Electronic Supplementary Material (ESI) for Organic and Biomolecular Chemistry
This journal is © The Royal Society of Chemistry 2011
6
'-boronic acid-9,9'-dioctyl-3,3'-bi(9H–carbazole) (13). n-BuLi (2.8 M in hexanes, 1.5mL, 4.2 mmol)
was added dropwise to a solution of 9 (1.4 g, 2.2 mmol, 1.6 eq) in anhyd THF (15 mL) at –78˚C. The
mixture was stirred at this temperature for 1.5 h, then B(OCH ) (0.7 ml, 7 mmol, 3 eq) was added and
3
3
the mixture was stirred for 16 h while allowing the temperature to rise to 20 ˚C. HCl (10 mL, 2 M) was
added, the organic layer separated, the aqueous layer extracted with CH Cl , the organic layer drided
2
2
4
over MgSO ,and evaporated to dryness and purified using a silica gel column (EtOAc : Petroleum ether
1
=
1:5) and 10 was obtained as a white solid (444 mg, yield 34 %). H NMR (300 MHz, CDCl ): δ = 8.42
3
(
s, 1 H), 8.33 (s, 1 H), 8.21 (d, 1 H, J = 7.8 Hz), 7.83 (d, 2 H J = 7.2 Hz), 7.63 (s, 1 H), 7.40–7.53 (m, 4
H), 7.21–7.27 (m, 2 H), 7.06 (dd, 1 H, J = 8.7 Hz J = 2.4 Hz), 4.33 (m, 4 H, N-CH ), 1.92 (m, 4 H, N-
CH -CH ), 1.23–1.40 (m, 20 H), 0.89 (m,6 H, CH -CH ); C NMR (75 MHz, CDCl ): δ =140.1, 139.6,
2
1
3
2
2
2
3
3
1
2
8
33.9, 133.5, 129.4, 126.1, 125.6, 122.3, 119.0, 110.9, 109.2, 81.3, 43.4, 31.9, 29.5, 29.3, 29.1, 27.4,
–
1
2.7, 14.2.; IR (KBr): nu(tilde) (cm ) =3214, 2925, 2852, 1527, 1597, 1474, 1451, 1342, 1151, 1132,
+
77, 796, 745, 719 ; TOFMS (EI) (M ) C40
H49BN
2
O
2
: 600.6403, found 600.6400.
6
'-bromo-9,9'-dioctyl-6-(9-octyl-9H-carbazol-3-yl)-3,3'-bi(9H-carbazole) (14). 6 (209 mg, 0.65
(30 mg, 0.03 mmol ) were added into a 50 mL
flask. Degassed toluene (15 mL) and degassed aqueous K CO solution (5 mL, 2 M) was then added into
the flask. The solution was kept at 90˚C and stirred vigorously under nitrogen for 48 h. The resulting
3 4
mmol), 13 (784 mg, 0.97 mmol, 1.5 eq) and Pd(PPh )
2
3
solution was extracted with excess CH
2
Cl
2
, dried by MgSO
4
, and purified using a silica gel column
1
(
CH
2
Cl
2
: Petroleum ether = 1:20) and 14 as white solid was obtained (310 mg, yield 49.8 %). H NMR
(
300 MHz, CDCl ): δ = 8.53 (s, 2 H), 8.53 (s, 1 H), 8.47 (s, 1 H), 8.41 (s, 1 H), 8.23 (d, 1 H, J = 7.5 Hz),
3
7
1
1
1
.83–7.90 (m, 4 H), 7.72 (s, 1 H), 7.47–7.55 (m, 7 H), 7.23 (m, 1 H), 4.32–4.40 (m, 6 H, N-CH
2
), 1.92–
):140.9,
13
2 2 2 3
.99 (m, 6 H, N-CH -CH ), 1.28 (m, 30 H), 0.90 (m, 9 H, CH -CH ); C NMR (75 MHz, CDCl
3
39.9, 139.6, 133.9, 133.4, 128,3, 126.3, 125.7, 125.6, 124.9, 123.8, 123.7, 123.5, 123.3, 122.5, 120.5,
19.0, 118.8, 111.6, 110.3, 109.2, 108.9, 108.8, 43.3, 31.9, 29.5, 29.4, 29.3, 29.0, 27.4, 27.3, 22.7, 14.1;
–
1
IR (KBr): nu(tilde) (cm ) =2925, 1600, 1472, 1347, 1270, 1227, 1206, 1150, 1054, 874, 797, 745, 727 ;
+
TOFMS (EI) calcd for (M ) C60
H70BrN
3
: 913.1220, found 913.1225.
8