J Incl Phenom Macrocycl Chem
0
was removed in vacuo. The residue was dissolved in
122.0 (C3 ), 96.3, 97.5 (benzimidazolyl Ar CH), 69.0, 69.2
CH Cl and 3b was precipitated with hexanes, collected,
2
(OCH ), 48.1 (benzylic CH ), 30.4, 30.4 (OCH CH ),
2
2
2
2
2
1
washed with hexanes, and air-dried (0.76 g, 92 %). H and
18.66, 18.69 (CH CH ), 13.6 (CH ).
2 3 3
1
3
C NMR resonances as above.
Palladium complex 5a
Benzimidazolium salt 4a
Palladium(II) acetate (26 mg, 0.12 mmol) was added, with
stirring, to a solution of 4a (100 mg, 0.11 mmol) in DMF
(10 mL) and the mixture was heated at 90 °C for 3 d. The
solvent was removed in vacuo and the residue was re-
crystallised from acetone/hexanes to yield the product as a
white powder (64 mg, 58 %). Found C, 57.28; H, 5.58; N,
5.14. C H N O Br Pd requires C, 57.46; H, 5.59; N,
A solution of 3a (0.35 g, 1.02 mmol) and 1,2-bis(bro-
momethyl)benzene (0.13 g, 0.50 mmol) in toluene (17 mL)
was stirred at reflux under nitrogen for 4 d. The solution was
concentrated to *5 mL then 4a was precipitated with hex-
anes, collected, washed with hexanes, and dried under
vacuum to yield a white powder (0.41 g, 87 %). Found C,
5
0
58
4
4
2
6
1.69; H, 6.44; N, 5.26. C H N O Br Á(2H O) requires C,
5.36 %; d (500.13 MHz, CDCl ): 7.96 (m, 2H, xylylene
5
0
60
4
4
2
2
H
3
2
Ar H), 7.78 (4H, Ar H), 7.77 (d, 2H, J
6
1.48; H, 6.60; N, 5.73 %; d (600.13 MHz, d -DMSO): 9.66
= 15.2 Hz,
H,H
H
6
(
s, 2H, NCHN), 7.55–7.70 (m, 16H, Ar H, xylylene Ar H,
benzylic CHH), 7.57 (m, 2H, xylylene Ar H), 7.36 (s, 2H,
benzimidazolyl Ar CH), 7.14 (s, 2H, benzimidazolyl Ar CH),
3
.08 (s, 4H, benzylic CH ), 4.06 (t, 4H, J
benzimidazolyl Ar CH), 7.20–7.25 (m, 6H, Ar H), 6.54 (s,
2
2H, benzimidazolyl Ar CH), 5.43 (d, 2H, J
6
= 6.4 Hz,
= 15.2 Hz,
H,H
2
H,H
3
OCH ), 4.03 (t, 4H, JH,H = 6.4 Hz, OCH ), 1.72–1.78
benzylic CHH), 4.07 (m, 4H, OCH ), 3.76 (m, 4H, OCH ),
2 2
2
2
(
2 9 m, 8H, 2 9 OCH CH ), 1.46–1.53 (2 9 m, 8H,
2
1.85 (m, 4H, OCH CH ), 1.67 (m, 4H, OCH CH ), 1.54
2 2 2 2
2
3
9 CH CH ), 0.99 (t, 6H, J
2
= 7.4 Hz, CH CH ), 0.98
2
(m, 4H, CH CH ), 1.40 (m, 4H, CH CH ), 1.00 (t, 6H,
2 3 2 3
2
3
H,H
3
3
t, 6H, J
3
3
JH,H = 7.4 Hz, CH CH ), 0.90 (t, 6H, J
(
= 7.4 Hz, CH CH ); d (125.77 MHz, DMSO-
= 7.4 Hz,
H,H
H,H
2
3
C
2
3
d6): 149.4, 149.9 (benzimidazolyl Ar CO), 140.0 (NCHN),
CH CH ); d (125.77 MHz, DMSO-d ): 170.8 (NCN),
2
3
C
6
1
1
1
32.9 (Ar C), 131.8 (xylylene Ar C), 130.0, 130.2, 130.3,
30.8 (Ar CH), 125.1 (benzimidazolyl Ar C), 124.8 (Ar CH),
24.6 (benzimidazolyl Ar C), 96.0, 96.7 (benzimidazolyl Ar
147.6, 147.9 (benzimidazolyl Ar CO), 136.1 (Ar C), 135.3
(xylylene Ar C), 133.9 (xylylene Ar CH), 130.4
(benzimidazolyl Ar C), 129.8 (Ar CH), 129.7 (xylylene Ar
CH), 129.0 (Ar CH), 128.4 (benzimidazolyl Ar C), 126.4
(Ar CH), 97.7, 98.1 (benzimidazolyl Ar CH), 69.9, 70.1
CH), 68.9, 69.0 (OCH ), 48.0 (benzylic CH ), 30.4, 30.5
2
2
(
OCH CH ), 18.7, 18.7 (CH CH ), 13.7, 13.8 (CH ).
2 2 2 3 3
(
OCH ), 52.1 (benzylic CH ), 31.2, 31.4 (OCH CH ), 19.2,
2
2
2
2
Benzimidazolium salt 4b
19.4 (CH CH ), 13.9, 14.0 (CH ).
2 3 3
A solution of 3b (0.14 g, 0.33 mmol) and 1,2-bis(bro-
momethyl)benzene (0.04 g, 0.16 mmol) in CH CN
Palladium complex 9
3
˚
Palladium(II) acetate (42 mg, 0.19 mmol) and 3 A mole-
(
15 mL) was stirred at reflux under nitrogen overnight. The
solvent was removed in vacuo and the residue was purified
via column chromatography (gradient elution with MeOH/
EtOAc) to give 4b as an orange solid (0.15 g, 85 %). Found
C, 52.69; H, 5.03; N, 9.30. C H N O Br Á(1.5H O) re-
cular sieves were added, with stirring, to a solution of 4b
(150 mg, 0.13 mmol) in CH CN (10 mL) and the mixture
3
was heated at reflux for 20 h. The solvent was removed in
vacuo and the residue was dissolved in CH Cl and crude 9
2
5
0
56
8
12
2
2
2
quires C, 52.32; H, 5.18; N, 9.76 %; dH (500.13 MHz,
was precipitated with hexanes, collected, and purified by
column chromatography on neutral alumina (eluting with
CH Cl ) to give 9 as an orange powder (30 mg, 20 %).
DMSO-d ): 9.98 (s, 2H, NCHN), 9.21 (d, 2H,
6
4
0
3
J3
0
0
= 2.6 Hz, H3 ), 9.00 (dd, 2H,
J
0
0
= 8.7 Hz,
0
,5
,5
5 ,6
2
2
4
0
3
= 2.6 Hz, H5 ), 8.47 (br d, 2H, J
J3
0
0
B,C
= 8.7 Hz, H6 ),
Found C, 46.70; H, 4.66; N, 7.35. (C H N O Br
88 102 12 16 4-
7
.77 (s, 2H, benzimidazolyl Ar CH), 7.50-7.55 (m, 2H,
Pd )Á(0.5CH Cl ) requires C, 46.93; H, 4.58; N, 7.42 %; d
3
2
2
H
3
xylylene Ar H), 7.28–7.33 (m, 2H, xylylene Ar H), 7.30 (s,
(500.13 MHz, CD Cl ): 9.34 (br d, 2H, J = 8.7 Hz,
B,C
2
2
4
H ), 8.62 (d, 2H, JA,B = 2.6 Hz, H ), 8.13 (dd, 2H,
2
4
H, benzimidazolyl Ar CH), 6.28 (br s, 4H, benzylic CH2),
.09 (br s, 4H, OCH ), 3.96 (br s, 4H, OCH ), 1.68–1.77
C
A
3
4
JB,C = 8.7 Hz, JA,B = 2.6 Hz, H ), 7.71 (d, 2H,
2
2
B
3
(
2 9 m, 8H, 2 9 OCH CH ), 1.41–1.52 (2 9 m, 8H,
2
JH,H = 7.1 Hz, xylylene Ar H), 7.61-7.65 (m, 2H, xy-
2
3
9 CH CH ), 0.96 (t, 12H, J
2
0
= 7.4 Hz, CH CH ),
2
lylene Ar H), 7.54-7.58 (m, 2H, xylylene Ar H), 7.45 (s,
2
3
H,H
3
3
.95 (t, 6H, J
= 7.4 Hz, CH CH ); d (125.77 MHz,
2H, benzimidazolyl Ar CH), 7.20 (s, 2H, benzimidazolyl
3
Ar CH), 7.10 (d, 2H, J
H,H
2
3
C
DMSO-d ): 149.6, 150.4 (benzimidazolyl Ar CO), 144.9,
6
= 7.8 Hz, xylylene Ar H), 6.85
H,H
0
0
0
1
49.0 (C2 and C4 ), 140.9 (NCHN), 133.2 (C6 ), 131.7
0
(s, 2H, benzimidazolyl Ar CH), 6.35 (s, 2H, benzimida-
2
zolyl Ar CH), 5.94 (d, 2H, JH,H = 14.3 Hz, benzylic
0
(
xylylene Ar C), 130.8 (C1 ), 130.1 (C5 ), 128.4, 129.6
xylylene Ar CH), 124.6, 126.6 (benzimidazolyl Ar C),
2
CHH), 5.45 (d, 2H, J
(
= 14.3 Hz, benzylic CHH), 5.17
H,H
1
23