H. Meier et al.
FULL PAPER
CHO) ppm; 13C NMR (100.6 MHz, CDCl3): d = 14.0 (CH3), 22.6 31.8
(CH2, superimposed), 35.6 (CH), 56.7 (NCH2), 112.8, 126.2, 126.8, 126.8,
126.8, 127.2, 127.5, 130.1 (aromat. CH), 123.1, 126.9, 127.1, 129.0, 129.1,
131.8 (olefin. CH), 124.4, 135.4, 135.4, 135.6, 137.8, 138.1, 143.4, 148.2 (ar-
omat. Cq) ppm; FD MS: m/z (%): 820 (100) [M]+ ; elemental analysis
calcd (%) for C59H81NO (820.3): calcd. C 86.39, H 9.95, N 1.71; found: C
86.39, H 9.84, N 1.77.
N,N-Bis(2-hexyloctyl)-4-[(E)-2-(4-{(E)-2-[4-((E)-2-{4-[(E)-2-phenylethen-
yl]phenyl}ethenyl)phenyl]ethenyl}phenyl)ethenyl]aniline (4a): This com-
pound was prepared from 3c and 8a as described in Method B. The
crude product was purified by column chromatography on silica gel with
1
CHCl3, yielding 24% of a yellow wax. H NMR (400 MHz, CDCl3): d =
0.87 (t, 12H; CH3), 1.24 (m, 40H; CH2), 1.83 (m, 2H; CH), 3.21 (d, 4H;
NCH2), 6.61 (m, 2H; aromat. H), 6.86 (d, 3J = 16.0 Hz, 1H; olefin. H),
7.04 (d, 3J = 16.0 Hz, 1H; olefin. H), 7.11 (m, 6H; olefin. H), 7.25 (m, 1
H; aromat. H), 7.35 (m, 4H; aromat. H), 7.46 (m, 4H; aromat. H), 7.50
(m, 10H; aromat. H) ppm; FD MS: m/z (%): 894 (100) [M]+ ; C66H87N
(894.4): after careful drying in vacuum the compound still contained
some solvent; therefore a correct elemental analysis could not be ob-
tained.
4-((E)-2-{4-[(E)-2-(4-{(E)-2-[4-((E)-2-{4-[Bis(2-hexyloctyl)amino]phen-
yl}ethenyl)phenyl]ethenyl}phenyl)ethenyl]phenyl}ethenyl)benzaldehyde
(4c): This compound was prepared from 3c and 7 as described in Meth-
od A. The crude product was purified by column chromatography on
silica gel with CH2Cl2 as eluent, yielding 62% orange crystals; m.p. 195
1
8C; H NMR (400 MHz, CHCl3): d = 0.87 (t, 12H; CH3), 1.24 (m, 40H;
CH2), 1.83 (m, 2H; CH), 3.20 (d, 4H; NCH2), 6.61 (m, 2H; aromat. H),
6.86 (d, 3J = 16.4 Hz, 1H; olefin. H), 7.03 (d, 3J = 16.3 Hz, 1H; ole-
fin. H), 7.09, 7.12, 7.24, (3 m, 6H; olefin. H), 7.35 (m, 2H; aromat. H),
7.45 (m, 4H; aromat. H), 7.50 (™s∫, 4H; aromat. H), 7.52 (™s∫, 4H; aro-
mat. H), 7.64 (m, 2H; aromat. H), 7.85 (m, 2H; aromat. H), 9.97 (s, 1H;
CHO) ppm; FD MS: m/z (%): 923 (100) [M+H]+ ; elemental analysis
calcd (%) for C67H87NO (922.4): C 87.24, H 9.51, N 1.52; found: C 87.18,
H 9.38, N 1.69.
4-((E)-2-{4-[Bis(2-hexyloctyl)amino]phenyl}ethenyl)benzonitrile
(1b):
This compound was prepared from 6 and 8b as described in Method A.
The crude product was purified by column chromatography on silica gel
with petroleum ether (b.p. 40 708C)/ethyl acetate 30:1, yielding 70% of
yellow crystals; m.p. 608C; 1H NMR (200 MHz, CDCl3): d = 0.87 (t, 12
H; CH3), 1.25 (m, 40H; CH2), 1.84 (m, 2H; CH), 3.23 (d, 4H; NCH2),
6.63 (m, 2H; aromat. H), 6.82 (d, 3J = 16.4 Hz, 1H; olefin. H), 7.12 (d,
3J = 16.4 Hz, 1H; olefin. H), 7.36 (m, 2H; aromat. H), 7.48 (m, 2H; aro-
mat. H), 7.56 (m, 2H; aromat. H) ppm; 13C NMR (100.6 MHz, CDCl3): d
= 14.1 (CH3), 22.7 31.9 (CH2, superimposed), 35.6 (CH), 56.7 (NCH2),
109.0, 123.2, 143.1, 148.8 (aromat. Cq), 119.5 (CN), 121.3, 132.8 (ole-
fin. CH), 112.6, 126.1, 128.2, 132.4 (aromat. CH) ppm; FD MS: m/z (%):
613 (100) [M]+ ; elemental analysis calcd (%) for C43H68N2 (613.0): C
84.25, H 11.18, N 4.57; found: C 84.35, H 11.19, N 4.65.
Diethyl benzylphosphonate (8a), diethyl 4-cyanobenzylphosphonate (8b)
and diethyl 4-nitro-benzylphosphonate (8d): These compounds were pre-
pared according to the literature: 8a,[66] 8b,[67, 68] 8d.[69]
N,N-Bis(2-hexyloctyl)-4-[(E)-2-phenylethenyl]aniline (1a): This com-
pound was prepared from 6 and 8a as described in Method B. The crude
product was purified by column chromatography on silica gel with petro-
leum ether (b.p. 40 708C), yielding 57% of a yellow oil. 1H NMR
(200 MHz, CDCl3): d = 0.89 (t, 12H; CH3), 1.27 (m, 40H; CH2), 1.85
4-{(E)-2-[4-((E)-2-{4-[Bis(2-hexyloctyl)amino]phenyl}ethenyl)phenyl]-
ethenyl}benzonitrile (2b): This compound was prepared from 1c and 8b
as described in Method A. The crude product was purified by column
chromatography on silica gel with petroleum ether (b.p. 40 708C)/Et2O
20:1, yielding 57% of yellow crystals; m.p. 1038C; 1H NMR (400 MHz,
CDCl3): d = 0.87 (t, 12H; CH3), 1.25 (m, 40H; CH2), 1.84 (m, 2H; CH),
3
(m, 2H; CH), 3.22 (d, 4H; NCH2), 6.64 (d, 2H; aromat. H), 6.88 (d, J =
16.4 Hz, 1H; olefin. H), 7.04 (d, 3J = 16.4 Hz, 1H; olefin. H), 7.18 (m, 1
H; aromat. H), 7.35 (m, 4H; aromat. H), 7.47 (m, 2H; aromat. H) ppm;
13C NMR (100.6 MHz, CDCl3): d = 14.1 (CH3), 22.7 31.9 (CH2, superim-
posed), 35.6 (CH), 56.8 (NCH2), 112.8, 126.0, 126.5, 127.6, 128.6 (aro-
mat. CH), 123.6, 129.0 (olefin. CH), 124.5, 138.5, 148.1 (aromat. Cq) ppm;
FD MS: m/z (%): 588 (100) [M]+ ; elemental analysis calcd (%) for
C42H69N (588.0): C 85.79, H 11.83, N 2.38; found: C 85.88, H 12.16, N
2.66.
3
3.21 (d, 4H; NCH2), 6.63 (m, 2H; aromat. H), 6.86 (d, J = 16.1 Hz, 1H;
olefin. H), 7.05 (d, 3J = 16.1 Hz, 1H; olefin. H), 7.06 (d, 3J = 16.1 Hz, 1
H; olefin. H), 7.18 (d, 3J = 16.1 Hz, 1H; olefin. H), 7.36 (m, 2H; aro-
mat. H), 7.46 (™s∫, 4H; aromat. H), 7.55 (m, 2H; aromat. H), 7.61 (m, 2
H; aromat. H) ppm; 13C NMR (100.6 MHz, CDCl3): d
= 13.8 (CH3),
22.4 31.6 (CH2, superimposed), 35.4 (CH), 56.5 (NCH2), 110.1, 124.1,
134.2, 138.8, 141.9, 148.2 (aromat. Cq), 112.6, 126.1, 126.5, 127.0, 127.5,
132.2 (aromat. CH), 118.8 (CN), 122.7, 125.5, 129.5, 132.1 (ole-
fin. CH) ppm; FD MS: m/z (%): 715 (100) [M]+ ; elemental analysis
calcd (%) for C51H74N2 (715.2): C 85.65, H 10.43, N 3.92; found: C 85.56,
H 10.48, N 3.90.
N,N-Bis(2-hexyloctyl)-4-((E)-2-{4-[(E)-2-phenylethenyl]phenyl}ethenyl)-
aniline (2a): This compound was prepared from 1c and 8a as described
in Method A. The crude product was purified by column chromatography
on silica gel with petroleum ether (b.p. 40 708C), yielding 36% of a
yellow wax. 1H NMR (400 MHz, CDCl3): d = 0.89 (t, 12H; CH3), 1.26
(m, 40H; CH2), 1.84 (m, 2H; CH), 3.22 (d, 4H; NCH2), 6.64 (m, 2H; ar-
omat. H), 6.88 (d, 3J = 16.4 Hz, 1H; olefin. H), 7.05 (d, 3J = 16.4 Hz, 1
H; olefin. H), 7.10 (™s∫, 2H; olefin. H), 7.24 (m, 1H; aromat. H), 7.36
(m, 4H; aromat. H), 7.46 (m, 4H; aromat. H), 7.51 (m, 2H; aro-
mat. H) ppm; 13C NMR (100.6 MHz, CDCl3): d = 14.1 (CH3), 22.7 31.9
(CH2, superimposed), 35.6 (CH), 56.8 (NCH2), 112.7, 126.2, 126.4, 126.8,
127.4, 127.6, 128.7 (aromat. CH), 123.2, 127.8, 128.5, 129.0 (olefin. CH),
124.4, 135.5, 137.5, 137.9, 148.1 (aromat. Cq) ppm; FD MS: m/z (%): 691
(100) [M+H]+ ; elemental analysis calcd (%) for C50H75N (690.2): C
87.02, H 10.95, N 2.03; found: C 86.72, H 10.95, N 1.97.
4-[(E)-2-(4-{(E)-2-[4-((E)-2-{4-[Bis(2-hexyloctyl)amino]phenyl}ethenyl)-
phenyl]ethenyl}phenyl)ethenyl]benzonitrile (3b): This compound was
prepared from 2c and 8b as described in Method B. Recrystallization
from ethyl acetate gave 55% of orange crystals; m.p. 1628C; 1H NMR
(400 MHz, CDCl3): d = 0.88 (t, 12H; CH3), 1.26 (m, 40H; CH2), 1.84
(m, 2H; CH), 3.22 (d, 4H; NCH2), 6.64 (m, 2H; aromat. H), 6.87 (d, 3J
= 16.1 Hz, 1H; olefin. H), 7.05 (d, 3J = 16.1 Hz, 1H; olefin. H), 7.07 (d,
3J = 16.2 Hz, 2H; olefin. H), 7.13 (d, 3J = 16.3 Hz, 1H; olefin. H), 7.19
(d, 3J = 16.2 Hz, 1H; olefin. H), 7.36 (m, 2H; aromat. H), 7.46 (m, 4H;
aromat. H), 7.51 (™s∫, 4H; aromat. H), 7.56 (m, 2H; aromat. H), 7.61 (m,
2H; aromat. H) ppm; 13C NMR (100.6 MHz, CDCl3): d = 14.1 (CH3),
22.7 31.9 (CH2, superimposed), 35.6 (CH), 56.7 (NCH2), 110.5, 124.1,
135.3, 135.3, 138.0, 138.2, 141.9, 148.2 (aromat. Cq), 112.7, 126.2, 126.8,
126.8, 126.8, 127.3, 127.6, 132.5 (aromat. CH), 119.0 (CN), 123.1, 126.3,
127.1, 129.1, 129.2, 132.0 (olefin. CH) ppm; FD MS: m/z (%): 817 (100)
[M]+ ; elemental analysis calcd (%) for C59H80N2 (817.3): C 86.71, H 9.87,
N 3.43; found: C 86.51, H. 9.71, N 3.18.
N,N-Bis(2-hexyloctyl)-4-{(E)-2-[4-((E)-2-{4-[(E)-2-phenylethenyl]phen-
yl}ethenyl)phenyl]ethenyl}aniline (3a): This compound was prepared
from 2c and 8a as described in Method B. The crude product was recrys-
tallized from ethyl acetate, yielding 38% of yellow crystals; m.p. 1588C;
1H NMR (400 MHz, CDCl3): d = 0.88 (t, 12H; CH3), 1.26 (m, 40H;
CH2), 1.84 (m, 2H; CH), 3.22 (d, 4H; NCH2), 6.64 (m, 2H; aromat. H),
6.87 (d, 3J = 16.1 Hz, 1H; olefin. H), 7.05 (d, 3J = 16.1 Hz, 1H; ole-
fin. H), 7.10 (m, 2H; olefin. H), 7.11 (™s∫, 2H; olefin. H), 7.25 (m, 1H;
aromat. H), 7.36 (m, 4H; aromat. H), 7.46 (m, 4H; aromat. H), 7.50 (™s∫,
4H; aromat. H), 7.51 (m, 2H; aromat. H) ppm; 13C NMR (100.6 MHz,
CDCl3): d = 14.1 (4C; CH3), 22.7 31.9 (CH2, superimposed), 35.6 (CH),
56.7 (NCH2), 112.7, 126.2, 126.5, 126.8, 126.8, 126.8, 127.6, 127.6, 128.7
(aromat. CH), 123.2, 127.4, 128.3, 128.4, 128.4, 129.0 (olefin. CH), 124.4,
135.5, 136.5, 136.9, 137.4, 137.9, 148.1 (aromat. Cq) ppm; FD MS: m/z
(%): 793 (100) [M+H]+ ; elemental analysis calcd (%) for C58H81N
(792.3): C 87.93, H 10.30, N 1.77; found: C 87.54, H 10.02, N 1.73.
4-((E)-2-{4-[(E)-2-(4-{(E)-2-[4-((E)-2-{4-[Bis(2-hexyloctyl)amino]phen-
yl}ethenyl)phenyl]ethenyl}phenyl)ethenyl]phenyl}ethenyl)benzonitrile (4
b): This compound was prepared from 3c and 8b as described in Meth-
od B. The crude product was recrystallized from ethyl acetate/MeOH 2:1,
yielding 24% of orange crystals; m.p. >2408C; 1H NMR (400 MHz,
CDCl3): d = 0.86 (t, 12H; CH3), 1.25 (m, 40H; CH2), 1.81 (m, 2H; CH),
3
3.19 (d, 4H; NCH2), 6.55 (m, 2H; aromat. H), 6.80 (d, J = 16.1 Hz, 1H;
3
olefin. H), 6.96 (d, J = 16.1 Hz, 1H; olefin. H), 7.02 (m, 2H; olefin. H),
7.07 (m, 3H; olefin. H), 7.14 (d, 3J = 16.3 Hz, 1H; olefin. H), 7.29 (m, 2
H; aromat. H), 7.40 (m, 4H; aromat. H), 7.46 (™s∫, 4H; aromat. H), 7.48
368
¹ 2004 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Chem. Eur. J. 2004, 10, 360 370