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Isothiocyanates. XVIII. The synthesis and infrared spectra of (p-isothiocyanatophenyl) alkyl sulfides and (p-isothiocyanatophenyl) alkyl sulfones

M. Uher, K. Antoš, P. Kristián, and Ľ. Drobnica

Department of Organic Chemistry and Department of Microbiology and Biochemistry, Slovak Technical University, Bratislava

Abstract: cf. preceding abstr. The synthesis and ir spectra of the series of (p-isothiocyanatophenyl) alkyl sulfides (I) and sulfones (II) and their intermediates was described. Nine I and II and 11 intermediates were new compds. I and II of the general formulas RSC6H4NCS-p and RO2SC6H4NCS-p were prepd. (type, R, and m.p. or b.p./torr given): I, Me, 56°; I, Et, 25°; I, iso-Pr, 120°/2; I, Bu, 145°/3; I, amyl, 150°/2; I, hexyl, 180°/3; I, heptyl, 130°/3; I, n-octyl, 68-70° (170°/3, and 160°/1); I, n-decyl, 42°; I, cetyl, 58-60°. II, Me, 130°; II, Et, 117°; II, iso-Pr, 107°; II, Bu, 68-70°; II, amyl, 96-8° II, hexyl, 68-71°; II, heptyl, 56°; II, n-octyl, 70°; II, n-decyl, 58°, II, cetyl, 88°. All I and II were synthesized by the thiophosgene method starting from the corresponding amines. Starting with Na2S2 and p-nitrochlorobenzene, Na p-nitrothiophenol was formed which, after adding the corresponding alkyl halide, is changed into (p-nitrophenyl) alkyl sulfide. Na2S2 must be free of insol. S. The following (p-nitrophenyl) alkyl sulfides were synthesized (alkyl and m.p. given): hexyl, 25-6°; heptyl, 27-9°; n-decyl, 43-5°. By heating Fe powder, and the corresponding nitro derivs. in glacial AcOH and H2O these (p-aminophenyl) alkyl sulfides were synthesized (alkyl and m.p. or b.p./torr given): hexyl, 130°/5; heptyl, 165°/3; n-decyl, 42° and 210°/3. These (p-nitrophenyl) alkyl sulfones were synthesized (alkyl and m.p. given): amyl, 60°; hexyl, 40-3°; heptyl, 30-3°; n-decyl, 42-4°; cetyl, 77-80°. The ir spectra of I and II were detd. and the frequencies tabulated. An absorption max. of νasym. NCS was at the frequency ∼940 cm.-1. There was a difference in the absorption bands due to νasym. NCS; one max. was at 2100 cm.-1, the other at 2040 cm.-1.

Full paper in Portable Document Format: 211-2a44.pdf (in Slovak)

Chemical Papers 21 (1-2) 44–56 (1967)