GB2117375A

GB2117375A - N-Alkylsulfonyl- and N- alkoxycarbonyl-substituted alkanesulfonanilides and derivatives thereof

Info

Publication number: GB2117375A
Application number: GB08235064A
Authority: GB
Inventors: James Rodney Throckmorton; Sharon Linda Ruffing; Tomas Lee Fridinger
Original assignee: Minnesota Mining and Manufacturing Co
Current assignee: 3M Co
Priority date: 1979-01-29
Filing date: 1982-12-08
Publication date: 1983-10-12
Also published as: FR2447372B1; GB2117375B; IL59240A; GB2042526B; DE3002906A1; BR8000528A; IL59240A0; GB2042526A; CH644357A5; JPS55129263A; FR2447372A1

Abstract

Compounds of the formula: <IMAGE> wherein R<1> and R<2> are selected from alkyl groups containing from 1 to 4 carbon atoms and monohalomethyl, R<3> is an alkyl group containing from 1 to 4 carbon atoms or phenyl, Q is -SO2- or <IMAGE> of which the carbon atom is bonded directed to the nitrogen atom, A is halogen or CF3, B is hydrogen or halogen and n is 0-2, the compounds meeting at least one of the conditions: (1) at least one of R<1> and R<2> is monohalomethyl; (2) Q is <IMAGE> and (3) at least one of A and B is halogen. These compounds are useful as plant growth modifiers.

Description

1 GB 2 117 375 A 1

SPECIFICATION N-Alkylsulfony]- and N-alkoxycarbonyi-substituted alkanesulfonanil ides and derivatives thereof

This invention relates to the use of Walkylsulfonyl and Walkoxycarbonyl substituted alkanesulfonanilides substituted in the para position by alkylthio, alkyisuifiny], alkylsulfonyl, aryithio, aryisuifinyl and aryisuifonyl groups and additionally substituted by halogen and/or trifluoromethyl as 5 herbicidal agents and plant growth modifying agents. The invention also relates to compositions containing the compounds.

More particularly, the invention relates to a method for regulating the growth of higher plants which comprises contacting said plants with an effective amount of a compound of the formula R 2 QNSO 2 R B 0) 10 S(O)n R 3 wherein R' and R2 are selected from alkyl groups containing from 1 to 4 carbon atoms and monohalomethyl (chloromethyl, bromomethyl, iodomethyl or fluoromethyl), R3 is an alkyl group containing from 1 to 4 carbon atoms or phenyl, Q is -SO2-- or 0 11 -OC- of which the carbon atom is bonded directly to the nitrogen atom of the formula, A is halogen or CF3, B 15 is hydrogen or halogen and n is 0-2.

The invention also relates to compositions for killing or modifying the growth of higher plants comprising a compound of formula 1 dispersed in an agriculturally acceptable extending medium.

Furthermore, those compounds of formula 1 in which at least one of the following three 20 conditions exists:

(1) at least one of R' and R 2 is monohalomethy]; (2) Q is 0 11 -OC-1- and (3) at least one of A and B is halogen; and novel and form a separate aspect of the invention. The compounds 1 can be prepared according to the reaction sequences outlined below: Method 1 11 111 1V NO 2 NO 2 NH 2 13- 0 B 0 (2) B 0 1 SR 3 SR 3 Vii V1 v l, R 2 QNSO R 1 HNS0 R N (SO 2 R)2 A 2 A 2 AY B (D 0 (5) B 0) (6) '1 -1 SR 3 SR 3 SR 3 2 GB 2 117 375 A 2.

2 VIII 1X TIV NH NH 2 NH 2 BA A _0 p. B__0 B-0 (2) SR 3 Oxi. cl,, 'L- ion V11 A R 2 QNso 2 R B 0 SR 3 X R 2 QNS0 2 R B-0 3 S(O) n R Step (1) of Method 1 is carried out by heating a compound of the indicated structure 11 together with a slight excess of an alkanethiol or ary[thiol in a suitable solvent in the presence of the appropriate amount of base. The solvent is one in which the reactants are soluble such as a lower alkanol (e.g.

ethanol or methanol), dimethyl sulfoxide or dimethyl formamide. 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 inorganic bases are alkali metal hydroxides such as sodium and potassium hydroxides, calcium hydride and the like. The product is isolated by conventional methods.

Alternatively, where R 3 is an alkyl group, step (1) can be carried out by stirring a methylene chloride solution of 11 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 utilized. Ordinarily the alkanethiol in dilute aqueous base is reacted with onehalf an equivalent of compound 11 dissolved in methylene chloride in the presence of triethylbenzylammonium chloride (the phase transfer catalyst). However, when a branched thiol, such as 2propanethiol or 2-methyl-2propanethiol, is utilized, additional quantities of base and thiol are required for the best yields due to side reactions with the methylene chloride.

The reaction of step (2) is a reduction of the nitro group of the intermediate Ill. Chemical or catalytic methods well known to the art are successful. Raney nickel is one suitable catalyst for the reduction. Product is isolated by conventional methods.

The reaction of step (3) of Method 1 is the sulfonylation of the compound /V with a sulfonyl chloride (R1S02C1) in the presence of base. If one to two equivalents of the sulfonyl chloride are used, a 25 mixture of monoand bis-(suifonylated) product can be obtained. If two or more equivalents of the sulfonyl chloride are reacted in the presence of a strong base, more of the bis(sulfonylated) product is obtained. Suitable bases for the reaction of step (3) are organic and inorganic bases such as pyridine, triethylamine, dimethylcyclohexylamine, substituted pyridines and the like. Liquid bases in excess can be used to eliminate the need for a solvent. Stronger bases promote the formation of bis(sulfonylated) product over mono(sulfonylated) product.

Step (4) is the mono(suffonylation) of the intermediate 1V. This reaction is sometimes favored by a base weaker than pyridine, such as 3-bromopyridine, in order to provide good yields of the desired product.

Steps (5) and (6) are the sulfonylation of the mono(sulfonylated) product V1 with either the 35 sulfonyl chloride of step (3) to give the product V, or with a different sulfonyl chloride or an acyl chloride (carboalkoxy chloride) to give the product V11. Steps (5) and (6) may be carried out on product V1 or on its salt.

Note that V and V11 both comply with formaula 1.

The reaction of step (1) of Method 2 involves the formation of a suitably substituted 4-thiocyano- 40 aniline from the substituted aniline by means of a conventional procedure. The reaction of step (2) involves the alkylation or arylation of the thiocyano moiety. These reactions can be carried out utilizing various techniques. For example, the thiocyano moiety can be alkylated in an alcoholic sodium cyanide solution. In this reaction the alcohol determines the alkyl group. Alternatively, a sodium mercaptide can be first formed from the thiocyano moiety and it can then by alkylated or aryiated. Alkylation can be carried out, for example, by utilizing an alkylating agent such as an alkyl halide (methyl iodide). Arylation can be accomplished by treating an aqueous dimethyl formamide solution of the sodium mercaptide with cuprous oxide and an aryl halide, preferably iodobenzene. The resulting compounds can then be further processed by the procedure of Method 1.

1 4 3 GB 2 117 375 A 3 The oxidation step is carried out using generally known methods such as hydrogen peroxide in acetic acid, sodium metaperiodate and the like. The suifoxide compound (n=l) is produced when equimolar amounts of the oxidizing agent and the reactant are utilized, whereas the sulfone (n=2) is prepared directly utlilizing 2 moles (or a slight excess) of the oxidizing agent per mole of reactant.

in addition to the specific reactions shown, compound V1 can be first oxidized (to compounds in which n is either 1 or 2) then further reacted as in step (5) or step (6) of Method 1 to give the corresponding compound X The herbicidal activity of the compounds of the invention has been determined using screening tests against greenhouse plantings. Both preand post-emergence activity are determined in a direct screen against selected weed species. The following weeds are examples of weeds which are used for 10 these tests.

Grasses Giant foxtail (Setaria faber!) Barnyardgrass (Echinochloa crus-gaffl) Crabgrass (Digitaria ischaemum) 15 Quackgrass (Agropyron repens) Yellow nutsedge (Cyperus esculentus) Broadleaves Pigweed (Amaranthus retroflexus) Purslane (Portulaca oleracea) 20 Wild mustard (Brassica kaber) Field bindweed (Convolvulus arvensis)

The test chemicals are dissolved in a small amount of acetone or other suitable solvent and then diluted with water to give a concentration of 2000 ppm. From this concentration aliquots are diluted to give a final concentration of 500 ppm. Eighty mi. of this solution are added to a 6-inch pot containing 25 the weed seeds to give a concentration equal to 5 lb/acre. All subsequent waterings are made from the bottom. Two pots are used per treatment. Data are taken 2 to 3 weeks after treatment and recorded as percent pre-emergence kill for each species compared to the untreated controls.

To assess post-emergence activity, the same weed mixtures are allowed to grow from two to three weeks until the grasses are approximately 1 to 3 inches and the broad-leaves 1 to 1-1/2 inches 30 tall. They are sprayed for approximately 10 seconds or until good wetting of the leaf surfaces occurs with a 2000 ppm solution as described above.

Data are taken two to three weeks after treatment and recorded as percent kill for each species compared to the untreated controls.

The compounds of this invention are broadly active as herbicides. The mechanism(s) by which 35 this herbicidal activity is effected is not presently known. However, the compounds of this invention also show various types of plant growth modifying activity. Plant growth modification as defined herein is any deviation from natural development, for example, defoliation, stimulation, stunting, retardation, desiccation, tillering, dwarfing, regulation and the like. This plant growth modifying activity is generally observed as the compounds of the invention begin to interfere with certain processes within the plant. 40 If these processes are essential, the plant will die if treated with a sufficient dose of the compound. However, the type of growth modifying activity observed varies among types of plants.

For application to plants, the compounds can be finely divided and suspended in any of the usual aqueous media. In addition, spreading agents, wetting agents, sticking agents or other adjuvants can be added as desired. Dry powders, as such or diluted with inert materials such as diatomaceous earth, 45 can likewise be used as dusts for this purpose. The preparations are coated on the plants or the ground is covered when pre-emergence control is desired. Application is made with the usual sprayers, dust guns and the like. Application rates are at 0.5 to 20 lbs/acre in general, but may be increased or reduced according to individual circumstances of use.

The compounds of the invention may advantageously be combined with other known herbicides 50 to broaden or maximize the weed spectrum controlled by herbicidal compositions of this invention or to better control a weed not well controlled by specific compounds of the invention. Among these other known herbicides are phenoxy herbicides, e.g. 2,4-D 2,4,5-T, silvex and the like, carbamate herbicides, thiocarbamate and dithiocarbamate herbicides, substituted urea herbicides, e.g. diuron, monuron and the like, triazine herbicides, e.g. simazine and atrazine, chloroacetamide and chlorinated 55 aliphatic acid herbicides, chlorinated benzoic and phenylacetic acid herbicides such as chloramben and other herbicides such as trifluralin, paraquat, nitralin and the like. Furthermore, herbicidal compositions containing compounds of the invention may contain, in addition, nematicides, fungicides, insecticides, fertilizers, trace metals, soil conditioners, other plant growth regulators and the like. Such combinations are clearly envisioned in this invention.

The compounds which are presently preferred for use in the process of the present invention are:

4 GB 2 117 375 A 4 Table N-methyisu Ifony]-4-ethylth io-2-trifl uorom ethyl m ethan esu Ifonani lide, N-m ethyisu lfonyi-4-ethyisu Ifonyi-2-trifi uorom ethyl m eth a nesu Ifona nil ide, N-methyisuifony]-4-t-butyithio-2-trif luoromethyimethanesu Ifonanilide, N-chloromethyisuifony]-4-ethyithio-2trifluoromethylchloromethanesuifonanili de, N-chloromethyisuifonyi-4ethyisuifonyi-2-trif 1 uororn ethyl ch loro metha nesu Ifonan i lide, Ncarboethoxy-4-methylth lo-2-trifl uorom ethyl m eth an esu Ifonan i lide, N-ca rboethoxy-4-m ethyisu Ifi nyl-2-trifi uorom ethyl m etha nesu Ifona nil ide, and N-ca rboethoxy-4-m ethyisu Ifonyl-2-trifl uoro methyl m etha n esu Ifonani 1 ide.

The following examples are given for the purpose of further illustrating the present invention but 10 are not intended, in any way, to be limiting on the scope thereof. All parts are given by weight unless otherwise specifically noted.

The subject matters of the various examples are as follows:

Examples 1-3

The preparation of compounds N by step (1) of Method 1.

Examples 4-5 The preparation of compounds IV by step (2) of Method 1 Example 6

Example 7

The preparation of compounds V1 by step (4) of Method The preparation of compounds IX by step (1) of Method 2.

Examples 8-10 The preparation of compounds IV by step (2) of Method Example 11

2.

The preparation of compounds V by step (3) of Method 1.

Examples 12-13 The preparation of compounds X by the Oxidation method.

Example 14

The preparation of compounds V by step (5) of Method 1.

Example 15

The preparation of compounds VII by step (6) of Method 1 and carrying out an analogous reaction 30 on compounds in an oxidated state (i.e. in which n is 1 or 2).

Example 1 2-Nitro-B-ethyithiobenzotrifluoride 35 A solution of 5-chi oro2-nitrobenzotrifl uo ride (150 g., 0.67 mole) and benzyitriethyiammonium 35 chloride (15 g., 0.067 mole) phase transfer catalyst in methylene chloride (1500 mi.) is added to a cold W-51C.) stirred solution of sodium hydroxide (53.2 g., 1.33 mole) and ethanethiol (97.47 g., 1.57 mole) in water (1200 mi.) over a 1.5-2 hour period. The reaction mixture is allowed to come to room temperature and is stirred for 17 hours. Thin layer chromatography on silica gel with 10 percent ether40 90 percent petroleum ether (b.p. 30-601C.) diluent indicates all of the 5-chloro-2nitrobenzotrifluoride has reacted. The methylene chloride layer is then separated from the aqueous layer and washed with water. The methylene chloride is removed by evaporation leaving 2-nitro-5-ethylthiobenzotrifl uo ride as an oil. Additional compounds also prepared using the general method of Example 1 hereof are as follows:

2-nitro-5-isopropyithiobenzotrifluoride, an oil, 2-nitro-5-tert-butylthiobenzotrifluoride, an oil.

Example 2

2-Nitro-5-methyithiobenzotrifluoride The sodium salt of methanethiol is formed by stirring a solution of methanethiol (100 g., 2.0 50 moles plus a slight excess), sodium hydroxide (80 g., 2.0 moles) and ethanol (2 liters) under nitrogen at 0-5'C. for 1 hour. To this solution is rapidly added 5-chloro-2- nitrobenzotrifluoride (451.2 g., 2.0 moles). The solution is allowed to warm to room temperature overnight and then refluxed 4 hours cooled, filtered and the solvent evaporated off under reduced pressure. The resulting oil is poured into cold water (one liter), extracted with methylene chloride, dried over magnesium sulfate and the solvent 55 4 GB 2 117 375 A 5 evaporated under reduced pressure to afford a yellow solid. Recrystallization from hexane affords a product having a melting point of 47-50'C.

Analysis: %C %H %N Calculated for C.H.F3NO2 S: 40.5; 2.5; 5.9 Found: 40.4; 2.5; 5.6. 5 Example 3 2-Nitro-5-phenylthiobenzotrifluoride A solution of 2-n itro-5-ch lorobenzotrif luo ride (33.8 g., 0.15 mole), benzenethiol (16.6 g., 0,15 mole) and ethanol (150 mi.) is heated to its reflux temperature under nitrogen. To this solution is slowly added a solution of sodium hydroxide (6 g., 0.15 mole) and water (7 mi.) at such a rate that refluxing 10 continues with no external heating. The solution is then heated at its reflux temperature for an additional two hours, filtered hot, and the filtrate cooled. The resulting precipitate is collected by filtration and recrystallized from hexane to afford a yellow solid, m.p. 65-670C.

Analysis: %C %H %N Calculated for C1.H.F3 N02S: 52.2; 2.7; 4.7 15 Found: 52.2; 2.6; 4.7.

Example 4 4-Ethylthio-2-trifluoromethylani line A solution of 64 percent aqueous hydrazine (48.4 g., 1.5 mole) is added dropwise to a warm (500C.) stirred solution of 2-nitro-5-ethyithiobenzotrifluoride in 95 percent ethanol (1200 mi.). After all 20 of the hydrazine is added, the reaction mixture is heated under reflux overnight. Thin layer chromatography indicates all of the nitro compound is reduced. The reaction mixture is then filtered and concentrated under reduced pressure. The residual golden colored liquid is taken up in methylene chloride and washed with water. The methylene chloride is removed by evaporation leaving the product, 4-ethylth io-2-trifl uoro methyl an 11 i ne.

Additional compounds also prepared utilizing the same general method are as follows:

4-methyithio-2-trifluoromethylaniline, an oil, 4-isopropyithio-2-trifluoromethylaniline, an oil, 4-tert-butylthio-2-trifluoromethylaniline, m.p. 68-700C.

Example 5 4-Phenylthio-2-trifluoromethylaniline 2-Nitro-5-phenylthiobenzotrifluoride (25.6 g., 0.86 mole) in ethanol (500 mi.) is reduced over Raney nickel at about 45 psi of hydrogen gas. After hydrogen uptake is complete the mixture is deactivated with elemental sulfur, filtered and the filtrate evaporated to afford product as an oil. The infrared spectrum shows an absorption at 2.9 g (strong NH band). The product crystallized on standing 35 to give a solid, m.p. 63-651C.

Example 6

2,5-Dichloro-4-ethyithiomethanesuifonanilide Methanesulfonyl chloride (11.5 g., 0.10 mole) is added dropwise to a cold (1 0-200C.) stirred solution of 2,5-dich loro-4-ethyithioani line (21.9 g., 0. 10 mole) in 3bromo-pyridine (23.7 g., 0. 15 40 mole) and the mixture is stirred overnight at room temperature. The reaction is broken up with a mortar and pestle, washed with water and filtered to recover product. Recrystallization from methylene chloride-hexane gives a grey solid, m.p. 143-1440C.

The following compounds are prepared utilizing the same general method:

2-fluoro-4-methyithloethanesuifonanilide, m.p. 69-71 "C., 2-fluoro4-methyithiomethanesuifonanilide, m.p. 133-1351C., 2-fluoro-4-methyithiochloromethanesuifonanilide, a solid, 2-bromo-4-isopropyithiomethanesuifonanilide, m.p. 82-84'C., 2-bromo-4-isopropyithioethanesuifonanilide, m.p. 62-641C., 2-bromo-4-ethyithioethanesuifonanilide, m.p. 77.5-79.51C., 2-chloro-4-phenyithiomethanesuifonanilide, m.p. 79.5-81 'C., 2-bromo-4-phenyithiomethanesuifonanilide, m.p. 74.5-751C., 2-fluoro-4-phenylthiomethanesulfonanilide, m.p. 1 25-125.5'C.' 4-phenylthio-2-trifluoromethylethanesuifonanilide, a solid, 2-bromo-4-phenyithiochloromethanesuffonanilide, m.p. 71-72.5'C.' 2-chloro-4-phenyithiochloromethanesuifonanilide, m.p. 73-74'C., 2-fluoro-4-phenylthiochlorom etha nesu Ifona nil ide, m.p. 83-83.5'C.

6 GB 2 117 375 A 6 Example 7

4-Thiocyano-2-trifluoromethylaniline To a cold (0-50C.) stirred solution of 2-aminobenzotrifluoride (6.44 g., 0.04 mole) and sodium thiocyanate (9.72 g., 0. 12 mole) in methanol (100 mO is added dropwise a solution of bromine (6.6 g., 0.42 mole) in methanol (25 mi.) saturated with sodium bromide. The solution is stirred for 20 minutes following the addition of bromine and then poured into water (750 mi.) and neutralized with sodium carbonate. The resulting oil is taken up in methylene chloride and dried. Removal of the drying agent and solvent gives 4-thlocyano-2-trifluoromethylaniline as an oil that solidifies on standing (8.4 g., 96 percent yield). A purified sample has a melting point of 53-551C. and the following analysis.

Analysis: %C %H %N Calculated for C.H.F. N 2S: 44.0; 2.3; 12.8 Found: 43.7; 2.3; 12.9.

The following additional compounds are prepared using the same general method: 2-chloro-4-thiocyanoaniline, m.p. 63-651C., 2-bromo-4-th iocya noa nil ine, m.p. 74-790C., 2-fluoro-4-thiocyanoaniline, an oil, and 2,5dichloro-4-thiocyanoaniline, m.p. 111-1151 C.

Example 8

4-Methylthio-2-trifluoromethylaniline A solution of 4-thiocyano-2-trifluoromethylaniline (1.09 g., 0.005 mole) and sodium cyanide 20 (0.125 g., 0.0025 mole) in methanol (50 mi.) is refluxed for about 16 hours. Methanol is removed from the cool reaction mixture by evaporation under reduced pressure, the residue is taken up in methylene chloride, washed with water and dried. Removal of the drying agent and solvent gives the product as a yellow oil (1 g., 91 percent yield).

The following additional compounds are prepared utilizing the same general method: 4-isopropyithio-2-trifluoromethylaniline, an oil, 4-n-p ropyith io-2-trif luorom ethyl an! 1 i ne, an oil, and 2-chloro-4methy[thioaniline, an oil.

Example 9 30 4-Methylthio-2-trifluoromethylaniline prepared using an alternate procedure A solution of 4-thiocyano-2-trifluoromethyla ni line (2.1 g., 0.01 mole) in ethanol (25 mi.) is added to a stirred solution of sodium sulfide nonahydrate (2.4 g., 0.01 mole) in water (5 mi.), and the mixture is warmed (500C.) for 40 minutes. Methyl iodide (1.55 g., 0.011 mole) is added to the warm reaction all at once, and stirring is continued for 2 hours. Thin layer chromatography on silica gel with 50 percent hexane-50 percent methylene chloride diluent alongside an authentic sample shows that all Of 35 the thiocyano compound is reacted to produce the desired product.

The following additional compounds are prepared utilizing the same general method:

4-ethyithio-2-trifluoromethylaniline, an oil, 4-isopropyithio-2-trifluoromethylaniline, an oil, 4-methyithio-2-chloroaniline, an oil, 40 4-ethyithio-2-chloroaniline, an oil, 4-isopropylth io-2-ch loroa nil i ne, an oil, 4-ethyithio-2,5-dichloroaniline, an oil, 4-methylthio-2-fluoroaniline, an oil, 4-isopropyithio-2-bromoaniline, an oil, 45 4-ethyithio-2-bromoaniline, an oil, 4-ethylthio-2-fluoroaniline, an oil, 4-ethyithio-2-iodoaniline, an oil, 4-isopropyithio-2-fluoroaniline, an oil, and 4-methyithio-2-bromoaniline, an oil. 50 Example 10

2-Bromo-4-phenyithioani line A solution of 2-bromo-4-thiocyanoaniline (91.6 g., 0.4 mole) and dimethylformamide is added dropwise to a solution of sodium suifide (0.48 mole) and water under nitrogen, and the resulting solution is heated at 501C. for 1 hour. Cuprous oxide (34.33 g., 0.24 mole) and iodobenzene (97.9 g., 55 0.48 mole) are added and the mixture is heated at a heating bath temperature of 1500C. for 4.5 hours.

The reaction is quenched with water, methylene chloride is added, and the resulting mixture is filtered through filter aid to remove suspended solids. The aqueous and organic layers are separated and the aqueous layer is extracted three times with methylene chloride. The methylene chloride extracts are combined, washed with water and dried. Removal of the drying agent and methylene chloride gives the 60 desired product.

7 GB 2 117 375 A 7 A purified sample melts at 61-631C.

Analysis: %C %H M Calculated for C12H10BrNS: 51.44; 3.6; 5.0 Found: 51.9; 3.6; 5.0.

The following compounds can be prepared utilizing the same general procedure: 2-chloro-4-phenyithioaniline, a solid, and 2-fluoro-4phenyithioaniline, a solid.

Example 11 N-Methyisuifonyl-4-ethyithio-2trifluoromethyimethanesulfonanilide Methanesulfonyl chloride (22.2 g., 0.19 mole) is added dropwise to a cold (0-50C.) stirred 10 solution of 4-ethylth io-2-trifl uoro methyl an Hine (0.077 mole) in pyridine (49 g., 0.62 mole). The solution is stirred at room temperature overnight, poured into ice water with stirring to give Nmethyisu Ifo ny]- 4-ethylth io-2-trifl uorom ethyl m etha nesu Ifona nil ide as a tan solid. Recrystallization from methylene chloride-hexane gives pure product, m.p. 137-1390C.

Analysis: %C %H %N 15 Calculated for Cl H 14NO4S3: 35.0; 33; 3.7 Found: 35.1; 3.6; 3.7.

Additional compounds prepared using the same general formula are as follows:

N-ethyisuifonyi-4-methyithio-2-trifluoromethylethanesuifonanilide, an oil, N-methyisu Ifonyl-4-n-propylth io-2-trifl uorom ethyl m eth a nesu Ifona ni lide, a solid, N-methyisuifony]-4-tert-butyithio-2-trifluoromethyimethanesuifonanillde, m.p. 911-931C., N-ethyisuifonyi-4-ethyithio-2-trifluoromethylethanesuifonanilide, m.p. 119-121 'C., N-ethyisuifonyi-4-isopropyithio-2-trifluoromethylethanesuifonanilide, an oil, N-n-propyisu Ifonyl-4-m ethylth io-2-trifl uoromethylpropa nesu Ifona nil ide, an oil, N-n-butyisuifonyi-4-methyithio-2-trifluoromethyibutanesuifonanilide, an oil, N-methyisu Ifony]-4-m ethylth lo-2-trifi uoro methyl meth a nesu Ifona ni lide, m.p. 147-1540C., N-methyisu Ifonyl-4-phenylth io-2-trifl uorom ethyl m etha n esu Ifon an flid e, m.p. 145-1480C., N-ch lorom ethyisu Ifonyl-4-ethylthio-2-trif 1 uorom ethylch lorom ethanesu Ifona nil ide, m.p. 89 93.C., N-ethyisu Ifonyl-4-tert-butylth io-2-trifl u oro methyl ethanesu Ifonan i 1 ide, m.p. 99-101 OC., 30 N-methyisuifonyi-4-ethyithio-2-chloromethanesuifonanilide, m.p. 122-1250c. , and N-chloromethyisuifonyi-4-ethyithio-2-chlorochloromethanesuifonanilide, m. p. 96-9711C.

Example 12

N-Chloromethyisuifonyi-4-ethyisuifiny]-2trifluoromethylchloromethanesuifona niline To a stirred solution of N-chloromethyisuifonyl-4-ethyithio-2- trifluoromethylchloromethanesulfonanilide (4.46 g., 0.01 mole) in glacial acetic acid (100 mi.) is added 30 percent hydrogen peroxide (0.01 mole). The solution is stirred overnight at room temperature. An additional amount of percent hydrogen peroxide (0.001 mole) is added and stirring continued overnight, and then treated with water. The aqueous mixture is extracted with methylene chloride, washed with water and dried.

Removal of the drying agent and solvent gives a solid, m.p. 166-1680C.

Analysis: %C M %N Calculated for Cl 1 H 12C12F3NO 5S3: 2 8.6; 2.6; 3.0 Found: 28.9; 2.6; 3.1.

The following compounds can also be prepared utilizing the same general formula: N-methyisuifony]-4-methyisuifinyi-2trifluoromethyimethanesulfonanilide, N-m ethyisu lfonyi-2-ethyisu Ifiny]2-trifl uorom ethyl m eth anesu Ifon ani lid e, and N-methyisuifony]-4phenyisuifinyi-2-trifluoromethyimethanesuifonanilide.

Example 13

N-Chloromethyisuifony]-4-ethyisuifony]-2trifluoromethylchloromethanesuifona nilide To a stirred solution of N-chloromethyisuifonyi-4-ethylthio-2- trifluoromethylchloromethanesulfonanilide (2.23 g., 0.005 mole) in glacial acetic acid (50 ml.) is added 30 percent hydrogen peroxide (0.02 mole). The solution is heated at reflux for 2.5 hours, water is added, and the mixture is cooled. The resulting precipitate is collected by filtration, washed with water and dried to give a white solid, m.p. 160-1651C.

Analysis: %C %H %N 55 Calculated for Cl 1H12C12F.NO 6S3: 27.6; 2.5; 2.9 Found: 27.7; 2.4; 2.9.

8 GB 2 117 375 A 8 An additional compound prepared using the same general method is as follows: N-m ethyisu Ifonyl-4-ethyisu Ifonyl-2-trif 1 uorom ethyl m eth a nesu Ifona n i 1 ide, m.p. 167-1 69,1C. The method can also be used to prepare the following compounds: N-m ethyisu Ifonyl-4-m ethyisu Ifonyl-2- trifluorom ethyl m ethanesu Ifonan il ide and N-methyisuifonyi-4- phenyisuifony]-2-trifluoromethyimethanesuifonanilide.

Example 14 N-Methyisuifonyl-4-ethylthio-2-trif 1 uoro methyl metha nesu Ifo nanil ide Dimethylcyclohexylamine (2.57 g., 0.02 mole) is added dropwise to a cold (5-11 OIC.) stirred solution of 4-ethy[thio-2-trifi u o rom ethyl m eth anesu Ifonani lid e (1.5 g., 0.005 mole) and methanesulfonyl chloride (0.86 g., 0.0075 mole) in benzene and the solution allowed to warm to room 10 temperature and stirring continued for about 72 hours. Thin layer chromatography on siliqa gel with either methylene chloride eluant, or with a 50 percent ether-50 percent petroleum ether (b.p. 30 601C.) eluant, or with a 25 percent ethyl acetate-75 percent petroleum ether (b.p. 30-601C.) eluant alongside an authentic sample shows that all of the methanesulfonanilide is reacted to produce the desired N-methyisuifonyimethanesuifonanilide product.

N-methyisuifonyl-2,5-dichloro-4-ethylthiomethanesuifonanilide, m.p. 1451481C., N-ethyisu Ifonyl-4-m ethylth lo-2-f 1 u oroetha n esu Ifona nil ide, m.p. 94-961C., N-methyisuifonyi-4-methyithio-2-fluoromethanesuifonanilide, m.p. 1511531C.' N-chloromethyisuifonyl-4-methyithio-2-fluorochloromethanesulfonanilide, m. p. 142-1430C., 20 N-methyisuifonyi-4-isopropylthio-2-bromomethane sulfonanllide, m.p. 811- 831C., N-ethyisuifonyi-4-isopropyithio-2-bromoethanesuifonanilide, m.p. 64-670C., and N-ethyisuifony]-4-ethyithio-2-bromoethanesuifonanilide, m.p. 95-970C.

Example 15 25 N-Carboethoxy-4-methyithio-2-trifluoromethyl m ethanesuIfona nil ide To a cold W-51'C.) stirred solution of 4-methylth io-2-trif 1 uorom ethyl m eth anesu Ifona nil ide (5.7 g., 0.02 mole) in pyridine (20 mi.) is added dropwise ethyl chloroformate (2.3 g., 0.024 mole). The solution is stirred overnight at room temperature and then poured into cold (0-50C.) dilute hydrochloric acid. The solid is collected by filtration, washed with water and air dried. Recrystallization from hexane-methylene chloride gives tan crystals, m.p. 93-950C.

Analysis: %C %H %N Calculated for C12H14173NO4S2: 40.4; 3.9; 3.9 Found: 40.3; 4.0; 3.9.

Additional compounds prepared using the same general procedure are as follows: N-carboethoxy-4-ethyithio-2-trifluoromethyI methane sulfonanilide, m.p. 76-781C., N-ch loromethylsu!fonyi-4-ethyith io-2trifl u orom ethyl methanesu Ifona nil ide, m.p. 90-931C., N-ca rboethoxy4-p henylth io-2-trifl u oro methyl m eth a nesu Ifon a nil ide, N-ca rboethoxy-4-phenylth lo-241 u orom ethanesu Ifona nil ide, N-carboethoxy4-phenyithio-2-chloromethanesuifonanilide, N-carboethoxy-4-phenyithio-2bromomethanesuifonanilide, N-carboethoxy-4-phenyithio-2fluorochloromethanesuifonanilide, N-carboethoxy-4-phenyithio-2chlorochloromethanesuifonanilide, N-carboethoxy-4-phenyithio-2bromochloromethanesuifonanilide, N-carboethoxy-4-pheny[thio-2trifluoromethylethanesuifonanilide.

The following compounds are prepared by reacting compounds of structure V1 except that they 45 are in a higher oxidation state (i.e. n is 1 or 2) in a manner analogous to step (6) of Method 1.

N-ca rboethoxy-4-m ethyisu If inyl-2-trifl uorom ethyl m eth a nesu Ifona n i 1 ide, an oil, N-carboethoxy-4-m ethyisu Ifonyl-2-trif 1 uorom ethyl m eth a nesu Ifo na nil ide, m.p. 148-1 500C.' N-ca rboethoxy-4-ethyisu Ifiny]-2-trifl uorom ethyl m eth a nesu Ifona nil ide, an oil, N-ca rboethoxy-4-ethyisu Ifony]-3-trif 1 uorom ethyl m eth a nesu Ifona n i 1 ide, an oil, N-carboethoxy-4-ph enyisu If iny 1-2-trifl uoro methyl m eth an esu Ifona nil ide, a solid, N-carboethoxy-4-phenyisuifonyi-2-trifluoromethyimethanesuifonanilide, a solid, N-carboethoxy-4-phenyisuifinyi-2-trifluoromethylethanesuifonanilide, a solid, N-carboethoxy-4-phenyisuifonyi-2-trifluoromethylethanesuifonanilide, a solid, N-carboethoxy-4-phenyisuifinyi-2-fluoromethanesuifonanilide, a solid, N-carboethoxy-4-phenyisuifinyi-2-fluorochloromethanesuifonanilide, a solid, N-carboethoxy-4-phenyisuifonyl-2-fluorochloromethanesuifonanilide, a solid, N-carboethoxy-4-phenyisuifinyi-2-chloromethanesuifonanilide, a solid, N-carboethoxy-4-phenyisuifonyl-2-chloromethanesulfonanilide, a solid, N-carboethoxy-4-phenyisuifinyl-2-chforochloromethanesuifonanilide, a solid, 9 GB 2 117 375 A 9 N-carboethoxy-4-phenyisuifonyi-2-chlorochloromethanesuifonanilide' a solid, N-carboethoxy-4-phenyisuifiny]-2-bromomethanesuifonanilide, a solid, N-carboethoxy-4-phenyisuifonyi-2-bromomethanesuifonanilide, a solid, N-carboethoxy-4-phenyisuifinyi-2-bromochloromethanesuifonanilide, a solid, and N-carboethoxy-4-phenyisulfonyl- 1 bromochloromethanesuifonanilide, a solid.

Claims

Claims 1. A compound of the formula

R 2 QNS0 2 R B 0) S(O) n R 3 wherein R' and R 2 are selected from alkyl groups containing from 1 to 4 carbon atoms and monohalomethyl, R' is an alkyl group containing from 1 to 4 carbon atoms or phenyl, Q is -SO27or10 0 11 -OG- of which the carbon atom is bonded directly to the nitrogen atom, A is halogen or CF3, B is hydrogen or halogen and n is 0-2, and in which at least one of the following three conditions exists: (1) at least one of R' and R2 1S monohalomethyl; (2) Q is 0 11 -OC-1- (3) at least one of A and B is halogen.
2. A compound according to claim 1 selected from the Table herein.
3. A compound according to claim 1 and substantially as hereinbefore described in any of 25 Examples 1 to 5.

Printed for Her Majesty's Stationery Office by the Courier Press, Leamington Spa, 1983. Published by the Patent Office, Southampton Buildings, London, WC2A lAY, from which copies may be obtained

3. A compound according to claim 1 and substantially as hereinbefore described in any of 20 Examples 11 to 15; and New claims or amendments to claims filed on 18 April 1983. Superseded claim 3 New or amended claim: