5822
H. M. Lee et al. / Tetrahedron 60 (2004) 5807–5825
0
lium dibromide (3b). Yield: 51%. Anal. calcd for
0
1
4
.6.2. 1,1 -Di(3-methoxybenzyl)-3,3 -ethylenediimidazo-
Mp 230–234 8C. H NMR (300.13 MHz, DMSO-d ): d 3.87
6
(s, 6H, CH ), 4.78 (s, 4H, CH ), 7.76 (s, 4H, imi-H), 9.28
3
2
1
3
1
C H Br N O : C, 51.08; H, 5.00; N, 9.93. Found: C,
2
(s, 2H, NCHN). C{ H} NMR (75.48 MHz, DMSO-d ): d
6
4
28
2
4
2
1
5
(
1.11; H, 5.10; N, 9.90. Mp 205–207 8C. H NMR
300.13 MHz, DMSO-d ): d 3.77 (s, 6H, OCH ), 4.81
33.6 (CH ), 48.2 (CH ), 122.3 (imi-C), 123.7 (imi-C), 137.1
3
2
(NCHN).
6
3
(
s, 4H, NCH ), 5.43 (s, 4H, ArCH N), 6.96 (virtual t,
2 2
3
JHH¼7.4 Hz, 4H, 4-, 6-CH), 7.08 (s, 2H, 2-CH), 7.33
4.7. A typical procedure for the preparation of
compound 4
3
(
7
virtual t, J ¼7.4 Hz, 2H, 5-CH), 7.80 (s, 2H, imi-H),
HH
1
3
1
.87 (s, 2H, imi-H), 9.48 (s, 2H, NCHN). C{ H} NMR
75.48 MHz, DMSO-d ): d 48.3 (NCH ), 51.9 (ArCH N),
(
A mixture of 1a (3.2 g, 16.9 mmol) and 1,2-dichloroethane
(0.67 mL, 0.84 mmol) was stirred in THF (30 mL) at reflux
for 2 d. The solvent was removed completely under
vacuum. Dichloromethane was added to the residue to
give a white solid, which was filtered and dried under
vacuum.
6
2
2
5
5.3 (OCH ), 114.3, 114.3 (2-, 6-C), 120.4 (4-C), 122.7
3
(
2£imi-C), 130.1 (5-C), 135.9 (1-C), 136.7 (NCHN), 159.5
(
3-C).
0 0
.6.3. 1,1 -Di(4-fluorobenzyl)-3,3 -ethylenediimidazo-
4
1
lium dibromide (3c). Yield: 49%. Mp 288–289 8C. H
NMR (300.13 MHz, DMSO-d ): d 4.78 (s, 4H, NCH ), 5.47
0
0
4.7.1. 1,1 -Di(4-methoxybenzyl)-3,3 -ethylenediimidazo-
lium dichloride (4a). Yield: 17%. Anal. calcd for
C H Cl N O : C, 60.63; H, 5.94; N, 11.78. Found: C,
6
2
3
3
(
s, 4H, ArCH N), 7.26 (virtual t, J ¼ J ¼8.3 Hz, 4H,
), 7.75
HH HF ortho
2
HF
HH
3
4
CHmeta), 7.51 (virtual t, J ¼ J ¼6.3 Hz, CH
24 28
2 4 2
1
(s, 2H, imi-H), 7.85 (s, 2H, imi-H), 9.41 (s, 2H, NCHN).
1
C{ H} NMR (75.48 MHz, DMSO-d ): d 48.4 (s, NCH ),
60.61; H, 5.89; N, 11.68. Mp 265–268 8C. H NMR
(300.13 MHz, DMSO-d ): d 3.75 (s, 3H, OCH ), 4.77 (s, 4H,
3
1
6
2
6
3
2
3
5
1.2 (s, ArCH N), 115.8 (d, J ¼21.9 Hz, Cmeta), 122.7
CH ), 5.35 (s, 4H, CH ), 6.96 (d, JHH¼8.6 Hz, 4H,
), 7.76 (s, 2H,
HH ortho
2
CF
2
2
3
3
(
s, imi-C), 122.9 (s, imi-C), 130.9 (d, J ¼8.3 Hz, Cortho),
CF
CHmeta), 7.38 (d, J ¼8.6 Hz, 4H, CH
1
1
observed.
36.7 (s, NCHN), 162.2 (d, J ¼245.3 Hz, CF), C
not
imi-H), 7.79 (s, 2H, imi-H), 9.53 (s, 2H, NCHN).
CF
ipso
0 0
.7.2. 1,1 -Di(3-methoxybenzyl)-3,3 -ethylenediimidazo-
lium dichloride (4b). Yield: 35%. Anal. calcd for
4
0
mide (3d). Yield: 52%. Anal. calcd for C H Br N :
0
4
.6.4. 1,1 -Dibenzyl-3,3 -ethylenediimidazolium dibro-
C H Cl N O : C, 60.63; H, 5.94; N, 11.78. Found: C,
2 4 2
2
2
24
2
4
24 28
1
C, 52.40; H, 4.80; N, 11.11. Found: C, 52.36; H, 4.82; N,
1
60.61; H, 5.90; N, 11.68. Mp 108–110 8C. H NMR
(300.13 MHz, DMSO-d ): d 3.77 (s, 6H, OCH ), 4.80 (s, 4H,
1
d ): d 4.77 (s, 4H, NCH ), 5.45 (s, 4H, PhCH N), 7.41
1.20. Mp 259–264 8C. H NMR (300.13 MHz, DMSO-
6
3
3
NCH ), 5.40 (s, 4H, ArCH N), 6.95 (d, JHH¼7.7 Hz,
6
2
2
2
2
3
(
(
s, 10H, Ph-H), 7.75 (s, 2H, imi-H), 7.84 (s, 2H, imi-H), 9.38
1
4H, 4-, 6-CH), 7.06 (s, 2H, 2-CH), 7.33 (t, J ¼7.7 Hz,
HH
1
3
s, 2H, NCHN). C{ H} NMR (75.48 MHz, DMSO-d ): d
6
2H, 5-CH), 7.80 (s, 2H, imi-H), 7.82 (s, 2H, imi-H), 9.59
(s, 2H, NCHN).
4
8.4 (NCH ), 52.0 (PhCH N), 122.8 (2£imi-C), 128.3
), 128.7 (C ), 128.9 (C ), 134.5 (C ), 136.7
meta para ortho ipso
2
2
(
(
C
0 0
4.7.3. 1,1 -Di(4-fluorobenzyl)-3,3 -ethylenediimidazo-
NCHN).
1
lium dichloride (4c). Yield: 8%. Mp 263–265 8C.
NMR (300.13 MHz, DMSO-d ): d 4.79 (s, 4H, NCH ), 5.45
H
0
dazolium dibromide (3e). Yield: 35%. Anal. calcd for
0
4
.6.5. 1,1 -Di(1-naphthalenemethyl)-3,3 -ethylenediimi-
6
2
3
3
(s, 4H, ArCH N), 7.25 (virtual t, J ¼ J ¼8.9 Hz, 4H,
), 7.79
HH HF ortho
2
HF
HH
3
4
C H Br N : C, 59.62; H, 4.67; N, 9.27. Found: C, 59.58;
2
H, 4.70; N, 9.31. Mp 242–244 8C. H NMR (300.13 MHz,
DMSO-d ): d 4.72 (s, 2H, NCH ), 5.92 (s, 4H, ArCH N),
CHmeta), 7.51 (virtual t, J ¼ J ¼7.0 Hz, CH
3
0
28
4
1
(s, 2H, imi-H), 7.83 (s, 2H, imi-H), 9.61 (s, 2H, NCHN).
6
2
2
0
ide (4d). Yield: 34%. Anal. calcd for C H Cl N : C,
0
7
imi-H), 8.01–8.07 (m, 6H, Ar-H), 9.28 (s, 2H, NCHN).
.50–7.63 (m, 8H, Ar-H), 7.69 (s, 2H, imi-H), 7.78 (s, 2H,
4.7.4. 1,1 -Dibenzyl-3,3 -ethylenediimidazolium dichlor-
2
2
24
2 4
1
3
1
C{ H} NMR (75.48 MHz, DMSO-d ): d 48.5 (NCH ),
2
63.62; H, 5.82; N, 13.49. Found: C, 63.76; H, 6.03; N, 13.97.
1
6
5
Ar-C),122.99(imi-Cor Ar-C), 125.63, 126.44, 127.25, 127.85,
0.1 (ArCH N), 122.7 (imi-C or Ar-C), 122.91 (imi-C or
Mp 260 8C. H NMR (300.13 MHz, DMSO-d ): d 4.82
6
2
(s, 4H, NCH ), 5.46 (s, 4H, PhCH N), 7.41 (s, 10H, Ph-H),
2
2
1
3
1
128.9, 129.7, 130.4, 130.4, 133.4 (Ar-C), 136.9 (NCHN).
7.84 (s, 4H, imi-H), 9.65 (s, 2H, NCHN). C{ H} NMR
75.48 MHz, DMSO-d ): d 48.3 (NCH ), 52.0 (PhCH N),
(
6
2
2
0
0
mide (3f). Yield: 45%. Anal. calcd for C H Br N : C,
4
.6.6. 1,1 -Di(mesityl)-3,3 -ethylenediimidazolium dibro-
122.7 (imi-C), 122.9 (imi-C), 128.3 (Cmeta), 128.7 (Cpara),
128.9 (Cortho), 134.6 (Cipso), 137.0 (NCHN).
2
6
32
2 4
5
Mp .320 8C. H NMR (300.13 MHz, DMSO-d ): d 1.98 (s,
5.73; H, 5.76; N, 10.00. Found: C, 55.69; H, 5.72; N, 10.01.
1
0
0
4.7.5. 1,1 -Di(1-naphthalenemethyl)-3,3 -ethylenediimi-
dazolium dichloride (4e). Yield: 44%. Anal. calcd for
C H Cl N : C, 69.90; H, 5.47; N, 10.87. Found: C, 69.65;
6
1
2H, o-CH ), 2.33 (s, 6H, p-CH ), 4.98 (s, 4H, CH ), 7.14
3 3 2
(
(
s, 4H, m-CH), 8.00 (s, 2H, imi-H), 8.06 (s, 2H, imi-H), 9.51
1
3
0
28
2 4
3
1
1
s, 2H, NCHN). C{ H} NMR (75.48 MHz, DMSO-d ): d
6
H, 5.53; N, 10.61. Mp 248 8C (dec). H NMR (300.13 MHz,
DMSO-d ): d 4.72 (s, 2H, NCH ), 5.91 (s, 4H, ArCH N),
7.48–7.62 (m, 8H, Ar-H), 7.70 (s, 2H, imi-H), 7.77 (s, 2H,
imi-H), 8.01–8.07 (m, 6H, Ar-H), 9.37 (s, 2H, NCHN).
C{ H} NMR (75.48 MHz, DMSO-d ): d 48.4 (NCH ),
6
50.0 (ArCH N), 122.7, 122.9, 123.0 (imi-C, Ar-C), 125.6,
2
1
1
1
7.0(o-CH ), 20.6 (o-CH ), 48.7 (CH ), 123.3 (imi-C),
3 3 2
24.4 (imi-C), 129.3 (Cortho), 130.9 (Cpara), 134.1 (Cmeta),
38.0 (NCHN), 140.5 (Cipso).
6
2
2
1
3
1
2
0
mide (3g). Yield: 79%. Anal. calcd for C H Br N : C,
0
4
.6.7. 1,1 -Di(methyl)-3,3 -ethylenediimidazolium dibro-
126.4, 127.2, 127.7, 128.9, 129.7, 129.7, 130.3, 133.4
(Ar-C), 137.0 (NCHN).
1
0
16
2 4
3
4.12; H, 4.58; N, 15.91. Found: C, 34.23; H, 4.60; N, 15.89.