ꢁ
1
O (489.70 g mol ): C, 80.94; H, 8.44; N,
C
33
H
40ON
2
, 0.5 H
2
(E,E,E,E)-1,5-Bis-{4-[2-(4-dibutylaminophenyl)vinyl]phenyl}
penta-1,4-dien-3-one (6). Obtained according to the general,
previously described, procedure starting from (E)-4-[2-(4-di-
butylaminophenyl)vinyl]benzaldehyde (450 mg, 1.4 mmol),
propanone (50 mL, 0.7 mmol) in 30 mL ethanol and an
5
.72; found: C, 80.48; H, 8.16; N, 5.54%.
(
E,E,E,E,E,E,E,E,E,E)-1,21-Bis-[4-(dibutylamino)phenyl]
heneicosa-1,3,5,7,9,12,14,16,18,20-decaen-11-one (4). Ob-
tained according to a slightly modified general procedure
and starting from (E,E,E,E)-9-[4-(dibutylamino)phenyl]nona-
ꢁ
1
aqueous NaOH solution (7.5 mol L , 670 mL, 5 mmol).
Purification by column chromatography, eluting with pentane–
propanone (82 : 18) and crystallizing in ethanol led to 335 mg
2
,4,6,8-tetraenal (630 mg, 1.86 mmol), propanone (69 mL, 0.93
mmol) in 40 mL ethanol and an aqueous NaOH solution (7.5
1
of the desired solid with 72% yield: mp = 159 1C; H NMR
ꢁ1
(499.83 MHz, CDCl ) d: 7.72 (d, J = 16 Hz, 2H, H ), 7.56
3
2,3
3
mol L , 1.3 mL, 9.3 mmol): after 12 h reaction at 50 1C,
aldehyde (56 mg, 0.18 mmol) are again added and the mixture
was allowed to react for an other 12 h in the same conditions.
Purification by column chromatography on silica, eluting with
dichloromethane led to 246 mg of the pure black product while
(
5 6
d, J5,6 = 8.5 Hz, 4H, H ), 7.48 (d, J5,6 = 8.5 Hz, 4H, H ),
7
.38 (d, J11,12 = 9.0 Hz, 4H, H11), 7.10 (d, J8,9 = 16.0 Hz, 2H,
), 7.05 (d, J2,3 = 16.0 Hz, 2H, H ), 6.88 (d, J8,9 = 16.0 Hz,
H, H ), 6.61 (d, 4H, H , J = 9.0 Hz), 3.28 (t, J = 7.1 Hz,
H
9
2
2
8
8
12 11,12
H, N–CH –CH ), 1.61 (m, 8H; CH –CH –CH ), 1.35 (sextet,
2
2
2
2
2
2
07 mg of a mixture of the desired product (193 mg) with 14
J = 7,2 Hz, 8H, CH –CH –CH ), 0.95 (t, J = 7.2 Hz, 12H,
3
2
2
mg of 12-(4-dibutylaminophenyl)dodeca-3,5,7,9,11-pentaen-2-
one (purity determined by NMR) was also obtained (38%
1
3
CH3). C NMR (CDCl ): d (ppm): 188.81 (C ), 148.17 (C ),
3
1
13
1
142.86 (C ), 140.84 (C ), 132.93 (C ), 130.60 (C ), 128.86 (C ),
3
7
4
9
5
yield): mp = 200 1C (decomposition); H NMR (499.84 MHz,
1
28.09 (C11), 126.31 (C
6
), 124.54 (C
2
), 124.04 (C10), 122.61
–CH –CH ), 20.34
). UV-Vis (CHCl ): lmax (e) =
43 (18480); 340 (36960); 466 (54350). Anal. calcd for
CDCl
3
) d: 7.33 (dd, J = 15.0 Hz, J = 11.5 Hz, 2H, H
d, Jb,c = 9.0 Hz, 4H, H ), 6.64 (m, 4H), 6.55 (d, Jc,b = 9.0 Hz,
H, H ), 6.49 (m, 6H), 6.33 (m, 8H), 3.29 (t, J = 7.5 Hz, 8H,
3
,), 7.26
(
C
8
), 111.61 (C12), 50.78 (CH
2
), 29.48 (CH
2
2
2
(
b
(
CH –CH –CH ), 14.00 (CH
2
2
3
3
3
4
c
2
N–CH ), 1.54 (m, 8H, CH –CH –CH ), 1.34 (m, 8H,
2
2
2
2
ꢁ
1
1
CH –CH –CH ), 0.94 (t, J = 7.5 Hz, 12H, CH ). C NMR
3
49 60 2 2
C H N O, 0.5 H O (693.03 g mol ): C, 83.83; H, 8.76; N,
2
2
3
3
3
.99; found C, 83.64; H, 8.84; N, 4.02%.
(
CDCl
3
) d: 189.22 (C
1
), 148.70 (C
d
), 143.44 (C
3
), 142.86 (CH),
1
38.99 (CH), 138.07 (CH), 135.78 (CH), 131.37 (CH), 130.76
), 124.93 (C ), 124.73 (CH),
), 30.12 (CH ), 20.96 (CH ), 14.62
): lmax (e) = 301 (29032); 394 (55915);
40 (123650). Anal. calcd for C49 64ON , 0.5 H O (706.06 g
(
E,E)-1,5-Bis-[4-(4-dibutylaminophenylazo)phenyl]penta-
(
2 CH), 128.84 (CH), 128.70 (C
b
a
1
,4-dien-3-one (7). Obtained according to the general proce-
1
12.21 (C
c
), 51.40 (CH
2
2
2
dure starting from 4-(4-dibutylaminophenylazo)benzaldehyde
(
CH
3
). UV-Vis (CHCl
3
(
400 mg, 1.2 mmol), propanone (44 mL, 0.6 mmol) in 30 mL
ethanol and an aqueous NaOH solution (7.5 mol L , 600 mL,
.5 mmol). Purification by crystallization in ethanol led to 287
1
mg of a dark red solid (70% yield): mp = 144 1C. H NMR
499.83 MHz, CDCl ) d: 7.86 (m, 8H, H et H11); 7.78 (d, J3,2
= 16.0 Hz, 2H. H ), 7.71 (d, J = 8.5 Hz, 4H, H ), 7.13 (d,
5
H
2
2
ꢁ1
ꢁ
1
mol ): C, 83.35; H, 9.28; N, 3.97; found C, 83.37; H, 9.10; N,
4
4
.08%.
(
3
6
Typical general synthetic procedure for compounds 5–7. To a
3
5,6
5
solution of (E)-4-[2-(4-diethylaminophenyl)vinyl]benzalde-
hyde (500 mg,1.8 mmol) and propanone (66 mL, 0.9 mmol)
in 40 mL ethanol, was dropwise added an aqueous sodium
J2,3 = 16.0 Hz, 2H, H ), 6.68 (d, J
2
11,12
= 9.5 Hz, 4H, H12),
3.36 (t, J = 7.5 Hz, 8H, N–CH –CH ), 1.62 (m, 8H;
2
2
CH –CH –CH ), 1.38 (sext, J = 7.5 Hz, 8H, CH –CH –CH ),
2
2
2
2
2
3
ꢁ
1
13
0.97 (t, J = 7.5 Hz, 12H, CH3). C NMR (CDCl ) d: 188.61,
154.56, 150.93, 143.29, 142.73, 135.30, 129.26, 125.62, 122.72,
hydroxide solution (7.5 mol L , 900 mL, 6.75 mmol). After 5
h stirring at 60 1C and in darkness, the reaction mixture was
filtered. The solid obtained was first washed with hexane then
ether, before being purified by column chromatography, and
eluting with dichloromethane; it afforded 330 mg of a red
solid.
3
111.13, 50.99, 29.50, 20.30, 13.96. UV-Vis (CHCl ): l
3
max
(e) =
265 (20620); 334 (25775); 503 (89690). Anal. calcd for
ꢁ
1
C H N O, 0.5 H O (705.98 g mol ): C, 76.56; H, 8.14; N,
4
5
56
6
2
11.90; found C, 76.30; H, 8.01; N, 12.07%.
(
E,E,E,E)-1,5-Bis-{4-[2-(4-diethylaminophenyl)vinyl]phenyl}
1
References
penta-1,4-dien-3-one (5). 65% yield: mp = 280 1C H NMR
499.83 MHz. CDCl ) d: 7.71 (d, J = 15.8 Hz, 2H, H ), 7.57
1
¨
(a) J. E. Ehrlich, X.-L. Wu, I.-Y. S. Lee, Z.-Y. Hu, H. Rockel, S. R.
(
3
2,3
3
Marder and J. W. Perry, Opt. Lett., 1997, 22, 1843; (b) Y. Morel,
A. Irimia, P. Najechalski, Y. Kervella, O. Stephan, P. L. Baldeck
and C. Andraud, J. Chem. Phys., 2001, 114, 5391.
(
d, J5,6 = 8.4 Hz, 4H, H ), 7.48 (d, J = 8.4 Hz, 4H, H6),
5 5,6
7
.39 (d, J11,12 = 8.8 Hz, 4H, H ), 7.1 (d, J = 16,1 Hz, 2H,
11 8,9
2
J. Liu, Y. W. Zhao, J. Q. Zhao, A. D. Xia, L. J. Jiang, S. Wu, L.
Ma, Y. Q. Dong and Y. H. Gu, J. Photochem. Photobiol., B, 2002,
H
9
), 7.05 (d, J2,3 = 15.8 Hz, 2H, H
2
), 6.87 (d, J8,9 = 16.1 Hz,
2
H, H
Hz, 8H, CH
CDCl ) d: 188.81 (C
32.95 (C ), 130.58 (C
24.54 (C ), 124.23 (C10), 122.70 (C
), 12.64 (CH ). UV-Vis (CHCl
22090); 339 (44370); 509 (80960). Anal. calcd for
8
), 6.65 (d, J11,12 = 8.8 Hz, 4H, H12), 3.38 (q, J = 7.0
6
8, 156.
1
3
), 1.18 (t, J = 7.0 Hz, 12H, CH
), 147.74 (C13), 142.85 (C ), 140.81 (C
), 128.86 (C ), 128.16 (C11), 126.32 (C
3
). C NMR
3 (a) J. H. Strickler and W. W. Webb, Opt. Lett., 1991, 16, 1780; (b)
D. A. Parthenopoulos and P. M. Rentzepis, Science, 1989, 245,
2
(
3
1
3
7
6
),
),
843.
W. Denk, J. H. Strickler and W. W. Webb, Science, 1990, 248, 73.
1
1
4
9
5
4
5 (a) B. H. Cumpston, S. P. Ananthavel, S. Barlow, D. L. Dyer, J. E.
2
8
), 111.62 (C12), 44.41
): lmax (e) = 257
(
(
CH
2
3
3
Ehrlich, L. L. Erskine, A. A. Heikal, S. M. Kuebler, I.-Y. S. Lee,
¨
D. McCord-Maughon, J. Qin, H. Rockel, M. Rumi, X.-L. Wu, S.
R. Marder and J. W. Perry, Nature, 1999, 398, 51; (b) K.-S. Lee,
M.-S. Kim, H.-K. Yang, B.-K. Soo, H.-B. Sun, S. Kawata and P.
Fleitz, Mol. Cryst. Liq. Cryst., 2004, 424, 35; (c) K.-S. Lee,
ꢁ1
C H N O, 0.5 H O (580.81 g mol ) C, 83.49; H, 7.69; N,
41
44
2
2
4
.75; found C, 83.68; H, 7.64; N, 4.90%.
1
612 | New J. Chem., 2006, 30, 1606–1613
This journal is ꢂc the Royal Society of Chemistry and the Centre National de la Recherche Scientifique 2006