3094 J . Org. Chem., Vol. 67, No. 9, 2002
Gasparrini et al.
diluted with dry diethyl ether (150 mL) and filtered. The
filtrate was evaporated and the residue chromatographed to
give the title compound (2.41, 79%) as a thick oil: 1H NMR
(200 MHz, CDCl3) δ 4.20 (s, 2 H; CH2), 7.05-7.17 (m, 1 H; Ar
H), 7.20-7.40 (m, 7 H; Ar H), 7.90 (d, J ) 7.5 Hz, 1 H; Ar H);
13C NMR (50 MHz, CDCl3) δ 48.69 (CH2), 91.12 (C), 127.02
(CH), 127.85 (CH), 128.52 (CH), 129.62 (CH), 131.42 (CH),
133.23 (C), 140.27 (CH), 144.18 (C), 201.86 (C) (2 aromatic CH
overlapped); IR (film) ν˜ 3000, 1696 cm-1; MS (70 eV) m/z (%)
322 (7) [M]+, 231 (100), 203 (34), 104 (13), 91 (44), 76 (76).
Anal. Calcd for C14H11IO (322.1): C, 52.20; H, 3.44. Found:
C, 52.30; H, 3.43.
n on e O-Meth yloxim e (5): yield 75%; E/ Z ratio 69:31; pure
samples of the Z isomer (2) could not be obtained by any kind
of chromatography, even by preparative tlc. The spectral data
reported below for 2 were recorded with a sample of the pure
(Z)-oxime obtained by kinetic resolution as a residue of the
Suzuki arylation of 2 to give the naphthyl derivatives 10 and
11. MS (70 eV) (E + Z): m/z (%) 305 (3) [M + 2]+, 303 (4)
[M]+, 273 (35), 271 (37), 199 (10), 197 (10), 91 (100). Anal. Calcd
for C15H14BrNO (304.2) (E + Z): C, 59.22; H, 4.63; N, 4.60.
Found: C, 59.30; H, 4.62; N, 4.62. E isomer (5): oil; 1H NMR
(200 MHz, CDCl3) δ 3.99 (s, 3 H; OCH3), 4.10 (s, 2 H; CH2),
6.90-7.00 (m, 1 H; Ar H), 7.05-7.22 (m, 7 H; Ar H), 7.47-
7.54 (m, 1 H; Ar H); 13C NMR (75 MHz, CDCl3) δ 36.24 (CH2),
62.67 (CH3), 122.83 (C), 127.06 (CH), 127.74 (CH), 129.00 (CH),
130.02 (CH), 130.62 (CH), 131.96 (CH), 133.53 (CH), 136.42
Gen er a l P r oced u r e for th e P r ep a r a tion of Oxim es.15
A mixture of the ketone (10 mmol) and hydroxylamine
hydrochloride (for oxime 7) or O-methylhydroxylamine hydro-
chloride (for oximes 1-6, 10, and 11) (15 mmol) in pyridine
(2.5 mL)/ethanol (25 mL) was refluxed for 3-4 h. The solvent
was evaporated and the residue repeatedly chromatographed,
as described for each compound, to separate the E and Z
isomers.
(C), 137.82 (C), 159.12 (C); IR (film) ν˜ 3000, 1430, 1045 cm-1
.
Z isomer (2): oil; 1H NMR (300 MHz, CDCl3) δ 3.80 (br s, 2 H;
CH2), 3.85 (s, 3 H; OCH3), 6.55-6.65 (m, 1 H; Ar H), 7.05-
7.15 (m, 4 H; Ar H), 7.15-7.25 (m, 3 H; Ar H), 7.50-7.60 (m,
1 H; Ar H); 13C NMR (75 MHz, CDCl3) δ 41.92 (CH2), 62.69
(CH3), 121.02 (C), 127.40 (CH), 127.47 (CH), 129.02 (CH),
129.83 (CH), 130.22 (CH), 133.11 (CH), 136.42 (C), 136.67 (C),
156.92 (C) (2 aromatic CH overlapped); IR (film) ν˜ 3000, 1460,
(Z)-1-(2-Br om op h en yl)-2-p h en yl-1-eth a n on e Oxim e (7)
and (E)-1-(2-Br om op h en yl)-2-p h en yl-1-eth a n on e Oxim e:
eluent light petroleum (40-70 °C)/diethyl ether (98:2 v/v); yield
97%; E/ Z ratio 55:45; MS (70 eV) (E + Z) m/z (%): 391 (12)
[M + 2]+, 289 (11) [M]+, 273 (16), 271 (15), 210 (8), 91 (100).
Anal. Calcd for C14H12BrNO (290.2) (E + Z): C, 57.95; H, 4.16;
N, 4.82. Found C, 58.15; H, 4.17; N, 4.83. E isomer: mp 120-
123 °C (from light petroleum/benzene); 1H NMR (200 MHz,
CDCl3) δ 4.05 (s, 2 H; CH2), 6.85-6.95 (m, 1 H; Ar H), 6.95-
7.20 (m, 7 H; Ar H), 7.40-7.50 (m, 1 H; Ar H), 9.28 (br s, 1 H;
OH); 13C NMR (50 MHz, CDCl3) δ 35.64 (CH2), 122.75 (C),
127.13 (CH), 127.75 (CH), 129.01 (CH), 130.09 (CH), 130.74
(CH), 131.85 (CH), 133.60 (CH), 136.25 (C), 137.67 (C), 159.84
(C); IR (CHCl3) ν˜ 3580, 3311, 3000, 1450, 1025 cm-1. Z isomer
(7): mp 91.3-92.5 °C (from light petroleum/benzene); 1H NMR
(200 MHz, CDCl3) δ 3.75 (br s, 2 H; CH2), 6.55-6.70 (m, 1 H;
Ar H), 7.00-7.20 (m, 7 H; Ar H), 7.45-7.55 (m, 1 H; Ar H),
8.92 (br s, 1 H; OH); 13C NMR (50 MHz, CDCl3) δ 41.86 (CH2),
120.96 (C), 127.50 (CH), 129.04 (CH), 129.93 (CH), 130.20
(CH), 130.47 (CH), 133.20 (CH), 136.10 (C), 158.33 (C) (2 CH
overlapped and 1 C nonvisible); IR (CHCl3) ν˜ 3575, 3318, 3000,
1051, 1019 cm-1
.
(Z)-1-(2-Iod op h en yl)-2-p h en yl-1-et h a n on e O-Met h yl-
oxim e (3) and (E)-1-(2-Iod op h en yl)-2-p h en yl-1-eth a n on e
O-Meth yloxim e (6): preparative tlc, eluent light petroleum
(40-70 °C)/toluene (30:70 v/v); yield 69%; E/ Z ratio 75:25; MS
(70 eV) (E + Z) m/z (%) 351 (44) [M]+, 319 (66), 260 (9), 245
(20), 229 (13), 192 (12), 91 (100). Anal. Calcd for C15H14INO
(351.2) (E + Z): C, 51.30; H, 4.02; N, 3.99. Found: C, 51.40;
H, 4.01; N, 3.99. E isomer (6): oil; 1H NMR (300 MHz, CDCl3)
δ 4.03 (s, 3 H; OCH3), 4.07 (s, 2 H; CH2), 6.88 (d, J ) 8.0 Hz,
1 H; Ar H), 6.92-7.00 (m, 1 H; Ar H), 7.10-7.25 (m, 6 H; Ar
H), 7.82 (d, J ) 7.5 Hz, 1 H; Ar H); 13C NMR (50 MHz, CDCl3)
δ 36.51 (CH2), 62.64 (CH3), 97.53 (C), 127.10 (CH), 128.39 (CH),
129.00 (CH), 130.12 (CH), 130.53 (CH), 131.13 (CH), 136.22
(C), 139.94 (CH), 141.47 (C), 160.52 (C); IR (film) ν˜ 3000, 1430,
1042 cm-1. Z isomer (3): oil; 1H NMR (300 MHz, CDCl3) δ
3.80 (AB, J ) 14.2 Hz, ∆ν ) 57.4 Hz, 2 H; CH2), 3.86 (s, 3 H;
OCH3), 6.50 (dd, J ) 7.6, 1.4 Hz, 1 H; Ar H), 6.94 (ddd, J )
8.0, 8.0, 1.6 Hz, 1 H; Ar H), 7.08-7.29 (m, 6 H; Ar H), 7.80 (d,
J ) 8.0 Hz, 1 H; Ar H); 13C NMR (75 MHz, CDCl3) δ 41.96
(CH2), 62.67 (CH3), 95.38 (C), 127.46 (CH), 128.10 (CH), 129.01
(CH), 129.19 (CH), 130.12 (CH), 130.31 (CH), 136.34 (C),
139.49 (CH), 141.16 (C), 158.72 (C); IR (film) ν˜ 3000, 1430,
1450, 1220, 1025 cm-1
.
(Z)-1-(2-Ch lor op h en yl)-2-p h en yl-1-eth a n on e O-Meth yl-
oxim e (1) and (E)-1-(2-Ch lor op h en yl)-2-p h en yl-1-eth a -
n on e O-Meth yloxim e (4): eluent light petroleum (40-70 °C)/
toluene (30:70 v/v); yield 73%; E/ Z ratio 66:34; MS (70 eV) (E
+ Z) m/z (%) 261 (3) [M + 2]+, 259 (8) [M]+, 229 (36), 227 (100),
192 (9), 168 (8), 153 (22), 91 (82). Anal. Calcd for C15H14ClNO
(259.7) (E + Z): C, 69.36; H, 5.43; N, 5.39. Found: C, 69.55;
H, 5.41; N, 5.37; E isomer (4): oil; 1H NMR (200 MHz, CDCl3)
δ 3.92 (s, 3 H; OCH3), 4.05 (s, 2 H; CH2), 6.90-7.30 (m, 9 H;
Ar H); 13C NMR (50 MHz, CDCl3) δ 36.00 (CH2), 62.61 (CH3),
126.99 (CH), 127.17 (CH), 128.94 (CH), 129.87 (CH), 130.32
(CH), 130.44 (CH), 131.82 (CH), 133.32 (C), 135.87 (C), 136.47
(C), 158.11 (C); IR (film) ν˜ 3000, 1433, 1045 cm-1. Z isomer
(1): oil; 1H NMR (200 MHz, CDCl3) δ 3.73 (s, 2 H; CH2), 3.80
(s, 3 H; OCH3), 6.59 (dd, J ) 7.5, 1.8 Hz, 1 H; Ar H), 6.95-
1047 cm-1
.
(Z)-1-(2-Br om op h en yl)-2-p h en yl-1-eth a n on e O-Eth yl-
oxim e (9). A mixture of the (Z)-oxime 7 0.23 g, 0.8 mmol),
bromoethane (1.13 g, 1.2 mmol), and potassium carbonate (0.8
g, 5.8 mmol) in DMSO (30 mL) was kept at 55 °C in a sealed
Pyrex tube with magnetic stirring for 12 h. The final mixture
was poured into water and extracted with diethyl ether. The
organic phase was dried, the solvent was evaporated, and the
residue was chromatographed to give the pure (Z)-oxime 9 as
an oil (0.08 g, 30%): 1H NMR (200 MHz, CDCl3) δ 1.15 (t, J )
7.2 Hz, 3 H; OCH2CH3), 3.73 (vbr s, 2 H; PhCH2), 4.05 (q, J )
7.2 Hz, 2 H; OCH2CH3), 6.46-6.56 (m, 1 H; Ar H), 7.00-7.20
(m, 7 H; Ar H), 7.42-7.52 (m, 1 H; Ar H); 13C NMR (75 MHz,
CDCl3) δ 15.51 (CH3), 42.05 (PhCH2), 70.30 (OCH2), 121.08
(C), 127.33 (CH), 127.38 (CH), 128.98 (CH), 129.92 (CH),
130.08 (CH), 130.21 (CH), 133.08 (CH), 133.56 (C), 136.70 (C),
156.57 (C); MS (70 eV) m/z (%) 319 (1) [M + 2]+, 317 (1) [M]+,
273 (17), 271 (18), 91 (100). Anal. Calcd for C16H16BrNO
(318.2): C, 60.39; H, 5.06; N, 4.40. Found: C, 60.57; H, 5.08;
N, 4.39.
7.18 (m, 7 H; Ar H), 7.27 (dd, J ) 8.0, 1.4 Hz, 1 H; Ar H); 13
C
NMR (50 MHz, CDCl3) δ 41.92 (CH2), 62.64 (CH3), 126.82 (CH),
127.41 (CH), 128.99 (CH), 129.69 (CH), 129.95 (CH), 130.09
(CH), 131.80 (C), 134.41 (C), 136.44 (C), 155.86 (C) (2 aromatic
CH overlapped); IR (film) ν˜ 3000, 1450, 1058, 1022 cm-1. An
NOE experiment (400 MHz, toluene-d8) was carried out on the
E/ Z mixture by irradiating the methylene signal that is
independent of the temperature (4.17 ppm). Since only the E
isomer could experience a positive NOE effect between the
methylene and the methoxy group, the observed outcome (2%)
on the (E)-OMe group (3.85 ppm) confirmed that the (E)-oxime
is not responsible for the observed splitting of the signals as
function of temperature.
(E)-1-[2-(1-Na p h th yl)p h en yl]-2-p h en yl-1-eth a n on e O-
Meth yloxim e (10) and (Z)-1-[2-(1-Na p h th yl)p h en yl]-2-
p h en yl-1-eth a n on e O-Meth yloxim e (11). According to a
reported procedure,16 a benzene (11 mL) solution of oximes 2
and 5 (ca. 1:1, 0.53 g, 1.75 mmol overall amount) was treated
(Z)-1-(2-Br om op h en yl)-2-p h en yl-1-eth a n on e O-Meth yl-
oxim e (2) and (E)-1-(2-Br om op h en yl)-2-p h en yl-1-eth a -
(15) Vogel, A. I. Practical Organic Chemistry, 4th ed.; Longmans:
London, 1969; p 345.
(16) Miyaura, N.; Yamagi, T.; Suzuki, A. Synth. Commun. 1981, 11,
513.