Maymona M. Kandeel

New Polymer Syntheses IV. Synthesis and Characterization of New Polyamides Containing Bis-Benzthiazolyl Sulphone Units in the Main Chain

Bis(2-aminobenzthiazolyl) sulphone (BABS) was used as a new starting material for preparing polyamides. These polyamides were prepared by reacting BABS with adipoyl, sebacoyl, isophthaloyl and terephthaloyl dichlorides, and also with 4,4′-azodibenzoyl chloride or 3,3′-azodibenzoyl chloride, utilizing the solution polycondensation technique at low temperature. In addition, the model compound was synthesized by condensing the BABS with benzoyl chloride. Characterization of the monomer, model compound and the polyamides was accomplished by 1H NMR, IR and elemental analyses. The polyamides had reduced viscosities of 0.25–0.63 dI/g in DMF or DMSO at 25 °C. All the polymers dissolved readily at room temperature in polar aprotic solvents. The thermal stability of the polymers was evaluated by TGA and DSC measurements.

SYNTHESIS OF 4′-NITROPHENYL-2-AMINOBENZTHIAZOL-6-YL SULFIDES AND 4′-NITROPHENYL-2–AMINOBENZTHIAZOL-6-YL SULFONES CONTAINING DITHIOCARBAMATE

Abstract 2-Amino-6-[(p-nitrophenyl)thio]benzthiazol (1) reacted with carbon disulfide in the presence of concentrated aqueous sodium hydroxide and with N,N-dimethylformamide as solvent, to form the sodium salt of dithiocarbonimidic acid. This compound was reacted without further purification with one mole of methyl iodide to give monoalkylated product (2). Reaction with two moles of methyl iodide gave the dialkylated product (3). Reaction of (2) with anthranilic acid yielded 2-(2,3-dihydro-2-thioxo4(1H) quinoxa linon-3–yl)-6-[(p-nitrophenyl)thio]benzthiazol (4). Reaction of (3) with ophenylenediamine gave 2-(2-benzimidazolylamino)-6-[(p-nitrophenyl)thio]-benzthiazole (5). And reaction of (3) with potassium salt of anthranilic acid gave 2-(2-imino benzoxazine)+[(pnitrophenyl) thio]benzthiazol (6). (6) was condensed with a range of aromatic amine to form the 3-aryl quinazolinones (7d). Oxidation of compounds (4–7) using H2O2 in glacial acetic acid afforded the corresponding diary1 sulfones (8–11).

SYNTHESIS AND SOME REACTIONS OF 4′- NITROPHENYL-BENZTHIAZOL-6-YL SULFIDES AND 4′-NITROPHENYL-BENZTHIAZOL-6-YL-SULFIDES CONTAINING THIAZOLIDINONES

Abstract 2-(2′-Thioxo-4′-oxo-thiazolidin-3′-yl)-6-(p-nitrophenylthio) benzthaazole 1 has been prepared and was condensed with aromatic aldehydes to give the corresponding 5-arylidenethiazolidinones 2. Bromination of compound 2 gave 5-(α,β-dibromoarylidene)thiazolidinones 3. Reaction of the dibromo compound 3 with o-aminophenol gave spiro(benzomorpholine-2″,5′-thiazolidine) derivatives 4. Reaction of 2 with hydrazine hydrate or phenylhydrazine gave the azine compounds 5. The reactivity of 1 with nitrous acid, nitroso compounds, acid chlorides and diazonium salts was examined. Oxidation of compounds 4, 5, 7 and 8 using H2O2/AcOH mixture gave the corresponding diarylsulfones 10, 11, 12 and 13.

SYNTHESIS OF 4′-NITROPHENYL-BENZTHIAZOL- 6-YL SULFIDES AND 4′-NITROPHENYL- BENZTHIAZOL-6-YL SULFONES CONTAINING THIAZOLIDINONES

Abstract 2-Amino-6 (p-nitrophenylthio)benzthiazol (1) reacted with carbon disulfide in the presence of aqueous sodium hydroxide in N,N-dimethylformamide as solvent, to form the sodium salt of the dithiocarbon imidic acid. Without further purification, this salt was alkylated with sodium chloroacetate and treated with HCl to give the corresponding thiazolidinone (2). The thiazolidinone (2) underwent oxidation to the corresponding sulfone (3) when treated with AcOH/H2O2 and condensed easily with aromatic aldehydes, to give the corresponding 5-arylidinethiazolidinones (4), which after oxidation with H2O2,/ AcOH gave the sulfones (7). Sulfone (3), condensed with aromatic aldehydes, led to the same com pounds (7). Thiazolidinone (2) reacted with either one or two equivalents of an aromatic amine pro ducing compounds 5 and 6, respectively. The latter were oxidized with H2O,/AcOH to give the sulfones 8 and 9.

SOME REACTIONS ON 2-(2-THIOXO-4-OXO-THIAZOLIDIN-3-YL)-6-(4-NITROPHENYLTHIO)BENZTHIAZOLE

Abstract 2-(2-thioxo-4-oxo-thiazolidin-3-yl-)-6-(4-nitrophenylthio)-benzthiazole 1was prepared and condensed with two moles of aromatic amine to give the corresponding 2,4-diarylimino thiazolidines 2 a-b. The latter compounds undergo cycloaddition reaction with chloroacetylchloride and thioglycolic acid to give spiro compounds 5 a-b and 6 a-b The reaction of 1 with hydrazine hydrate afforded 2-hydrazono compound 3. Reaction of 3 with phenyl isothiocyanate gave the corresponding thiosemicarbazone 9. Cyclocondensation of chloroacetic acid with 9 afforded compound 10. Also, condensation of 3 with aromatic aldehydes gave the corresponding Schiffs bases 11 a-c. Reaction of compound 1 with malononitrile gave compound 4 which was reacted with sulfur in presence of diethylamine to give thienothiazole derivative 14. Compound 4 was reacted also with carbon disulfide in presence of triethylamine to afford thiopyranthione 15. Furthermore, the active methylene of 4 couples with benzene diazonium chloride followed by cyclization to give thiazolopyridazine derivative 17. Oxidation of compounds 5 a-b, 6 a-b, 10, 11 a-c, 14, 15 and 17 using H2O2/ACOH mixture afforded the corresponding diarylsulfones 7 a-b, 8 a-b, 12, 13 a-c, 18, 19 and 20.