DD257069A1 - METHOD FOR THE PRODUCTION OF TRISUBSTITUTED N-METHYL-ARENSULFONAMIDES TRISUBSTITUTED IN THE METHYL GROUP - Google Patents

Abstract

The invention relates to a process for the preparation of trisubstituted on the methyl group N-methyl-arensulfonamiden, which are obtained by reaction of open-chain, bridged or cyclic N-Arensulfonyl-iminothio (dithio) carbonic acid diesters with Grignard compounds. The aim of the invention is to find an uncomplicated to be realized process for the preparation of the title compounds, the u. a. as intermediates for the production of pesticides and pesticides as well as pharmaceuticals may have meaning.

Description

Alkoxy grouping with Cr to C ₆ skeleton or a phenoxy radical, which may optionally be substituted as formulated for the phenylthio, or, if Y is Q, k can take values between zero and three and X and Y for a Ι , ω-Alkylenedithio fragment having Cr to C ₄ skeleton and R ^{1 has} the above meaning, with Grignard compounds of general formula III in which Z is a halogen atom and R ² and η have the abovementioned meaning, in a molar ratio of approximately 1: 3 produced.

It has proved convenient to prepare the title compounds I by combining solutions of the Grignard compound of the general formula III in aliphatic ethers having 4 to 8 carbon atoms, cyclic ethers such as 1,4-dioxane or tetrahydrofuran or in mixtures of the above solvents with aromatic hydrocarbons, such as benzene or toluene, with the N-Arensulfonyl-iminothio (dithio) carbonic diester of general formula II in one of the abovementioned solvents at temperatures between 0 ⁰ C and the boiling temperature of the solvent used in each case with exclusion of moisture and air ,

The N-methyl-arensulfonamide of the general formula I are obtained after customary hydrolytic workup of the reaction mixture in an acidic medium as colorless, crystalline compounds. The advantage of the invention is that N-methyl arenesulfonamides of general formula I can be prepared by using the readily available N-arenesulfonyliminothio (dithio) carbonic acid diester of general formula II (Gompper, R .; Hagele, W .: Chem. Ber. 99 [1966] 2885; Neidlein, R .; Haussmann, W .: Arch. Pharmaz.300 [1967] 553; Neidlein, R. Krüil, H .: Arch. Pharmaz. 304 [1971] 763; Neidlein, R., Klotz, UJ: Chemist Kunz, R .: Chem. Ber. 99 [1966] 2900; Hans, M., Hartwig, R .; Dehne, H .: Wiss. Z. Pad. Hochschule "Liselotte Herrmann" Güstrow, Math.-naturwiss., Fac. 20 [1982] 49; Hans, M .; Dehne, H., Hartwig, R .; Z. Chem. 26 [1986] 204) and Grignard compounds of general formula III can be produced in a straightforward manner.

embodiment

The invention will be explained in more detail with reference to the following example and the data of the table, without being limited thereto.

To 500 ml of a 0.60 molar (0.03 mol) ethereal solution of phenylmagnesium bromide under argon atmosphere and stirring at room temperature 0.01 mol (2.75g) p-toluenesulfonylimino-dithiokohlensäuredimethylester, dissolved in 30ml of tetrahydrofuran, is slowly added dropwise. The reaction can be observed on the discoloration and self-heating of the reaction solution. First, it is continued at room temperature and then heated at reflux for 1 hr. After cooling, the reaction solution is added slowly in about 100mi 0.5molare HCI-ice-water mixture. The organic solvents are i. Vak. distilled off, wherein the water-insoluble N-trityl p-toluenesulfonamide precipitates in crystalline form. After suction, the crude product is recrystallized from ethanol. This gives a crystalline, colorless substance of mp. 239-242 ° C.

Yield .: i: 2.3 g (56 % D.Th.] H 5.61 η R ² N 3.39 S 7.75 Y. Mp. from Il Y solution I H 5,47 0 H N 3.53 S 8.02 (%) ( ⁰ C) X SCH ₃ medium ¹ Analytical data: C ₂₆ H ₂₃ NO ₂ S (413.55) NH 3308; SO ₂ V 0 4-CI 155.1315 46 243-245 SCH ₃ SCH ₃ B / THF Calculated: C 75.51 : N-methyl-arensulfonamide 0 H I 18 261-265 SCH ₃ SCH ₃ B / THF Gefunder C 75.62 0 H 56 239-242 SCH ₃ SC ₂ Hg E / THF IR / cm- ¹ /: R ¹ 0 H 51 228-231 SC ₂ H ₅ SC ₂ H ₅ T / THF Table 1: H 0 4-CI 48. 239-240 SC ₂ H ₅ SCH ₃ B / THF Ser. H 1 H 12 209-212 SCH ₃ B / THF No. 4-CH ₃ 1 H 77 200-202 S- (CH ₂ JS Q (k = 3) B / THF 1 4-CI 1 H 42 200-202 SCH ₃ SCH ₃ B / THF 2 4-Br 1 H 78 191-193 SCH ₃ OC ₆ H ₄ CI (4) E / THF 3 4-CH ₃ 1 H 81 191-193 SCH ₃ SC ₂ H ₅ B / THF 4 H 1 H 84 180-182 SC ₂ Hg SC ₂ H ₅ B / E 5 H 83 181-183 SC ₂ H ₆ B / THF 6 4-CH ₃ 7 4-CH ₃ 8th 4-CI 9 4-Br 10 11 12

1 B = benzene, E = diethyl ether, T = toluene, THF = tetrahydrofuran

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Claims (2)

Invention claim: 1. A process for the preparation of N-methyl-arensulfonamiden of the general formula I in which R ¹ and R ^{2 are the} same or different located in the same or different positions substituents, such as halogen atoms, alkyl, alkylthio or alkoxy with Ct to C. ₄ skeleton or phenyl or phenoxy radicals, optionally also nitro groups and η integer values between zero and two can occupy, characterized by, that open-chain, bridged or cyclic N-arylsulfonyl-iminothio (dithio) carbonic diester of the general formula II, in X is an alkylthio group with C ₁ - to C ₆ skeleton or a phenylthio radical which is optionally mono- or polysubstituted, identically or differently, in different positions, for example by halogen atoms, alkyl, alkylthio or alkoxy groups with C ₁ - to C ₄ skeleton and Y may have the same meaning as X, or for an alkoxy moiety with C ₁ - to C ₆ -GeKiSt or a phenoxy radical, which may optionally be substituted as formulated for the phenylthio, or, when Y is Q, k can take values between zero and three, and X and Y is a 1, ω Alkylenedithio fragment having C2 to C ₄ skeleton and R ^{1 has} the meaning given above, with Grignard compounds of general formula III, in which R ² and η have the abovementioned meaning in a molar ratio of approximately 1: 3 in organic Solvents, preferably in aliphatic ethers having 4 to 8 carbon atoms, cyclic ethers, such as 1,4-dioxane or tetrahydrofuran or in mixtures of the above solvents with aromatic hydrocarbons, such as benzene or toluene at temperatures between 0 ⁰ C and , Boiling temperature of the solvent used in each case be implemented. 2. The method according to item 1, characterized in that the reactions are carried out in the absence of moisture and air. For this 1 page formulas Field of application of the invention The invention relates to a process for the preparation of trisubstituted on the methyl group N-methyl-arensulfonamiden, which are used as intermediates u. a. for the production of pesticides and pesticides as well as pharmaceuticals. Characteristic of the known technical solutions Methods for the preparation of the inventively substituted N-methyl-arensulfonamide have not been described. N-alkyl (or N-aryl) substituted Arensulfonamide are known to be mainly from Arensulfonsäurechloriden and alkyl or aryl amides or by alkylation or arylation of Arensulfonamiden or salts thereof. (Huntress, EH; Autenrieth, JS: J. Amer., Soc., 62 [1940] 511; Huntress, EH; Carten, F .: J. Amer., 63, 1941, 3446; Muth, F .; - In: Methods of Organic Chemistry Bd.lX./Hrsg .: E.Müller .- Stuttgart: Georg Thieme Verlag, 1955. - p.599-648). The abovementioned processes permit the production of the title compounds, if at all, only via unreasonably complex, multistep synthesis steps. Object of the invention The aim of the invention is to find a simple, versatile method for the preparation of the title compounds in high yields from readily available starting materials in a manner which is easy to implement in a preparative manner. Explanation of the essence of the invention The compounds which can be prepared by the process of the invention are N-methylarene sulfonamides of the general formula I in which R ¹ and R ^{2 are} identical or different substituents, located in identical or different positions, such as, for example, halogen atoms, alkyl , Alkylthio or Alkoxygruppierungen with Ci- to C ₄ skeleton or phenyl or phenoxy radicals, optionally also nitro groups and η can take integer values between zero and two. The novel N-methyl-arensulfonamides of the general formula I are obtained by reacting open-chain, bridged or cyclic N-arylsulfonyl-iminothio (dithio) carbonic acid diesters of the general formula II in which X is an alkylthio group with C ₁ to C ₆ skeleton or is a phenylthio radical which may optionally be monosubstituted or polysubstituted, identically or differently, in different positions, for example by halogen atoms, alkyl, alkylthio or alkoxy groups with C _{1 to} C ₄ skeleton and Y has the same meaning as X, or for one