1
708; H NMR (CDCl
dichloromethane (2 ꢀ 50 mL), the extracts washed with water
3
, ppm) d 8.48 (2H; d, J = 2 Hz; H-1),
(
3 ꢀ 50 mL), dried and the solvent evaporated under vacuum.
8.30 (2H; d, J = 8 Hz; H-4), 7.95 (2H; q, J = 2 and 8 Hz; H-
0 0
This afforded a brown solid (227 mg). Sublimation (120 1C, 0.1
mbar) afforded yellow crystals (186 mg, 89%). Mp 265–266 1C
3), 7.43 (2H; d, J = 1 Hz; H-3 ), 7.03 (2H; d, J = 1 Hz; H-5 ),
0
0
00
2.66 (4H; t, J = 7 Hz; H-1 ), 1.67 (4H; m; H-2 ), 1.45–1.24
00 13
2
8
ꢁ1
1
(
lit, 265 1C); IR (NaCl, cm ) 1671, 1592, 1447, 1311, 1279,
(12H; m) and 0.92 (6H; t, J = 7 Hz; H-6 ); C NMR (CDCl3,
1
161, 951, 911, 856 and 733; H NMR (CDCl , ppm) d 8.55
ppm) d 14.4, 22.9, 29.2, 30.7, 30.8, 31.9, 122.6, 123.7, 127.3,
128.5, 130.4, 132.0, 134.4, 140.6, 141.9, 145.3 and 182.7; MS
3
(
2H; d, J = 2 Hz; H-1), 8.39 (2H; d, J = 8 Hz; H-4), 8.02 (2H;
ꢁ
1
(MALDI) 545 g mol , C34
+
H
ꢁ1
dd, J = 2 and 8 Hz; H-3), 7.74 (4H; m) and 7.57–7.42
H
46
O
2
S
2
requires 542 g mol ;
1
3
6H; bm); C NMR (CDCl
(
3
, ppm) d 125.8, 127.6, 128.2,
microanalysis: calc: C, 75.5%, H, 6.7%, S, 11.9%; found: C,
74.0%, H, 6.7%, S, 11.0%; UV-Vis spectrum (chloroform,
nm) lmax (e) 305 (29,500), 347 (30,300) and 396 (18,100).
1
28.3, 128.4, 129.4, 132.5, 132.6, 139.2, 147.2 and 183.2; MS
ꢁ
1
MALDI) 362 g mol , C26
+
ꢁ1
;
(
H
16
O
2
H
requires 361 g mol
UV-Vis spectrum (chloroform, nm) lmax (e) 283 (49,500), 309
0
(
27,900) and 355 (13,200).
2,6-Di(furan-2 -yl)-9,10-anthraquinone (3e). Following the
above procedure bistriflate 2 (250 mg, 0.58 mmol) was reacted
with furan-2-boronic ester (193 mg, 1.74 mmol) and palla-
dium[0]tetrakis(triphenylphosphine) (65 mg, 58 mmol). This
0
2
,6-Di(thien-2 -yl)-9,10-anthraquinone (3b). Following the
above procedure bistriflate 2 (1.00 g, 2.31 mmol) was reacted
with thiophen-2-boronic acid (652 mg, 5.09 mmol) and palla-
dium[0]tetrakis(triphenylphosphine) (110 mg, 95 mmol). This
gave compound 3e (171 mg, 87%). TGA: Tdec, 278 1C; IR
ꢁ1
(
NaCl, cm ) 1670, 1597, 1494, 1460, 1310, 1275, 1022, 966,
1
2
8
gave compound 3b (528 mg, 61%). Mp 228–229 1C (lit,
9
8
3
07, 884, 800 and 744; H NMR (CDCl and d-TFA, ppm) d
ꢁ1
2
28 1C); IR (KBr, cm ) 1668, 1590, 1424, 1357, 1313, 1214,
.51 (2H; d, J = 2 Hz; H-1), 8.31 (2H; d, J = 8 Hz; H-4), 8.09
0
1
165, 905, 824, 741 and 711; H NMR (CDCl
1
3
, ppm) d 8.53
(
2H; dd, J = 2 and 8 Hz; H-3), 7.60 (2H; d, J = 2 Hz; H3 ),
0
(
2H; d, J = 2 Hz; H-1), 8.33 (2H; d, J = 8 Hz; H-4), 8.01 (2H;
0
7
.04 (2H; d, J = 4 Hz; H5 ) and 6.58 (2H; dd, J = 4 and 2 Hz;
dd, J = 2 and 8 Hz; H-3), 7.60 (2H; dd, J = 1 and 4 Hz; H-3 ),
0
0
13
H-4 ); C NMR (CDCl
3
and d-TFA, ppm) d 108.7, 110.3,
12.5, 129.2, 129.3, 131.3, 134.3, 137.7, 144.9, 151.7 and 185.1;
7
.46 (2H; dd, J = 1 and 5 Hz; H-4 ) and 7.18 (2H; dd, J = 4
1
0
13
and 5 Hz; H-5 ); C NMR (CDCl
3
, ppm) d 124.1, 125.9,
ꢁ1
+
MS (MALDI) 342 g mol , C H O H requires 341 g
2
2
12
4
1
27.8, 128.6, 128.9, 130.8, 132.2, 134.5, 140.4, 142.4 and 182.7;
+
ꢁ1
mol ; microanalysis: calc: C, 77.7%, H, 3.6%; found: C,
ꢁ1
MS (MALDI) 373 g mol , C22
ꢁ
H
12
O
2
S
2
H
requires 373 g
76.8%, H, 3.3%; UV-Vis spectrum (chloroform, nm) lmax (e)
304 (22,200), 338 (15,500) and 397 (6,800).
1
mol ; microanalysis: calc: C, 70.9%, H, 3.2%, S, 17.2%;
found: C, 70.7%, H, 2.7%, S, 16.8%; UV-Vis spectrum
(
(
chloroform, nm) lmax (e) 301 (34,300), 340 (37,500) and 384
19,500).
Pinacol ester of 4-hexylthiophene-2-boronic acid (5). 3-Hex-
ylthiophene (3.05 g, 18.1 mmol) and tetrahydrofuran (50 mL,
anhydrous) were placed in a flame-dried round-bottomed flask
0
0
0
2
,6-Bis(9 ,9 -dioctylfluoren-2 -yl)-9,10-anthraquinone
(3c).
(
1-neck, 100 mL) fitted with a septum, under nitrogen. The
Following the above procedure bistriflate 2 (159 mg, 0.37
mmol) was reacted with the pinacol ester of 9,9-dioctylfluor-
ene-2-boronic acid (400 mg, 0.77 mmol) and palladium[0]
tetrakis(triphenylphosphine) (44 mg, 38 mmol). This gave
compound 3c (291 mg, 80%). Mp (DSC) 160 1C; IR (NaCl,
mixture was cooled down to ꢁ78 1C and stirred at this
temperature for five min. Butyl lithium (8.0 mL, 20 mmol)
was added dropwise, using a syringe, and the mixture was
stirred at ꢁ78 1C for 2 h. 2-Isopropoxy-4,4,5,5-tetramethyl-
1
,3,2-dioxaborolane (11.1 mL, 54.1 mmol) was finally added
ꢁ
1
cm ) 2927, 2855, 1673, 1592, 1466, 1312, 1291, 967, 831 and
quickly and the mixture was left to heat up to room tempera-
ture and stirred for 12 h. The solvent was then evaporated off
under vacuum to afford a colourless oil which was dissolved in
dichloromethane (50 mL), washed with aqueous hydrochloric
acid (0.1 M, 2 ꢀ 30 mL), water (3 ꢀ 50 mL), dried over
magnesium sulfate, filtered off and the solvent evaporated
under vacuum. Chromatography (silica, petroleum ether/ethyl
1
46; H NMR (CDCl
7
3
, ppm) d 8.66 (2H; d, J = 2 Hz; H-1),
.45 (2H; d, J = 8 Hz; H-4), 8.12 (2H; dd, J = 2 and 8 Hz;
8
H-3), 7.84 (2H; d, J = 8 Hz), 7.80–7.70 (6H; m), 7.42–7.33
00
(
6H; m), 2.05 (8H; dd, J = 5 and 11 Hz; H-1 ), 1.29–0.98
00
(
40H; m), 0.80 (12H; t, J = 7 Hz; H-8 ) and 0.68 (8H; bm; H-
00
13
); C NMR (CDCl , ppm) d 14.3, 22.9, 24.1, 29.5, 30.3,
2
3
1
1
9
C
3
2.0, 40.7, 55.6, 120.4, 120.6, 121.8, 123.3, 125.7, 126.6, 127.2,
27.9, 128.4, 132.3, 132.6, 134.4, 137.9, 140.6, 142.4, 147.8,
51.5, 152.2 and 183.5; microanalysis: calc: C, 87.7%, H,
acetate 90/10) afforded the desired product as a colourless oil
ꢁ1
(
3.76 g, 71%). IR (NaCl, cm ) 2974, 2929, 2857, 1545, 1445,
1
380, 1326, 1270, 1214, 1144, 1027, 961, 854, 772 and 685; H
1
ꢁ
1
.0%; found: C, 87.5%, H, 9.4%; MS (MALDI) 985 g mol
,
NMR (CDCl ) d 7.47 (1H; d, J 1 Hz; H-5), 7.21 (1H; d, J 1 Hz;
+
ꢁ1
3
72
H
88
O
2
H
requires 986 g mol ; UV-Vis spectrum (chloro-
0
0
H-3), 2.63 (2H; t, J = 7 Hz; H-1 ), 1.60 (2H; m; H-2 ), 1.34
form, nm) lmax (e) 315 (53,600), 338 (38,200; sh) and 398
23,500).
13
0
(
12H; s; Me), 1.29 (6H; m), 0.89 (3H; t, J = 7 Hz; H-6 );
NMR (CDCl ) d 15.3, 22.7, 24.5, 30.4, 31.1, 33.7, 35.2, 83.9,
ꢁ
128.4, 138.8, 138.9 and 146.1 ppm; MS (EI/CI) 294 g mol ,
C
(
3
1
0 0
,6-Bis(4 -hexylthien-2 -yl)-9,10-anthraquinone (3d). Follow-
2
+
ꢁ1
C
16
H27BO
2
SH requires 295 g mol
.
ing the above procedure bistriflate 2 (500 mg, 1.16 mmol) was
reacted with the pinacol ester of 4-hexylthiophene-2-boronic
acid (850 mg, 2.90 mmol) and palladium[0]tetrakis(triphenyl-
phosphine) (110 mg, 95 mmol). This gave compound 3d
X-Ray crystallography
Single crystals suitable for X-ray crystallography of 3a, 3b and
3c were obtained from toluene, mounted in inert oil and
transferred to the cold gas stream of the diffractometer.
ꢁ1
(
437 mg, 70%). Mp (DSC) 164 1C; IR (NaCl, cm ) 2930,
852, 1669, 1592, 1440, 1315, 1296, 1210, 945, 908, 836, 746 and
2
This journal is ꢂc the Royal Society of Chemistry and the Centre National de la Recherche Scientifique 2007
New J. Chem., 2007, 31, 1585–1593 | 1587