2642 Bull. Chem. Soc. Jpn., 75, No. 12 (2002)
Synthesis of 1-Aryl-2,2,2-trifluoroethylamines
NMR (CDCl3) δ 88.18 (d, 3F, J = 7.3 Hz). MS m/z (%) 268 (M+,
2), 199 (19), 187 (6), 162 (19), 106 (45), 94 (19), 91 (100). Found:
C, 62.64; H, 5.60; N, 10.38%. Calcd for C14H15F3N2: C, 62.68; H,
5.64; N, 10.44%.
7.5 Hz), 3.94 (d, 1H, J = 13.3 Hz), 3.61 (d, 1H, J = 13.3 Hz). 19F
NMR (CDCl3) δ 86.98 (d, 3F, J = 7.5 Hz). MS m/z (%) 297 (M+,
14), 228 (49), 190 (53), 148 (21), 120 (46), 106 (100), 91 (95).
Found: C, 60.49; H, 4.74; N, 4.74%. Calcd for C15H14F3NO2: C,
60.60; H, 4.75; N, 4.71%.
Benzyl[2,2,2-trifluoro-1-(1-methyl-1H-pyrrol-3-yl)ethyl]-
1
amine (5a): A colorless oil. H NMR (CDCl3) δ 7.30 (s, 5H),
4,6-Bis(1-benzylamino-2,2,2-trifluoroethyl)benzene-1,3-diol
1
6.59 (s, 1H), 6.58 (d, 1H, J = 2.0 Hz), 6.14 (d, 1H, J = 2.0 Hz),
4.04 (q, 1H, J = 7.5 Hz), 3.91 (d, 1H, J = 13.6 Hz), 3.75 (d, 1H, J
= 13.6 Hz), 3.63 (s, 3H), 1.70 (br, 1H). 19F NMR (CDCl3) δ 87.19
(d, 3F, J = 7.5 Hz). MS m/z (%) 268 (M+, 2), 199 (44), 186 (5),
163 (37), 162 (25), 112 (17), 106 (50), 94 (31), 91 (100). Found:
C, 62.59; H, 5.62; N, 10.41%. Calcd for C14H15F3N2: C, 62.68; H,
5.64; N, 10.44%.
(13): A colorless oil. H NMR (CDCl3) δ 10.66 (br, 2H), 7.29
(m, 10H), 6.69, 6.57 (s, 1H), 6.48 (s, 1H), 4.19 (q, 2H, J = 8.1
Hz), 3.99 (d, 2H, J = 13.4 Hz), 3.60 (d, 1H, J = 13.4 Hz), 2.43
(br, 2H). 19F NMR (CDCl3) δ 86.95 (d, 3F, J = 8.1 Hz). MS m/z
(%) 484 (M+, 4), 415 (7), 308 (20), 286 (7), 149 (4), 106 (63), 91
(100). Found: C, 59.69; H, 4.60; N, 5.71%. Calcd for
C24H22F6N2O2: C, 59.50; H, 4.58; N, 5.78%.
Benzyl(2,2,2-trifluoro-1-furan-2-yl-ethyl)amine (6a):
A
Benzhydryl[2,2,2-trifluoro-1-(1H-indol-3-yl)ethyl]amine
(2b): A colorless oil. 1H NMR (CDCl3) δ 8.18 (br, 1H), 7.33 (s,
5H), 7.24 (s, 5H), 7.01–7.69 (m, 5H), 4.88 (s, 1H), 4.32 (m, 1H),
2.30 (m, br, 1H). 19F NMR (CDCl3) δ 88.21 (d, 3F, J = 7.6 Hz).
MS m/z (%) 380 (M+, 4), 311 (17) 263 (28), 261 (21), 182 (100),
167 (91), 106 (16). Found: C, 72.49; H, 5.01; N, 7.21%. Calcd for
C23H19F3N2: C, 72.62; H, 5.03; N, 7.36%.
yellowish oil. 1H NMR (CDCl3) δ 7.45 (m, 1H), 7.31 (s, 5H), 6.40
(m, 2H), 4.21 (q, 1H, J = 7.3 Hz), 3.92 (d, 1H, J = 13.3 Hz), 3.70
(d, 1H, J = 13.3 Hz), 2.04 (br, 1H). 19F NMR (CDCl3) δ 87.83 (d,
3F, J = 7.3 Hz). MS m/z (%) 255 (M+, 1), 186 (7), 149 (18), 91
(100). HRMS m/z Found: 255.0869. Calcd: 255.0871.
Benzyl[2,2,2-trifluoro-1-thiophen-2-yl]ethyl]amine (7a):
1
A yellowish oil. H NMR (CDCl3) δ 7.31 (s, 5H), 7.28 (m, 1H),
Benzhydryl[2,2,2-trifluoro-1-(1H-pyrrol-2-yl)ethyl]amine
1
7.05 (m, 2H), 4.42 (q, 1H, J = 7.2 Hz), 3.94 (d, 1H, J = 13.5 Hz),
3.72 (d, 1H, J = 13.5 Hz), 1.70 (br, 1H). 19F NMR (CDCl3) δ
87.30 (d, 3F, J = 7.2 Hz). MS m/z (%) 271 (M+, 16), 202 (98),
165 (10), 150 (61), 106 (70), 91(100). Found: C, 57.64; H, 4.43;
N, 5.11%. Calcd for C13H12F3NS: C, 57.55; H, 4.46; N, 5.16%.
4-(1-Benzylamino-2,2,2-trifluoroethyl)-N,N-dimethylani-
(3b): Colorless plates, mp 91–93 °C. H NMR (CDCl3) δ 8.35
(br, 1H), 7.32 (s, 5H), 7.28 (s, 5H), 6.80 (m, 1H), 6.19 (m, 2H),
4.82 (d, 1H, J = 5.3 Hz), 4.15 (m, 1H), 2.30 (m, br, 1H). 19F NMR
(CDCl3) δ 87.74 (d, 3F, J = 7.2 Hz). MS m/z (%) 330 (M+, 0.3),
263 (14), 261 (18), 182 (24), 167 (100), 165 (21), 152 (13), 128
(12), 106 (10). Found: C, 68.99; H, 5.18; N, 8.36%. Calcd for
C19H17F3N2: C, 69.08; H, 5.19; N, 8.48%.
1
line (8a): Colorless grains, mp 48–49 °C. H NMR (CDCl3) δ
7.28 (s, 5H), 7.23 (d, 2H, J = 8.7 Hz), 6.71 (d, 1H, J = 8.7 Hz),
4.01 (q, 1H, J = 7.5 Hz), 3.85 (d, 1H, J = 13.8 Hz), 3.57 (d, 1H, J
= 13.8 Hz), 2.96 (s, 6H), 1.92 (br, 1H). 19F NMR (CDCl3) δ 87.57
(d, 3F, J = 7.5 Hz). MS m/z (%) 308 (M+, 80), 239 (100), 202
(38), 148 (30), 91 (51). Found: C, 66.30; H, 6.20; N, 8.99%. Cal-
cd for C17H19F3N2: C, 66.22; H, 6.21; N, 9.09%.
Benzhydryl[2,2,2-trifluoro-1-(1-methyl-1H-pyrrol-2-yl)eth-
yl]amine (4b):
Colorless plates, mp 79–81 °C. 1H NMR
(CDCl3) δ 7.32 (s, 5H), 7.29 (s, 5H), 6.58 (m, 1H), 6.24 (m, 1H),
6.17 (m, 1H), 4.84 (d, 1H, J = 3.1 Hz), 4.10 (m, 1H), 3.25 (s, 3H),
2.20 (m, br, 1H). 19F NMR (CDCl3) δ 87.60 (d, 3F, J = 7.1 Hz).
MS m/z (%) 344 (M+, 0.2), 263 (10), 262 (29), 182 (100), 167
(90), 165 (30), 162 (68), 152 (16), 112 (16), 106 (12), 104 (20), 94
(33). Found: C, 69.59; H, 5.55; N, 8.08%. Calcd for C20H19F3N2:
C, 69.75; H, 5.56; N, 8.13%.
4-(1-Benzylamino-2,2,2-trifluoroethyl)phenol (9a): Color-
1
less grains, mp 91–92 °C. H NMR (CDCl3) δ 7.28 (s, 5H), 7.27
(d, 2H, J = 8.5 Hz), 6.84 (d, 1H, J = 8.5 Hz), 4.05 (q, 1H, J = 7.5
Hz), 3.83 (d, 1H, J = 13.6 Hz), 3.61 (d, 1H, J = 13.6 Hz), 1.70
(br, 1H). 19F NMR (CDCl3) δ 87.60 (d, 3F, J = 7.5 Hz). MS m/z
(%) 281 (M+, 5), 212 (100), 175 (54), 125 (3), 91 (30). Found: C,
64.09; H, 5.01; N, 4.86%. Calcd for C15H14F3NO: C, 64.05; H,
5.02; N, 4.98%.
Benzhydryl[2,2,2-trifluoro-1-(furan-2-yl)ethyl]amine (6b):
1
A yellowish oil. H NMR (CDCl3) δ 7.42 (m, 1H), 7.33 (s, 5H),
7.27 (s, 5H), 6.35 (m, 2H), 4.78 (s, 1H), 4.18 (m, 1H), 2.35 (br,
1H). 19F NMR (CDCl3) δ 88.06 (d, 3F, J = 7.2 Hz). MS m/z (%)
331 (M+, 3), 263 (28), 262 (20), 254 (26), 182 (13), 167 (94), 165
(28), 152 (8), 149 (100), 104 (32). HRMS m/z Found: 331.1182.
Calcd: 331.1184.
2-(1-Benzylamino-2,2,2-trifluoroethyl)phenol (10a):
A
colorless oil. 1H NMR (CDCl3) δ 10.50 (s, 1H), 7.33 (s, 5H), 7.25
(m, 1H), 7.01 (m, 2H), 6.82 (d, 1H, J = 8.3 Hz), 4.27 (q, 1H, J =
7.7 Hz), 3.97 (d, 1H, J = 13.0 Hz), 3.61 (d, 1H, J = 13.0 Hz),
2.36 (br, 1H). 19F NMR (CDCl3) δ 87.26 (d, 3F, J = 7.7 Hz). MS
m/z (%) 281 (M+, 29), 212 (66), 127 (4), 106 (12), 91 (100).
Found: C, 63.89; H, 5.05; N, 4.82%. Calcd for C15H14F3NO: C,
64.05; H, 5.02; N, 4.98%.
Benzhydryl[2,2,2-trifluoro-1-(thiophen-2-yl)ethyl]amine
(7b): A yellowish oil. 1H NMR (CDCl3) δ 7.34 (s, 5H), 7.26 (s,
5H), 7.23 (m, 1H), 6.99 (m, 2H), 4.87 (d, 1H, J = 2.9 Hz), 4.30
(m, 1H), 2.23 (m, br, 1H). 19F NMR (CDCl3) δ 87.51 (d, 3F, J =
7.4 Hz). MS m/z (%) 347 (M+, 0.3), 278 (7), 270 (24), 263 (19),
262 (11), 182 (45), 167 (90), 165 (100), 152 (17), 115 (23), 104
(23). Found: C, 65.86; H, 4.65; N, 3.87%. Calcd for C19H16F3NS:
C, 65.69; H, 4.64; N, 4.03%.
4-(1-Benzylamino-2,2,2-trifluoroethyl)-2,6-dimethylphenol
(11a): A colorless oil. 1H NMR (CDCl3) δ 7.29 (s, 5H), 6.99 (s,
2H), 4.70 (br, 1H), 3.98 (q, 1H, J = 7.4 Hz), 3.82 (d, 1H, J = 13.6
Hz), 3.62 (d, 1H, J = 13.6 Hz), 2.25 (s, 6H), 1.60 (br, 1H). 19F
NMR (CDCl3) δ 87.79 (d, 3F, J = 7.5 Hz). MS m/z (%) 309 (M+,
21), 240 (100), 218 (8), 203 (11), 150 (8), 106 (50), 91 (96).
Found: C, 65.89; H, 5.91; N, 4.48%. Calcd for C17H18F3NO: C,
66.01; H, 5.87; N, 4.53%.
4-[1-(Benzhydrylamino)-2,2,2-trifluoroethyl]-N,N-dimethyl-
aniline (8b):
Colorless crystals, mp 75–76 °C. 1H NMR
(CDCl3) δ 7.34 (s, 5H), 7.27 (s, 5H), 7.15 (d, 2H, J = 8.8 Hz),
6.71 (d, 2H, J = 8.8 Hz), 4.73 (d, 1H, J = 0.9 Hz), 3.92 (m, 1H, J
= 7.9 Hz), 2.98 (s, 6H), 2.32 (m, br, 1H). 19F NMR (CDCl3) δ
87.92 (d, 3F, J = 7.9 Hz). MS m/z (%) 384 (M+, 6), 315 (12), 262
(13), 202 (20), 167 (100), 165 (21), 152 (21), 122 (11). Found: C,
71.79; H, 6.02; N, 7.23%. Calcd for C23H23F3N2: C, 71.86; H,
6.03; N, 7.29%.
4-(1-Benzylamino-2,2,2-trifluoroethyl)benzene-1,3-diol (12):
A colorless oil. 1H NMR (CDCl3) δ 7.30 (m, 5H), 6.86 (d, 2H, J =
7.9 Hz), 6.44 (s, 1H), 6.40 (d, 1H, J = 7.9 Hz), 4.19 (q, 1H, J =