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PAPER
1H NMR (DMSO-d6): d = 8.86 (d, 1 H, J = 7.5 Hz), 7.83 (t, 1 H,
J = 7.8 Hz), 7.05 (d, 1 H, J = 9.0 Hz), 6.91 (t, 1 H, J = 7.5 Hz), 6.89
(d, 2 H, J = 8.5 Hz), 6.77 (d, 2 H, J = 8.0 Hz), 6.62 (d, 2 H, J = 7.5
Hz), 6.24 (d, 2 H, J = 8.0 Hz), 2.12 (s, 3 H), 2.09 (s, 3 H).
13C NMR (DMSO-d6): d = 154.6, 142.2, 141.3, 136.5, 133.6, 130.1,
129.6, 129.3, 128.1, 127.8, 122.8, 120.3, 112.3, 30.6, 30.5.
1.0 Hz), 7.09 (d, 4 H, J = 8.0 Hz), 7.00 (td, 2 H, J = 7.0, 1.0 Hz),
6.73 (tt, 2 H, J = 7.2, 1.0 Hz), 6.45 (dt, 4 H, J = 7.5, 1.0 Hz).
13C NMR (DMSO-d6): d = 144.8, 141.9, 132.2, 129.2, 125.9, 125.5,
123.5, 119.0, 117.1, 113.6, 113.0.
MS (EI): m/z (%) = 238 [100, (1/2 M+ – 2 H)], 137 [29, C6H4N2S
(thiadiazolopyridine moiety) + 1].
MS (ESi): m/z = 343 (M+), 223 (RDA).
Anal. Calcd for C26H20N6S2: C, 64.98; H, 4.19; N, 17.49. Found: C,
64.76; H, 4.18; N, 17.39.
Anal. Calcd for C19H18N4O: C, 73.67; H, 5.30; N, 16.36. Found: C,
73.63; H, 5.38; N, 16.57.
1-Phenyl-2-(2H-[1,2,4]thiadiazolo[2,3-a]pyridin-2-yliden)etha-
none (11)
To a stirred solution of 9 (0.51 g, 2 mmol) in MeOH (30 mL) was
added nitrosobenzene (0.21 g, 2 mmol). After 2 h, the product was
collected by suction filtration and recrystallised from cyclohexane;
yield: 54%; pale yellow needles; mp 229–231 °C. (Lit.12a mp 228–
229 °C.
N-[1,3-Diaryl-4-(arylimino)-1,3-diazetidin-2-ylidene]-N-phe-
nylamines 7; General Procedure
The filtrate from the preparation of 4 (see the general procedure
above) was evaporated, after the removal of 4. The brownish resi-
due was chromatographed (SiO2/CHCl3). The first fraction gave the
product.
IR (KBr), 1H NMR,13C NMR and MS (EI) analyses and elemental
N-[1,3-Diphenyl-4-(phenylimino)-1,3-diazetidin-2-ylidene]-N-
analyses agree with the known data for 11.12a
phenylamine (7a)
Yield: 22%; pale yellow needles; mp 162–163 °C. (Lit.15 mp 165–
166 °C).
References
1H NMR and 13C NMR analyses agree with the known data for 7a.15
(1) (a) Tanaka, T.; Morishima, Y.; Watanabe, K.; Shibutani, T.;
Yasuoka, M.; Shibano, T. Cardiovasc. Res. 1993, 27, 1374.
(b) Pawlak, D.; Adamkiewicz, M.; Mayszko, J.; Takada, A.;
Myliwiec, M.; Buczko, W. J. Cardiovasc. Pharmacol. 1998,
32, 266. (c) Pawlak, D.; Pawlak, K.; Chabielska, E.;
Mayszko, J.; Takada, A.; Myliwiec, M.; Buczko, W.
Thromb. Res. 1998, 90, 259. (d) Shibano, T.; Tanaka, T.;
Morishima, Y.; Yasuoka, M.; Watanabe, K.; Fujii, F. Arch.
Int. Pharmacodyn. Ther. 1992, 319, 114.
(2) (a) Skogvall, S. PCT Int. Appl. WO 0236114, 2002; Chem.
Abstr. 2002, 136, 363846. (b) Skogvall, S. PCT Int. Appl.
WO 0236113, 2002; Chem. Abstr. 2002, 136, 363862.
(c) Skogvall, S. PCT Int. Appl. WO 0064441, 2000; Chem.
Abstr. 2000, 133, 329581.
(3) (a) Stanovnik, B.; Tiler, M. Synthesis 1972, 308.
(b) Fiksdahl, A.; Wentrup, C. ARKIV0C 2000, i, 438; http://
Chem. Soc., Perkin Trans. 2 2000, 1841. (d) Marchalín, M.;
Svïtlík, J.; Martvoň, A. Collect. Czech. Chem. Commun.
1981, 46, 2557.
N-{1,3-Bis(4-chlorophenyl)-4-[(4-chlorophenyl)imino]-1,3-di-
azetidin-2-ylidene}-N-(4-chlorophenyl)amine (7b)
Yield: 30%; pale yellow needles; mp 155–156 °C.
1H NMR (CDCl3): d = 8.24 (d, 4 H, J = 9.0 Hz), 8.15 (d, 4 H, J = 8.5
Hz), 7.47 (d, 4 H, J = 9.0 Hz), 7.44 (d, 4 H, J = 8.5 Hz).
13C NMR (CDCl3): d = 142.2, 138.1, 135.2, 129.0, 129.0, 127.0,
123.7.
N-{1,3-Bis(4-methylphenyl)-4-[(4-methylphenyl)imino]-1,3-di-
azetidin-2-ylidene}-N-(4-methylphenyl)amine (7c)
Yield: 30%; pale yellow needles; mp 152–153 °C.
1H NMR (CDCl3): d = 8.18 (d, 4 H, J = 8.5 Hz), 8.11 (d, 4 H, J = 8.5
Hz), 7.29 (d, 4 H, J = 8.5 Hz), 7.28 (d, 4 H, J = 8.5 Hz), 2.44 (s, 6
H, 2 CH3), 2.42 (s, 3 H, 2 CH3).
13C NMR (CDCl3): d = 141.9, 141.9, 140.0, 129.3, 129.3, 125.6,
122.2, 21.5, 21.3.
(4) (a) Kamal, A.; Sattur, P. B. Synthesis 1985, 892. (b) Usui,
H.; Watanabe, Y.; Kanao, M. J. Heterocycl. Chem. 1993, 30,
551. (c) Troschuetz, R.; Grün, L. Arch. Pharm. (Weinheim,
Ger.) 1993, 326, 913. (d) Joshua, C. P.; Thomas, S. K.
Heterocycles 1982, 19, 531.
N-(2¢-Pyridinyl)acetothioacetamide (8) and N-(2¢-Pyridi-
nyl)benzoylthioacetamide (9)
Compounds 8 and 9 were prepared according to the known proce-
dure.12a–d
(5) (a) Matveev, Yu. I.; Sereda, S. V.; Samarai, L. I. Ukr. Khim.
Zh. 1995, 61, 37; Chem. Abstr. 1996, 124, 342625.
(b) Paetzel, M.; Bohrisch, J.; Liebscher, J. Liebigs Ann.
Chem. 1991, 975. (c) Okawa, T.; Osakada, N.; Shoji, E.;
Kakehi, A. Tetrahedron 1997, 53, 16061. (d) Bödeker, J.;
Courault, K.; Köckritz, A.; Köckritz, P. J. Prakt. Chem.
1983, 325, 463.
N-(2¢-Pyridinyl)acetothioacetamide (8)
Yield: 42%; light yellow needles; mp 84–86 °C (Lit.12a mp 83.5–
84 °C).
N-(2¢-Pyridinyl)benzoylthioacetamide (9)
Yield: 35%; yellow needles; mp 90–91 °C (Lit.12a mp 91–92 °C).
(6) (a) Bal’on, Ya. G.; Paranyuk, V. E. J. Org. Chem. USSR
1980, 16, 1910. (b) Zimmer, H. J. Prakt. Chem. 1978, 320,
625.
(7) Zaleska, B.; Socha, R.; Grochowski, J.; Serda, P.; Szneler, E.
J. Org. Chem. 2003, 68, 2334.
(8) Zaleska, B.; Bazanek, T.; Socha, R.; Karelus, M.;
Grochowski, J.; Serda, P. J. Org. Chem. 2002, 67, 4526.
(9) Zaleska, B.; Trzewik, B.; Grochowski, J.; Serda, P. Synthesis
2003, 2559.
(10) Zaleska, B.; Socha, R.; Ciechanowicz-Rutkowska, M.;
Pilati, P. Monatsh. Chem. 2000, 131, 1151.
{N,N¢-Diphenyl-1,2-bis-[1,2,4]thiadiazolo[2,3-a]pyridin-2-
yliden}ethane-1,2-diamine (10)
To a stirred solution of 8 (0.29 g, 1.5 mmol) in MeOH (5 mL) were
added nitrosobenzene (0.16 g, 1.5 mmol) and one drop of 25% aq
solution of NaOH (as a catalyst). After 2 h, the product was collect-
ed by suction filtration; yield: 39%; white powder; mp 234–235 °C
(dec.).
IR (KBr): 3348, 3317, 1629, 1600, 1564, 1546, 1496 cm–1.
1H NMR (DMSO-d6): d = 8.67 (s, 2 H, 2 NH), 7.86 (dt, 2 H, J = 7.0,
1.0 Hz), 7.71 (dt, 2 H, J = 9.0, 1.0 Hz), 7.41 (ddd, 2 H, J = 9.0, 7.0,
Synthesis 2004, No. 18, 2975–2979 © Thieme Stuttgart · New York