Synthesis of some N-Aryl- p-Toluene Sulfonamide Compounds

ABSTRACT A number of acetylenic amine (4a-e) were synthesis from propagyl p-(p-toluene sulfonamido) benzoate (3) with secondary amines via Mannich reaction. The carbonyl isothiocynate compound (5) was synthesized from the reaction of the corresponding benzoyl chloride with potassium thiocynate. This compound was converted to the corresponding thiourea compounds (6a-e), thiocarbomate (7a-d) and (8a-e) by their reaction with different amines, alcohols and phenols respectively. The structure of the synthesized compounds have been elucidated by their physical and spectral methods.


EXPERIMENTAL
Uncorrected melting points were determined using Electrothermal 9300 melting point apparatus.IR spectra were recorded by Infrared spectrophotometer Model Tensor 27 Bruker Co. using KBr discs.UV spectra were measured on Shimadzu UV-1650 pc, UV-Visible Spectrophotometer.

Preparation of N-[4-(p-Toluene Sulfonamido) benzoyl]-N \ -Substituted thiourea (6a-e) : (Sasaki et al., 1980)
To a solution of compound (5) (0.01 mole, 3.32g) in methylene chloride (15 ml), a suitable amine (0.01 mole) was added dropwise with stirring.The mixture was reflexed for (24) hrs, then filtered and the filtrate was poured on crushed ice.The precipitated material was filtered off, washed with cold water and recrystallized from ethanolwater.The physical and the spectral data were listed in Table (2).

Preparation of N-[4-(p-Toluene Sulfonamido) benzoyl]-O-Substituted thiocarbamate (7a-d) and(8a-e): (March, 1977 and Sasaki et al., 1980)
A mixture of compound (6) (0.01 mole, 3.32g), alcohol or phenol compound (0.01 mole) and potassium hydroxide (2 mg) in toluene 3ml was refluxed for 4hrs.The mixture was cooled and the precipitate was filtered off, washed with water and recrystallized from ethanol.The physical and the spectral data were listed in  PDF created with pdfFactory Pro trial version www.pdffactory.comRESULTS AND DISCUSSION Many of sulfonamide compounds, which are well known as sulfa drug (Kutzuig,1992), possessing biological activity (Ossman and Pharmazi, 1975;Ahuja et al., 1989).Accordingly, some new sulfonamide compounds containing acetylenic amino, thiourea and thiocarbamate moieties have been synthesized.The aim of the introducing such moieties in the skeleton structure of the sulfonamido compounds might prove the biological activity of these compounds.Therefore acetylenic compound (3) was synthesized by the reaction of the corresponding acid chloride with propagyl alcohol.The structure of compound (3) was confirmed by it ' s IR spectrum, which showed a characteristic weak band at 2100 cm -1 related to the terminal C≡C bond stretching and a weak band at 3305 cm -1 for ≡C−H bond stretching.Compounds (3) was converted to the corresponding acetylinic amine (4a-e) through mannich reaction (Karlen et al.,1970), by its reaction with secondary amine and paraformaldehyde in presence of catalytic amount of cuprous chloride .The formation of acetylinic amine derivatives were obtained according to the mechanism of mannich reaction (March, 1977) , Scheme (2).
PDF created with pdfFactory Pro trial version www.pdffactory.com The benzoyl isothiocyanate (5) was synthesized by the reaction of 4-(p-toluene sulfonamido) benzoyl chloride with potassium isothiocyanate.The IR spectral data of this compound were given in Table (2).The main absorption bands are for N=C=S which appeared at (2554 and 1925 cm -1 ) related to asymtric and symmetric vibration respectively (Kearney et al., 1998).While the UV spectrum showed λmax at (286 nm) related to (n→π * ) transition (Finar, 1977).The compound (5) was used as synthone for compounds (6a-e) and (7a-e).

Table 1 :
Physical properties and spectral data for compounds (3) and ( 4a-e) I.