means of conventional methods.

In step (3) according to method 1, bis (alkyl sulpho- using two or more equivalents of the alkanesulfonyl chloride and excess base. Step (4) is the partial hydrolysis of bis (alkylsulfonyl) the associations. This is a base hydrolysis reaction with high exchange using a strong base, such as potassium hydroxide and methanol. 7803934-4 Alternatively, the precursor can be converted in step (3) directly to the product in step (4) using a mono- (alkylsulfonylation) reaction using an equivalent valent of the alkanesulfonyl chloride and an equivalent base.

However, the two-step process is usually easier to perform and is preferred. Suitable bases for step (3) and for mono- (alkylsulfonylation) are organic or inorganic bases, such as pyridine, triethylamine, dimethylcyclohexylamine and substituted pyridines.

Step (5) of method 1 is performed using con- conventional oxidation methods; such as hydrogen peroxide in vinegar acid, sodium metaperiodate and the like. The sulfoxide compound (n = 1) is formed when equimolar amounts of the oxidizing agent and the reactant is used, while the sulfone (n = 2) is prepared directly using 2 moles (or a small excess shot) of the oxidizing agent per mole of the reactant.

The reaction according to step (1) in method 2 includes reaction between 2-aminobenzotrifluoride and hydrogen cyanide or a salt thereof to form 4-thiocyano-2-trifluoro- methylaniline. Suitable salts include alkali metal (sodium or potassium), cuprous and ammonium thiocyanates.

The reaction is carried out in the presence of bromine or chlorine and also in the presence of an alkali metal bromide or chloride and a suitable solvent such as methanol. The 2-aminobenzotrifluoride can also be simply reacted. electrolytically with the thiocyanate.

Step (2) involves reaction between the product from step (1) and an alkanesulfonyl chloride (R1SO2Cl) to give the corresponding 4-thiocyano-2-trifluoromethylalkane sulfonanilide or with an excess of alkanesulfonyl the chloride to form N-alkylsulfonyl-4-thiocyano-2- -trifluoromethylalkanesulfonanilide, using the river general procedure and reaction conditions at step (3) according to method 1.

Step (3) involves alkylation of the thiocyano moiety of the product from the previous step in the presence of a strong base and the alcohol RZOH. When the previous product is N-alkylsulfonyl-4-thiocyano-2-trifluoromethylalkanesulfonyl 7803934-4 '15 6 anilide, is simultaneously hydrolyzed to bis (alkylsulfonyl) group pretty partial. The conditions under which this reaction are analogous to those in the hydrolysis reaction in steps (4) in method l.

It appears from the previous reaction scheme that 4-Alkylthio-2-trifluoromethylanilines can be formed directly from the corresponding 4-thiocyano-2-trifluoromethylaniline, which is prepared by step (1) according to method 2. This reaction can be performed using various conventional methods faranden. For example, the thiocyano moiety can be alkylated in an alcohol holic sodium cyanide solution. In this reaction, more the alcohol alkyl group. Alternatively, captide is first formed from the thiocyano moiety and can then be alkylated. using an alkylating agent, such as a alkyl iodide (methyl iodide). The compound obtained is the the same as the product in step (2) according to method 1 and can » of course further treated by the procedures of method l. _ Step (1) of method 3 is performed using the procedure procedures, which are identical to those in steps (3) and (4) in method l. Alternatively, it can be performed in a single step, as indicated earlier in the discussion of steps (3) and (4) in method 1. The bromination of the 4-position of the ring and the reaction to replace the 4-bromine atom with the 4-alkyl- part (steps (2) and (3) in method 3) are performed using reversal of known procedures. For example, bromine can be added a stirred solution of the 2-trifluoromethylalkanesulfonanilide in a water-alcohol solvent, and thioalkylation the step can be performed by heating a mixture of cuprothioalkoxide, the 4-bromo compound, pyridine and quinoline, after which the whole is poured into a mixture of acid and wet ice and the desired product is recovered, e.g. by extraction, distillation and / or recrystallization.

The various steps in the methods of the invention is normally carried out at about 0-50 ° C, except for oxidizing (for the formation of the compounds of formula I where n is 1 or 2), which is suitably carried out at reflux the temperature. All steps are usually performed at atmospheric print. 7803934-4 7 As previously stated, the compounds according to the invention (of formula I) plant growth modifier, the concept of herbicide, activity (which is suitably determined by so-called screen method tests with regard to greenhouse using it in U.S. Pat. 3,996,277 test procedure). The one specified here the plant growth modification consists of all deviations from natural development, such as defoliation, stimulation, inhibition, dehydration, shrinkage, regulation and the like. This plant growth modifying activity is generally observed when the compounds of the invention begin to act certain processes in the plant. m these processes are essential, the plant will die if treated with one adequate dose of the compound.

The observed type of growth-modifying activity The variety varies greatly among different types of plants. Among the particularly important activities are the following: Selective control of rhizomartate Johnson grass in crops, which the Johnson grass usually haunts, such as cotton. increase in sugar yield in sugar cane. In this case, suitably, the compound is usually applied in an amount of about 0, o1-o, 2 g / mz at about 3-12 weeks before cutting off the sugar cane.

Inhibition of grass growth (which is valuable, as it reduces the number of times the grass has to be mowed).

Activity is obtained at doses as low as 4 mg active ingredient per m2 on growing grass. The maximum dosage on grass depends on the sensitivity of the grass during the the things. From an economic point of view, the lowest the effective dosage, usually about 0.1-0.3 g / m 2.

The compounds of formula I, wherein R 1 is methyl and R 2 is ethyl, and the compounds wherein R 1 is methyl or ethyl and R 2 is tert-butyl, being preferred classes due to their high level of activity. ' The compounds of formula I, wherein R 1 is ethyl and R 2 is methyl, constitute a preferred class because of their ability to selectively control Johnson grass in cornfields.

The compounds of formula I, wherein R 1 is ethyl and R 2 is 7803934-4 8 -ethyl, is a preferred class because of their ability to control rhizomartateJohnsongrass selectiveti.grains- and soybean fields. 2 1 is methyl and R Compounds of formula I, wherein R is isopropyl, is a preferred class because of their ability to control rhizomartate Johnson grass selectivity soybean field. ' The following examples are given for the purpose of further illustrate the present invention, but the examples are by no means intended to limit the scope of the invention. All parts refers to weight, unless otherwise specifically stated.

EXAMPLE 1 2-Nitro-5-ethylthiobenzotrifluoride.

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) to a cold (0-5 ° C), stirred solution of sodium hydroxide (53.2 g, 1.33 mol) and ethanethiol (97.47 g, 1.57 mol) in water (1200 ml) for a period of 1.5-2 hours. The mixture was allowed to warm to room temperature and stirred for 17 hours.

Thin layer chromatography on silica gel with 10% ether - 90% petroleum ether (b.p. 30-É0 ° C) diluent indicated that all 5-chloro-2-nitrobenzotrifluoride had reacted. Methy- the chlorine chloride layer is separated from the water layer and washed with water. The methylene chloride was removed by evaporation, whereby 2-nitro-5-ethylthiobenzotrifluoride remains was left as an oil.

This compound was also prepared using the general method of Example 1 of U.S. Pat. scripture 3 996 277.

Additional compounds, which were also prepared with using the general method of Example 1, the jande: 2-nitro-5-isopropylthiobenzotrifluoride, and oil, 2-nitro-5-tert-butylthiobenzotrifluoride; an oil.

EXAMPLE 2 4-Ethylthio-2-trifluoromethylaniline. A 64% aqueous solution of hydrazine (48.4 g, 1.5 mol) 7803934-4 9 was added dropwise to a warm (50 ° C), stirred solution of 2-Nitro-5-ethylthiobenzotrifluoride in 95% ethanol (1200 ml).

After all the hydrazine had been added, the reaction was heated. the mixture under reflux overnight. Thin layer chromatography indicated that all the nitro compound rats. The reaction mixture was then filtered and concentrated under reduced pressure. The remaining, gold the colored liquid was taken up in methylene chloride and washed with water. The methylene chloride was removed by evaporation and leaving the product, 4-ethylthio-2-trifluoromethyl- aniline. ' This compound was also prepared using the general method of Example 2 of U.S. Pat. scriptures 3 996 271. ' Additional compounds, which were also prepared with using the general method of Example 2, is as follows: 0 4-isopropylthio-2-trifluoromethylaniline, and oil, 4-tert-butylthio-2-trifluoromethylaminoin, m.p.

EXAMPLE 3 N-ethylsulfonyl-4-methylthio-2-trifluoromethylethanesulfonyl anilide.

Ethanesulfonyl chloride (16.1 g, 0.125 mol) was added dropwise. to a cold (Ö, 5 ° C), stirred 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, poured into ice water and 12 N hydrochloric acid (100 ml) with stirring to give N-ethylsulfonyl-4-methyl- thio-2-trifluoromethylethanesulfonanilide in the form of an oil.

Additional compounds prepared using using the same general methodology, are as follows: N-methylsulfonyl-4-ethylthio-2-trifluoromethylmethanesulfonyl anilia, mp 130-13s ° c. _ N-methylsulfonyl-4-n-propylthio-2-trifluoromethylmethanesulfonyl anilia, a solid. ' N-methylsulfonyl-4-tert-butylthio-2-trifluoromethylmethane sulfonanilide, mp 91-93 ° C. 7803934-4 'N-ethylsulfonyl-4-ethylthio-2-trifluoromethylethanesulfonyl anilide, a solid.

N-ethylsulfonyl-4-isopropylthio-2-trifluoromethylethane sulfbnanilide, an oil.

N-n-propylsulfonyl-4-methylthio-2-trifluoromethylpropane sulfonanilide, an oil. ' N-n-butylsulfonyl-4-methylthio-2-trifluoromethylbutanesulfonyl anilide, an oil.

Exemgel 4 _ 4-Methylthio-2-trifluoromethylethanesulfonanilide.

A solution of N-ethylsulfonyl-4-methylthio-2-trifluoro- methyl ethanesulfonanilide and 85% potassium hydroxide (10 g, 0.15 mol) in methanol (300ml) was stirred for about 2.5 days at room temperature. The solvent was evaporated under reduced pressure. pressure and the residue was taken up in hot water, filtered and then acidified with 12 N hydrochloric acid. Product was taken up in methylene chloride and dried. Removal of the desiccant and the solvent gave an oil which crystallized lysed on treatment with hexane. Recrystallization from ' methylene chloride-hexane gave a gold solid with a melting point of sz-ss ° c._ ' Analysis: % C% H% N Calculated for ci0ul2F3No2s2 = 40.1; 4.0; 4.1 Found: 39.9; 4.0; 4.6 Additional compounds prepared using of the general method of Example 4, was as follows: 4-n-propylthio-2-trifluoromethylmethanesulfonanilide, k.p. iso-1s6 ° c / s mm f 4-ethylthio-2-trifluoromethylmethanesulfonanilide, mp 50-51 ° C .. 4-tert-butylthioyl-2-trifluoromethylmethanesulfonanilide, mp 98-110 ° C. _ 4-ethylthio-2-trifluoromethylethanesulfonanilide, an oil. 4-isopropylthio-2-trifluoromethylethanesulfonanilide, mp 51-53 ° C. 7 4-methylthio-2-trifluoromethylpropanesulfonanilide, mp 67-70 ° C. 4-methylthio-2-trifluoromethylbutanesulfonanilide, mp 46-5500. 4-t-butylthio-2-trifluoromethylethanesulfonanilide, mp 67-69 ° C. 7803934-4 ll EXAMPLE 5 4-methylsulfinyl-2-trifluoromethylethanesulfonanilide.

To a stirred solution of 4-methylthio-2-trifluoro- methyl ethanesulfonanilide (3 g, 0.01 mol) in glacial acetic acid (25 ml) 30% hydrogen peroxide (1.3 g, 0.01 mol) was added. Solution stirred overnight at room temperature, preheated cis to reflux and then treated with water. The the aqueous mixture was extracted with methylene chloride, washed with water and dried. Removal of drying the solvent and the solvent of a yellow oil. Crystallization from methylene chloride-hexane gave a white solid.

Analysis: % C% H% N H12F3NO2S2: 38.0; 3.8; 4.4 Found: 38.0; 3.8; 4.4.

The following compounds were also prepared using Calculated for CIO using the same general method: 4-ethylsulfinyl-2-trifluoromethylmethanesulfonanilide, an oil. 4-tert-butylsulfinyl-2-trifluoromethylethanesulfonanilide, mp 133-13s ° c. 4-ethylsulfinyl-2-trifluoromethylethanesulfonanilide, a yellow pasta.

EXAMPLE 6 4-methylsulfonyl-2-trifluoromethylethanesulfonanilide.

To a stirred solution of 4-methylthio-2-trifluoromethyl- ethanesulfonanilide (1.5 g, 0.005 mol) in glacial acetic acid (15 ml) 30% hydrogen peroxide (2.3 g, 0.02 mol) was added. The solution heated at reflux for 2.5 hours, water was added and the mixture is cooled. The resulting precipitate was collected by filtration, washed with water and dried to give a white solid with a melting point of 156-15900.

Analysis: % C% H § N H1F3NO4S2: 36.2; 3.6; 4.2 Found: 36.2; 3.6; 4.1 The following compounds were also prepared using Calculated for C10 using the same general method: 7803934-4 IS 12 4-ethylsulfonyl-2-trifluoromethylmethanesulfonanilide, mp 141-144 ° C. 4-propylsulfonyl-2-trifluoromethylmethanesulfonanilide, mp 155-1ss ° C. 4-tert-butylsulfonyl-2-trifluoromethylethanesulfonanilide, mp 143-147 ° C. 'g 4-isopropylsulfonyl-2-trifluoromethylmethanesulfonanilide, mp 134-143 ° C. 4-tert-butylsulfonyl-2-trifluoromethylmethanesulfonanilide, mp 195-2oo ° C. _ - 4-ethylsulfonyl-2-trifluoromethylethanesulfonanilide, mp az-ss ° c. . 4-methylsulfonyl-2-trifluoromethylpropanesulfonanilide, mp 152-1s7 ° c. '' 4-methylsulfonyl-2-trifluoromethylbutanesulfonanilide, mp 93-113 ° C.

EXAMPLE 7 4-Thiocyano-2-trifluoromethylaniline. _ To a cold (0-5 ° C), stirred solution of 2-aminobenzo trifluoride (6.44 g, 0.04 mol) and sodium thiocyanate (9.72 g, 0.12 mol) in methanol (100 ml) was added dropwise to a solution. of bromine (6.6 g, 0.42 mol) in methanol (25 ml) saturated with sodium bromide. The solution was stirred for 20 minutes followed by addition of bromine and then poured into water (750 ml) and neutralized with sodium carbonate. The oil obtained was taken up in methylene chloride and dried. Removal of drying and the solvent gave 4-thiocyano-2-trifluoromethyl- aniline in the form of an oil, which solidified when allowed to stand (8.4 g, 96% yield). A purified sample had a melting point of 52-55 ° C and the following analysis. ' Analysis: \ % C% H% N Calculated for C 8 H 5 F 3 N 2 S: 44.0; 2,; 12.8 43.7; 2, 12.9.

Found: 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) 7803934-4 13 in methanol (50 ml) was refluxed for about 16 hours. Methanol was removed from the cold reaction mixture by steam at reduced pressure, the residue was taken up in methylene chloride, washed with water and dried. Removal of the desiccant and the solvent gave the product as a yellow oil (1 g, 91% yield).

The following additional compounds were prepared by reversal of the same general method: 4-isopropylthio-2-trifluoromethylaniline, and oil 4-n-propylthio-2-trifluoromethylaniline, an oil.

EXAMPLE 9 4-methylthio-2-trifluoromethylaniline prepared by reversal of an alternative procedure.

A solution of 4-thiocyano-2-trifluoromethylaniline (2.1 g, 0.01 mol) in ethanol (25 ml) was added to a stirred solution of sodium sulfide nonohydrate (2.4 g, 0.01 mol) in water (5 ml) and the mixture was heated (50 ° C) for 40 minutes. Methyl- iodide (1.55 g, 0.011 mol) was added to the hot reaction medium. mixing at once and stirring was continued for 2 hours; Thin layer chromatography on silica gel with SO% hexane - 50% methylene chloride as diluent showed together with a authentic test, that all the thiocyano compound reacted for to give the desired product.

EXAMPLE '10 ' 4-bromo-2-trifluoromethylmethanesulfonanilide. _ To a stirred solution of 2-trifluoromethylmethanesulfonic acid anilide (prepared from 2-aminobenzotrifluoride using procedures analogous to those of Example 3 and 4) in a solvent mixture of water-ethanol (40 ml - 150 ml) was added bromine (6.7 g, 0.042 mol) dropwise. Reactional the mixture was heated »then to reflux and reflux The reaction was continued for 2 hours. The reaction mixture was cooled and placed under vacuum to remove most of it the solvent. The remaining oil was taken up in methylene chloride (100 ml) and residual water were removed with a separatory funnel, and the methylene chloride solution was dried. Remove of the desiccant and the methylene chloride gave an oil which solidified on treatment with hexane. The solid recrystallizes 7803934-4 _ 14 was removed from hexane-methylene chloride and had a melting point of 62 ° C.

Analysis: _% c sa su Calculated for c 8 H 7 BrF 3 No 2 S = 30.2; 2.2; <4.4 Found: - 30.5; 2.2; 4.4.

EXAMPLE ll 4-Isopropylthio-2-trifluoromethylmethanesulfonanilide.

Cuprothioisopropoxide was prepared by stirring a mixture of isopropyl mercaptan (1.5.2 g, 0.2 mol), kurpoooxide (14.3 g, 0.1 mol) and ethanol (250 ml) at flow overnight. Removal of the solvent by evaporation and washing of the remaining solid with ethanol gave 26.6 g of product A mixture of cuprothioisopropoxide (3.1 g, 0.022 molL) 4-Bromo-2-trifluoromethylmethanesulfonanilide (6.3 g, _ 0.09898 mol), pyridine (30 ml) and quinoline (30 ml), heated was taken at 190 ° C for 2 hours after dissolution was reached. Reactive The ionic solution was then cooled to 10 ° C and poured into one mixture of 12 N hydrochloric acid-wet ice and the mixture ex- was treated with chloroform. The chloroform was evaporated and it the residual oil was heated for 2 hours with 5% sodium oxide (300 ml). The basic medium was clarified by treatment. charcoal, washed with methylene chloride and acidifying was then added to give an oil. The oil was extracted with me-_ tylene chloride and the combined extracts were dried and stripped. to give 4.5 g of product. Distillation gave 2.3 g product (mp 130-1S0 ° C / 5 mmHg), which was further purified by recrystallization from hexane-methylene chloride. It is- product, 4-isopropylthio-2-trifluoromethylmethanesulphide phonanilide, had a melting point of 56-66 ° C.

Analysis: % c% H.% N Calculated for c 11 H 14 F 3 No 2 S 2 = 2 42.2; 4.5; 4.5 Found: 41.6; 4.4; 4.4. 4-n-propylthio-2-trifluoromethylmethanesulfonanilide, med a melting point of 150-165 ° C / 5 mmHg, was also prepared with use of the same general method. 7803934-4 \ EXAMPLE 12 4-ethylthio-2-trifluoromethylmethanesulfonanilide.

N-methylsulfonyl-4-thiocyano-2-trifluoromethylmethanesul- phonanilide (4.5 g, 0.012 mol), prepared from 4-thio- cyano-2-trifluoromethylaniline (according to Example 7) with use of a method which is analogous to that of the pile 3, was added to a solution of 85% potassium hydroxide (2.4 g, 0.036 mol) in ethanol (100 ml). This solution was stirred at room temperature overnight, the ethanol evaporated was then dissolved and the residue was heated with water. The water The mixture was filtered and the filtrate was acidified. was given to give an oil. Extraction of the oil with methylene chloride, drying, washing with water and removal of the methylene chloride gave the desired product in the form of a oil. ' 4-Isopropylthio-2-trifluoromethylmethanesulfonanilide (an oil) was also prepared using this preparation. farande.

PLANT GROWTH REGULATORY HERBICID INFORMATION Information is presented in Examples 13-16 regarding the biological activity of a number of compounds according to the invention and also some known compounds. each of the compounds is designated in these examples with a three-digit number, specifying: its structure lucky. Thus, with reference to formula I, the first shows the number of carbon atoms in the group R1, the second digit shows the number of carbon atoms in the group R2 and the third the number shows the value of n. The known compounds are given first followed by compounds of the invention, which at least structurally from the known compounds (120-122 and 210-212) and thereafter by other compounds according to the invention. The associations are as follows: 110. 4-Methylthio-2-trifluoromethylmethanesulfonanilide (the compound of Example 4 of U.S. Patent 3,996,277) 112. 4-Methylsulfonyl-2-trifluoromethylmethanesulfonanilide (the compound of Example 6 of U.S. Patent 3,996,277) 7803934-4 16 120. 4-Ethylthio-2-trifluoromethylmethanesulfonamide (compound of Example 4) 121. 4-Ethylsulfinyl-2-trifluoromethylmethanesulfonanilide (compound according to the first preparation after pel 5) _ 122. 4-Ethylsulfonyl-2-trifluoromethylmethanesulfonanilide (compound according to the first preparation after pel 6) 210. 4-Methylthio-2-trifluoromethylethanesulfonanilide (compound of Example 4) 211. 4-Methylsulfinyl-2-trifluoromethylethanesulfonanilide (compound of Example 5) 212. 4-Methylsulfonyl-2-trifluoromethylethanesulfonanilide (compound of Example 6) 220. 4-Ethylthio-2-trifluoromethylethanesulfonanilide (the fourth preparation after example 4) 222. 4-Ethylsulfonyl-2-trifluoromethylethanesulfonanilide (the sixth preparation after Example 6) 130. 4-Isopropylthio-2-trifluoromethylmethanesulfonanilide (compound of Example 11) 132. 4-Isopropylsulfonyl-2-trifluoromethylmethanesulfonanilide (the fourth preparation after example 6) 140. 4-tert-butylthio-2-trifluoromethylmethanesulfonanilide (the third preparation after Example 4) 142. 4-tert-butylsulfonyl-2-trifluoromethylmethanesulfonanilide (the fifth preparation after Example 6) 230. 4-Isopropylthio-2-trifluoromethylethanesulfonanilide (the fifth preparation after Example 4) 240. 4-tert-butylthio-2-trifluoromethylethanesulfonanilide (the eighth preparation after example 4) 242. 4-tert-butylsulfonyl-2-trifluoromethylethanesulfonanilide (the third preparation after Example 6).

EXAMPLE 13 Herbicidal activity - selective control of rhizomartate Johnson grass in the presence of cotton, corn and soybeans 7803954-4 17 The following pre-emergence greenhouse tests show that some compounds of the present invention control established rhizamutate Johnson grass (Sorghum halepense (L. Pers.)) Under application conditions that are tolerated of cotton, corn and soybeans. A formerly known association with similar chemical structure behaves in a similar way with respect to cotton but not with respect to maize and soybeans.

The test was performed as follows: Low plastic planting boxes that were 12 x 20 x 2 inches was used for the test. Each was filled with pasteurized soil 0.75 inches from the top edge. A generous handful Johnson grass rhizaua: buried throughout the plantation the area of the box. The soil was packed and 30 grains of each corn, cotton and soybean were placed in three rows ten each. Another quarter of an inch of soil was added, which covered all the seeds.

The planting boxes were immediately sprayed with diluted compositions of the indicated compounds at given conditions (calculated as pounds of the compounds per country). Applied ratios were 2, 1, 0.5 and 0.25 pounds per acre. Three repetitions of each relationship and compound was used. The containers were placed in a plant house and water access as needed.

Six weeks after treatment, they were evaluated with respect to growth inhibition and phytotoxicity in holding to untreated control containers. Grading the schedule and the results obtained were as follows: GROWTH INHIBITING EVALUATION A - equal to the control B - easy to l / 4 growth inhibition C - moderate 1/4 to 1/2 growth inhibition D - 1/2 to 3/4 growth inhibition E - 3/4 to complete growth inhibition PHYTOTOXICITY EVALUATION l - no damage or normal crop 2 - slight damage or slight reduction of the crop 7803934-4 18 3 - moderate damage or moderate reduction of the crop 4 - serious damage or severe reduction of the crop - all plants killed or no crop. 1 Apply amount of toxic evaluations rhizome Johnson- goose pounds per association acres 2 112 2.0 1.0 0.5 0.25 2.0 1.0 0.5 0.25 2.0 1.0 0.5 0.25 2.0 1.0 0.5 0.25 211 130 132 v ur o ta n ra U nu U c: m ru U ru m E Growth inhibition and phyto- l-'l-'NNNNhâNNNwhl-blßubuß cotton W ha P üviv w Sv W 9! W> * 1> 9 ä fl tv v r- r- h- r- h- | - | ~ r- w- PI rf r- »I h- h- | ~ maize E 5 OOUUUWNWPWPUNEUH na us as as n-.u .u un | - r- ns a-n 4 »ua E PFWUIPZPIPUMHMIIIUIIIM ° iâ2§22š. l-'l-'NNNNNNhnßubnbnbnlbab-Ih EXAMPLE 14 Herbicidal activity - selective control in different crop-weed combinations a number of An effective selective herbicide in a given herbicide -crop combination is one that will control or eradicate weeds in an application condition, at which it is tolerated by the crop (ie the crop is the main objectively unaffected). 7803934-4 3 19 The following weed and crop species were planted in tangular low plastic planting boxes containing pastas risered sandy loam.

Weed- Grass rhizomes Cataracts Gröggg Gooseberry Johnson- Nut Grass Cotton Wild oats grass Corn Loose grass Soybeans Chicken wheat Rice Sorghum Sugar beet The planting boxes were immediately sprayed with dilute compositions of the indicated compounds at given conditions (calculation in pounds by the association per acres). The applied amounts were 2, 1, 0.5, 0.25 and £ 0.125 per acre. Two repetitions of each amount and compound were used. The containers were placed in a greenhouse and watered as needed.

Four weeks after treatment, they were evaluated in relation to untreated control containers. Out- the valuation schedule and the results obtained were jande: HERBICID EVALUATION WITH REGARD TO WEEDS E = excellent, 90-100% dead G = good, 70-90% dead F = acceptable, 60-70% dead P = poor, less than 60% dead TOLERANCE OR RESPONSIBILITY OF CROPS FOR TREATMENT LINGARNA S = susceptible - shows damage, reduction of the crop or phytotoxic growth. l T = tolerant - no discernible difference in ratio to untreated control. 7803934-4 Pre- Quantity Los fi e- oats * grass Chickens- Johnson- Beef- Soy- Sugar- millet grass grass Cotton Corn hen Wheat Rice Sorrel beets (pound Goose- Wild- acres) herb ning E-fBBBBBEIE-'FE-IE-IBBHE-'E- * HHHBHC-IBBE-IHI-IE-UE-O WE-IE- * E-WEH UJ-UJVJUIE-GVJVJWUJUJVJUJUIVJVJWVJUJVJVJWWWCDE-'E-IFÛVJVJVIEWHE-IE- * B VJVJUJE- * E- * VJZÛVJVJE-IUJUJUÄVJE-IU) UIUIIVJVJUJKDWUJE-'WVJVIVJWVJEIE- * E-'H WWW) VJE-IVÄVJIÛVIHV) VJUIWUJUJIÛUJVIVIVJUIVJUIVJUIVJIÅE-GE-'VJE-'E-'l-IH UJf-QIDI / lf / JBQWVJI / JV) VJVJVJVJVIVJVJVIVJE- fl E-IE-'E-IHC-OE-'E-'l- * FFIE-IE-IHE-IH UIVJVIVIBUIUJVJWUJWHERE-IV! VJE-OE-IHWI / JWWBE-IE-IE- fl i-'EIE-IFEIFH F * E-'BBE-'E-'E- * E- * EIE-lE-IE- * E-lE-'C- fl E-'E-IEGE-IBE-IE- * E-'BE-IF- IE-GE-IE-'I-'E-'HHHE-I 4 U fl n fl- aßa fl a flflfi f fl ß-D-n fi- aBJErJLNLUUßnNDuBJUL fl- ß fl nlø fl- n fl ulhâ-: Dn fl nih fl- N E fl BJUEh fl- IIJWE fl OLuüJIzJWI-XJEIEYJÖOÖUObDuLlJ-CLD-LLO-nlL fl- L fi- L E fl E fl LD-LWBJNOLEIJ fi JhJ fl- alhi flfi JBJE fl Cl-EIJOll-n fl n fi-: UUD-D-Bn fl q fl qlll fl- Q. lL fl- Lß-øß-oülítlf-ÜIJÜCÜLIJEYJLLBJi fl ivJC fl O fi JC fl Uß-a fl- nDnO-O-a fi- aß-BJWO-ß-m EIUO- »D-: D-: BIEIJEIJIÜÜEIJErJE flfi JLlåIIJf fl CIJ fi JC fl NULD-» fl nll- fi u fl a fl a fl n fi- nßußnß-n D-nß- fl- D-ß-E flfi- Lß fl mih fl nßn fl- Fh fi- ND-LQ-BJLIJLLLLLLNQLLLD-nß fl- a ln th LUN LUN L L N N L N N LDN l L N N-UN OOL fi Nr-IOOLONHOOl fi NI-IOOL fi Nr-100mN fi QOmNHOQmNr-I u ... que-u .. v .... .u-u.- n ... nu ... n- .. oc: C Û Q D Q Go QS (Vr-lOOONI-IOOOCUFIOOONr-lOOONu-IODONI-IOOONI-IOOO 110 120 210 220 130 140 240 7803934-4 S 21 EXAMPLE 15 Plant growth regulation - tobacco shoot control Tobacco growers normally top growing tobacco plants some time (eg 2-4 weeks) before harvest to remove the main end bud, thereby the side bud growth and the leaf size increases. However, unwanted also occurs re-growth after topping, leaving several buds competes to become the new head end knob in each.

Such regrowth, which is referred to as tobacco shoots, results in significant reductions in the total the replacement of tobacco leaves and consequently in large economic losses in industry.

Extensive research work has been carried out within the area of tobacco shot suppression by the US Department of Department of Agricultural and others to identify chemical treatments that can reduce or prevent shoot growth up to the harvest with little or no damage to the plant (phytotoxicity).

The following greenhouse experiments show that some of the the compounds of the present invention are active tobacco suppressants, ie they suppress effectively the growth of tobacco shoots until after the normal harvest time (about 1 month after treatment), while one earlier known compound with similar chemical structure does not have this property.

Tobacco plants of the variety Xanthii were planted about in 6 inch pots when the plants were 2-3 inches high. When they had grown to the bud stage (ie the flowering stage, at which the flower first appears), it was separated upper quarter of the plant from the lower 3/4 parts of the plant. The plants were then sprayed with diluted 1000 ppm and 500 ppm) solutions of the compounds in acetone and placed in greenhouses. Two repetitions of 10000 ppm- test and three repetitions of the 500 ppm test for each compound was used. 7803934-4 22 The plants were evaluated for shoot growth. inhibition and phytotoxicity (damage to the whole plant) 1 in relation to untreated controls according to jañde schema.

SHOT GROWTH INHIBITING EVALUATION A - equal to the control B - easy to 1/4 growth inhibition C - moderate 1/4 to 1/2 growth inhibition D - 1/2 to 3/4 growth inhibition l E - 3/4 to fuiistänaig growth inhibition PHYTOTOXICITY EVALUATION 1 - no damage or normal crop 2 - slight damage or slight reduction of the crop 3 - moderate damage or moderate reduction of the crop 4 - serious damage or severe reduction of the crop S - all plants killed or no crop 7803934-4 t 23 Applicers - Shot growth inhibition and phytotoxicity Feed rate evaluation - days' after application unit (ppm) 10 20 40 60 112 1000 Al Al A1 A1 500 A1 A1 A1 A1 120 1000 01 Bl cl A1 500 111 Bl Bl Al 122 1000 nl 01 nl Al 500 A1 Al A1 A1 210 1000 Bl Bl nl A1 500 El cl 01 A1 211 1000 01 cl cl Bl 500 Bl Bl cl Al 212 1000 Bl Bl cl A1 soo cl A1 A1 A1 220 1000 Bl El cl -A1 500 01 01 Bl A1 222 1000 Bl Bl Bl Al 500 01 Al Bl Al 130 1000 Al A1 Al A1 _ 500 A1 Al Al Al 132 1000 A1 A1 Al A1 500 Al A1. Al A1 142 1000 Bl A1 Al Al 500 Al A1 Al Al 230 1000 A1 A1 A1 A1 500 Al A1 A1 Al 242 1000 nl cl cl A1 500 Al A1 Al A1 7803934-4 24 EXAMPLE 16 Plant growth regulation - citrus (orange) Acidity reduction The right balance between sweetness and acidity (syr-_ is of critical importance for the taste of citrus fruit products. In fact, the relationship serves between these two factors (suitably measured) as one index of taste. Test procedures for the determination of sweetness (often referred to as "BRIX sweetness" or simply "BRIX") and acid determinations are described in the article "The Florida Department of Citrus Cooperative Chemical screening Programs for Citrus ", Proc. Int. Soc. Citri- culture 1977, vol. 2, pp. 692-696 and in the one quoted there the literature. In general, BRIX / acid ratios are desired of about 13 before the harvest of oranges for production of juice. A 10% increase in the BRIX / acid ratio (comparable brought with the control) is considered an important advantage and increases slightly below 10% are significant. Both year (growing season) and the orange variety affects the BRIX and the acid readings and therefore can only test experiments during the same year and using the same orange variety compared in a meaningful way.

Acceptable sweetness for the processed fruit can not developed by simply adding sugar or sweetening sources from other fruits without disturb the essential taste of the product. According to Florida law no sugar (or other additive) can be used if the product is to be sold as “orange juice.” The fruit increases normally in sweetness as it matures further on the trees and higher ratios of sweetness to acidity can therefore expected from later harvests. However, this is economical mechanically disadvantageous and possibly still not achieved the desired relationship. Mixture of fruit parts can also help and in practice mix large amounts of Florida orange juice for use in frozen concentrates orange juice with orange juice from other orange cultivating States in order to obtain the right balance between sweetness and acidity. 7803934-4 A potentially more attractive solution to the problem is the use of a growth regulator on citrus trees before harvest to increase the ratio of sweetness to acidity.

Lead arsenate has been found to have this effect and has been used earlier. However, it does have some drawbacks its future use unlikely. These include environmental and safety factors and a too high reduction of the acidity, which accompanies its use (which results in an unacceptably flat taste). It is in themselves the work is now illegal to use pencil senate on oranges in Florida (although it can still be used on grape fruit) and from the end of 1980 it is illegal to use turn this on any citrus fruit in California. The The United States Environmental Protection Agency has issued a “REBUTABLE PRESUMPTION AGAINST REGISTRATION TION ”(RPAR) order regarding its use. Of these reasons, it is important to find a suitable alternative growth regulator to increase the sweetness ratio and acidity of citrus fruits.

An extensive research program has been implemented of the citrus industry to identify compounds such as would have the effect of increasing the sweetness and reducing the acidity in oranges. However, only a few positive examples pel found. The main examination test used in this program is an orange tree branch test as described in the article in the above cited Proc. Int. Soc. Citri- culture. This test requires 1 liter of test solution and at least fruits are evaluated per batch. Three repetitions turned per test chemical, all applied to the same tree.

The unripe fruit is normally sprayed in June, the test samples harvested around 1 December and a control sample taken from each treated tree at harvest time (control the samples are collected for all trees sprayed on a particular day). The BRIX sweetness and acidity are determined for each party. The results of this branch test have been found to be good correlate with the current observation from the whole trees. 7803934-4 26 The following results have been obtained using of the orange tree branch test to evaluate compounds according to the present invention in comparison with the better known compounds 110 and 112.

Orange variant / Pre- Appli- BRIX /% deviation test year ening cerad acid- from untreated amount of relationship control (png) long Hamlin / 1977 110 1000 10.67 -9.6 "112 1000 10.63 -9.9 "control 0 11.80 0 Hamlin / 1978 120 1000 20.00 14.4 "122 1000 _ 20.29 16.1 211 1000 16.01 -8.4 v 212 1ooo 17.56 0.5 "220 1000 18.46 5.6 "222 1000 16.75 -4.2 "130 1000 15.98 -8.6 "132 1ooo 17.55 0.4 "control 0 17.48 0 Hamlin / 1978 220 1000 19.10 8.9 Test 2 Ham1in / 197a- 222 1ooo 18.09 3.1 Test 2 control 0 17.54 '0 Follow-up of the whole tree test has also been carried out to further evaluate the associations according to the finding. In this test procedure, two whole trees are sprayed (two exactly equal) for each concentration and compound.

As in the initial examination, it is sprayed unripe fruit in June and the test samples (40 fruits per trees) are harvested around 1 December. Control samples are taken from three trees near the test trees (40 fruits from each control tree) and the control samples are collected.

The results obtained were as follows: 7803934-4 27 Orange variant / Pre- Appli- BRIX /% deviation consists uned cerad acid- from untreated amount of relationship control (ppm) countries Valencia 120 1000 9.13 9.5 "121 1000 9.08 8.9 "122 1500 9.25 10.9 "control 0 8.34 0 Hamlin / 1979 120 1000 14.85 16.8 "121 1000 14.98 17.9 "122 1000 15.04 18.3 "control 0 12.71 0 The following is shown by data from Examples 13-16: Compound 120 is active as a selective herbicide to control loose grass of cotton, sugar beet, wheat and rice as well as wild oats in wheat and rice and as a plant growth regulator to increase the ratio between sweetness and acidity of oranges, while the known association 110 does not exhibit these activities.

In addition, the compound 120 is active as a selective herbicide to control wild oats, chicken millet, Johnson- -grass and beef grass in cotton and sugar beet and as one plant growth regulator to control tobacco shoots growth.

Compound 121 is active as a plant growth regulator. to increase the sweetness to acidity ratio of oranges.

Compound 122 is active as a plant growth regulator. to increase the sweetness to acidity ratio of oranges, while the previously known compound 112 does not have this activity.

In addition, the association controls 122 tobacco shot growth at an application rate of 1000 ppm, while compound III2 is totally inactive in the tested applications the quantities. 7803934-4 ^ l5 28 Compound 210 is active as a herbicide to control loot grass in cotton, corn and sugar beet; and wild oats, chicken millet and Johnson grass and cattle grass and corn; and Johnson grass in rice, while the formerly known association 110 does not have these activities. ' In addition, compound 210 is active as a selective herbicide to control wild oats, chicken millet, John- sunflower and nut grass in cotton and sugar beet and as a plant growth regulator to control tobacco shoot growth.

Compound 211 is active as a selective herbicide to control Johnson grass in maize and as a plant growth regulator to control tobacco shoot growth.

Compound 212 is active as a plant growth regulator. lator to control tobacco shoot growth at a application rate of 1000 ppm, while the previously known compound 112 is totally inactive in this application amount.

Compound 220 is active as a selective herbicide to control cotton lozenges and sugar beets; wild oats, loot grass and chicken millet and Johnson grass in maize; and wild oats, loot grass and Johnson soybean grass beans; and as a plant growth regulator to increase the ratio of sweetness to acidity'hos oranges, while the prior art compound 110 does not have these activities teter.

In addition, the compound 220 is active as a selective herbicide against wild oats, chicken millet, Johnson grass and beef grass in cotton and sugar beet and as a plant plant regulator to control tobacco shoot growth at application rates of 500 and 1000 ppm.

Compound 222 is active as a plant growth regulator. to control tobacco shoot growth when applied quantities of 500 and 1000 ppm, while the former known compound 112 does not have this activity. 7803934-4 in 29 Compound 130 is active as a selective herbicide to control gooseberries and cotton grass, soybean beans and sugar beets; and wild oats, chicken millet, Johnson- -grass and beef grass in soybeans, while the previously known association 110 does not share these activities.

In addition, the compound 130 is active as a selective herbicide to control wild oats, chicken millet, Johnson- -grass and beef grass in cotton and sugar beet.

Compound 132 is active as a selective herbicide to control Johnson grass in soybeans, while the prior art compound 112 does not have this activity.

In addition, compound 132 is active for control Johnson grass in cotton.

Compound 140 is active as a selective herbicide to control chicken millet in corn and soybeans, while association 110 does not have these activities.

In addition, compound 140 is active for control chicken millet in cotton and sugar beet.

Compound 142 has activity as a plant growth agent. regulator to control tobacco shoot growth at 1000 ppm and at 10 day intervals after application.

Compound 240 is active as a selective herbicide to control loose grass in cotton, maize, soybeans, wheat, rice, sorghum and sugar beet, while the former known compound 110 does not have these activities.

Compound 242 is active as a plant growth regulator. lator to control tobacco shoot growth at a application rate of 1000 ppm, while the previously known compound 112 does not have this activity.

Claims (4)

7803934-4 10 15 20 25 30 30 * PATENT REQUIREMENTS A compound of formula 1 HNSOZR CFa s (mnnz for use as a plant growth modifier, in which compound R1 and R2 are independently alkyl groups containing 1-4 carbon atoms, and n is 0-2, provided that R1 and R2 are not both methyl, and agriculturally acceptable salts thereof. A compound according to claim 1, characterized in that R 1 is methyl and R 2 is ethyl or R 1 is ethyl and R 2 is methyl or ethyl. A compound according to claim 1, k n a n e t e c k n a d thereof; that it is 4-ethylthio-2-trifluoromethylmethanesulfonyl anilide. Use as a plant growth modifier of a compound of the formula æmsoznl CF3 s (o) nnz or agriculturally acceptable salts thereof, wherein R1 and R2 are independently alkyl groups containing 1-4 carbon atoms and n is 0-2, provided that R2 is not both methyl.