MXPA98005645A - N-arylsulfilimine compounds and their use as catalysts in the preparation of n-arylarylsulfonamide compounds - Google Patents

Abstract

N-arylsulfilimine compounds, such as S,S-dimethyl-N-(2,6-dichlorophenyl)sulfilimine, were prepared and found to catalyze the reaction of aromatic sulfonyl chloride compounds, such as 2-chlorosulfonyl-7-fluoro-5-ethoxy[1,2,4]-triazolo[1,5-c]pyrimidine, with aromatic amine compounds, such as 2,6-dichloroaniline, to form N-arylarylsulfonamide compounds, such as N-(2, 6-dichlorophenyl)-7-fluoro-5-ethoxy-[1,2,4]triazolo[1,5-c]pyrimidine-2-sulfonamide. The aryl moiety of the N-arylsulfilimine catalyst and the aryl moiety of the aromatic amine compound were generally chosen to be identical.

Description

COMPU THESE OF N-ARILSULFILIMINE AND ITS USE AS CATALYSTS IN THE PREPARATION OF COMPOUNDS OF N-AR1LARILSU LFONAMIDA The present invention relates to the use of N-aryl sulphimymine compounds as catalysts in the reaction of aromatic sulfonyl chloride compounds with aromatic amines to form N-arylarylsulfonamide compounds and to novel N-arylsulphimycin compounds. The preparation of N-arylarylsulfonamide compounds by the The reaction of aromatic sulfonyl chloride compounds with aromatic amine compounds typically yields unsatisfactory results because the reaction is slow and the yields are poor. The preparation of such compounds wherein the aromatic amine compound and / or the aromatic sulfonyl chloride compound possesses one or, In particular, two ortho substituents are frequently unsatisfactory in particular due to the steric deactivation effect and, when the substituents are electron withdrawers, the electronic deactivation effect of ortho substituents. Pyridine, picolines and lutidines have long been known to catalyze the reaction of many compounds of sulfonyl chloride with amines to form sulfonamides. Recently, it was reported that a mixture of a pyridine base and dimethyl sulfoxide gave improved results in many cases (U.S. Patent 5, 177,206). Many N-arylarylsulfonamide compounds are known in the art to be valuable herbicides and methods to obtain them more easily and in improved yields are desirable. A number of substituted N-phenylsulfiimine compounds are known, for example from J. Org. Chem .. 39. 3365-3372 (1974), and the preparation and more of the chemistry of these compounds have been reviewed in the literature, for example, in Russian Chemical Reviews. 59. 819-831 (1990). Certain of these compounds have been reported to be useful intermediates for further synthesis. For example, rearrangement of such compounds having at least one unsubstituted ortho position to obtain 2-alkylthiomethyl-aniline compounds has been reported in U.S. Patent 4,496,765. The use of N-phenylsulfilimine compounds as catalysts for the preparation of sulfonamides has not been reported. It has now been found that N-arylsulfilimine compounds catalyze the reaction of aromatic sulfonyl chloride compounds with aromatic amines to form N-arylarylsulfonamide compounds. The effect is especially important in such reactions involving a relatively unreactive aromatic sulfonyl chloride compound and / or a relatively unreactive aromatic amine compound. Higher reaction rates and improved yields are obtained. The invention includes a process for the preparation of an N-arylarylsulfonamide compound of Formula IV: Q-SO2NH-AR wherein Q and AR each independently represent a portion of aromatic hydrocarbyl or of aromatic heterocyclyl which comprises combining a sulfonyl chloride compound of Formula I I: Q- -S02CI wherein Q is as defined above with an amine compound of Formula I I I: AR- N H2 wherein AR is as defined above in the presence of an aromatic tertiary amine base and a catalytic amount added of an N-arylsulfilimine compound of Formula I: R / AR'- N = S \ R 'wherein R represents methyl, ethyl or n-propyl; R 'represents R, benzyl or phenyl; or R and R 'together represent tetramethylene; and AR 'represents a portion of aromatic hydrocarbyl or aromatic heterocyclyl.

It is greatly preferred that AR 'in the sulfilimine compound is selected to be identical with AR in the amine compound. The preparation of an N-arylarylsulfonamide compound of Formula IV wherein AR represents a phenyl, pyridinyl, or a 1-alkylpyrazolyl portion optionally having 1 to 3 substituents selected from F, Cl, Br, I, NO2, CN, O (C3 C4 alkenyl), or O (C3-C4 alkynyl); d-C4 alkyl, O (d-C4 alkyl), N (C? -C4 alkyl) 2, S (d-C4 alkyl), SO2 (d-C4 alkyl), CO2 (dC alkyl), CONH (d-C4) alkyl), or CON (d-C4 alkyl) 2 (each alkyl optionally mono to fully substituted with fluorine); or phenyl or phenoxy (each optionally possessing 1 to 3 substituents selected from the group consisting of F, Cl, Br, CN, CF3, NO2, and CH3), is a preferred embodiment of the invention. A process for the preparation of N-arylarylsulfonamide compounds of Formula I I I, wherein AR represents an aromatic portion selected from a) a substituted phenyl portion of the formula: wherein A represents F, Cl, Br, NO2, CN, C? -C fluoroalkyl, CO2 (C? -C4 alkyl), CONH (C? -C4 alkyl), CON (C? -C4 alkyl) 2, SO2 ( C? -C4 alkyl), or SO2 (C? -C fluoroalkyl); B represents d-C4 alkyl, F, Cl, Br, 0 (d-C4 alkyl), 0 (d-C4 * fluoroalkyl), S (d-C alkyl), S (d-C4 fluoroalkyl), N (C? -C alkyl) 2; or phenyl, phenoxy or phenylthio each optionally possessing 1 to 3 substituents selected from the group consisting of F, Cl, Br, CN, CF3, N02, and CH3; and D and J each independently represents H or CH3 with the proviso that at least one of D and J represents H; b) a substituted 3-pyridinyl portion of the formula: wherein 15 L and M each independently represent H, C? -C4 alkyl, dC4 fluoroalkyl, 0 (C1-C4 alkyl), O (dC fluoroalkyl), 0 (C2-C alkoxyalkyl), O (C3-C4 alkenyl), O (C3-C alkynyl), S (C? -C4 alkyl), S (C? -C4 fluoroalkyl), SO2 (d-C4 alkyl), SO2 (d-C4 fluoroalkyl), F, Cl, Br , I, CN, NO2, C6H5, CO2 (C? -C4 alkyl), CO2 (C3-C4 alkenyl), CO2 (C3-C4) Alkynyl), CON (C? -C4 alkyl) 2, or CONH (C? -C alkyl), with the proviso that not more than one of L and M represents H; and T represents H, F, Cl, Br, I, CH3, or CF3; or c) a portion of 3-, 4- or 5-pyrazolyl substituted with a C1-C3 alkyl group in the 1-position, with at least one Cl, Br, i or CF3, and Optionally, with an OCH3 or CH3 group are sometimes especially preferred. Such compounds wherein Q represents 5-amino-1, 2,4-triazin-3-yl or a [1, 2,4] triazolo [1, 5-a] pyrimidin-1-yl, [1, 2, 4] triazolo [1, 5-c] pyrimidin-2-i !, or [1, 2,4] triazolo [1, 5-a] pyridin-2-yl each substituted with one or more F, Cl groups, Br, I, C1-C3 alkyl, C1-C3 fluoroalkyl, O (d-C3 alkyl) constitute a class of special interest because the resulting compounds of Formula II I are valuable herbicidal compounds or are intermediates for the preparation of valuable herbicidal compounds . The invention further includes substituted N-arylsulfilimine compounds of Formula I: R / AR'- N = S R 'wherein R represents methyl, ethyl, or n-propyl; R 'represents R, benzyl or phenyl; or R and R 'together represent tetramethylene; and AR 'represents an aromatic portion selected from a) a substituted phenyl portion of the formula: wherein A represents F, Cl, Br, N02, CN, C? -C4 fluoroalkyl, CO2 (d-C4 alkyl), CON H (d-C4 alkyl), CON (d-C4 alkyl) 2, SO2 (C1- C alkyl), or S02 (C? -C4 fluoroalkyl); B represents d-C4 alkyl, F, Cl, Br, O (dC alkyl), O (d-C4 fluoroalkyl), S (C? -C alkyl), S (C? -C4 fluoroalkyl), N (C? C4 alkyl) 2; or phenyl, phenoxy or phenylthio each optionally possessing 1 to 3 substituents selected from the group consisting of F, Cl, Br, CN, CF3, N02, and CH3; and D and J each independently represents H or CH3 with the proviso that at least one of D and J represents H; c) a substituted 3-pyridinyl portion of the formula: wherein L and M each independently represent H, C? -C4 alkyl, Ci-C4 fluoroalkyl, O (d-C4 alkyl), O (C1-C fluoroalkyl), O (C2-C4 alkoxyalkyl), O (C3- C alkenyl), O (C3-C4 alkynyl), S (dC alkyl), S (C? -C4 fluoroalkyl), SO2 (C? -C4 alkyl), SO2 (dC fluoroalkyl), F, Cl, Br, I, CN, NO, C6H5, CO2 (d-C4 alkyl), CO2 (C3-C4 alkenyl), CO2 (C3-C4 alkynyl), CON (C? -C alkyl) 2, or CONH (C? -C4 alkyl), with the proviso that no more than one of L and M represents H; and T represents H, F, Cl, Br, I, CH3, or CF3; or c) a 3-, 4- or 5-pyrazolyl portion substituted with a C1-C3 alkyl group in the 1-position, with at least one Cl, Br, I or CF3, and optionally, with an OCH3 or CH3 group. The catalytic N-arylsulfilimine compounds of the invention, which may be represented by Formula I: / AR'- N = S \ R ' or, alternatively, through the formula: - + R / AR'- N- S \ R ' they are characterized by having a nitrogen-sulfur semipolar ligature. This ligature can be shown as a double ligature, the sulfur atom of which is tetravalent as in Formula I, or can be shown as a simple bond, the nitrogen atom of which is negatively charged and the sulfur atom of which is positively charged as in Formula la. Compounds possessing such ligatures are often referred to as ylides. For simplicity, the compounds of the invention are shown herein to be compounds having the structure of Formula I with the understanding that these compounds are the same as the compounds shown. # for having the structure of Formula la. The substituents on the sulfur atom are R and R ', wherein R represents methyl, ethyl or n-propyl and R' represents R, phenyl, or benzyl; or wherein R and R 'together represent tetramethylene. Such compounds, wherein R and R 'represent both methyl are generally preferred. The portion attached to the nitrogen atom is AR, which represents a portion of aromatic hydrocarbyl or aromatic heterocyclyl. This * definition is inclusive of all aromatic hydrocarbons and portions of Aromatic heterocyclyl, whether or not these portions possess substituents. Examples of suitable aromatic hydrocarbyl moieties include phenyl, naphthyl, phenanthrenyl and indenyl. Examples of suitable aromatic heterocyclic portions include pyridinyl, pyrimidinyl, pyridazinyl, pyrazinyl, 1,3,5-triazinyl, quinolinyl, -quinazolinyl, quinoxalinyl, furanyl, thienyl, pyrrolyl, oxazolyl, thiazolyl, imidazolyl, pyrazolyl, 1,4-oxadiazolyl, 1,4-oxadiazolyl, 1,3-thiadiazolyl, 1,4-thiadiazolyl , 1, 2,4-triazolyl, benzofuranyl, benzo [b] thienyl, indolyl, [1, 2,4] triazolo [1, 5-a] pyrimidinyl, [1, 2,4] triazolo [1, 5-c] ] pyrimidinyl, [1, 2,4] triazolo [1, 5-a] pyridinyl, pyrazolo [1, 5,20 ajpyrimidinyl, and [1, 2,4] triazolo [1, 5-a] [1, 3, 5] triazinyl. AR 'is preferably a substituted phenyl portion, a substituted pyridinyl moiety or a substituted pyrazolyl moiety. Compounds wherein AR 'represents a substituted phenyl or substituted pyridinyl moiety are often of special interest.

The substituents possessed by the hydrocarbyl portions and # AR aromatic heterocyclyl include any substituent that is stable in the presence of other substituents on the N-arylsulphimymine compound and which does not react with the starting materials used to make the sulphimymine compound. Suitable substituents include F, Cl, Br, I, N02, CN, C? -C8 alkyl, 0 (d-C8 alkyl), 0 (C3-C3 alkenyl), 0 (C3-C8 alkenyl), N (d-) C8 alkyl) 2, S (d-C8 alkyl), S (C3-C8 alkenyl), S (C3-C8 alkenyl), SO2 (C? -8 alkyl), SO2 (C3-C8 alkenyl), # S02 (C3-C8 alkenyl), CO2 (C? -C8 alkyl), CO2 (C3-C8 alkenyl), CO2 (C3-C8) alkenyl), CON H (d-C8 alkyl), CON (C? -C8 alkyl) 2, Si (C? -8 alkyl) 3, phenyl, phenoxy, thiophenoxy, pyridinyloxy, and pyridinylthio. Each alkyl in the substituents noted above can be mono to fully substituted with fluorine or mono or disubstituted with, for example, Cl, Br, I, NO2, CN, C? -C8 alkyl, O (d-C8 alkyl), N ( d-C8 alkyl) 2, S (d-C8 alkyl), or SO2 (d-C8 Alkyl), CO2 (C? -C8 alkyl), CONH (d-C8 alkyl), CON (C? -C8 alkyl) 2, or Si (d-C8 alkyl) 3. Each portion of phenyl, phenoxy, thiophenoxy, pyridinyloxy and pyridinylthio in the substituents noted above can be mono- or tri-substituted with, for example, F, Cl, Br, I, NO, CN, C? -C8 alkyl, O (C? C8 alkyl), N (C? -C8 alkyl) 2, S (d-C8 alkyl), or SO2 (C? -C8 alkyl), CO2 (C? -C8 alkyl), CONH (d-C8 alkyl), CON (C? -C8 alkyl) 2, and Si (C? -C alkyl) 3. Preferred substituents include F, Cl, Br, I, NO2, CN, O (C3-C alkenyl), or O (C3-C4 alkynyl); d-C alkyl, O (C1-C4 alkyl), N (C? -C alkyl) 2, S (C? -C4 alkyl), SO2 (d-C4 alkyl), CO2 (d-C alkyl), CONH (C? -C alkyl), or CON (d-C alkyl) 2 (each alkyl optionally mono to completely substituted with fluorine); or phenyl or phenoxy (each # optionally possessing 1 to 3 substituents selected from the group consisting of F, Cl, Br, CN, CF3, N02, and CH3). Phenyl, pyridinyl and 1-alkylpyrazolyl portions possessing one to three such substituents 5 are frequently preferred. One embodiment of the invention which is frequently of special interest are compounds of Formula I wherein AR 'represents a substituted phenyl portion of the formula: where A represents F, Cl, Br, NO, CN, d-C4 fluoroalkyl, CO2 (d-C) Alkyl), CONH (C? -C4 alkyl), CON (d-C4 alkyl) 2, SO2 (d-C4 alkyl), or SO2 (C? -C4 fluoroalkyl); B represents C? -C alkyl, F, Cl, Br, O (C? -C alkyl), O (C? -C4 fluoroalkyl), S (C1-C alkyl), S (C1-C4 fluoroalkyl), N (C? -C4 alkyl) 2; or phenyl, phenoxy or phenylthio each optionally possessing 1 to 3 substituents selected from the group consisting of F, Cl, Br, CN, CF3, NO2, and CH3; and D and J each independently represents H or CH3 with the proviso that at least one of D and J represents H. Compounds of this type wherein A represents F, Cl, Br, CF3, NO2, or CO2CH3; B represents F, Cl, Br, CH 3, OCH 3; D represents H or CH3; and J represents H are frequently preferred. Such compounds Wherein Ar 'represents 2,6-dichlorophenyl, 2,6-difluorophenium, 2-chloro-6-fluorophenyl, 2-methoxycarbonyl-6-methylphenyl, 2-chloro-6-methoxycarbonylfenyl, ^ ~ 2-f luoro-6-methoxycarbonylfenyl, 2-methoxy-6- (trifluoromethyl) phenol, 2,6-dichloro-3-methylphenyl and 2,6-difluoro-3-methylphenyl are often especially preferred . Another embodiment of the invention which is often of special interest are compounds of Formula I wherein AR 'represents a substituted 3-pyridinyl moiety of the formula: wherein L and M each independently represents H, d-C4 alkyl, C? -C fluoroalkyl, O (C? -C4 alkyl), O (C? -C4 fluoroalkyl), O (C2-C4 alkoxyalkyl), O (C3-C4 alkenyl), O (C3-C4 alkynyl), S (C1-C4 alkyl), S (C? -C4 fluoroalkyl), SO2 (C? -C4 alkyl), SO2 (d-C4 fluoroalkyl), F, Cl, Br, I, CN, NO2, C6H5, CO2 (d-C4 alkyl), CO2 (C3-C4 alkenyl), CO2 (C3-C4 alkynyl), CON (C1-C alkyl) 2, or CONH (C? -C4 alkyl), with the condition of that no more than one of L and M represents H; and T represents H, F, Cl, Br, I, CH3, or CF3. Such compounds wherein AR 'represents a 2- (chloro, bromo or tpfluoromethyl) -4- (C? -C2 alkyl) -3-pyridinyl, or 4-methoxycarbonyl-3-pyridinyl are frequently more preferred. Specifically preferred AR 'portions of this type include 2-fluoro-4-methyl-3-pyridinyl, 2-chloro-4-methoxy-3-pyridinyl, 2-chloro-4-ethoxy-3-pyridinyl, 2-chloro- ^ 4- (1-methylethoxy) -3-pyridinyl, 2-chloro-4-propoxy-3-pyridinyl and 4-methoxycarbonyl-3-pyridinyl. A third embodiment of the invention which is often of special interest are compounds of Formula I wherein AR 'represents A portion of 3-, 4-, or 4-pyrazolyl substituted with a d-C3 alkyl group in the 1-position, with at least one Cl, Br, I or CF3, and, optionally, with an OCH3 or CH3 group . Compounds of this type wherein AR 'represents a portion of 1-methyl-4-halo-3-pyrazolyl, 1-methyl-4-halo-5-pyrazolyl or 1-tf-ethyl-3- (trifluoromethyl) - 5- (methyl, methoxy or halo) -4-pyrazolyl are sometimes most preferred. The term "alkyl" as used herein includes linear, branched and cyclic alkyl portions. Examples include methyl, ethyl, 1-methylethyl, butyl, 2-methylpropyl, 1,1-dimethyl-ethyl, cyclopropyl, and cyclopropylmethyl. The term fluoroalkyl includes alkyl portions replaced with up to the maximum possible number of fluorine atoms. Examples include trifluoromethyl, 2-fluoroethyl, and 1,1, 2,2-tetrafluoroethyl. The term "halo" includes fluoro, chloro, bromo and iodo. Some specifically preferred compounds of Formula I include S, S-dimethyl-N- (2,5-dichlorophenyl) sulphimimine, S, S-dimethyl-N- (2,6-20 dichloro-3-methylphenyl) sulphimimine, S, S -dimethyl-N- (2,6-difluorofenyl) sulphimimine, S, S-dimethyl-N- (2,6-difluoro-3-methylphenyl) sulfimlimin, S, S-dimethyl-N- (2 -chloro-6-fluorophenyl) sulphimimine, S, S-dimethyl-N- (2-methoxycarbonyl-6-chlorophenyl) sulphimimine, S, S-dimethyl-N- (2-methoxycarbonyl-6-fluorophenyl) sulphonimine, S, S -dimethyl-N- (2-methoxycarbonyl-6-methylphenyl) sulphimimine, S, S-dimethyl-N- (2-methoxy-6-trifluoromethyl) phenyl) sulfyrimine, S, S-dimethyl-N- (2-fluoro-4-methyl-3-pyridinyl) sulphimimine, S, S-dimethyl-N- (2-chloro-4-methoxy-3-pyridinyl) sulphimimine, S, S-dimethyl-N- (1 -ethyl-5-methyl-3- (trifluoromethyl) -4-pyrazolyl) sulfyrimine, S, S-dimethyl-N- (1-methyl-4-bromo-3-pyrazolyl) sulphimimine, and S, S-dimethyl -N- (1-methyl-5, 4-bromo-5-pyrazolyl) sulfilimine. The N-arylsulfilimine compounds of Formula I can be prepared by various general methods known in the art. The methods described in Chemical Reviews. 77. 409-435 (1977), • Svnthesis, 165-185 (1981), and Russian Chemical Reviews. 59. 819-831 10 (1990) and references cited herein may be used with only routine adaptation. It is often preferred to use the method of preparation which involves the reaction of a sulfoxide compound of the formula: R / O = S \ R ' wherein R and R 'are as defined for the compounds of Formula I with an arylamine compound of Formula Il la: AR'-NH2 wherein AR 'is as defined for the compounds of Formula I and an activator such as sulfur trioxide, 2-sulfobenzoic acid cyclic anhydride, trifluoroacetic anhydride, chloride of carbonyl or chloride oxalyl. The reaction mixture is treated with a base, such as an alkali metal hydroxide, to complete the process. The process is generally carried out at temperatures between about -70 ° C and about 20 ° C in an organic solvent, such as dichloromethane. Typically, a mixture of the activator and the solvent is prepared and cooled to the desired reaction temperature and the sulfoxide compound is then added. After a short reaction period, the arylamine compound is added and allowed to react for one to four hours. Finally, an aqueous solution of an alkali metal hydroxide is added and the phases are separated. The product of The compound of N-arylsulfilimine can be recovered by evaporative removal of the volatile organic components from the reaction mixture and can be purified by conventional means, such as by recrystallization. However, it is not necessary to recover the compound; the N-arylsulfilimine compound can be used as a catalyst in the form of the solution in an organic solvent obtained in the separation of the phases. Alternatively, the N-arylsulfilimine compounds of Formula I can be prepared by reacting a sulfide compound of the formula R-S-R 'with an arylamine compound of Formula I l and chloride. The process is generally carried out at temperatures between about -20 ° C and about 20 ° C in an organic solvent, such as dichloromethane. Typically, a solution of the sulfide compound in the solvent is prepared and cooled to the desired reaction temperature. Approximately one molar equivalent of chlorine is added and Then approximately one molar equivalent of each of the arylamine compound and an aromatic tertiary amine base, such as # pyridine, a picoline, a collidine, a (mono or poly) halopyridine, nicotinamide, ethyl nicotinate, quinoline and the like are added. Alternatively, an aqueous base, such as a solution of a hydroxide Alkali metal or carbonate can be used as the base. After a short reaction period, a solution of an N-arylsulfilimine compound as a solution in an organic solvent is formed. The N-arylsulfilimine compound can be recovered by means of , f conventional or can be used in the form of the solution in a obtained organic solvent. The aromatic tertiary amine hydrochloride by-product sub-product obtained when an aromatic tertiary amine base is used can be removed from the mixture by extraction with water before use, if desired. The N-arylsulfilimine compounds of Formula I are useful as catalysts in the preparation of N-arylarylsulfonamide compounds of Formula IV: Q- SO2NH-AR by the reaction of aromatic sulfonyl chloride compounds of Formula I I: Q- SO2Cl with arylamine compounds of Formula I II: AR- NH2 wherein Q and AR each independently represents a portion of aromatic hydrocarbyl or aromatic heterocyclyl. A N-arylsulphimyl compound of Formula I wherein the AR 5 portion is identical with the AR portion of the arylamine compound of Formula I I I is very frequently used and is highly preferable. The use of an N-arylsulphimymine catalyst wherein AR 'is different from the AR portion of the arylamine compound generally produces an N- compound. * arylarylsulfonamide of Formula IV, wherein AR is the AR 'of the catalyst N-arylsulphyrimine in addition to the desired compound of Formula IV wherein AR is the AR portion of the arylamine compound. This generally reduces the performance based on the sulfonyl chloride compound and can create a significant separation problem. It is essential that the AR 'of the N-arylsulfilimine compound is identical to the AR of the A compound of arylamine when the N-arylarylsulfonamide compound prepared is an agricultural chemical or a pharmaceutical chemist, since the commercial utility of such chemicals would be compromised by the presence of the related compounds that are formed when the AR 'portion is not identical to the AR portion. The portions AR of the compounds of Formula III which are employed in the process of the invention are the same as those described and characterized herein by the portions AR 'of the N-arylsulphimine catalysts of Formula I. The preferences by categories of AR, by substituents, and by substituent patterns specific ones are the same as those described for AR '.

The Q portion of the compounds of Formula I I represents a portion of aromatic hydrocarbyl or aromatic heterocyclyl. This definition is inclusive of all portions of aromatic hydrocarbyl and aromatic heterocyclyl whether or not these portions possess substituents Examples of suitable aromatic hydrocarbyl moieties include phenyl, naphthyl, phenanthrenyl and indenyl. Examples of suitable aromatic heterocyclic portions include pyridinyl, pyrimidinyl, pyridazinyl, pyrazinyl, 1,3-triazinyl, quiolinyl, quinazolinyl, quinoxalinyl, furanyl, thienyl, pyrrolyl, oxazolyl, thiazolyl, imidazolyl, pyrazolyl, 1,4-oxadiazolyl, 1,4-oxadiazolyl, 1,4-thiadiazolyl, 1,4-thiadiazolyl, 1,4-triazolyl, benzofuranyl, benzo [b] thienyl. , indolyl, [1, 2,4] triazolo [1, 5-a] pyrimidinyl, [1, 2,4] triazolo [1, 5-c] -pyrimidinyl, [1, 2,4] triazolo [1, 5 -a] pyridinyl, pyrazolo- [1, 5-a] pi rim idin ilo, and [1, 2,4] triazolo [1, 5-a] [1, 3,5] -triazinyl. The chloride compounds of Sulfonyl wherein Q represents substituted phenyl are very frequently employed and processes involving such compounds, especially E ^ * ~ such compounds having one or two ortho substituents are frequently preferred accordingly. The compounds wherein Q represents a substituted pyridinyl moiety, especially such compounds that possess at least one ortho substituent are also sometimes preferred. The sulfonyl chloride compounds wherein Q represents 5-amino-1, 2,4-triazin-3-yl or [1, 2,4] triazolo- [1, 5-a] pyridin-2-yl moiety are often of special interest. Substituents possessed by hydrocarbyl portions aromatic and heterocyclyl Q include any substituent that is stable in the presence of the other substituents in the 'f' aryl sulfonyl and which does not react with the arylamine compound or the sulfilimine catalyst. Suitable substituents include F, Cl, Br, I, N02, CN, d-C8 alkyl, O (d-C8 alkyl), O (C3-C8 alkenyl), O (C3-C8 alkenyl), N (d-) C8 alkyl) 2, S (d-C8 alkyl), S (C3-C8 alkenyl), S (C3-C8 alkenyl), SO2 (C1-C8 alkyl), SO2 (C3-C8 alkenyl), SO2 (C3-C8 alkenyl), C02 (d-C8 alkyl), CO2 (C3-C8 alkenyl), CO2 (C3-C8 alkenyl), CONH (d- C8 alkyl), CON (C? -8 alkyl) 2, Si (C? C8 alkyl) 3, phenyl, phenoxy, thiophenoxy, pyridinyloxy, and pyridinylthio. Each alkyl in the substituents noted above can be mono to fully substituted with fluorine or mono or disubstituted with, for example, Cl, Br, I, NO, CN, C? -C8 alkyl, O (C? -C8 alkyl), N (C? -C? Alkyl) ) 2, S (d-C8 alkyl), or SO2 (d-C8 alkyl), CO2 (d- C8 alkyl), CONH (d-C8 alkyl), CON (d-C8 alkyl) 2, or Si (d- C8 alkyl) 3. Each portion of phenyl, phenoxy, thiophenoxy, pyridinyloxy and pyridinylthio in the Substituents noted above may be mono- or trisubstituted with, for example, F, Cl, Br, I, NO2, CN, d-C8 alkyl, O (d-C8 alkyl), N (C? -8 ^^ alkyl) 2, S (C? -C8 alkyl), or SO2 (C? -C8 alkyl), CO2 (d-C8 alkyl), CONH (C? -C8 alkyl), CON (d-C8 alkyl) 2 , and Si (C? -C8 alkyl) 3. Preferred substituents include F, Cl, Br, I, NO, CN, O (C3-C20 alkenyl), or O (C3-C alkynyl); C1-C4 alkyl, O (C? -C4 alkyl), N (C? -C4 alkyl) 2, S (d-C4 alkyl), SO2 (C1-C4 alkyl), CO2 (C? -C4 alkyl), CONH (C? -C4 alkyl), or CON (C? -C4 alkyl) 2 (each alkyl optionally mono to completely substituted with fluorine); or phenyl or phenoxy (each optionally possessing 1 to 3 substituents selected from the group consisting of F, Cl, Br, CN, CF3, NO2, and CH3).

Compounds of fluoride or sulfonyl bromide compounds - Jfc corresponding to the sulfonyl chloride compounds of Formula II could be employed in the process of the invention in place of the compounds of Formula I I. The compounds of fluoride and sulfonyl bromide, however, are not commercially available. generally available, especially at a cost comparable to the cost of the compounds of Formula II, and are not commonly used. Some specifically preferred sulfonyl chloride compounds of formula II for use in the process of the invention include 2-chlorosulfonyl-5-ethoxy-7-fluoro [1, 2-4] -triazolo [1, 5-c] pyrimidine, 2-chlorosuifonyl-5-methoxy-8-fluoro [1, 2,4] triazolo [ 1, 5-c] pip "midin, 2-chloro-3,5-l-methoxy-7-methyl [1, 2,4] triazolo [1, 5-c] pyrimidine, 2-chlorosulfonyl-5-ethoxy-7 methyl [1, 2,4] triazolo [1, 5-a] pyrimidine, 2-chlorosulfonyl-5,7-dimethoxy [1, 2,4] triazolo [1, 5-a] -pyrimidine, 2-chlorosulfonyl-5 , 7- 15 dimethyl [1, 2,4] triazolo- [1, 5-a] pyrimidine, 2-chlorosulfonyl-5-methoxy-7-methyl [1, 2,4] -triazolo [1, 5] a] pyridine, and 2-chlorosulfonyl-5-methoxy-8-chloro [1, 2,4] triazolo [1, 5-a] pyridine The process is carried out by contacting a sulfonyl chloride compound of Formula II with an arylamine compound of Formula II I in the presence of an aromatic tertiary amine compound and a catalytic amount added of an N-arylsulphimyne compound of Formula I: R / AR'- = S \ R 'where AR', R, and R 'are as defined above, preferably in < * where AR is selected to be identical to AR in the arylamine compound. Any of the known methods for contacting the reagents and catalyst can be used. For example, the sulfonyl chloride compound of Formula II can be mixed with an organic solvent and then an arylamine compound of Formula II I, one molar equivalent or more of an aromatic tertiary amine , such as pyridine, a picoline , a collidine, a (mono or poly) halopyridine, # nicotinamide, quinoline and the like, and a catalytically effective amount of a N-arylsulphimine compound of Formula I are added. The amount of the arylamine compound of Formula I I I employed - including the arylamine compound contained in the N-arylsulphimimine catalyst - is at least about one molar equivalent. Quantities in excess of a molar equivalent are not detrimental to the process, but are generally not necessary. The reagents can be combined in any order. Frequently it is preferable to prepare the N-arylsulphimine catalyst of Formula I in a vessel and to add the arylamine compound of Formula II I, the sulfonyl chloride compound of Formula II, and the aromatic tertiary amine thereto. When AR of reagent arylamine and AR 'of the sulfilimine catalyst are selected to be identical, the arylamine reagent of Formula III may be present during the preparation of the N-arylsulphimymine catalyst; that is, an excess of arylamine can be used in the preparation of the N-arylsulphimymine catalyst and the excess employed as all or a portion of the arylamine reagent in the process. The product of N-arylarylsulfonamide * desired of Formula IV is prepared in the resulting reaction. A catalytically effective amount of the N-arylsulphyl compounds of Formula I can be easily determined for each preparation of N-arylarylsulfonamide by routine experimentation. In most cases, an amount between 2 and 30 percent mole of the amount of sulfonyl chloride compound of Formula II is employed. The process is generally carried out at a temperature between - # 20 ° C and 50 ° C. The lower limit is because the reaction becomes too slow to be practical at very low temperatures and the higher limit is because the N-arylsulfilimine catalysts become unstable at elevated temperatures. Temperatures between 0 ° C and 30 ° C are frequently preferred. The pressure in the reactor is not believed to be critical; pressures near atmospheric are generally preferred. Continuous and effective mixing is usually useful. A reaction period of 30 minutes to 16 hours is typical for the process to be completed. The reaction is generally carried out under essentially anhydrous conditions. Solvents that are suitable for such processes are solvents Organic compounds in which the aromatic sulfonyl chloride compound of formula II, the N-arylsulphimine compound of Formula I, and the arylamine compound of Formula I I I have some solubility and which are inert with respect to the reagents employed. Suitable solvents include acetonitrile, butyronitrile, benzonitrile, dichloromethane, 1,2,2-dichloroethane, tetrahydrofuran, 1,2-dimethoxyethane, toluene, chlorobenzene, and the like. Sufficient organic solvent is used to facilitate the agitation of the reaction mixture and, thereby, achieve homogeneity and promote good contact between the reagents. The aromatic tertiary amine base used is a factor to determine the results obtained. Pyridine or a picoline (2-, 3-, or 4-picoline, or a mixture) are frequently preferred because they are the least expensive. Quinoline and nicotynamide are also sometimes preferred because, in some cases, higher yields are effected. The base that is optimal in any specific situation depends on the nature of other reagents employed, including the N-arylsulphimymine catalyst, and the nature (particularly the pKa) of the N-arylarylsulfonamide product being prepared. The by-product formation of N-arylbisarylsulfonimide can be minimized and the yield of the desired N-arylarylsulfonamide can be maximized by the selection of the most appropriate tertiary amine base. The optimum aromatic tertiary amine base for any combination of aryl sulfonyl chloride compound and arylamine compound can be determined by routine experimentation. The N-arylarylsulfonamide products of Formula IV can be recovered from the process medium by standard procedures, including by filtration to collect insoluble solids and by extracting the final reaction mixture with water and removing the solvent and any other volatile material by evaporation, preferably under reduced pressure. The products obtained in the recovery can be + • purified generally by standard procedures, such as recrystallization. The aromatic sulfonyl chloride compounds of Formula I I and the arylamine compounds of Formula I I I are known in the art or can be prepared by routine adaptation of the methods described in the art. The following examples are provided to illustrate the invention. They should not be interpreted as limiting the claims. 10 EJ EMPLOS 1 . Preparation of N- (2,6-difluorophenyl) -S.S-dimethyl-sulfilimine A paste of 2.39 g (grams) (13.0 mmol (millimoles)) of anhydride Cyclic 2-sulfobenzoic acid in 20 ml (milliliters) of dichloromethane was prepared and cooled to 3 ° C. To this was added 0.85 ml (0.94 g., 12 mmol) of dimethyl sulfoxide (DMSO) in the form of drops over a period of 1 min with stirring and cooling. The temperature was raised to 5 ° C and the mixture became homogeneous. After 5 min, 1.41 g (11 mmol) of 2,6-difluoroaniline was added with stirring and cooling over a period of 2 min. A white precipitate formed and the temperature rose to 9 ° C. After 2 hours, the precipitate, which amounted to 3.2 g, was collected by filtration and made into 15 ml of fresh dichloromethane. Ten ml of 2N aqueous sodium hydroxide was added and the mixture was stirred. The Two light liquid phases which formed were separated and the organic phase was dried over magnesium sulfate and concentrated by evaporation under reduced pressure to obtain a clear oil. This oil was dissolved in 5 ml of ether and 5 ml of cyclohexane was added. The mixture was cooled to 5 ° C and the white needles that formed were collected by filtration and dried to obtain 0.88 g of the title compound. 1 H NMR [300 MHz] (CD3CN) ppm: 6.80-6.75 (m, 2H), 6.64-6.5 (m, 1 H), 2.70 (s, 6H); Mass Spectrum (m / z): 189 (M +, 75), 174 (M + -CH 3, 100), 159 (M + -C 2 H 6, 90). 2. Preparation of N- (2,6-dichlorophenyl) -S, S-dimethyl-sulphylamine A paste of 23.9 g (130 mmol) of 2-sulfobenzoic acid cyclic anhydride in 205 ml of dichloromethane was prepared and cooled to 4 ° C. To this was added 9.46 g (120 mmol) of dimethyl sulfoxide in three portions over a period of 3 to 4 min with stirring and cooling, rinsing the vessel with about 10 ml of dichloromethane to insure complete transfer. The temperature rose to between 5 and 6 ° C. After 10 min, 17.9 g (1 10 mmol) of 2,6-dichloroaniline was added with stirring and cooling over a period of 4 min. A white precipitate formed. After 90 min, the mixture was a thick paste and the temperature was 15 ° C. The mixture was treated with 207 g of 1 N and then 5 ml of 50 percent aqueous sodium hydroxide. The two clear liquid phases that formed were separated and the aqueous phase was extracted with 150 ml of dichloromethane. The organic phase and extract were combined and washed with 100 ml of water, dried over magnesium sulfate, filtered and concentrated by evaporation under reduced pressure to obtain a light golden oil. This oil was crystallized from diethyl ether to obtain the title compound in two batches weighing 1.94 and 2.03 g (16 percent theory) as a white solid. 5 1 H N MR [300 MHz] (CD3CI) ppm: 7.21 -7.18 (d, 2H), 6.68-6.63 (dd, 1 H), 2.68 (s, 6H); Mass Spectrum (m / z): 221 (M +, 50), 206 (M + -CH 3, 100), 191 (M + -C 2 H 6, 45). 3. Preparation of N- (2-chloro-6-methoxycarbonylphenyl) -S, S-10 dimethylsulphimimine Method A) A solution of 5.0 ml (0.068 mol) of dimethyl sulfide in 80 ml of dichloromethane was prepared in a round bottom flask and it was cooled to -10 ° C. Chlorine gas (4.6 g, 0.065 mol) was added to the vapor space of the flask through a spray tube with cooling and stirring and, after about 2 min, 12 g (0.065 mol) of methyl 3-chloroanthranilate was added (2-chloro-6-methoxycarbonyl-phenylamine) with stirring and cooling. After about 2 min, 10.2 g (0.13 mol) of pyridine was added slowly with stirring and cooling and the mixture was allowed to react at -10 ° C for 10 min. The The mixture was analyzed by HPLC (high pressure liquid chromatography) (5 mm pack of Shandon Hypersil Phenyl, 60:40:01 levigant acetonitrile: water: phosphoric acid, and UV detector set at 237 nm (nanometer)) and it was found to be 20 percent methyl 3-chloroanthronilate and 80 percent of the title compound (normalized on these two substances). The volatile components of the mixture were removed by evaporation under reduced pressure to obtain the title compound in crude form as a white solid. 1H NMR [300 MHz] (CD3CI) ppm: 7.82 (dd, 1H, J = 1.3, 8.1), 7.69 (dd, 1H, J = 1.3, 8.1), 7.33 (t, 1H, J = 8.1), 3.89 (s, 3H9, 3.37 (s, 6H); Ultraviolet spectrum: maximum at 213 and 298 nm; Mass Spectrum (m / z): 246 (M +, 60), 184 (M + -SC2H6, 100), 154 (M + -OSC3H8, 65) The following compounds were prepared in a similar manner: N- (2-chlorophenyl) -S, S-dimethylsulphimycin; 1H NMR [300 MHz] (CD3CN) ppm: 7.52 (dd, 1H, J = 7.7, 1.7), 7.49 (dd, 1H, J = 7.7, 1.8), 7.35 (dt, 1H, J = 7.6, 1.7), 7.29 (dt, 1H, J = 7.6, 1.7), 2.56 (s, 6H); Ultraviolet spectrum: maximum at 210 and 260 nm; N- (2-methoxy-6- (trifluoromethyl) phenyl) -S, S-dimethyl-sulphylamine; 1H NMR [300 MHz] (CD3CN) ppm: 7.43 (t, 1H, J = 8.0), 7.30 (d, 1H, J = 8.0), 7.24 (d, 1H, J = 8.0), 3.93 (s, 3H) 3.29 (s, 6H); 2,6-dichloro-3-methylphenyl) -S, S-dimethyl-sulphonimine; • NMR [300 MHz] (CD3CN) ppm: 7.10 (d, 1H, J = 8.2), 6.61 (d, 1H, J = 8.2), 2.84 (s, 6H), 2.27 (s, 3H); Mass Spectrum (m / z): 236 (MH +), 208, 195, 174, 147; N- (2-methoxycarbonylphenyl) -S, S-dimethylsuflimine; • NMR [300 MHz] (CD3CN) ppm: 7.92 (dd, 1H, J = 8.0, 1.5), 7.48 (dt, 1H, J = 7.8, 1.4), 7.14 (d, 1H, J = 8.1), 7.06 ( dt, 1H, J = 8.1, 1.0), 3.85 (s, 3H), 2.56 (s, 6H); N- (2-methyl-6-nitrophenyl) -S, S-dimethylsu! Fimiline; 1 H NMR [300 MHz] (CD 3 CN) ppm: 7.82 (d, 1 H, J = 8.2), 7.58 (d, 1 H, J = 7.4), 7.34 (brdd, 1 H, J = 7.8, 7.3), 3.38 (s, 6H), 2.48 (s, 3H); 13C NMR [75.5MHz) (CD3CN) ppm: 146.0, 138.5, 137.4, 132.6, 128.2, 124.6, 33.9, 19.3; N- (2-chloro-4- (1-methylethoxy) -3-pyridinyl) -S, S-dimethyl-sulphorylimine; H NMR [300 MHz] (CD3CN) ppm: 8.08 (d, 1 H, J = 5.8), 7.03 (d, 1 H, J = 5.8), 4.8 (septet, 1 H, J = 6.1), 3.26 (s) , 6H), 1 .37 (d, J = 6.0, 6H); N- (5-bromo-2-pyridinyl) -S, S-dimethylsulphimimine; • N MR [300 MHz] (CD3CN) ppm: 8.21 (d, 1 H, J = 2.3), 7.74 (dd, 1 H, J = 8.8, 2. 4), 6.98 (d, 1 H, J = 8.8), 3.36 (s, 6H).

Method B) A mixture of 7.3 g (94 mmol) of dimethyl sulfoxide and 100 ml of dichloromethane was prepared and cooled to -60 ° C and then 19.8 g (94 mmol) of trifluoroacetic anhydride was added slowly with stirring. A white solid formed in about 5 min at which time a solution of 24 g (130 mmol) of methyl 6-chloroanthranilate in 15 ml of dichloromethane was added slowly with stirring. The mixture was allowed to react and warm to about 0 ° C with stirring. The white solid that formed first was redissolved. The mixture was then neutralized with 70 ml of 10 percent by weight potassium hydroxide in water with stirring for 30 min. The mixture turned brown. The organic phase was separated and the aqueous phase was extracted twice with dichloromethane. The organic phase and the extracts were combined and concentrated by evaporation under reduced pressure. The brown tarry residue was triturated with diethyl ether to induce solidification, recovered by filtration and washed with diethyl ether to obtain the title compound in crude form as a greenish-brown solid. It was found by HPLC that the solid consists of about 80 percent of the title compound and about 20 percent of methyl 6-chloroanthranilate.

Method C) A solution of 3.2 g (0.039 mol) of sulfur trioxide in 6 ml of dichloromethane was cooled to 0 ° C and 1.4 g (0.018 mol) of dimethyl sulfoxide was added slowly with stirring and cooling. After 10 min, 3.3 g (0.018 mol) of methyl 6-chloroanthranilate was added as a solid with stirring and cooling. The mixture was allowed will react for 15 min and then 2.8 g (0.035 mol) of pyridine is added. It was determined by HPLC that the resulting solution contained the title compound and unreacted methyl 6-chloroanthranilate in a ratio of 61:39. 4. Preparation of N- (2-chloro-6-methoxycarbonylphenyl) -S, S-tetramethylene-sulphonimine A solution of 3.0 ml (34 mmol) of tetrahydrothiophene and 50 ml of dichloromethane was cooled to -10 ° C and then 2.3 g ( 32 mmol) of chlorine was sprayed with cooling and stirring. An amount of 6.3 g (34 mmol) of methyl 6-25-chloroanthranilate and then 5.4 g (68 mmol) of pyridine were added. It was found that the ratio of the title compound to unreacted methyl 6-chloroanthranilate in the product mixture was 65:35 by HPLC. 1 H NMR [300 MHz] (CD3CN) ppm: 7.78 (d, 1 H, J = 8.0), 7.44 (d, 1 H, J = 8.0), 5 6.64 (t, 1 H, J = 8.0 =, 3.63 (s, 3H), 3.24 (m, 4H), 2.37 (m, 2H), 2.16 (m, 2H), Ultraviolet spectrum: maximum at 220 nm, Mass Spectrum (m / z): 272 (MH +, 100 ), 240 (M + -OCH4, 15), 184 (M + -SC4H8, 100), 87 (SC4H7 +, 40).

. Preparation of N- (2-chloro-6-methoxycarbonylphenyl) -S-methyls-10-phenylsulphimimine A solution of 3.0 g (24 mmol) of methyl phenyl sulfide in 30 ml of dichloromethane was cooled to -10 ° C and 1 .7 g (24 mmol) of chlorine was sprayed with cooling and stirring. To this were added with cooling and stirring 4.5 g (24 mmol) of solid methyl 6-chloroanthranilate and then 3.8 g (48 mmol) of pyridine. The product mixture contained the title compound and methyl 6-chloroanthranilate in a ratio of 60:40 as determined by HPLC. Ultraviolet spectrum: maximum at 215 and 300 nm; Mass Spectrum (m / z): 308 (MH +, 40), 276 (M + -OCH4, 35), 261 (M + -OC2H7, 10), 184 (M + -SC7H8, 35), 124 (SC7H8 +, 40). 6. Preparation of N- (2,4,6-trichlorophenyl) -S, Sd-methyl-sulphylamine A solution of 1.1 ml (15 mmol) of dimethyl sulfide in 170 ml of dichloromethane was cooled to -10 ° C and 0.90 g ( 13 mmol) of chlorine additions through a spray tube with cooling and stirring.

Subsequently 23.3 g (120 mmol) of 2,4,6-trichloroaniine and then # 22 g (170 mmol) of quinoline were added with cooling and stirring. The resulting product was a mixture of the title compound and unreacted 2,4,6-trichloroaniline. 7. Preparation of N- (4-bromo-1-methyl-5-pyrazolyl) -S, S-dimethylsulphimimine A solution of 0.60 ml (8.2 mmol) of dimethyl sulfide in 30 ml of dichloromethane was cooled to -20 °. C and 0.50 g (7.0 mmol) of chlorine are "^ r added through a spray tube with cooling and stirring.

Subsequently, 1.0 g (5.7 mmol) of 5-amino-4-bromo-1-methylpyrazole and then 1.0 g (12.7 mmol) of pyridine were added with cooling and stirring. A 2 ml aliquot of this mixture was removed and the light yellow solids present were collected by filtration and washed with deuteroacetonitrile. 15 1 H NMR [300 MHz] (CD3CN / D2O) ppm: 7.58 (s, 1 H), 3.77 (s, 3H), 3.17 (s, 6H). 8. Preparation of N- (2,6-dif-luo-phenyl) -8-f-luoro-5-methoxy-2,41-triazolori-5-clpyrimidine-2-sulfonamide using catalyst Sulfilimine A mixture consisting of 1.4 g (11 mmol) of 2,6-difluoroaniline, 0.86 g (11 mmol) of pyridine, and 30 ml of dry acetonitrile was prepared and cooled to 1 -3 ° C. N- (2,6-difluorophenyl) -S, S-dimethylsulphimimine (0.15 g, 0.78 mmol) was added and then 2.7 g (10 mmol) of 2-chlorosulfonyl-8-fluoro-5-methoxy [1, 2, 4-] triazole [1,5-c] pyrimidine in 10 ml of dry acetonitrile was added dropwise over a period of 30 s with stirring and cooling to the yellow solution. An exotherm raising the temperature to 10 ° C was observed and a white precipitate formed gradually. After 80 min, the mixture was analyzed quantitatively by HPLC using standards and it was found that 70 percent of the chlorosulfonyl compound was converted to the title compound, 24 percent was converted to N, N-bis ((8-fluoro-5- methoxy [1, 2,4] triazolo [1, 5-c] pyrimidin-2-yl) sulfonyl) -2,6-difluorophenylamine and 4 parts were converted to 8-fluoro-5-methyloxy [1, 2.4 ] triazolo [1, 5-c] -pyrimidine-2-sulfonic acid. 9. Preparation of N- (2,6-dichlorophenyl) -7-fluoro-5-ethoxy-1, 2,4-triazolo [1,5-clpyrimidine-2-sulfonamide using sulfilimine catalyst. A mixture consisting of 7.33 g (42.5 mmol) of 2,6-dichloroaniline, 14.13 g 847.4 mmol) of 94.2 percent purity 2-chlorosulfonyl-7-fluoro-5-ethoxy [1, 2,4] triazolo- [1, 5-c] pyrimidine, 6.72 g (55.0 mmol) of nicotinamide, and 81 .4 g of dry acetonitrile was prepared and cooled to 4 ° C. N- (2,6-dichlorophenyl) -SS-dimethylsulphimimine (1.15 g, 5.15 mmol) was then added with stirring and cooling. Cooling and stirring were maintained for 3 hours and then the mixture was allowed to warm to room temperature. After 6 hours, the mixture was analyzed quantitatively by HPLC using standards and the yield of the title compound was found to be 87 percent of the theory. A yield of 3 percent of 7-fluoro-5-ethoxy [1, 2,4] -triazolo [1,5- 25 c] pyrimidine-2-sulfonic acid was also found.

. Preparation of N- (2-chloro-6-methoxycarbonyl-phenyl) -7-fluoro-5-ethoxy-1, 2,4-triazole-1, 5-clpyrimidine-2-sulfonamide using sulphimimine catalyst without recovering a solution of 0.7 ml (96 mmol) of Dimethyl sulphide in 20 ml of dichloromethane was prepared in a round bottom flask and cooled to -10 ° C. Chlorine gas (0.60 g, 85 mmol) was added to the vapor space of the flask through a spray tube with cooling and stirring and, after about 2 min, 18 g (97 mmol) of 3-chloroanthranilate Methyl (2-chloro-6-methoxycarbonylphenylamine) was added with stirring and cooling. After about 2 min, 9.8 g (124 mmol) of pyridine was added slowly with stirring and cooling and the mixture was allowed to react at -10 ° C for 10 min. A solution of 21 g (75 mmol) of 2-chlorosulfonyl-7-fluoro-5-ethoxy [1, 2,4] triazolo- [1, 5-c] pyrimidine In 90 ml of dichloromethane was prepared, cooled to 0 ° C and then added with cooling and stirring. The reaction was essentially completed by HPLC analysis in 5-6 hours. After settling overnight, about 50 ml of dichloromethane was removed by distillation and 50 ml of 2-propanol was added. He The remaining dichloromethane was removed by distillation until the upper temperature was 62-64 ° C and the kettle temperature was 72-74 ° C. The resulting 2-propanol paste was cooled to 5 ° C and, after 30 min, filtered. The collected solids were rinsed with 2x50 ml of methanol and air dried to obtain 29.8 g (85 percent theory) of the title compound.

The same product was obtained in a similar way using the # N- (2-chloro-6-methoxycarbonylphenyl) -S, S-tetramethylene-sulphonimine product mixture of Example 4 as the catalyst. A 9 ml portion of that product was diluted with 75 ml of dichloromethane, the solution was cooled to -10 ° C, and 9.3 g (50 mmol) of methyl 3-chloroanthranilate and then 4.8 g (60 mmol) of pyridine were added. they were added with cooling and stirring. 2-Chlorosulfonyl-7-fluoro-5-ethoxy [1, 2,4] triazolo [1, 5-c] -pyrimidine (15.5 g of 91 pure percent, 50 mmol) was added with cooling to 0- _____ mf 2 ° C. The reaction was completed in 6 hours and a yield of 90 percent of the purity title compound of 98 percent was obtained in recovery. The same product was obtained in a similar way using the . N- (2-chloro-6-methoxycarbonylphenyl) -S-methyl-S-phenylsulphimimine product mixture of Example 5 as the catalyst. A performance of 55 percent of a purity product of 98 percent was obtained. The following compounds were prepared in a similar manner using N- (2-chloro-6-methoxycarbonylphenyl) -S, S-dimethylsulfilimine as the catalyst: N- (2-chloro-6-methoxycarbonylphenyl) -7,8-dichloro [1,4] triazolo [1,5-c] pyrimidine-2-sulfonamide, a white solid obtained in about 85 percent yield; 'NMR [300 MHz] (D6-DMSO) ppm: 1 1 .15 (s, 1 H), 7.70 (d, 1 H, J = 8.0), 7.68 (d, 1 H, J = 7.8), 7.47 ( dd, 1 H, J = 8.0, 7.8), 4.68 (q, 2H, J = 7.0), 3.71 (s, 3H), 1.45 (t, 3H, J = 7.0); N- (2-chloro-6-methoxycarbonylpheni) -7-fluoro-5-methoxy- [1,2,4] triazoIo [1,5- c] pyrimidine-2-sulfonamide, a white solid obtained in about 70 percent of performance; 5 1 H NMR [300 MHz] (D 6 -DMSO) ppm: 11.1 (s, 1H), 7.70 (d, 1H, J = 7.9), 7.68 (d, 1H, J = 7.9), 7.46 (t, 1H, J = 7.9), 7.36, /.36 (s, 1H), 4.23 (s, 3H), 3.67 (s, 3H); 'Ww N- (2-chloro-6-methoxycarbonylphenyl) -8-chloro-5-ethoxy-7-fluoro [1, 2,4] triazolo [1,5- 10 c] pyrimidine-2-sulfonamide, a yellow solid clear obtained in approximately 80 percent yield; 1H NMR [300 MHz] (De-DMSO) ppm: 11.15 (s, 1H), 7.71 (d, 1H, J = 8.0), 7.70 (d, 1H, J = 7.9), 7.47 (dd, 1H, J = 8.0, 7.9), 4.68 (q, 2H, J = 7.1), 3.71 (s, 3H), 1.45 (t, 3H, J = 7.1); and 15 N- (2-chloro-6-methoxycarbonylphenyl) -7-chloro-5-ethoxy [1,2,4] triazolo [1,5- c] pyrimidin-2-suphonamide, a pale yellow solid obtained in approximately 82 percent of performance; 'H NMR [300 MHz] (D6-DMSO) ppm: 11.0 (s, 1H), 7.79 (s, 1H), 7.71 (d, 1H, 20 J = 8.0), 7.68 (d, 1H, J = 7.9) , 7.46 (dd, 1H, J = 8.0, 7.9), 4.68 (q, 2H, J = 7.1), 3.69 (s, 3H), 1.45 (t, 3H, J = 7.1). 11. Preparation of N- (2,6-dichlorophenyl) -7-fluoro-5-ethoxy-ri, 2,41-triazole-1,5-clpyrimidine-2-sulfonamide using sulphimimine catalyst without recovering A first solution containing about 76 mmol of 2-chlorosulfonyl- 7-fluoro-5-ethoxy [1, 2,4] triazolo [1, 5-c] pyrimidine in about 1 10 g of dichloromethane was prepared by combining 21.8 g of 75 percent purity (approximately 38 mmol) of bis (5-ethoxy-7-fluoro [1, 2,4] triazolo [1, 5-c] pyrimidin-2-yl) disulfide, 16.0 g of water and 190 g of dichloromethane, cooling the mixture to 5 ° C and adding 15.1 g (240 mmol) of chlorine gas with stirring and cooling over a period of 75 min. Another 73.0 g of water were added and the phases separated. The aqueous phase was extracted with 22.0 g of dichloromethane. The two fresh dichloromethane solutions were combined and a total of 18.3 g of water and the dichloromethane was removed by azeotropic distillation using a Dean-Stark trap. Another 105.8 g of dichloromethane were added and another 101.5 g of solvents removed by azeotropic distillation. Another approximately 10 g of dichloromethane was used to facilitate transfer to a holding vessel. A second solution of 1.35 g (22 mmol) of dimethyl sulfide in 68.2 g of dichloromethane was prepared in a round bottom flask and cooled to about 7 ° C. The gaseous chlorine (1.5 g, 21 mmol) was added to the vapor space of the flask through a spray tube with cooling and stirring, and after about 3 min, 15.3 g (94 mmol) of 2.6 g. dichloroaniline, 19.4 g (160 mmol) of nicotinamide, and 32.2 dichloromethane were added with stirring and cooling. After 30 min, 7.6948 g of 1,4-dichlorobenzene (internal standard for subsequent gas-liquid chromatographic analysis) and then the first prepared solution was added with stirring. The reaction mixture was allowed to warm slowly to room temperature and was analyzed by gas-liquid chromatography for the disappearance of the chlorosulfonyl starting material. After 4.5 hours, the mixture was diluted with 42.8 g of water and the resulting paste was filtered to recover the solids. The solids were re-pulped in a mixture of 41.7 g of water and 40.2 g of 2-propanol and re-recovered by filtration and then re-pulped in 13.2 g of 2-propanol and recovered again by filtration. The recovered solids were dried under reduced pressure at 40 ° C to obtain 26.9 g of 95 percent purity sulfonamide product (83 percent theory) as determined by quantitative H PLC using an external standard. There was another 4.8 percent of the theory product in the leaks. 12. Preparation of N- (2,6-dichlorophenyl) -7,8-dichloro-f1 .2.41-triazolori, 5-clpyrimidin-2-sulfonamide using sulphimimine catalyst without recovering A solution of 0.6 ml (8 mmol) of dimethyl sulfide in 65 ml of dichloromethane was cooled to -20 ° C and then 0.4 g (6 mmol) of chlorine was slowly sprayed with stirring and cooling to keep the temperature below -15 ° C. A mixture of 5.0 g (31 mmol) of 2,6-dichloroaniline and 6.3 g (49 mmol) of quinoline was then added with cooling and stirring to form a mixture of sulphilline catalyst, unreacted 2,6-dichloroaniline and quinoline. The mixture was allowed to warm to 0 ° C and 10 g (45 mmol) of 2-chlorosulfonyl-7,8-di-chlorotl-1-triazoloyl-c-pyrimidine were added with stirring and cooling. The mixture was allowed to warm to about 20 ° C and stir for about 16 hours. Then it was diluted with 50 ml of methanol and the solids that formed were collected by filtration, washed 2x30 ml with methanol, and dried to obtain 6.2 g (80 percent theory) of the title compound as a white solid having maximum uv at 210 and 270 nm. 1 H NMR [300 MHz] (D6-DMSO) ppm: 8.6 (brs, 1 H), 7.44 (d, 2H, J = 8.2), 7.32 (dd, 1 H, J = 8.2), 4.72 (q, 2H , J = 7.1), 1.50 (t, 3H, J = 7.1). The following compounds were prepared in a similar manner using the same sulfilimine catalyst: N- (2,6-dichlorophenyl) -7-fluoro-5-methoxy [1, 2,4] triazolo- [1,5-c] pyrimidine- 2-sulfonamide, a white-grayish solid obtained at approximately 21 percent yield: 'H NMR [300MHz] (D6-DMSO) ppm: 8.21 (s, 1 H), 7.44 (d, 2H, J = 8.3), 7.33 ( dd, 1 H, J = 8.3), 6.98 (d, 1 H, J = 1 .1), 4.28 (s, 3H); N- (2,6-dichlorophenyl) -8-chloro-7-fluoro-5-ethoxy [1, 2,4] -triazolo [1, 5-c] pyrimidine-2-sulfonamide, a whitish solid obtained in approximately 85 percent yield; 'H NMR [300MHz] (CD3CN) ppm: 7.45 (d, 2H, J = 8.3), 7.34 (dd, 1 H, J = 8.3), 4.73 (q, 2H, J = 7.1), 1.51 (t, 3H , J = 7.1); N- (2,6-dichlorophenyl) -7-chloro-5-ethoxy [1, 2,4] triazolo- [1, 5-c] pyrimidine-2-sulfonamide, a white solid obtained in about 90 percent of performance; 1H NMR [300MHz] (CD3CN) ppm: 8.29 (brs, 1 H), 7.47 (s, 1 H), 7.44 (d, 2H, J = 8.2), 7.33 (dd, 1 H, J = 8.2), 4.70 (q, 2H, J = 7.1), 1 .51 (t, 3H, J = 7.1); N- (2,6-d-chlorofenyl) -7-fluoro-5- (1-methyletoxy) [1, 2, 4] -triazolo [1, 5-c] pyrimidine-5-sulfonamide, a brown solid -slight yellow obtained in approximately 77 percent yield; 1 H NMR [300MHz] (D6-DMSO) ppm: 7.82 (d, 2H, J = 8.2), 7.35 (d, 1 H, J = 8.2), 7.32 (s, 1 H), 5.47 (septet, 1 H , J = 6.1), 1 .46 (d, 6H, J = 6.1); 13C NMR [75.5MHz] (De-DMSO) ppm: 165.9, 161.9 (JC-F = 242.3), 157.1 (JC.F = 15.2), # 10 150.4, 148.6 (JC-F = 26.0), 135.9, 130.3, 128.7, 86.4 (JC-F = 41.3), 76.6, 21.2. 13. Preparation of N-2-chlorophenyl-S-dimethylsulphimimine and its use as a catalyst to prepare N- (2-chlorophenyl) -4-methylbenzenesulfonamide A solution of 12.1 ml (0.17 mol) of dimethyl sulfide in 150 ml dichloromethane was cooled to -10 ° C and then 10.8 g (0.15 mol) of chlorine was slowly sprayed with stirring and cooling to keep the temperature below -10 ° C. To this were added 19.1 g (0.15 mol) of 2-chloroaniline and then 38.7 g (0.30 mol) of quinoline with cooling and stirring to form the sulfilimine catalyst. An aliquot of 105 g of the 272 g mixture was diluted with 200 ml of dichloromethane and then 25.5 g (0.20 mol) of 2-chloroaniline, 38.7 g (0.30 mol) of quinoline and finally 47.6 g (0.25 mol) of 4-methyl chloride. Benzenesulfonyl were added with cooling (-10 ° C) and stirring. The mixture was allowed to warm to room temperature and was stirred for 2 days.

The volatile components were then removed by w evaporation under reduced pressure and the oily residue obtained was dissolved in 300 ml of dichloromethane. The resulting solution was washed with 200 ml of 1 N aqueous hydrochloric acid and the wash water was back-extracted with 100 ml of dichloromethane. The combined organic phases were dried over magnesium sulfate and concentrated by evaporation under reduced pressure. The residue was dissolved in 175 ml of acetonitrile and re-precipitated by adding 200 ml of water slowly. The solids that were formed were collected by filtration, washed with 2-propanol, and dried under reduced pressure to obtain 44.7 g (64 percent theory) of the title compound as a whitish solid. 1 H NMR [300MHz] (CD3CN) ppm: 9.93 (s, 1 H), 7.60 (d, 2H, J = 8.2), 7.37 (d, 1 H, J = 7.4), 7.33 (d, 2H, J = 8.0), 7.24 (m, 2H), 7.16 (ddd, 1 H, J = 7.8, 5.2, 3.7), 2.33 (s, 3H); 13C NMR [75.5MHz] (D6-DMSO) ppm: 143.1, 137.5, 133.6, 130.1, 129.8, 129.5, 128.8, 127.6, 127.3, 126.9, 126.6, 20.9. 15. Sulphilimine-catalyzed preparation of N- (2,6-difluoro-phenyl) -5-methyl-1, 2,4-l-triazole, 5-alpyrimidine-2-sulfonamide A solution of 7.0 ml (0.096 mol) of dimethyl sulfide in 70 ml of dichloromethane was cooled to -10 ° C and then 5.5 g (0.078 mol) of chlorine was slowly sprayed with stirring and cooling to keep the temperature below -10 ° C. To this was added with cooling and stirring 10.0 g (0.078 mol) of 2,6-difluoroaniline and then 50.0 g (0.39 mol) of quinoline to form the sulfilimine catalyst. An aliquot of 105 g of the 317 g mixture was diluted with 135 ml of dichloromethane and Then 10.0 g (0.078 mol) of 2,6-difluoroaniline and 0.095 mol of 2-chlorosulfonyl-5-methyl [1,2,4] triazolo [1,5-a] pyrimidine were added with * stirring and cooling to 0 ° C. After 20 min, 8.4 g (0.065 mol) of quinoline was added with stirring and the mixture was allowed to warm to room temperature overnight. The resulting mixture was filtered to collect the title compound as an insoluble light brown solid. The filtrate was washed with 150 ml of 1 N aqueous hydrochloric acid and the wash water was back-extracted with dichloromethane. The combined organic phases were dried over magnesium sulfate and filtered to remove the magnesium sulfate. The magnesium sulfate was extracted with 50 ml of acetonitrile, which was added to the filtrate. The filtrate was concentrated under reduced pressure and the solid residue obtained was pulped in water. The solids were collected by filtration and dried to obtain the title compound. The additional title compound was obtained from the filtrates. In all, 29.8 g of the title compound (87 percent theory) were obtained as a white solid. 1 HN MR [300MHz] (CD3CN) ppm: 7.71 (d, 2H, J = 8.7), 7.53 (d, 2H, J = 8.7), 7.33 (tt, 1 H, J = 8.5, 6.1), 6.98 (dd) , 2H, J = 8.3, 8.2).

. Sulphurimine-catalyzed preparation of N- (2-methoxy-6- (trifluoromethyl) phenyl) -5-ethoxy-7-fluorori .2.41-azolo-p.5-clpyrimidine-2-sulfonamide A mixture containing about 10 mmol of N- (2-methoxy-6- (trifluoromethyl) phenyl-S, Sdmethyl-sulphonimine in about 17 ml of dichloromethane solution prepared as in Example 3A, omitting the recovery step, was diluted with 30 ml of dichloromethane and 10.0 g (52 mmol) of 2-methoxy-6- (trifluoromethyl) anililine, 4.6 (58 mmol) of pyridine, and 54 mmol of 2-chlorosulfonyl-5-ethoxy-7-fluoro [1, 2,4] - triazolo [1, 5-c] pyrimidine dissolved in 30 ml of dichloromethane were added sequentially with stirring at about -10 ° C. The mixture was allowed to stir overnight.A small amount of pyridine was added and The mixture was allowed to stir for a further 6 hours, the volatiles were then removed by evaporation under reduced pressure and the remaining thick paste was diluted with 30 ml. Methanol The solids present were recovered by filtration, re-pulped in methanol, and recovered again, washed with methanol and dried. The title compound was obtained as a yellow solid in 63 percent yield (14.9 g). 1 H NMR [300MHz] (CD3CN) ppm: 8.06 (1 s, 1 H), 7.47 (dd, 1 H, J = 8.5), 7.31 (d, 1 H, J = 8.1), 7.15 (d, 1 H , J = 8.4), 6.98 (d, 1 H, J = 1 .5), 4.73 (q, 2H, J = 7.1), 3.27 (s, 3H), 1.52 (t, 3H, J = 7.1). 16. Sulphurimine-catalyzed preparation of N- (2-chloro-4- (1-methyletoxy) -3-pyridinyl) -5-ethoxy-7-f luorof 1.2.4ltriazolo-f1.5-cl-pyrimidine-2-sulfonamide A mixture containing about 10 mmol of N- (2-chloro-4- (1-methylethoxy) -3-pyridinyl-S, S-dimethylsulphimimine in about 18 ml of dichloromethane solution prepared as in Example 3A omitting the recovery step , was diluted with 45 ml of dichloromethane and 4.5 g (24 mmol) of 3-amino-2-chloro-4- (1-methylethoxy) -pyridine, 3.2 g (41 mmol) of pyridine, and 36 mmol of 2-chlorosulfonyl 5-Ethoxy-7-fluoro [1, 2,4] -triazolo [1,5-cjpyrimidine dissolved in 19 ml of dichloromethane were added sequentially with stirring and cooling to about -10 [deg.] C. The mixture was allowed to stir The volatiles were then removed by evaporation under reduced pressure.The solid residue was dissolved in acetonitrile and methanol 1.1 and 0.5N aqueous hydrochloric acid was added until solids were recovered by filtration, washed 2x75 ml with water and dried to obtain 11.0 g (73 percent theory) of the title compound as a white solid. Another 1 .7 g (1 1 percent theory) of product was obtained from the aqueous phases by extraction. 1 H NMR [300MHz] (CD3CN) ppm: 10.6 (s, 1 H), 8.16 (d, 1 H, J = 5.8), 7.41 (s, 1 H), 7.1 1 (d, 1 H, J = 5.9 ), 4.71 (d, 1 H, J = 7.0), 4.56 (septet, 1 H, J = 6.0), 1.45 (t, 3H, J = 7.0), 0.82 (d, 6H, J = 6.0). 17. Sulphurimine catalyzed preparation of N- (5-bromo-2-pyrimidinyl) -4-methyl-phenylsulfonamide A mixture containing approximately 17 mmol of N-5-bromo-2-pyridinyl-S, S-dimethylsulphimin in approximately 30 ml of dichloromethane solution prepared as in Example 3A omitting the recovery step, was diluted with 43 ml of dichloromethane and then 10.0 g (58 mmol) of 2-amino-5-bromopyridine, 5.5 g (70 mmol) of pyridine, and 14.2 (74 mmol) of 4-methyIbenzenesulfonyl chloride were added sequentially with stirring and cooling to -10 ° C. The mixture was allowed to warm to 20 ° C with stirring. A white precipitate formed quickly. 1.6 g (20 mmol) of additional pyridine was added and the mixture allowed to settle for 3 days. Dichloromethane (25 ml) was added to dissolve all solids and the resulting solution was washed with 150 ml of 0.1 N aqueous hydrochloric acid. The aqueous layer was back-extracted with dichloromethane and the combined organic phases were dried over magnesium sulfate and concentrated by evaporation under reduced pressure. The yellow solid residue was recrystallized from 175 ml of acetonitrile and the resulting yellow solid (a first round of 8.3 g and a second round of 1.5 g) was recovered to obtain the title compound (41 percent theory). 1 H NMR [300MHz] (D6-DMSO) ppm: 1 1 .26 (s, 1 H), 8.26 (d, 1 H, J = 2.4), 7.87 (dd, 1 H, J = 8.8, 2.4) , 7.78 (d, 2H, J = 8.2), 7.34 (d, 2H, J = 8.1), 7.03 (d, 1 H, J = 8.8), 2.31 (s, 3H); 13C N MR [75.5MHz] (D6-DMSO) ppm: 150.4, 148.3, 143. 4, 140.8, 137.2, 129.5, 127.0, 1 13.7, 1 13.2, 20.9. 18. Sulphurimine catalyzed preparation of N- (2-methyl-6-nitro-phenyl) -4-chloro-3-nitrophenylsulfonamide A mixture containing about 22 mmol of N- (2-methyl-6-nitrophenyl) -S, S-dimethyl-sulphonimine in about 25 ml of dichloromethane solution prepared as in Example 3A, omitting the recovery step, was diluted with 15 ml of dichloromethane and then 11.0 g (72 mmol) of 2-methyl-6-nitroaniline, 15 g (120 mmol) of quinoline and, 24 g (95 mmol) of 4-chloro-3-nitrobenzenesulfonyl chloride were added sequentially with stirring and cooling to -10 ° C. The mixture was allowed to slowly warm to 20 ° C and was stirred overnight. 6.0 g (76 mmol) of additional pyridine were added in two equal portions. After a short time, 100 ml of acetonitrile was added and the resulting solution was washed with 1N aqueous hydrochloric acid. The aqueous phase was extracted with 50 ml of dichloromethane and then 50 ml of acetonitrile. The combined organic phases were dried over magnesium sulfate (washing the magnesium sulfate with 2x50 ml of acetonitrile), and The combined organic solutions were concentrated by evaporation under reduced pressure. The resulting oil was dissolved in warm 2-propanol and re-precipitated by adding 200 ml of 1 N aqueous hydrochloric acid. The resulting solids were recovered by filtration, washed with 2-propanol, and dried to obtain 18.5 g (66 g). percent theory) of the title compound. 1 H NMR [300MHz] (CD3CN) ppm: 7.71 (d, 2H, J = 8.7), 7.53 (d, 2H, J = 8.7), 7.33 (tt, 1 H, J = 8.2, 6.1), 6.98 (dd) , 2H, J = 8.3, 8.2). 19. Sulphurimine-catalyzed preparation of N- (4-bromo-1-methyl-5-15 pyrazolyl) -5-ethoxy-7-fluoro [1,24-triazolo-p, 5-clpyrimidine-2-sulfonamide A mixture containing approximately 53 mmol of N- (4-bromo-1-methyl-5-pyrrazolyl) -S, S-dimethylsulphimimine in about 28 ml of dichloromethane solution prepared in Example 7 omitting the recovery step, cooled to -10 ° C and 1.0 g (5.7 mmol) of 5-amino-4-bromo-1-20 methylpyrazole, 0.54 g (6.8 mmol) of pyridine, 1.8 mmol of 2-chlorosulfonyl-5-ethoxy-7-fluoro- [1, 2,4] triazolo [1, 5-c] pyrimidine, and 5 ml of dichloromethane were added sequentially with stirring and cooling to about -10 ° C. The mixture was allowed to stir at room temperature for 2 days. The solids present were recovered by filtration, washed with a small amount of 2-propoanol, and dried to obtain 5.7 g of the title compound as a • ß »white solid. A purer sample amounting to 4.6 g (26 percent theory) was obtained by dissolving this in dimethyl sulfoxide and then adding water to re-precipitate it. 5 1 H NMR [300MHz] (CD3CN) ppm: 10.9 (s, 1 H), 7.86 (s, 1 H), 7.36 (d, 1 H, J = 0.72), 4.68 (q, 2H, J = 7.1 ), 3.68 (s, 3H), 1 .46 (t, 3H, J = 7.1).

. Sulphurimine catalyzed preparation of N- (2,6-difluoro-phenyl) -4-chlorobenzenesulfonamide A solution of 7.0 ml (96 mmol) of dimethyl sulfide in 70 ml of dichloromethane was prepared in a round bottom flask and cooled to - 10 ° C. Chlorine gas (5.5 g, 78 mmol) was added to the vapor space of the flask through a spray tube with cooling and stirring. After a short period, 10.0 g (78 mmol) of 2,6-difluoroaniline and Then 50 g (390 mmol) of quinoline were added with stirring and cooling. An aliquot of 109 g of the obtained 317 g mixture was diluted with 15 ml of dichloromethane and 13.5 g (105 mmol) of 2,6-difluoroaniline and then 27.3 g (125 mmol) of 4-chlorobenzenesulfonyl chloride were added with stirring and cooling at 0 ° C.

The mixture was stirred cold for 1 hour, an additional 8.4 g (65 mmol) of quinoline was added, and the mixture was allowed to warm to room temperature and stir overnight. The acetonitrile was added to dissolve the solids present and the resulting solution was washed with 1 N aqueous hydrochloric acid. The aqueous phase was extracted with a mixture of 70 ml of dichloromethane and 50 ml of acetonitrile. The organic phases were combined, diluted with 75 ml of acetonitrile, and dried over magnesium sulfate (washing the magnesium sulfate with 2x25 ml of acetonitrile). The combined organics were concentrated by evaporation under reduced pressure. The solid residue was dissolved in Aqueous methanol to 90 percent and the product was precipitated by adding 300 ml of water. The solids were collected by filtration, washed with water and dried to obtain 30.5 g of the title compound as a light brown solid. Another 4.0 g of the title compound were obtained * of the filtrate for a total of 34.5 g (87 percent theory). 10 1 H NMR [300MHz] (CD3CN) ppm: 7.71 (d, 2H, J = 8.7), 7.53 (d, 2H, J = 8.7), 7.33 (tt, 1 H, J = 8.5, 6.1 Hz), 6.98 (dd, 2H, J = 8.3, 8.2).

Claims (19)

1. REIVI NDICATIONS 1 . A substituted N-arylsulphimimine compound of the formula: 5 AR'- N = S \ R 'wherein R represents methyl, ethyl or n-propyl; * R 'represents R, benzyl or phenyl; 10 or R and R 'together represent tetramethylene; and AR 'represents an aromatic portion selected from d) a substituted phenyl portion of the formula: wherein A represents F, Cl, Br, NO2, CN, dC fluoroalkyl, CO2 (C? -C4 alkyl), CONH (C? -C4 alkyl), CON (C? -C4 alkyl) 2, SO2 (C? -C alkyl), or SO2 (C? -C fluoroalkyl); B represents C? -C4 alkyl, F, Cl, Br, O (C? -C alkyl), O (C? -C4 fluoroalkyl), S (C? -C alkyl), S (C? -C fluoroalkyl), N (C? -C alkyl) 2; or phenyl, phenoxy or phenylthio each optionally possessing 1 to 3 substituents selected from the group consisting of F, Cl, Br, CN, CF3, NO2, and CH3; and D and J each independently represents H or CH3 with the proviso that at least one of D and J represents H; e) a substituted 3-pyridinyl portion of the formula: wherein L and M each independently represent H, C? -C alkyl, d- C4 fluoroalkyl, O (C? -C4 alkyl), O (C1-C fluoroalkyl), O (C2-C alkoxyalkyl), 0 (C3 -C alkenyl), 0 (C3-C4 alkynyl), S (dC alkyl), S (dC fluoroalkyl), SO2 (C? -C4 alkyl), SOz (dC fluoroalkyl), F, Cl, Br, I, CN, NO2, C6H5, CO2 (C? -C4 alkyl), CO2 (C3-C4 alkenyl), CO2 (C3-C alkynyl), CON (C1-C4 alkyl) 2, or CONH (C? - C alkyl), with the proviso that not more than one of L and M represents H; and T represents H, F, Cl, Br, I, CH3, or CF3; or c) a 3-, 4- or 5-pyrazolyl moiety substituted with a d-C3 alkyl group in the 1-position, with at least one Cl, Br, I or CF3, and optionally, with an OCH3 or CH3 group.
2. 2. A compound according to claim 1, wherein R and R 'each represents methyl.
3. 3. A compound according to claim 1, wherein AR 'is a substituted phenyl portion and A represents F, Cl, Br, CF3, NO2, or CO2CH3; B represents F, Cl, Br, CH 3, OCH 3; D represents H or CH 3; and J represents H. 5
4. 4. A compound according to claim 1 wherein AR 'is a substituted pyridinyl moiety, wherein T represents H and a) M represents Cl, Br, or CF3 and L represents O (d-C3 alkyl) or O (C? -C3 alkenyl) or b) M represents F and L represents C1-C2 alkyl.
5. 5. A compound according to claim 1, wherein AR 'is a substituted pyrazolyl moiety selected from 1-methyl-4-halo-3-pyrazolyl, 1-methyl-4-halo-5-pyrazolyl and 1 - ethyl-3- (trifluoromethyl) -5- (methyl, methoxy, or halo) -4-pyrazolyl.
6. 6. A compound according to claim 3, which is one of S, S-dimethyl-N- (2,5-dichloro-3-methylphenyl) sulphonamine, S, S-dimethyl-N- (2, 5- 15 dichlorophenyl) sulphimimine, S, S-dimethyl-N- (2,6-difluorophenyl) sulphimimine, and S, S-dimethyl-N- (2-methoxycarbonyl-6-chlorophenyl) sulphonimine.
7. 7. A process for the preparation of an N-arylarylsulfonamide compound of the formula: Q-SO2NH-AR 20 wherein Q and AR each independently represent an aromatic hydrocarbyl or an aromatic heterocyclyl portion which comprises combining a sulfonyl of Formula: Q-SO2Cl wherein Q is as defined above with an amine compound of Formula: AR- N H2 wherein AR is as defined above in the presence of an aromatic tertiary amine base and a catalytic amount added with an N-arylsulphimine compound of Formula I: AR'- N = S \ R 'wherein R represents methyl, ethyl or n-propyl; R 'represents R, benzyl or phenyl; or R and R 'together represent tetramethylene; and AR 'represents a portion of aromatic hydrocarbyl or aromatic heterocyclyl.
8. 8. A process according to claim 7, wherein AR 'of the N-arylsulphimin compound is selected to be identical to AR in the amine compound.
9. 9. A process according to claim 8, wherein the N-arylsulphimin compound is a compound of any of claims 1 to 6.
10. 10. A process according to claim 8, wherein AR is selected from 2,6-dichloro-3-methylphenyl, 2,6-diclphenyl, 2,6-difluorophenyl, and 2-methoxycarbonyl-6-chlorophenyl. eleven .
11. A process according to claim 8, wherein Q represents a portion of substituted phenyl, substituted pyridinyl, [1, 2,4] triazolo [1, 5-c] primidin-2-yl substituted, [1, 2.4 ] substituted triazolo [1, 5-a] pyrimidine-2-yl, or [1, 2,4] triazolo [1, 5-a] pyridine-2-yl substituted.
12. 12. A process according to claim 1, wherein the substituents are selected from F, Cl, Br, I, NO2, CN, O (C3-C ahenynyl), or O (C3-C4 alkynyl); d-C4 alkyl, O (C? -C4 alkyl), N (dC alkyl) 2, S (C? -C4 alkyl), SO2 (d-C4 alkyl), CO2 (C? -C alkyl), CONH (C ? -C4 alkyl), or CON (C? -C alkyl) 2 (each alkyl optionally mono a completely substituted with fluorine); or phenyl or phenoxy (each optionally possessing 1 to 3 substituents selected from the group consisting of f, Cl, Br, CN, CF3, NO2, and CH3).
13. 13. A process according to claim 7, wherein the sulfonyl chloride compound is selected from 2-chlorosulfonyl-5-ethoxy-7- 15 fluoro [1, 2,4] triazolo [1, 5-c] pyrimidine , 2-chloro-sulfonyl-5-methoxy-8-fluoro [1, 2,4] triazolo [1, 5-c] pyrimidine, 2-chlorosulfonyl-5-methoxy-7-methyl [1, 2,4] triazolo [1, 5-c] pyrimidine, 2-chlorosulfonyl-5-ethoxy-7-methyl [1, 2,4] triazolo- [1, 5-c] primidine, 2-chlorosulfonyl-5-methyl [1, 2 , 4] triazolo- [1, 5-a] pyrimidine, 2-chlorosulfonyl-5,7-dimethoxy [1, 2,4] triazolo [1, 5- 20 ajpyrimidine, 2-chlorosulfonyl-5,7-dimethyl] , 2,4] -triazolo [1, 5-a] pyrimidine, 2-chlorosulfonyl-5-methoxy-7-methyl [1, 2,4] triazolo [1, 5-a] pyridine, and 2-chlorosulfonyl-5 -methoxy-8-chloro [1, 2,4] triazolo [1, 5-a] pyridine.
14. 14. A process according to claim 7, wherein the aromatic tertiary amine base is selected from pyridine, a picoline, 25 nicotinamide and quinoline.
15. 15. A process according to claim 7, wherein the sulfilimine catalyst is prepared essentially immediately before use and is used in the form of the reaction mixture in which it was prepared or in a partially purified form.
16. 16. A process according to claim 7, wherein the temperature is maintained at -20 to 50 ° C.
17. 17. A process according to claim 7, wherein the amount of catalyst used is between 2 to 30 percent mole of the aromatic sulfonyl chloride compound.
18. 18. A method of using an N-arylsulphimine compound of any of claims 1 to 6 to catalyze the reaction between an aromatic sulfonyl chloride compound of the formula: Q-SO2CI wherein Q represents a hydrocarbyl portion aromatic or aromatic heterocyclyl with an aromatic amine compound of the formula: ff AR-NH2 wherein AR represents an aromatic hydrocarbyl or aromatic heterocyclyl portion to obtain an N-arylarylsulfonamide compound of the Formula: Q- SO2NH-AR in where Q and AR are as defined above.
19. 19. A method of use according to claim 18, wherein AR 'of the N-arylsulphimin compound is selected to be identical to AR 25 of the aromatic amine compound.