PAPER
Synthesis of , -Bis(substituted benzylidene) cycloalkanones
265
, -Bis(substituted benzylidene)cycloalkanones; General Pro-
cedure
3f
Solid; mp 170–171 °C (Lit.20 mp 170 °C).
To a stirred mixture of cyclohexanone [1 (n = 2); 0.200 g, 2.04
mmol] and benzaldehyde [2 (R = Ph); 0.433 g, 4.08 mmol] in
MeCN (4 mL) was added NaI (0.306 g, 1 equiv) followed by drop-
wise addition of TMSCl (0.26 mL, 1 equiv). The reaction mixture
was stirred for 1 h at r.t. After complete conversion, as indicated by
TLC, the mixture was taken up into Et2O, washed with Na2S2O3 so-
lution, brine and dried (Na2SO4). Evaporation of the solvent afford-
ed a crude solid product, which was purified by successive
washings with petroleum ether (bp 60–65 °C) to give pure 3g in
95% yield. Liquid compounds were purified by short silica gel col-
umn chromatography Table 1).
IR (KBr): 3030, 2965, 2905, 1712, 1610 cm–1.
1H NMR (200 MHz, CDCl3): = 1.95 (m, 2 H), 3.00 (m, 2 H), 7.55–
7.20 (m, 8 H).
13C NMR (200 MHz, CDCl3): = 20.95, 25.77, 128.17, 128.81,
130.04, 133.37, 135.65, 137.11, 138.23, 151.62, 190.62.
MS: m/z = 184 (M+).
3g
Solid; mp 117–118 °C (Lit.21 mp 118 °C).
IR (KBr): 3070, 3025, 1672, 1570, 1485 cm–1.
3a
1H NMR (200 MHz, CDCl3): = 1.72–1.88 (m, 2 H), 2.82–2.98 (m,
4 H), 7.23–7.55 (m, 10 H), 7.80 (s, 2 H).
13C NMR (200 MHz, CDCl3): = 20.05, 23.81, 128.03, 128.17,
131.21, 135.16, 136.33, 137.27, 190.01.
Solid; mp 188–189 °C (Lit.17 mp 189 °C).
IR (KBr): 3050, 3019, 2905, 1682, 1630 cm–1.
1H NMR (200 MHz, CDCl3): = 3.10 (s, 4 H), 7.30–7.40 (m, 6 H),
7.53–7.60 (m, 6 H).
13C NMR (200 MHz, CDCl3): = 21.65, 128.12, 128.35, 131.04,
135.87, 144.32, 156.31, 192.25.
MS: m/z = 274 (M+).
3h
Solid; mp 156–158 °C.
IR (KBr): 2931, 1662, 1604, 1504 cm–1.
MS: m/z = 260 (M+).
3b
1H NMR (200 MHz, CDCl3): = 1.70–1.90 (m, 2 H), 2.80–2.95 (t,
4 H, J = 3 Hz), 7.00–7.15 (m, 4 H, ArH), 7.32–7.50 (m, 4 H, ArH),
7.70 (s, 2 H, J = 4 Hz, 2 C=CH).
Solid; mp 210–211 °C (Lit.18 mp 212 °C).
IR (KBr): 3035, 2843, 1692, 1627, 1596 cm–1.
13C NMR (200 MHz, CDCl3): = 22.83, 28.61, 115.17, 115.62,
132.06, 132.21, 135.65, 135.73, 160.06, 191.04.
1H NMR (200 MHz, CDCl3): = 3.05 (s, 4 H), 3.80 (s, 6 H), 6.90
(d, 4 H, J = 8.2 Hz), 7.35 (s, 2 H), 7.46 (d, 4 H, J = 8.2 Hz)
MS: m/z = 310 (M+).
13C NMR (200 MHz, CDCl3): = 21.30, 56.40, 117.84, 128.26,
130.89, 136.02, 143.83, 156.38, 193.14.
MS: m/z = 320 (M+).
Anal. Calcd for C20H16F2O: C, 77.33; H, 5.35. Found: C, 77.40; H,
5.20.
3i
Liquid.
3c
Solid; mp 229–230 °C (Lit.7 mp 230 °C).
IR (KBr): 3064, 2937, 2839, 1700, 1584, 1485 cm–1.
IR (KBr): 3109, 2844, 1702, 1606, 1523 cm–1.
1H NMR (200 MHz, CDCl3): = 1.80 (m, 2 H), 2.90 (t, 4 H, J = 2.8
Hz).
1H NMR (200 MHz, CDCl3): = 3.09 (s, 4 H), 7.38–7.78 (m, 8 H),
8.10 (s, 2 H).
13C NMR (200 MHz, CDCl3): = 22.64, 28.18, 118.71, 118.86,
120.07, 123.38, 125.08, 129.51, 129.66, 136.07, 136.36, 137.42,
156.62, 157.12, 189.51.
13C NMR (200 MHz, CDCl3): = 21.66, 125.53, 128.76, 130.78,
136.01, 141.85, 149.32, 194.01.
MS: m/z = 350 (M+).
MS: m/z = 458 (M+).
3d
Anal. Calcd for C32H26O3: C, 83.69; H, 5.52. Found: C, 83.82; H,
5.71.
Solid; mp 222–223 °C (Lit.19 mp 222.5 °C).
IR (KBr): 3023, 1667, 1612, 1580 cm–1.
3j
Liquid.
1H NMR (200 MHz, CDCl3): = 2.95 (s, 4 H), 7.12–7.56 (m, 16 H).
13C NMR (200 MHz, CDCl3): = 21.63, 121.02, 127.21, 128.05,
129.44, 130.73, 133.45, 135.62, 138.92, 194.62.
IR (KBr): 2928, 2865, 1729, 1623 cm–1.
1H NMR (200 MHz, CDCl3): = 0.90 (br t, 6 H), 1.08–1.60 (m, 10
H), 1.62–1.92 (m, 6 H), 2.10 (t, 4 H, J = 6 Hz), 2.20–2.55 (m, 6 H),
6.55 (t, 2 H, J = 8 Hz, 2 C=CH).
13C NMR (200 MHz, CDCl3): = 14.03, 22.53, 23.95, 28.44, 28.92,
29.05, 31.60, 31.83, 143.82, 155.40, 195.38.
MS: m/z = 312 (M+).
3e
Solid; mp 176–178 °C.
IR (KBr): 3155, 1670, 1590, 1545 cm–1.
1H NMR (DMSO-d6, 200 MHz): = 3.0 (s, 4 H), 7.10 (m, 1 H), 7.50
MS: m/z = 290 (M+).
Anal. Calcd for C20H34O: C, 83.02; H, 11.61. Found: C, 82.70; H,
11.80.
(m, 1 H), 7.70 (m, 2 H).
13C NMR (DMSO-d6, 200 MHz):
= 21.87, 128.29, 129.55,
132.01, 133.91, 134.73, 137.19, 194.04.
MS: m/z = 272 (M+).
3k
Liquid.
IR (KBr): 3060, 2920, 1715, 1623, 1571 cm–1.
1H NMR (200 MHz, CDCl3): = 7.0–7.75 (m, 16 H).
Anal. Calcd for C15H12O2: C, 66.14; H, 4.44. Found: C, 65.98; H,
4.53.
Synthesis 2004, No. 2, 263–266 © Thieme Stuttgart · New York