Bꢀrbara Noverges et al.
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(300 MHz, CDCl3, TMS): d=7.59–7.51 (m, 2H), 7.34–7.18
(m, 8H), 7.02 (dm, J=8.8 Hz, 2H), 6.68 (dm, J=8.8 Hz,
2H), 5.20 (s, 2H), 4.02 (s, 2H), 3.67 (s, 3H); 13C NMR
(75 MHz, CDCl3): d=158.1, 156.9, 138.1, 135.8, 129.6, 129.2,
128.8, 128.5, 128.5, 128.4, 127.9, 126.7, 114.0, 76.4, 55.3, 32.0;
HR-MS (EI): m/z=332.1650 (M+), calcd. for C22H22NO2:
332.1645.
HR-MS (EI): m/z=269.1410 (M+), calcd. for C17H19NO2:
269.1416.
AHCTUNGTREG(NNUN E/Z)-1-[4-(Trifluoromethyl)phenyl]propan-2-one O-ben-
zyloxime (3w): Isolated as a mixture (94:6) after column pu-
rification; yield: 90%; oil; 1H NMR (300 MHz, CDCl3,
TMS): d=7.45 (d, J=8.0 Hz, 2H), 7.37–7.23 (m, 5H), 7.19
(d, J=8.0 Hz, 2H), 5.06 (s, 2H), 3.43 (s, 2H), 1.70 (s, 3H);
13C NMR (75 MHz, CDCl3): d=156.3, 141.3 (q, J=1.1 Hz),
138.3, 134.7 (q, J=6.3 Hz), 129.4, 128.5, 128.1, 127.8, 125.6
(q, J=3.8 Hz), 124.3 (q, J=272.1 Hz), 75.7, 42.1, 14.2; HR-
MS (EI): m/z=307.1180 (M+), calcd. for C17H16F3NO:
307.1184.
(E)-1-Phenyl-2-[4-(trifluoromethyl)phenyl]ethanone
O-
benzyloxime (3p): Yield: 85%; white solid; mp 56–588C;
1H NMR (300 MHz, CDCl3, TMS): d=7.58–7.52 (m, 2H),
7.39 (d, J=8.2 Hz, 2H), 7.30–7.23 (m, 8H), 7.23–7.17 (m,
2H), 5.19 (s, 2H), 4.13 (s, 2H); 13C NMR (75 MHz, CDCl3):
d=155.7, 141.1, 137.7, 135.4, 129.5, 128.9, 128.7, 128.5, 128.4,
128.1, 126.5, 125.6 (q, J=3.8 Hz), 124.4 (q, J=271.8 Hz),
76.7, 32.8; HR-MS (EI): m/z=370.1414 (M+), calcd. for
C22H19F3NO: 370.1413.
3-Benzyl-6-ethoxy-5,6-dihydro-4H-1,2-oxazine (3x): Yield:
52%; colorless liquid; 1H NMR (300 MHz, CDCl3, TMS):
d=7.29–7.13 (m, 5H), 4.97 (t, J=2.6 Hz, 1H), 3.81 (dq, J=
9.7, 7.1 Hz, 1H), 3.52 (dq, J=9.7, 7.1 Hz, 1H), 3.46 (s, 2H),
2.17–2.01 (m, 1H), 1.88–1.73 (m, 3H), 1.13 (t, J=7.1 Hz,
3H); 13C NMR (75 MHz, CDCl3): d=159.3, 136.9, 129.0,
128.8, 127.0, 94.6, 63.4, 42.8, 23.2, 18.0, 15.2; HR-MS (EI):
m/z=220.1337 (M+H+), calcd. for C13H17NO2: 220.1332.
6-Ethoxy-3-[4-(trifluoromethyl)benzyl]-5,6-dihydro-4H-
(E)-2-(4-Methoxyphenyl)-1-phenylethanone O-acetylox-
1
ime (3q): Yield: 18%; colorless liquid; H NMR (300 MHz,
CDCl3, TMS): d=7.65 (dd, J=7.9, 1.5 Hz, 2H), 7.37–7.23
(m, 3H), 7.03 (d, J=8.4 Hz, 2H), 6.78–6.65 (m, 2H), 4.10 (s,
2H), 3.69 (s, 3H), 2.17 (s, 3H); 13C NMR (75 MHz, CDCl3):
d=169.0, 164.2, 134.2, 130.7, 129.6, 128.8, 127.7, 127.3, 114.4,
55.4, 33.6, 20.0; HR-MS (EI): m/z=283.1235 (M+), calcd.
for C17H17NO3: 283.1208.
1
1,2-oxazine (3y): Yield: 59%; pale yellow liquid; H NMR
(300 MHz, CDCl3, TMS): d=7.50 (d, J=8.1 Hz, 2H), 7.30
(d, J=8.1 Hz, 2H), 4.99 (t, J=2.6 Hz, 1H), 3.80 (dq, J=9.7,
7.1 Hz, 1H), 3.69–3.46 (m, 1H), 3.53 (d, J=2.8 Hz, 1H),
3.51 (d, J=2.8 Hz, 1H), 2.22–1.98 (m, 1H), 1.94–1.70 (m,
3H), 1.13 (t, J=7.1 Hz, 3H); 13C NMR (75 MHz, CDCl3):
d=158.5, 141.1, 129.3, 125.7 (q, J=3.8 Hz), 94.6, 63.5, 42.6,
23.1, 18.2, 15.2; HR-MS (EI): m/z=288.1205 (M+H+),
calcd. for C14H17F3NO2: 288.1206.
6-Ethoxy-3-(2-methylbenzyl)-5,6-dihydro-4H-1,2-oxazine
(3z): Yield: 65%; colorless liquid; 1H NMR (400 MHz,
CDCl3, TMS): d=7.14–6.99 (m, 4H), 4.97 (t, J=2.7 Hz,
1H), 3.79 (dq, J=9.7, 7.1 Hz, 1H), 3.57–3.41 (m, 3H), 2.25
(s, 3H), 2.12–1.95 (m, 1H), 1.85–1.72 (m, 3H), 1.12 (t, J=
7.1 Hz, 3H); 13C NMR (101 MHz, CDCl3): d=158.9, 137.3,
134.9, 130.6, 129.9, 127.1, 126.2, 94.5, 63.4, 40.6, 23.2, 19.6,
18.1, 15.2; HR-MS (EI): m/z=234.1491 (M+H+), calcd. for
C14H20NO2: 234.1489.
ACHTUNGTRENNUNG(E/Z)-3,3-Dimethyl-1-phenylbutan-2-one O-benzyloxime
(3r): Isomeric ratio (92:8); yield: 98%; colorless liquid;
1H NMR (300 MHz, CDCl3, TMS): d=7.27–6.99 (m, 10H),
5.00 (s, 2H), 3.66 (s, 2H), 1.01 (s, 9H); 13C NMR (75 MHz,
CDCl3): d=164.7, 138.3, 137.7, 128.5, 128.4, 128.3, 128.2,
127.6, 125.9, 75.7, 37.8, 31.8, 28.5; HR-MS (EI): m/z=
281.1783 (M+), calcd. for C19H23NO: 281.1780.
ACHTUNGTRENNUNG(E/Z)-1-(4-Methoxyphenyl)-3,3-dimethylbutan-2-one O-
benzyloxime (3s): Isomeric ratio (94:6); yield: 65%; color-
1
less liquid; H NMR (300 MHz, CDCl3, TMS): d=7.26–7.16
(m, 5H), 6.98–6.91 (m, 2H), 6.70–6.62 (m, 2H), 5.01 (s, 2H),
3.68 (s, 3H), 3.59 (s, 2H), 1.00 (s, 9H); 13C NMR (75 MHz,
CDCl3): d=165.0, 157.8, 138.4, 129.6, 129.5, 128.5, 128.3,
127.6, 113.7, 75.6, 55.3, 37.8, 30.8, 28.5; HR-MS (EI): m/z=
311.1850 (M+), calcd. for C20H25NO2: 311.1885.
A
(E)-1-(4-Methoxyphenyl)-2-phenylethanone O-methylox-
ime (3aa) [CAS: 146364-30-9]: Yield: 93%; white solid; mp
35–378C; 1H NMR (300 MHz, CDCl3, TMS): d=7.56–7.47
(m, 2H), 7.21–7.04 (m, 5H), 6.78–6.71 (m, 2H), 4.03 (s, 2H),
3.92 (s, 3H), 3.68 (s, 3H); 13C NMR (75 MHz, CDCl3): d=
160.5, 155.7, 137.0, 128.7, 128.5, 128.3, 127.9, 126.3, 113.9,
62.0, 55.4, 32.6; HR-MS (EI): m/z=225.1245 (M+), calcd.
for C16H17NO2: 225.1259.
one O-benzyloxime (3t): Isomeric ratio (98:2); yield: 80%;
colorless liquid; H NMR (300 MHz, CDCl3, TMS): d=7.34
(d, J=8.1 Hz, 2H), 7.23–7.05 (m, 7H), 4.97 (s, 2H), 3.67 (s,
2H), 1.01 (s, 9H); 13C NMR (75 MHz, CDCl3): d=163.9,
141.9, 138.0, 128.8, 128.6, 128.3, 128.0, 127.8, 125.2 (q, J=
3.8 Hz), 124.5 (q, J=271.9 Hz), 75.9, 37.8, 31.7, 28.3; HR-
MS (EI): m/z=350.1723 (M+H+), calcd. for C20H23F3NO:
350.1726.
(E)-1,2-Bis(4-methoxyphenyl)ethanone
O-methyloxime
A
(3ab) [CAS: 144889-01-0]: Yield: 78%; white solid; mp 39–
418C; H NMR (300 MHz, CDCl3, TMS): d=7.54–7.46 (m,
meric ratio (93:7); yield: 88%; colorless liquid; 1H NMR
(300 MHz, CDCl3, TMS): d=7.40–7.03 (m, 10H), 5.06 (s,
2H), 3.37 (s, 2H), 1.69 (s, 3H); 13C NMR (75 MHz, CDCl3):
d=157.3, 138.4, 137.1, 129.1, 128.6, 128.4, 128.0, 127.7, 126.8,
75.5, 42.2, 14.1; HR-MS (EI): m/z=239.1333 (M+), calcd.
for C16H17NO: 239.1310.
1
2H), 7.08–7.01 (m, 2H), 6.80–6.67 (m, 4H), 3.97 (s, 2H),
3.92 (s, 3H), 3.70 (s, 3H), 3.67 (s, 3H); 13C NMR (75 MHz,
CDCl3): d=160.4, 158.1, 156.1, 129.6, 128.9, 128.3, 128.0,
114.1, 113.9, 62.0, 55.4, 55.3, 31.7; HR-MS (EI): m/z=
285.1361 (M+), calcd. for C17H19NO3: 285.1365.
A
(E)-2-[4-(Trifluoromethyl)phenyl]-1-(4-methoxyphenyl)-
ethanone O-methyloxime (3ac): Yield: 68%; white solid; mp
36–388C; 1H NMR (300 MHz, CDCl3, TMS): d=7.54–7.47
(m, 2H), 7.43 (d, J=8.1 Hz, 2H), 7.24 (d, J=8.0 Hz, 2H),
6.83–6.73 (m, 2H), 4.09 (s, 2H), 3.93 (s, 3H), 3.72 (s, 3H);
13C NMR (75 MHz, CDCl3): d=160.7, 154.9, 141.2, 128.9,
127.9, 127.8, 127.5, 125.6 (q, J=3.7 Hz), 124.4 (q, J=
(3v): Isolated as a mixture (91:9) after column purification;
yield: 62%; colorless liquid; 1H NMR (300 MHz, CDCl3,
TMS): d=7.34–7.19 (m, 5H), 7.05–6.98 (m, 2H), 6.78–6.72
(m, 2H), 5.06 (s, 2H), 3.71 (s, 3H), 3.32 (s, 2H), 1.69 (s,
3H); 13C NMR (75 MHz, CDCl3): d=158.6, 157.6, 138.5,
130.1, 129.1, 128.4, 128.0, 127.7, 114.1, 75.5, 55.4, 41.4, 14.0;
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ꢄ 2013 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Adv. Synth. Catal. 2013, 355, 2327 – 2342