W.B. Motherwell, L.J. Storey / Journal of Fluorine Chemistry 126 (2005) 491–498
497
1
was heated at reflux for 20 h. The dark brown mixture was
cooled and SiO2 gel was added (1 g) with 1 M HCl (20
drops). This was stirred for 3 h, and the mixture was then
filtered and the solvent removed in vacuo. The crude product
was chromatographed on silica gel using 5% diethyl ether in
petroleum spirit (40–60).
2x 113.8, 119.2, 120.7, 125.1 (q, J = 281 Hz, CF3), 2x
126.7, 127.8, 128.4, 2x 128.6, 2x 129.4, 135.5, 145.5; MSEI
70 eV, m/z (rel. int.): 277 [M]+ (78%), 208 [M-CF3]+
(100%); HRMS calcd for C16H14F3N: 277.1078; obsd:
277.1094.
4.2.5.5. Phenyl-(1-naphthalen-20-yl-2,2,2-trifluoroethyl)-
amine (18e). 44%; mp: 71–73 8C; IR (CHCl3): n 3412,
1603, 1504; 1H NMR (300 MHz, CDCl3): d 4.45 (1H, br d,
3J = 6.7 Hz, NH), 5.11 (1H, dq, JHF = 7.2 Hz, JHH = 6.7 Hz,
4.2.5.1. Phenyl-(1-phenyl-2,2,2-trifluoroethyl)-amine
(18a). 60%; IR (film): n 3416, 1604, 1504, 1250, 1175,
1123; H NMR (300 MHz, CDCl3): d 4.30 (1H, br s, NH),
1
4.95 (1H, q, 3J = 7.3 Hz, CHCF3), 6.67 (2H, d, 3J = 8.2 Hz,
aromatic), 6.83 (1H, t, 3J = 7.3 Hz, aromatic), 7.19 (2H, m,
aromatic), 7.39–7.50 (5H, m, aromatic); 19F NMR
(282 MHz, CDCl3); d ꢀ74.5; 13C NMR (75 MHz, CDCl3):
d 60.5 (q, 2J = 30 Hz, CHCF3), 114, 119.2, 125.1 (q,
1J = 282 Hz, CF3), 127.8, 128.8, 129.0, 129.2, 133.9, 145.4;
MSEI 70 eV, m/z (rel. int.) 251 [M]+ (100%), 182 [M-CF3]+
(53%); HRMS calcd for C14H12F3N: 251.0922; obsd:
251.0918.
3
CHCF3), 6.71 (2H, d, J = 8.5 Hz, aromatic), 6.79 (1H, t,
3
3J = 7.3 Hz, aromatic), 7.18 (2H, t, J = 6.5 Hz, aromatic),
7.50–7.53 (2H, m, aromatic), 7.55 (1H, d, 3J = 8.5 Hz,
aromatic), 7.84–7.90 (3H, m, aromatic), 7.97 (1H, s,
aromatic); 19F NMR (282 MHz, CDCl3): d ꢀ74.0; 13C
NMR (75 MHz, CDCl3): d 60.7 (q, 2J = 30 Hz, CHCF3), 2x
1
113.9, 119.2, 124.8, 125.1 (q, J = 282 Hz, CF3), 126.4,
126.6, 2x 127.8, 128.0, 128.7, 2x 129.2, 131.3, 133.0, 133.4,
145.4; MSEI 70 eV, m/z (rel. int.): 301 [M]+ (50%), 232 [M-
CF3] (100%); HRMS calcd for C18H14F3N: 301.1078; obsd:
301.1076.
4.2.5.2. (4-Methoxy-phenyl)-(1-p-tolyl-2,2,2-trifluor-
oethyl)-amine (18b). 54%; IR (CHCl3): n 3374, 1695, 1600,
1515; 1H NMR (300 MHz CDCl3): d 2.33 (3H, s, CH3), 3.70
(3H, s, OCH3), 3.70 (1H, br s, NH), 4.76 (1H, q, 3J = 7.3 Hz,
Acknowledgements
3
CHCF3), 6.59 (2H, d, J = 8.8 Hz, aromatic), 6.72 (2H, d,
3
3J = 9.0 Hz, aromatic), 7.18 (2H, d, J = 8.0 Hz, aromatic),
The support of this work by Zeneca Plc (Syngenta) from
their Strategic Research Fund (SRF 281, 1997–1999) is
gratefully acknowledged. We thank Dr S. Lee (Astra-
Zeneca, Macclesfield) and Dr R. Salmon (Syngenta,
Bracknell) in particular for their helpful comments and
fruitful discussion.
3
7.32 (2H, d, J = 8.2 Hz, aromatic); 19F NMR (282 MHz,
CDCl3): d ꢀ74.6; 13C NMR (75 MHz, CDCl3): d 23.1 (CH3),
2
57.6 (OCH3), 61.5 (q, J = 29 Hz, CHCF3), 114.7, 115.8,
1
127.7, 128.4 (q, J = 271 Hz, CF3), 129.5, 138.9, 153.3;
MSEI 70 eV, m/z (rel. int.): 295 [M]+ (100%), 226 [M-CF3]+
(82%); HRMS calcd for C16H16F3NO: 295.1184; obsd:
295.1178.
References
4.2.5.3. Phenyl-[1-(4-methoxy-phenyl)-2,2,2-trifluor-
oethyl]-amine (18c). 33%; IR (CHCl3): n 3406, 1605, 1515,
1250, 1173, 1123; 1H NMR (300 MHz, CDCl3): d 3.69 (3H,
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3
s, OCH3), 4.17 (1H, br s, NH), 4.76 (1H, q, J = 7.2 Hz,
3
CHCF3), 6.54 (2H, d, J = 8.6 Hz, aromatic), 6.67 (1H, t,
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3J = 7.4 Hz, aromatic), 6.8 (2H, d, J = 6.6 Hz, aromatic),
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