Alkoxy-Substituted Hexastyrylbenzenes
FULL PAPERS
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(C-2, C-6), 127.3 (C-3, C-5), 130.3 (C-4), 136.3 (olefin CH),
OCH2), 6.43 (3H, d, J 16.7 Hz, outer olefin H), 6.88 (6H,
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159.0 (C-1); FD MS: m/z 288 (100%, M ); anal. calcd. for
AA' of AA'BB', aromat H), 6.98 (3H, d, J 16.7 Hz, inner
C20H32O (288.5): C 83.27, H 11.18; found: C 83.18, H 11.35.
olefin H), 7.42 (6H, BB', aromat H); 13C NMR (CDCl3): d
14.1 (CH3), 19.1 (CH3), 22.7, 26.1, 29.3, 29.4, 29.6, 31.9 (CH2,
partly superimposed), 68.2 (OCH2), 114.8, 127.4 (aromat CH),
126.1, 133.7 (olefin CH), 130.4, 133.0, 136.1, 158.9 (aromat Cq).
4-Vinylbenzonitrile (7e): commercially available.
FD MS: m/z 979 (100%, M ); anal. calcd. for C69H102O3
General Procedure for the Preparation of the 1,3,5-
Trimethyl-2,4,6-tristyrylbenzenes (9a e)
(979.6): C 84.60, H 10.50; found: C 84.31, H 10.36.
2,4,6-Tris[(E)-2-(4-cyanophenyl)ethenyl]-2,4,6-trimethyl-
benzene (9e): Yield 46%, colorless powder, mp 1998C
(recrystallized from acetone). 1H NMR (CDCl3): d 2.32
1,3,5-Tribromo-2,4,6-trimethylbenzene
(8)[30]
(9.0 g,
25.0 mmol), styrene 7a e (100.0 mmol), Pd(OAc)2 (1.0 g,
4.5 mmol) and tri-o-tolylphosphine (3.6 g, 11.8 mmol) were
dissolved under argon in 60 mL DMF/30 mL triethylamine and
heated to 1008C. As soon as the TLC control (SiO2, toluene)
indicated the end of the reaction, chloroform (50 mL) was
added and the solution filtered and evaporated. The residue
was dissolved in 100 mL chloroform and extracted with 50 mL
2 M HCl and 100 mL water. The organic layer was dried with
Na2SO4, concentrated and filtered through silica (10 Â 15 cm
SiO2, CH2Cl2).
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(9H, s, CH3), 6.52 (3H, d, J 16.7 Hz, outer olefin H), 7.26
(3H, d, 3J 16.7 Hz, inner olefin H), 7.57/7.65 (12H, AA'BB',
aromat H); 13C NMR (CDCl3): d 19.0 (CH3), 111.0, 133.5,
135.4, 141.7 (aromat Cq), 118.8 (CN), 126.7, 132.5 (aromat CH),
131.6, 133.2 (olefin CH). FD MS: m/z 501 (100%, M ); anal.
calcd. for C36H27N3 (501.4): C 86.20, H 5.43, N 8.38; found:
C 85.98, H 5.67, N 8.31.
1,3,5-Trimethyl-2,4,6-tris[(E)-2-(4-propoxyphenyl)ethenyl]-
benzene (9a): Yield 43%; colorless solid, mp 808C [recrystal-
lized from petroleum ether (bp 40 70 8C)]. 1H NMR (CDCl3):
d 1.06 (9H, t, CH3), 1.83 (6H, m, CH2), 2.38 (9H, s, CH3), 3.96
(6H, t, OCH2), 6.47 (3H, d, 3J 16.7 Hz, outer olefin H), 6.92
(6H, AA' part of AA'BB', aromat H), 7.02 (3H, d, 3J 16.7 Hz,
inner olefin H), 7.46 (6H, BB', aromat H); 13C NMR (CDCl3):
d 10.5 (CH3), 19.1 (CH3), 22.6 (CH2), 69.6 (OCH2), 114.7,
127.3 (aromat CH), 125.9, 133.7 (olefin CH), 130.2, 133.0,
General Procedure for the Preparation of the
Triphosphonates 10a e
A mixture of 2.00 mmol 9a e, 1.175 g (6.60 mmol) NBS and
13 mg (0.08 mmol) AIBN was refluxed in 20 mL dry CCl4, until
the whole succinimide was gathered on the surface. The
mixture was cooled to room temperature, filtered and the
volatile parts removed in the rotavapor. The residue was
heated with 3.88 g (23.35 mmol) triethyl phosphite to 1508C
and the formed bromoethane continuously removed. The
excess triethylphosphite was distilled off under reduced
pressure (3 kPa) and the raw product purified by column
filtration (6 Â 12 cm SiO2, ethyl acetate/acetone 1:1).
136.1, 158.8 (aromat Cq); FD MS: m/z 600 (100%, M ); anal.
calcd. for C42H48O3 (600.8): C 83.96, H 8.05; found: C 83.77, H
8.26.
1,3,5-Tris[(E)-2-(4-hexyloxyphenyl)ethenyl]-2,4,6-trimethyl-
benzene (9b): Yield 29%; colorless solid, mp 768C [recrystal-
lized from petroleum ether (bp 40 70 8C)]. 1H NMR (CDCl3):
d 0.91 (9H, t, CH3), 1.35 (12H, m, CH2), 1.46 (6H, m, CH2),
1.79 (6H, m, CH2), 2.35 (9H, s, CH3), 3.97 (6H, t, OCH2), 6.45
(3H, d, 3J 16.4 Hz, outer olefin H), 6.90 (6H, AA' of AA'BB',
aromat H), 7.00 (3H, d, 3J 16.4 Hz, inner olefin H), 7.43 (6H,
BB', aromat H); 13C NMR (CDCl3): d 14.0 (CH3), 19.1
(CH3), 22.6, 25.7, 29.2, 31.6 (CH2), 68.1 (OCH2), 114.7, 127.3
(aromat CH), 125.9, 133.7 (olefin CH), 130.2, 133.0, 136.1,
1,3,5-Tris[(diethoxyphosphoryl)methyl]-2,4,6-tris[(E)-2-
(4-propoxyphenyl)ethenylbenzene (10a): Yield 86%, viscous
oil. 1H NMR (CDCl3): d 1.02 (9H, t, CH3), 1.17 (18H, t, CH3),
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1.80 (6H, m, CH2), 3.48 (6H, d, j J(H,P) j 23.0 Hz, CH2P),
3.92 (18H, m, OCH2), 6.53 (3H, d, 3J 17.1 Hz, outer olefin H),
6.87 (6H, AA' of AA'BB', aromat H), 7.32 (3H, d, 3J 17.1 Hz,
inner olefin H), 7.45 (6H, BB', aromat H); 13C NMR (CDCl3):
d 10.4 (CH3), 16.3 (CH3), 25.5 (CH2), 30.2 (d, 1J(C,P)
136.6 Hz, CH2P), 62.1 (POCH2), 69.5 (OCH2), 114.6, 127.6
(aromat CH), 126.5, 133.7 (olefin CH), 128.3, 130.3, 139.3,
158.8 (aromat Cq). FD MS: m/z 727 (100%, M ); anal. calcd.
for C51H66O3 (727.1): C 84.25, H 9.15; found: C 84.24, H 9.29.
1,3,5-Tris[(E)-2-(4-decycloxyphenyl)ethenyl]-2,4,6-trime-
thylbenzene (9c): Yield 50%; colorless crystals, mp 678C
(recrystallized from acetone). 1H NMR (CDCl3): d 0.87 (9H,
t, CH3), 1.26 (36H, m, CH2), 1.45 (6H, m, CH2), 1.78 (6H, m,
CH2), 2.34 (9H, s, CH3), 3.96 (6H, t, OCH2), 6.44 (3H, d, 3J
16.7 Hz, outer olefin H), 6.89 (6H, AA' of AA'BB', aromat H),
6.98 (3H, d, 3J 16.7 Hz, inner olefin H), 7.42 (6H, BB', aromat
H); 13C NMR (CDCl3): d 14.1 (CH3), 19.1 (CH3), 22.7, 26.1,
29.3, 29.4, 29.6, 31.9 (CH2, partly superimposed), 68.2 (OCH2),
114.8, 127.4 (aromat CH), 126.1, 133.8 (olefin CH), 130.4,
158.9 (aromat Cq). FD MS: m/z 1009 (100%, M ); anal. calcd.
for C54H75O12P3 (1009.1): C 64.27, H 7.49; found: C 63.98, H.
7.77.
1,3,5-Tris[(diethoxyphosphoryl)methyl]-2,4,6-tris[(E)-2-
(4-hexyloxyphenyl)ethenyl]benzene (10b): Yield 62%, viscous
oil. 1H NMR (CDCl3): d 0.89 (9H, t, CH3), 1.17 (18H, t, CH3),
1.33 (12H, m, CH2), 1.44 (6H, m, CH2), 176 (6H, m, CH2), 3.48
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(6H, d, j J (H, P) j 22.9 Hz, CH2P), 3.94 (18H, m, OCH2),
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6.53 (3H, d, J 16.7 Hz, outer olefin H), 6.86 (6H, AA' of
AA'BB', aromat H), 7.33 (3H, d, 3J 16.7, inner olefin H), 7.45
(6H, BB', aromat H); 13C NMR (CDCl3): d 14.0 (CH3), 16.4
(CH3), 22.6, 25.7, 29.2, 31.6 (CH2), 30.2 (d, 1J(C,P) 136.6 Hz,
CH2P), 61.8 (POCH2), 68.1 (OCH2), 114.6, 127.7 (aromat CH),
126.4, 133.8 (olefin CH), 128.3, 129.9, 139.3, 158.9 (aromat Cq).
133.1, 136.1, 158.9 (aromat Cq). FD MS: m/z 895 (100%, M );
anal. calcd. for C63H90O3 (895.4): C 84.51, H 10.13; found: C
84.74, H 10.19.
1,3,5-Tris[(E)-2-(4-dodecyloxyphenyl)ethenyl]-2,4,6-trime-
thylbenzene (9d): Yield 37%, colorless powder, mp 588C
[recrystallized from petroleum ether (bp 40 70 8C)]. 1H NMR
(CDCl3): d 0.86 (9H, t, CH3), 1.25 (48H, m, CH2), 1.44 (6H,
m, CH2), 1.77 (6H, m, CH2), 2.33 (9H, s, CH3), 3.96 (6H, t,
FD MS: m/z 1135 (100%, M ); anal. calcd. for C63H93O12P3
(1135.3): C 66.65, H 8.26; found: C 66.31, H 8.50.
1,3,5-Tris[(E)-2-(4-decyloxyphenyl)ethenyl]-2,4,6-tris[(di-
ethoxyphosphoryl)methyl]benzene (10c): Yield 57%, viscous
oil. 1H NMR (CDCl3): d 0.85 (9H, t, CH3), 1.17 (18H, t, CH3),
Adv. Synth. Catal. 2003, 345, 1005 1011
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