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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)
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
- 1
Wamhoff H. In Comprehensive of Heterocyclic Chemistry Vol. 5:Katritzky AR.Rees CW. Elesevier; New York: 1996. p.705MissingFormLabel - For review see:
- 2a
Finley KA. Triazoles: 1,2,3, In Heterocyclic Compounds Vol. 29:Montgomery JA. John Wiley and Sons Inc.; New York: 1980.MissingFormLabel - 2b
Gilchrist TL.Gymer GE. In Advance in Heterocyclic Chemistry Vol. 16:Katritzky AR.Boulton AJ. Academic Press; New York: 1974. p.33MissingFormLabel - 2c
Gilchrist TL. Heterocyclic Chemistry 3rd ed.: Addiso Wesley Longman; Beijing: 1997. p.304 ; and ref. 1MissingFormLabel - 3
Abu-Orabi ST.Al-Hamdany R.Shahateet S.Abu-Shandi K. Heterocycl. Commun. 2000, 6: 443 - 4a
Bertelli L.Biagi G.Calderone V.Giorgi I.Livi O.Scartoni V.Barili PL. J. Heterocycl. Chem. 2000, 37: 1169 - 4b
Lonning PE. Eur. J. Cancer 2000, 36 (Suppl. 4): S81 - 5
Kirk-Othmer Encycopedia of
Chemical Technology
2nd ed.:
Wiley-Interscience;
New
York:
1964.
p.737
MissingFormLabel
- 6
Itoh Y.Ma FH.Hoshi H.Oka M.Noda K.Ukai Y.Kojima H.Nagano T.Toda N. Anal. Biochem. 2000, 287: 203 - 7
Mori Y,Osawa M,Hori M, andNagashima T. inventors; Eur. Pat. Appl. EP 1081250. ; Chem. Abstr. 2001, 134, 210398MissingFormLabel - 8
Philips D. Photochemistry 1971, 2: 795 - 9a
Yanase Y,Yoshikawa Y,Kawashima H,Takashi A, andAkase T. inventors; Jpn. Kokai Tokkyo Koho JP 2001072507. ; Chem. Abstr. 2001, 134, 233062MissingFormLabel - 9b
Yanase Y,Yoshikawa Y, andTakashi A. inventors; Jpn. Kokai Tokkyo Koho JP 2001072512. ; Chem. Abstr. 2001, 134, 233064MissingFormLabel - For example see:
- 10a
Allessandro DI.Patrizia S.Anonella C.Laura B.Allessandro M.Gianna R. Tetrahedron Lett. 1995, 36: 9031 - 10b
Kobayashi Y.Yamashita T.Takahashi K.Kuroda H.Kumadaki I. Chem. Pharm. Bull. 1984, 32: 4402 - 11 For example see:
Kadaba PK.Stanovnik B.Tisler M. Advances in Heterocyclic Chemistry Academic Press; New York, London: 1980. p.219 ; see also ref.2bMissingFormLabel - 12a
Filler R.Kobayashi Y.Yagupolskii LM. Organofluorine Compounds in Medical Chemistry and Biochemical Applications Elesevier; Amsterdam: 1993. - 12b
Smart BE. , J. Fluorine Chem. 2001, 109: 3 - 13a
Carpenter W.Haymaker A.Moore DW. J. Org. Chem. 1966, 31: 789 - 13b
Saunier YM.Danion-Bougot R.Danoin D.Carrie R. Tetrahetron 1976, 32: 1995 - 13c
Kobayashi Y.Fujino S.Hamana H.Hanzawa Y.Morita S.Kumadaki I. J. Org. Chem. 1980, 45: 4683 - 14
Peng WM.Zhu SZ.Jin GF. Tetrahedron 2001, 57: 5781 - 15a
Tozer MJ.Herpin T. Tetrahedron 1996, 52: 8619 - 15b
Burkholder CR.Dolbier WR.Medebielle M. J. Fluorine Chem. 2001, 109: 39 - 16a
Burkholder CR.Dolbier WR.Medebielle M. J. Org. Chem. 1998, 63: 5385 - 16b
Burkholder CR.Dolbier WR.Medebielle M.Ndedi A. Tetrahetron Lett. 1998, 39: 8853 - 17
Metzger JO. Angew. Chem. Int. Ed. 1998, 37: 2975 - 18
Balicki R. Pol. J. Chem. 1984, 58: 85 - 19
Chen QY.Jiang XK.Chen BQ. Scientia Sinica 1966, 4: 498 - 22
Norman SB.Plunkett AO. J. Chem. Soc., Chem. Commum. 1973, 188 - 23a
Goldsmith D.Soria JJ. Tetrahetron Lett. 1991, 32: 2457 - 23b
Funicello M.Spagnolo D.Sanirato P. J. Chem. Soc., Perkin Trans. 1 1990, 2971 - 24a
Burkholder C.Dolbier WR.Medebielle M.Aitmoliand S. Tetrahedron Lett. 2001, 42: 3077 - 24b
Burkholder C.Dolbier WR.Medebielle M. Tetrahedron Lett. 1997, 38: 821
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).