690
P. F. de Athayde-Filho et al.
PAPER
Mesoionic 2-(4-Chlorophenyl)-3-methyl–4-(4′-isopropylphe-
nyl)-1,3-thiazolium-5-thiolate (4)
Yield: 46% (2.39 g); mp 177 °C.
N-(4-Chlorobenzoyl)-N-methyl-C-phenylglycine (IIb)
N-Methyl-C-phenylglycine (3.60 g, 21.95 mmol) and 4-chloroben-
zoyl chloride (4.19 g, 21.95 mmol) were reacted according to the
general procedure giving the title compound in 65% yield (4.54 g);
mp 98 °C.
1H NMR (CDCl3): δ = 2.67 (s, 3 H, CH3N), 6.33 (s, 1 H, CH), 7.24–
7.37 (m, 9 H, Ph), 9.53 (1 H, NH).
IR (KBr): 3012 (CAr–H), 2959 [C–H, –(CH3)2], 2927 (C–H, CAr–
CH), 2870 (C–H, N–CH3), 1485 (N–CH3 asymmetric), 1431 (N–
CH3 symmetric), 1399 and 1384 [C–(CH3)2], 1285 (C–S–), 1085
(CAr–Cl).
13C NMR (DMSO-d6) δ = 35.1, 61.8, 128.5, 128.6, 128.7, 129.5,
131.4, 133.4, 133.6, 136.1 171.8, 173.7.
1H NMR (CDCl3): δ = 1.24 (d, 6 H, J = 6,3 Hz, CH3), 2.91 (septet,
1 H, J = 6.3 Hz, CH), 3.60 (s, 3 H, CH3N), 7.25–7.55 (m, 8 H, Ph).
13C NMR (DMSO-d6): δ = 23.8, 33.9, 40.6, 125.3, 126.8, 126.9,
129.7, 130.8, 131.0, 137.8, 141.6, 149.9, 152.7, 159.4.
N-4-N-methyl-C-4-isopropylphenylglycine (IIc)
N-methyl-C-4-isopropylphenylglycine (7.00 g, 47.30 mmol) and 4-
chlorobenzoyl chloride (8.27g 47.30 mmol) were reacted according
to the general procedure giving the title compound in75% yield
(10.16 g); white crystals; mp 146 °C.
MS: m/z (%) = 361 (10.16), 359 (23.61), 346 (5.85), 344 (15.37),
319 (19.53), 317 (48.69), 304 (4.20), 302 (10.47), 179 (6.71), 165
(100.00), 121 (26.68), 89 (8.16), 77 (3.90).
1H NMR (CDCl3): δ = 1.26 (d, 6 H, J = 6.0 Hz, CH3,), 2.75(s, 3 H,
CH3N), 2.92 (septet. 1 H, J = 6.0 Hz, CH), 6.39(s, 1 H, CH), 7.25–
7.41 (m, 8 H, Ph).
Anal. Calcd for C19H18ClNS2: C, 63.40, H, 5.04, N, 3.89. Found:
C, 63.44, H, 5.03, N, 3.80.
13C NMR (CDCl3): δ = 23.8, 33.7, 34.9, 60.8, 127.0, 128.3, 128.7,
128.8, 129.4, 130.4, 133.6, 136.1, 149.5, 171.9, 174.0.
Acknowledgement
The authors thank the Brazilian National Research Council (CNPq)
for a research grant and for bursaries.
Preparation of Mesoionic 2,4-Diaryl-3-methyl-1,3-thiazolium-
5-thiolates; General Procedure
The N-aroyl-N-methyl-C-arylglycine (16–20 mmol) was dissolved
in Ac2O (20 mL) and heated at 55 °C for 15 min with stirring. After
cooling to ambient temperature, CS2 (20 mL) was added and the re-
action mixture allowed to stand for 48 h. MeOH–H2O (1:1) was
then added until the mixture became cloudy, after standing for a fur-
ther 24 h the desired product formed as orange-red crystals, which
were recrystallized from MeOH.
References
(1) Cheung, K. K.; Galembeck, S. E.; Miller, J.; Oliveira, M. B.;
Pereira, A. B.; Simas, A. M. Acta Cryst., Sect. C 1991, 47,
2630.
(2) Simas, A. M.; Miller, J.; Maciel, M. A. M. 16a Reunião
Anual da SBQ – Caxambu – MG Resumo QT – 01 1993.
(3) Oliveira, M. B.; Miller, J.; Pereira, A. B.; Galembeck, S. E.;
Moura, G. L. C.; Simas, A. M. Phosphorus, Sulfur Silicon
Relat. Elem. 1996, 108, 75.
Mesoionic 2,4-Diphenyl-3-methyl-1,3-thiazolium-5-thiolate (2)
Yield: 51% (2.46 g) (Lit.14 55%); mp 183–184 °C (Lit.14 184 °C).
(4) Athayde-Filho, P. F.; Miller, J.; Simas, A. M. Can. J. Chem.
1998, 76, 864.
IR (KBr): 3025 (CAr–H), 2948 (C–H), 1482 (N–CH3 asymmetric),
1424 (N–CH3 symmetric), 1291 (C–S–).
(5) Athayde-Filho, P. F.; Miller, J.; Simas, A. M. Synthesis
2000, 1565.
(6) Athayde-Filho, P. F.; Miller, J.; Simas, A. M.; Sena, K. X. F.
R.; Chiappeta, A. A. Acta Farmaceutica Bonaerense 1999,
18, 17.
1H NMR (CDCl3): δ = 3.64 (s, 3 H, CH3N), 7.33–7.52 (m, 10 H,
Ph).
13C NMR (DMSO-d6): δ = 40.3, 126.6, 128.5, 128.9, 129.2, 129.3,
129.8, 131.0, 131.3, 140.7, 154.3 and 159.8.
(7) Moura, G. L. C.; Simas, A. M.; Miller, J. Chem. Phys. Lett.
1996, 257, 639.
(8) Bezerra, A. G. A. Jr.; Gomes, S. L.; Athayde-Filho, P. F.; da
Rocha, G. B.; Miller, J.; Simas, A. M. Chem. Phys. Lett.
1999, 309, 421.
MS: m/z (%) = 283 (100.00), 268 (8.94), 179 (7.60), 165 (88.99),
121 (28.83), 89 (8.51), 77 (4.60).
Anal. Calcd for C16H13NS2: C, 67.81, H, 4.62, N, 4.94. Found: C,
67.80, H, 4.42, N, 5.08.
(9) Pretsch, E.; Clerc, T.; Seibl, J.; Simon, W. Tabla para la
Elucidacion Estructural de Compuestos Orgánicos por
Metodos Espectroscopicos; Alhambra: Madrid, 1980, 215.
(10) Pavia, D. L.; Lampaman, G. M.; Kriz, G. S. Jr. Introduction
to Spectroscopy; W. R. Saunders Company: London, 1979,
34.
Mesoionic 2-Phenyl-3-methyl-4(4′-chlorophenyl)-1,3-thiazoli-
um-5-thiolate (3)
Yield: 51% yield (3.03 g); mp 158–159 °C.
IR (KBr): 3006 (CAr–H), 2916 (C–H), 1485 (N–CH3 asymmetric),
1431 (N–CH3 symmetric), 1285 (C–S–), 1096 (CAr–Cl).
(11) Shutske, G. M.; Agnew, M. N. J. Heterocycl. Chem. 1981,
18, 1025.
(100.00), 121 (25.21), 89 (7.78), 77 (3.31).
1H NMR (CDCl3): δ = 3.63 (s, 3 H, CH3N), 7.41–7.51 (m, 9 H, Ph).
13C NMR (DMSO-d6): δ = 40.5, 125.2, 128.7, 129.2, 129.8, 130.8,
131.2, 137.9, 141.2, 152.6, 160.7.
(12) Gilchrist, G. In Heterocyclic Chemistry; Longman Scientific
and Technical Press: New York, 1992, 2nd Ed., 15.
(13) Cheung, K. K.; Echevarria, A.; Galembeck, S. E.; Maciel,
M. A. M.; Miller, J.; Rumjanek, V. M.; Simas, A. M. Acta
Cryst., Sect. C 1992, 48, 1471.
(14) Bayer, H. D.; Huisgen, R.; Knorr, R.; Schaefer, F. C. Chem.
Ber. 1970, 103, 2581.
(15) Huisgen, R.; Funke, E.; Schaefer, F. C.; Gotthardt, H.;
Brunn, E. Tetrahedron Lett. 1976, 19, 1809.
MS: m/z (%) = 319 (23.79), 317 (65.77), 304 (2.37), 302 (5.52), 179
(6.17), 165.
Anal. Calcd for C16H12ClNS2: C, 60.46, H, 3.81, N, 4.41. Found: C,
60.28, H, 3.84, N, 4.04.
Synthesis 2003, No. 5, 685–690 ISSN 0039-7881 © Thieme Stuttgart · New York