PAPER
(E)-Trifluoromethyl Imines and Hydrazones
4099
HRMS: m/z [M + Na]+ calcd for C10H18F3NNa: 232.1289; found:
232.1278.
Supporting Information for this article is available online at
N-[(1E)-2,2,2-Trifluoroethylidene]pentan-1-amine (10)
IR (CHCl3): 1683 cm–1.
Acknowledgment
1H NMR (300 MHz, CDCl3): d = 0.90 (t, 3J = 6.6 Hz, 3 H), 1.22–
1.41 (m, 4 H), 1.60–1.77 (m, 2 H), 3.54–3.66 (m, 2 H), 7.60–7.65
(m, 1 H).
Italian MIUR and Università degli Studi di Roma ‘La Sapienza’
are gratefully acknowledged for financial support (PRIN
2007FJC4SF_005). We thank Dr. Davide Massari for experimental
support.
13C NMR (75 MHz, CDCl3): d = 13.7, 22.3, 29.2, 29.4, 60.5, 118.8
(q, 1JC–F = 274.0 Hz, CF3), 149.1 (q, 2JC–F = 38.0 Hz, CCF3).
19F NMR (282 MHz, CDCl3): d = –71.6 (d, 3JF–H = 4.2 Hz, 3F).
HRMS: m/z [M + Na]+ calcd for C7H12F3NNa: 190.0820; found:
References
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Ojima, I., Ed.; Wiley: Chichester, 2009.
190.0825.
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S.; Olah, G. A.; Török, B. J. Fluorine Chem. 2007, 128, 587.
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Fioravanti, S.; Pellacani, L.; Tardella, P. A. J. Org. Chem.
2006, 71, 6295. (c) Colantoni, D.; Fioravanti, S.; Pellacani,
L.; Tardella, P. A. Org. Lett. 2004, 6, 197.
4-Methyl-N-[(1E)-2,2,2-trifluoroethylidene]pentan-2-amine
(11)
IR (CHCl3): 1686 cm–1.
1H NMR (300 MHz, CDCl3): d = 0.85 (d, 3J = 6.4 Hz, 3 H), 0.88 (d,
3
3J = 6.4 Hz, 3 H), 1.21 (d, J = 6.3 Hz, 3 H), 1.29–1.62 (m, 3 H),
3.42–3.53 (m, 1 H), 7.61 (q, 3JH–F = 3.4 Hz, 1 H).
13C NMR (75 MHz, CDCl3): d = 21.7, 21.9, 23.0, 24.6, 46.0, 63.5,
118.9 (q, 1JC–F = 274.0 Hz, CF3), 147.3 (q, 2JC–F = 38.0 Hz, CCF3).
19F NMR (282 MHz, CDCl3): d = –71.6 (d, 3JF–H = 4.2 Hz, 3F).
HRMS: m/z [M + Na]+ calcd for C8H14F3NNa: 204.0976; found:
204.0983.
3-Methyl-N-[(1E)-2,2,2-trifluoroethylidene]butan-2-amine (12)
IR (CHCl3): 1681 cm–1.
3
1H NMR (300 MHz, CDCl3): d = 0.83 (d, J = 6.7 Hz, 3 H), 0.92
(d, 3J = 6.8 Hz, 3 H), 1.20 (d, 3J = 6.3 Hz, 3 H), 1.72–1.87 (m, 1 H),
3.02–3.11 (m, 1 H), 7.58 (q, 3JH–F = 3.4 Hz, 1 H).
13C NMR (75 MHz, CDCl3): d = 18.8 (2C), 19.0, 33.5, 71.7, 118.8
(q, 1JC–F = 274.6 Hz, CF3), 147.3 (q, 2JC–F = 37.9 Hz, CCF3).
19F NMR (282 MHz, CDCl3): d = –71.4 (d, 3JF–H = 4.2 Hz, 3F).
HRMS: m/z [M + Na]+ calcd for C7H12F3NNa: 190.1619; found:
(9) Fioravanti, S.; Pellacani, L.; Tardella, P. A.; Vergari, M. C.
Org. Lett. 2008, 10, 1449.
(10) Gong, Y.; Kato, K. J. Fluorine Chem. 2001, 108, 83.
(11) (a) Molteni, M.; Volonterio, A.; Zanda, M. Org. Lett. 2003,
5, 3887. (b) Iwata, S.; Ishiguro, Y.; Utsugi, M.; Mitsuhashi,
K.; Tanaka, K. Bull. Chem. Soc. Jpn. 1993, 66, 2432.
(12) Soloshonok, V. A.; Yasumoto, M. J. Fluorine Chem. 2007,
128, 170; and references therein.
(13) Soloshonok, V. A.; Ono, T. J. Org. Chem. 1997, 62, 3030.
(14) Crousse, B.; Bonnet-Delpon, D. In e-EROS: Encyclopedia
of Reagents for Organic Synthesis; Wiley: New York, 2005,
DOI: 10.1002/047084289X.rn00560.
(15) (a) Fuchigami, T.; Nakagawa, Y.; Nonaka, T. Tetrahedron
Lett. 1986, 27, 3869. (b) Neugebauer, F. A.; Umminger, I.
Chem. Ber. 1982, 115, 3706. (c) Tanaka, K.; Maeno, S.;
Mitsuhashi, K. Chem. Lett. 1982, 543.
(16) (a) Funabiki, K.; Nagamori, M.; Matsui, M.; Enders, D.
Synthesis 2002, 2585. (b) Enders, D.; Funabiki, K. Org.
Lett. 2001, 3, 1575.
190.1622.
(2R)-3,3-Dimethyl-N-[(1E)-2,2,2-trifluoroethylidene]butan-2-
amine (14)
[a]D –41.8 (c 2, CHCl3).
IR (CHCl3): 1682 cm–1.
1H NMR (300 MHz, CDCl3): d = 1.02 (s, 9 H), 1.27 (d, 3J = 6.5 Hz,
1 H), 3.00 (q, 3J = 6.5 Hz, 3 H), 7.58 (q, 3JH–F = 3.4 Hz, 1 H).
13C NMR (75 MHz, CDCl3): d = 16.7, 26.2 (3C), 33.9, 74.8, 119.0
(q, 1JC–F = 275.0 Hz, CF3), 147.2 (q, 2JC–F = 38.0 Hz, CCF3).
19F NMR (282 MHz, CDCl3): d = –71.9 (d, 3JF–H = 3.4 Hz, 3F).
HRMS: m/z [M + Na]+ calcd for C8H14F3NNa: 204.0976; found:
204.0967.
(1E)-Trifluoroacetaldehyde Cyclohexylhydrazone (16)
(17) Yeh, H. J. C.; Ziffer, H.; Jerina, D. M.; Boyd, D. R. J. Am.
IR (CHCl3): 1597 cm–1.
Chem. Soc. 1973, 95, 2741.
1H NMR (200 MHz, CDCl3): d = 1.51–1.82 (m, 6 H), 3.08–3.27 (m,
(18) Kanai, M.; Ueda, M. K. K.; Yasumoto, M.; Kuriyama, Y.;
Inomiya, K.; Ootsuka, T.; Katsuhara, Y.; Higashiyama, K.;
Ishii, A. J. Fluorine Chem. 2005, 126, 377.
(19) Ros, A.; Díez, E.; Marqués-López, E.; Martín-Zamora, E.;
Vázquez, J.; Iglesias-Sigüenza, J.; Pappalardo, R. R.;
Álvarez, E.; Lassaletta, J. M.; Fernández, R. Tetrahedron:
Asymmetry 2008, 19, 998.
4 H), 6.54 (q, 3JH–F = 4.0 Hz, 1 H).
13C NMR (50 MHz, CDCl3): d = 23.4, 25.7 (2C), 48.9 (2C), 112.1
(q, 2JC–F = 38.0 Hz, C-CF3), 118.2 (q, 1JC–F = 270.0 Hz, CF3).
19F NMR (282 MHz, CDCl3): d = –65.3 (d, 3JF–H = 4.0 Hz, 3F).
HRMS: m/z [M + Na]+ calcd for C7H11F3N2Na: 203.0772; found:
203.0782.
Synthesis 2010, No. 23, 4096–4100 © Thieme Stuttgart · New York