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DOI: 10.1055/s-2003-36784
Efficient Synthesis of 5-Fluoroalkylated 1H-1,2,3-Triazoles and Application of the Bromodifluoromethylated Triazole to Prepare New gem-Difluorinated Triazole Compounds
Publikationsverlauf
Publikationsdatum:
22. Januar 2003 (online)
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Abstract
A series of 5-fluoroalkylated 1H-1,2,3-triazoles was prepared in good yield by the regiospecific 1,3-dipolar cycloaddition reaction of the (Z) ethyl 3-fluoroalkyl-3-pyrrolidino-acrylates with aryl or benzyl azides. In the cases of benzyl azides, addition of Na2CO3 was crucial for a high yield of the triazoles. The tetrakis(dimethylamino)ethylene (TDAE) promoted reaction of the bromo-difluoromethylated 1H-1,2,3-triazole with aldehyde afforded a new class of novel gem-difluorinated triazole compounds.
Key words
acrylates - 1,3-dipolar cycloaddition - fluoroalkylated 1H-1,2,3-triazole - tetrakis(dimethylamino)ethylene - gem-difluorinated compound
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References
The analytical and spectroscopic data for triazole 3aa was demonstrated as an example. 5-Chlorodifluoromethyl-1-phenyl-1 H -1,2,3-triazole-4-carboxylic Acid, Ethyl Ester(3aa): Mp: 69.5-70.5 °C. [Found: C, 47.80; H, 3.35; N, 14.24. C12H10ClF2N3O2 requires C, 47.78; H, 3.34; N, 13.93%]. IR(film): 2982, 1723, 1593, 1560, 1497, 1375, 1296, 1254, 1238, 1153, 1094, 1058, 1008, 906, 771 cm-1. 1H NMR (60 MHz, CDCl3): δ = 1.47 (3 H, t, J = 7.0 Hz), 4.52 (2 H, q, J = 7.0 Hz), 7.34-7.74 (5 H, m). 19F NMR (56.4 MHz, CDCl3): δ = -44.5; EI-MS: m/z (%) = 302/304 (10/3) [M+ + 1], 256/258 (12/4), 245/247 (10/3), 189 (42), 170 (33), 144 (19), 77 (100) [Ph+].
21Crystallographic data (excluding structure factors) for the structures in this paper have been deposited with the Cambridge Crystallographic Data Center as supplementary publication numbers CCDC 196350. Copies of the data can be obtained, free of charge, on application to CCDC, 12 Union Road, Cambridge, CB2 1EZ, UK [Fax:+44(1223)336033 or e-mail: deposit@ccdc.cam. ac.uk].
255-(1,1-Difluoro-2-hydroxy-2-phenyl-ethyl)-1-pheny-l-1 H -1,2,3-triazole-4-carboxylic Acid, Ethyl Ester(7a): Mp: 146.0-148.0 °C. Found: C, 61.41; H, 4.78; N, 10.97. C19H17F2N3O3 requires C, 61.12; H, 4.59; N, 11.25. IR(film): 3445, 3065, 2984, 1778, 1717, 1595, 1546, 1497, 1249, 1231, 1170, 1077, 1014, 766, 738, 693 cm-1. 1H NMR (300 MHz, CDCl3): δ = 1.51 (3 H, t, J = 7.2 Hz), 4.01 (1 H, d, J = 3.9 Hz), 4.55 (2 H, q, J = 7.2 Hz), 5.63 (1 H, ddd, J = 12.7, 8.7, 3.9 Hz), 6.89-7.49 (10 H, m). 19F NMR (282 MHz, CDCl3): δ = -100.3 (AB-d, J = 273.0, 12.7, 8.7 Hz); EI-MS: m/z (%) = 373 (8) [M+], 353 (15), 328 (1), 300 (3), 281 (1), 104 (25), 77 (100) [Ph+], 51 (20).