A. J. McKinley, S. G. Stewart et al.
stage microscope. The reported retention factors (Rf) were acquired via
Thin Layer Chromatography (TLC) performed on Merck silica gel 60
F254 pre-coated aluminium sheets. Column chromatography was per-
formed by using silica gel 60 (0.04–0.063) supplied by Merck. Bulk Chro-
matography solvents were distilled prior to use.
protocol section on 1,3,5-tribromobezene (5). The spectral data for this
compound matched those reported in the literature.[45]
1,3,5-Tris(4-methoxystyryl)benzene (16): Reaction completed as indicated
in the general Heck protocol section on 1,3,5-tribromobezene (5).
1H NMR (500.1 MHz, CDCl3): d=3.84 (s, 9H; OMe), 6.93 (d, J=8.6 Hz,
6H), 7.01 (d, J=16.3 Hz, 3H; CH=CH), 7.15 (d, J=16.3 Hz, 3H; CH=
CH), 7.50 ppm (appd, 9H); 13C NMR (CDCl3): d=55.4, 114.3, 123.3,
126.6, 127.9, 128.7, 130.3, 138.5, 159.5 ppm. The spectral assignment
matched those reported in the literature.[45,46]
General protocol for Heck cross-coupling reactions: Halobenzene
(1 equiv), [Pd2ACHTUNGTRENNUNG(dba)3]·CHCl3 (2–15 mol%) and [(tBu)3PH]BF4 (10–
60 mol%) were added to a flame-dried Schlenk flask, which was subse-
quently dried under vacuum for 15 min before being dissolved in dry
THF. N-Methyldicyclohexylamine (4 equiv) and functionalised styrene
(3.3 equiv) were added via syringe. Progress of the reaction was moni-
tored by TLC (neat CH2Cl2) analysis. On completion of the reaction, the
residual THF was removed under vacuum and the crude material re-dis-
solved in CH2Cl2, filtered to remove any insoluble material before being
absorbed onto fine silica and eluting with a mobile phase in a range of
0:100 to 2:98 MeOH/CH2Cl2.
Methyl 2-(4-vinylphenyl)acetate: 1,8-Diazabicycloundec-7-ene (1.707 g,
7.69 mmol) was added to a magnetically stirred solution of 2-(4-vinylphe-
nyl)acetic acid (0.95 g, 5.92 mmol) in THF (10 mL) at 08C. The ensuing
solution was treated in one portion with MeI (0.47 mL, 1.09 g,
7.69 mmol) and the mixture was stirred at room temperature for 3 h
before being diluted with diethyl ether (20 mL). The mixture was then
washed with H2O (10 mL), HCl (2n, 10 mL), NaOH (2n, 10 mL), HCl
(2n, 10 mL), and H2O (10 mL). The organic phase was then dried
(Na2SO4), filtered and concentrated under reduced pressure to afford the
desired product as a white solid (59.8 mg, 58%). The spectral data
matched those reported in the literature. 1H NMR (400 MHz, CDCl3):
d=7.37 (d, J=7.3 Hz, 2H; H4/H6), 7.24 (d, J=7.3 Hz, 2H; H3/H7), 6.70
(dd, J=17.6, 12.0 Hz, 1H; H8), 5.73(d, J=17.6 Hz, 1H; H9), 5.23 (d, J=
12.0 Hz, 1H; H10), 3.69 (s, 3H; H11), 3.62 (s, 2H; H1).
General protocol for saponification reactions: The ester (1 equiv) and
LiOH (2 equiv per ester) were dissolved in 9:1 H2O/MeOH or H2O/
EtOH, depending upon the ester, and refluxed overnight. After cooling
to room temperature, the solvent was removed under reduced pressure,
and the remaining solution diluted with H2O, cooled in an ice-bath and
the pH adjusted to 3 by the addition of HCl (1m). The precipitate was
collected, filtered and product dried under vacuum.
2,2’,2’’-{[(1E,1’E,1’’E)-benzene-1,3,5-triyltris(ethene-2,1-diyl)]tris(ben-
zene-4,1-diyl)}triacetic acid- (17): Prepared through a Heck cross-cou-
pling reaction with between methyl 2-(4-vinylphenyl)acetate and 1,3,5-tri-
bromobenzene (8) followed by saponification. Trimethyl 2,2’,2’’-
{[(1E,1’E,1’’E)-benzene-1,3,5-triyltris(ethene-2,1-diyl)]tris(benzene-4,1-
diyl)}triacetate: Reaction completed as indicated in the general protocol
section on 1,3,5-tribromobezene (5) (200 mg, 0.63 mmol) and methyl 2-
(4-vinylphenyl)acetate (368 mg, 2.09 mmol) to produce triacetate as
a bright-yellow oil (190 mg, 50%). Rf =0.17 (20% ethyl acetate/hexane);
1H NMR (400 MHz, CDCl3): d=7.45 (s, 3H; H2), 7.43 (d, J=8.8 Hz,
6H; H5’/H7’), 7.22 (d, J=7.6 Hz, 6H; H4’/H8’), 7.09 (d, J=16.2 Hz, 3H;
H2’), 7.03 (d, J=16.2 Hz, 3H; H1’), 3.63 (s, 9H; H11’), 3.57 ppm (s, 6H;
H9’); 13C NMR (100 MHz, CDCl3): d=172.1 (C10’), 138.2 (C3’), 136.3
(C1), 133.6 (C6’), 129.8 (C5’/C7’), 129.0 (C2’), 128.5 (C1’), 126.9 (C4’/C8’),
124.1 (C2), 52.3 (C11’), 41.1 ppm (C9’); IR (neat): n˜ =3026, 2950, 1730
(C=O), 1585, 1512, 1434, 1153 cmÀ1; HRMS (API): calcd for CHO:
601.2590 [M+H]+; found: 601.2604; triacetate from above (454.8 mg,
0.77 mmol) and LiOH·H2O (292.7 mg, 6.98 mmol) were dissolved in
EtOH/H2O (1:9) (30 mL) and magnetically stirred at refluxed for 17 h.
The reaction mixture was then cooled, the solvent was removed under re-
duced pressure, and the remaining mixture was diluted with water
(10 mL). After cooling to 08C, HCl (1m) was added to the mixture until
the pH was adjusted to 3 and a grey precipitate resulted. The residue was
collected by vacuum filtration and was recrystallised from THF/H2O to
afford a light-brown solid (241 mg, 57%). M.p. 100–1088C; 1H NMR
(400 MHz, CDCl3): d=7.43 (d, J=8 Hz, 6H; H4’/H8’), 7.39 (s, 3H; H2),
7.23 (d, J=7.6 Hz, 6H; H5’/H7’), 7.08 (d, J=16.4 Hz, 3H; H2’), 6.99 (d,
J=16.4 Hz, 3H; H1’), 3.57 ppm (s, 6H, H9’); 13C NMR (100 MHz,
CDCl3): d=175.3 (C10’), 139.3 (C3’), 137.3 (C1), 135.3 (C6’), 130.5 (C5’/
C7’), 129.7 (C2’), 129.1 (C1’), 127.5 (C4’/C8’), 124.7 (C2), 41.5 ppm (C9’);
4,4’,4’’-(1E,1’E,1’’E)-2,2’,2’’-(Benzene-1,3,5-triyl)tris(ethene-2,1-diyl)-
tris(N,N-dimethylaniline) (8): Prepared as per the standard Heck cross-
coupling procedure. 1H NMR (500.1 MHz, CDCl3): d=2.99 (s, 18H;
CH3), 6.74 (appd, 6H; Ar-AA’-BB’), 6.95 (d, J=16.4 Hz, 3H; CH=CH),
7.14 (d, J=16.4 Hz, 3H; CH=CH), 7.48 (s, 3H), 7.46 ppm (appd, 6H;
Ar-AA’-BB’); 13C NMR (CDCl3): d=40.5, 112.5, 122.3, 124.5, 125.9,
127.6, 128.8, 138.5, 150.1 ppm; MS (70 ev; FAB): m/z: 514.9 (13%)
[MI+H]+, 513 (59%) [MI]+, 512 (100%) [MIÀH]+, 326.9 (10%), 207.0;
HRMS-EI+: calcd for C36H39N3: 513.3144; found: 513.3114; HRMS (EI+
): calcd: 512.3065 [MI+H]+; found: 512.3050.
1,3,5-Tris[(1E)-2’-(ethyl 4’’-benzoate)vinyl]benzene (9): Prepared as per
the standard Heck cross-coupling procedure by using 1,3,5-tribromoben-
zene (8) (1010 mg, 3.21 mmol), Pd
(tBu3)PHBF4 (560 mg, 1.93 mmol),
(dba)3.CHCl3 (882 mg, 0.85 mmol),
N,N-dicyclohexylmethylamine
(3.0 mL), ethyl 4-vinylbenzoate (1870 mg, 10.61 mmol) and THF
(40 mL). The product was eluted with 2:98 MeOH/CH2Cl2 and recrystal-
lized from CH2Cl2/EtOH to give 10 as an off-white powder, (1.86 g,
97%). This compound matched that previously reported by this group.[28]
1,3,5-Tris[(1E)-2’-(4’’-benzoic acid)vinyl]benzene (10): By using the stan-
dard saponification procedure, triester
9
(252.1 mg, 0.42 mmol),
LiOH.H2O (112.0 mg, 2.7 mmol) and 1:9 H2O/EtOH (20 mL) gave a ge-
latinous precipitate that was collected and recrystallized from THF/H2O
and dried to give the triacid 10 as a pale-brown powder (209 mg, 95%).
This compound matched that previously reported by this group.[28]
1,3,5-Tristyrylbenzene (11), 1,3,5-tris(4-methylstyryl)benzene (12) and
1,1’,1’’-[4,4’,4’’-(1E,1’E,1’’E)-2,2’,2’’-(benzene-1,3,5-triyl)tris(ethene-2,1-
diyl)tris(benzene-4,1-diyl)]triethanone (13): All compounds were pre-
pared according to the as per the standard Heck cross-coupling proce-
dure. The spectral data for this compound matched those reported in the
literature.[44]
IR (neat): n˜ =3026 (O H), 1701 (C=O) cmÀ1; HRMS (ESI): m/z: calcd
À
for C36H31O6: 559.2121 [M+H]+; found: 559.2120.
4,4’,4’’-(1E,1’E,1’’E)-2,2’,2’’-(Benzene-1,3,5-triyl)tris(ethene-2,1-diyl)tris(-
benzene-4,1-diyl)triacetate (14): Reaction completed as indicated in the
4,4’,4’’-[(1E,1’E,1’’E)-Benzene-1,3,5-triyltris(ethene-2,1-diyl)]triphenol
(19): Triacetate 14 (150 mg, 0.31 mmol) and K2CO3 (387 mg, 2.8 mmol)
were dissolved in MeOH/H2O (6 mL, 1:1) and magnetically stirred at
reflux for 20 h. After cooling, H2O (5 mL) was added and the mixture
was extracted with EtOAc (3ꢂ10 mL). The combined organic extracts
were washed with brine, dried (Na2SO4) and filtered. The solvent was re-
moved under reduced pressure to afford a crude oil that was then puri-
fied by column chromatography (100% ethyl acetate) to afford a brown
solid (92 mg, 83%). M.p. 135–1408C); Rf =0.47 (100% ethyl acetate);
1H NMR (400 MHz, CDCl3): d=7.52 (s, 3H; H2), 7.45 (d, J=8.4 Hz, 6H;
H5’/H7’), 7.19 (d, J=16.4 Hz, 3H; H2’), 7.03 (d, J=16.4 Hz, 3H; H1’),
6.80 ppm (d, J=8.8 Hz, 6H; H4’/H8’); 13C NMR (100 MHz, CDCl3): d=
158.3 (C6’), 139.6 (C1), 130.5 (C4’/C8’), 129.7 (C3’), 128.9 (C1’), 126.7 (C2’),
general Heck protocol section on 1,3,5-tribromobezene
5 (200 mg,
0.63 mmol) to produce triacetate 14 as a bright-yellow solid (188 mg,
58%). M.p. 105–1258C; Rf =0.2 (1:4 ethyl acetate/hexane); 1H NMR
(500.1 MHz, CDCl3): d=2.32 (s, 9H; CH3), 7.09 (d, J=16.2 Hz, 3H;
CH=CH), 7.11 (d, 6H; Ar-AA’-BB’), 7.18 (d, J=16.2 Hz, 3H; CH=CH),
7.54 (s, 3H), 7.55 ppm (d, 6H; Ar-AA’-BB’); 13C NMR (CDCl3): d=
169.6 (C9’), 150.3 (C6’), 138.1 (C1), 135.1 (C3’), 128.7 (C1’), 128.5 (C2’),
127.7 (C4’/C8’), 124.1 (C2), 122.0 (C5’/C7’), 21.3 ppm (C10’); IR (neat):
n˜ =3436, 1757 (C=O), 1505, 1370, 1215, 1197, 1165 cmÀ1; HRMS (ESI):
m/z: calcd for C36H30O6K: 597.1679; found: 597.1663.
4,4’,4’’-(1E,1’E,1’’E)-2,2’,2’’-(Benzene-1,3,5-triyl)tris(ethene-2,1-diyl)tri-
benzonitrile (15): Reaction completed as indicated in the general Heck
&
6
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ꢁ 2013 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Chem. Eur. J. 0000, 00, 0 – 0
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