Beilstein J. Org. Chem. 2012, 8, 371–378.
ential scanning calorimetry (DSC): Mettler-Toledo DSC 822e OCH3), 4.00 (t, J = 6.5 Hz, 2H, 13-H), 4.14 (t, J = 6.8 Hz, 2H,
(
heating/cooling rates were 5 or 10 K·min−1). Polarizing optical 4-H), 6.98–6.99 (m, 2H, 2'-H), 7.51–7.53 (m, 2H, 3'-H),
microscopy: Olympus BX50 polarizing microscope combined 7.63–7.64 (m, 2H, 6'-H), 7.68–7.69 (m, 2H, 7'-H) ppm;
with a Linkam TP93 central controller. X-ray diffraction 13C NMR (125 MHz, CDCl3) δ 25.7 (C-6), 26.0 (C-11), 28.4
(
WAXS): Bruker AXS Nanostar C diffractometer employing (C-5), 29.15 (C-12), 29.21, 29.33, 29.41, 29.45 (C-7, C-8, C-9,
Ni-filtered Cu Kα radiation (λ = 1.5418 Å). C-10), 41.4 (C-2), 52.4 (OCH3), 65.7 (C-4), 68.1 (C-13), 110.0
C-8'), 115.0 (C-2'), 119.1 (CN), 127.0 (C-6'), 128.3 (C-3'),
31.3 (C-5'), 132.6 (C-7'), 145.3 (C-4'), 159.8 (C-1'), 166.6
(C-3), 167.0 (C-1) ppm; ATR–FTIR : 2927 (m), 2854 (w),
(
6
-[(4'-cyano-[1,1'-biphenyl]-4-yl)oxy]hexyl
1
methyl malonate (11a)
Pyridine (150 mg, 1.69 mmol) and then methyl 3-chloro-3- 2225 (m), 1735 (s), 1603 (m), 1494 (m), 1249 (s), 1180 (m),
oxopropionate (10) (114 mg, 0.84 mmol) were added over 903 (m), 823 (m); ESIMS (m/z): 474.2 [M + Na]+, 452.2 [M +
1
0 min at 0 °C under a N2 atmosphere to a solution of 4'-((6- H]+; Anal. calcd for C27H33NO5: C, 71.82; H, 7.37; N, 3.10;
hydroxyhexyl)oxy)-[1,1'-biphenyl]-4-carbonitrile (9a) (500 mg, found: C, 71.66; H, 7.34; N, 3.03; Rf 0.76 (hexanes/EtOAc 2:1).
.69 mmol) in abs. CH2Cl2 (5 mL). The reaction mixture was
stirred at 0 °C for 1 h, then for 2 h at rt. The reaction was
1
6
-[(4'-cyano-[1,1'-biphenyl]-4-yl)oxy]hexyl
quenched with 1 N H2SO4 (3 mL). The aqueous layer was 2-cyanoacetate (13a)
extracted with CH2Cl2 (3 × 5 mL). The combined organic To a solution of 4'-((6-hydroxyhexyl)oxy)-[1,1'-biphenyl]-4-
layers were washed with brine (40 mL), dried over MgSO4 and carbonitrile (9a) (100 mg, 338 μmol) in abs. CH2Cl2 (2.5 mL)
evaporated under reduced pressure. The crude product was puri- were added sequentially a solution of cyanoacetic acid (12)
fied by column chromatography on silica gel (hexanes/EtOAc (32 mg, 376 μmol) in EtOAc (0.4 mL), a solution of DMAP
2
5
0:1) to give 11a as a colourless solid (188 mg, 0.48 mmol, (12 mg, 98 μmol) in abs. CH2Cl2 (0.8 mL) and then at 0 °C a
7%). Mp 49.1 °C; 1H NMR (500 MHz, CDCl3) δ 1.41–1.47 solution of dicyclohexylcarbodiimide (77 mg, 376 μmol) in abs.
(
m, 2H, 6-H), 1.49–1.55 (m, 2H, 7-H), 1.67–1.73 (m, 2H, 5-H), CH2Cl2 (2.5 mL). The reaction mixture was stirred at rt for
1
4
.79–1.85 (m, 2H, 8-H), 3.39 (s, 2H, 2-H), 3.74 (s, 3H, OCH3), 7.5 h, then evaporated under vacuum. The crude product was
.01 (t, J = 6.4 Hz, 2H, 9-H), 4.17 (t, J = 6.4 Hz, 2H, 4-H), 6.98 purified by column chromatography on silica gel (hexanes/
(
d, J = 8.5 Hz, 2H, 2'-H), 7.52 (d, J = 8.5 Hz, 2H, 3'-H), 7.64 (d, EtOAc 12:1) to give 13a as a colourless solid (72 mg,
J = 8.5 Hz, 2H, 6'-H), 7.69 (d, J = 8.5 Hz, 2H, 7'-H) ppm; 190 μmol, 59%). Mp 89.0 °C; 1H NMR (500 MHz, CDCl3) δ
3C NMR (125 MHz, CDCl3) δ 25.6, 25.7 (C-6, C-7), 28.4 1.43–1.49 (m, 2H, 6-H), 1.51–1.56 (m, 2H, 7-H), 1.71–1.76 (m,
1
(
(
C-5), 29.0 (C-8), 41.4 (C-2), 52.5 (OCH3), 65.6 (C-4), 67.8 2H, 5-H), 1.80–1.85 (m, 2H, 8-H), 3.45 (s, 2H, 2-H), 4.01 (t, J
C-9), 110.0 (C-8'), 115.0 (C-2'), 119.1 (CN), 127.0 (C-6'), = 6.4 Hz, 2H, 9-H), 4.23 (t, J = 6.3 Hz, 2H, 4-H), 6.98–6.99 (m,
1
28.3 (C-3'), 131.3 (C-5'), 132.6 (C-7'), 145.3 (C-4'), 159.7 2H, 2'-H), 7.52–7.53 (m, 2H, 3'-H), 7.63–7.64 (m, 2H, 6'-H),
(
C-1'), 166.6 (C-3), 167.0 (C-1) ppm; ATR–FTIR : 2936 (m), 7.68–7.69 (m, 2H, 7'-H) ppm; 13C NMR (125 MHz, CDCl3) δ
2
1
4
858 (w), 2224 (m), 1967 (w), 1730 (s), 1602 (m), 1494 (m), 24.7 (C-2), 25.5 (C-6), 25.6 (C-7), 28.3 (C-5), 29.0 (C-8), 66.9
246 (s), 1014 (m), 822 (s); ESIMS (m/z): 343.1 [M + K]+, (C-4), 67.8 (C-9), 110.0 (C-8'), 112.9 (C-1), 115.0 (C-2'), 119.1
18.1 [M + Na]+, 396.1 [M + H]+, 278.15 [C19H20NO]+; Anal. (CN), 127.0 (C-6'), 128.3 (C-3'), 131.3 (C-5'), 132.5 (C-7'),
calcd for C23H25NO5: C, 69.86; H, 6.37; N, 3.54; found: C, 145.2 (C-4'), 159.6 (C-1'), 162.9 (C-3) ppm; ATR–FTIR
9.47; H, 6.37; N, 3.47; Rf 0.56 (hexanes/EtOAc 2:1). 2941 (m), 2866 (w), 2225 (w), 1746 (m), 1602 (m), 1494 (m),
249 (m), 1180 (m), 903 (s), 723 (s); ESIMS (m/z): 385.1 [M +
:
6
1
10-[(4'-cyano-[1,1'-biphenyl]-4-yl)oxy]decyl
Na]+, 363.1 [M + H]+; Anal. calcd for C22H22N2O3: C, 71.91;
methyl malonate (11b)
H, 6.12; N, 7.57; found: C, 71.44; H, 6.06; N, 7.73; Rf 0.68
The ester 11b was obtained by the same procedure as described (hexanes/EtOAc 2:1).
above for 11a from 4'-((10-hydroxydecyl)oxy)-[1,1'-biphenyl]-
1
0-[(4'-cyano-[1,1'-biphenyl]-4-yl)oxy]decyl
4
-carbonitrile (9b) (560 mg, 1.60 mmol), methyl 3-chloro-3-
oxopropionate (10) (109 mg, 0.80 mmol) and pyridine (126 mg, 2-cyanoacetate (13b)
.60 mmol) in abs. CH2Cl2 (5 mL). The crude product was The cyanoacetic ester 13b was obtained by the same procedure
1
purified by column chromatography on silica gel (gradient: as described above for 13a from 4'-((10-hydroxydecyl)oxy)-
hexanes/EtOAc, 20:1, then 15:1) to give 11b as a colourless [1,1'-biphenyl]-4-carbonitrile (9b) (120 mg, 341 μmol), cyano-
solid (240 mg, 0.53 mmol, 65%). Mp 63.4 °C; 1H NMR acetic acid (12) (32 mg, 376 μmol), DMAP (13 mg, 102 μmol),
(
500 MHz, CDCl3) δ 1.31–1.35 (m, 10H, 6-H, 7-H, 8-H, 9-H, and dicyclohexylcarbodiimide (77 mg, 376 μmol) in abs.
1
1
0-H), 1.44–1.50 (m, 2H, 11-H), 1.61–1.67 (m, 2H, 5-H), CH2Cl2 (6.5 mL). The crude product was purified by column
.77–1.83 (m, 2H, 12-H), 3.38 (s, 2H, 2-H), 3.75 (s, 3H, chromatography on silica gel (hexanes/EtOAc 10:1) to give 13b
376