N,N-Bis{4-[N-(3-methylphenyl)-N-phenylamino]phenyl}tolyl-
N,N,NЈ,NЈ-Tetrakis(2,4-dimethylphenyl)-o-phenylenediamine 8
amine 4
General procedure as for compound 1. 1,2-Phenylenediamine
(2.50 g, 23.1 mmol), 2,4-dimethyl-1-iodobenzene (60.0 g,
256 mmol), copper powder (2.91 g, 46.2 mmol), K2CO3 (12.8 g,
924 mmol) and 18-crown-6 (0.50 g) were heated to 180 ЊC
for 24 h. Yield 42%; colourless solid, mp 271–272 ЊC (from
dichloromethane–light petroleum) (Found: C, 86.6; H, 7.35; N,
5.1. C38H40N2 requires C, 87.0; H, 7.7; N, 5.3%); λmax (CH2Cl2)/
nm 291 (log ε 5.35); νmax (KBr)/cmϪ1 3006m, 2948m, 2915m,
2858m, 1590m, 1494s, 1444m, 1378w, 1294m, 1270m, 1253m,
1221s, 1157w, 1127m, 1036m, 872w, 821m and 754m; m/z 524
(Mϩ, 30%).
General procedure as for compound 1. N,N-Bis(4-iodophenyl)-
tolylamine 13 (12.0 g, 23.5 mmol), N-(3-methylphenyl)-
N-phenylamine (13.0 g, 70.5 mmol), copper powder (5.36 g,
85.0 mmol), KOH (9.52 g, 238 mmol) and n-decane (5.00 g)
were refluxed at 173 ЊC for 24 h. Yield 63%, as a yellow crystal-
line solid, mp 237–238 ЊC (from cyclohexane) (Found: C,
86.6; H, 6.2; N, 6.55. C45H39N3 requires C, 86.9; H, 6.3; N,
6.8%); λmax (CH2Cl2)/nm 317 (log ε 6.04); νmax (KBr)/cmϪ1
3033m, 1583s, 1504s, 1483s, 1310s, 1268s, 835m, 819m, 777m,
750s, 695s, 560m and 526s; δH (250 MHz; C6D6) 2.15 (6H, s,
Me), 2.23 (3H, s, Me), 6.83–7.04 (5H, m, Ar) and 7.18–7.34
(25H, m, Ar); δC (62.9 MHz; C6D6) 21.2, 21.8, 122.3, 122.9,
124.3, 124.4, 125.3, 125.4, 125.6, 126.4, 130.0, 130.8, 132.9,
139.7, 143.4, 144.2, 146.3, 148.9 and 149.2 (one overlapping
peak); m/z 621 (Mϩ, 100%).
N,N,NЈ,NЈ-Tetra-4-tolyl-o-phenylenediamine 9
General procedure as for compound 1. 1,2-Phenylenediamine
(1.00 g, 9.26 mmol), 4-iodotoluene (16.2 g, 74.0 mmol), copper
powder (2.33 g, 37.0 mmol), K2CO3 (10.2 g, 74.0 mmol),
18-crown-6 (0.50 g) and o-dichlorobenzene (20 ml) were heated
to 180 ЊC for 18 h. Yield 69%; colourless solid, mp 144–145 ЊC
(from dichloromethane–light petroleum) (Found: C, 87.0;
H, 6.5; N, 5.5. C34H32N2 requires C, 87.1; H, 6.9; N, 6.0%);
λmax (CH2Cl2)/nm 301 (log ε 4.86); νmax (KBr)/cmϪ1 3026m,
2916m, 2858m, 1606s, 1590m, 1548w, 1506s, 1487s, 1446s,
1348w, 1315s, 1291s, 1265s, 1109m, 1048m, 1016m, 811s, 754s
and 708m; δH (250 MHz; CDCl3) 2.22 (12H, s, Me), 6.60–6.64
(8H, d, J 8.0, Ar), 6.87–6.90 (8H, d, J 8.0, Ar) and 6.97–7.06
(4H, m, Ar); δC (62.9 MHz; CDCl3) 20.8, 123.1, 124.6, 128.9,
129.0, 131.4, 143.8 and 145.5; m/z 468 (Mϩ, 100%).
N,N-Bis{4-[N-(3,4-dimethylphenyl)-N-phenylamino]phenyl}tolyl-
amine 5
General procedure as for compound 1. N,N-Bis(4-iodophenyl)-
tolylamine 13 (2.00 g, 3.91 mmol), N-(3,4-dimethylphenyl)-N-
phenylamine (2.50 g, 11.7 mmol), copper powder (1.30 g, 20.0
mmol), KOH (2.25 g, 56.2 mmol) and n-decane (10 ml) were
refluxed at 173 ЊC for 24 h. Yield 51%; yellow crystalline solid,
mp 248–249 ЊC (from cyclohexane–dichloromethane) (Found:
C, 87.0; H, 6.7; N, 6.3. C47H43N3 requires C, 86.9; H, 6.7; N,
6.5%); λmax (CH2Cl2)/nm 319 (log ε 6.91); νmax (KBr)/cmϪ1
3030m, 2918m, 2851m, 1592s, 1503s, 1450m, 1308s, 1268s,
1218m, 824m, 749m, 695s, 568m and 514m; δH (250 MHz;
C6D6) 2.03 (6H, s, Me), 2.12 (6H, s, Me), 2.14 (3H, s, Me), 6.94–
7.06 (5H, m, Ar) and 7.19–7.37 (23H, m, Ar); δC (62.9 MHz;
C6D6) 19.5, 20.2, 21.2, 122.4, 123.5, 123.7, 125.2, 125.4, 125.9,
127.2, 129.9, 130.7, 131.3, 132.0, 132.6, 138.2, 143.7, 143.9,
146.4, 146.7 and 149.4; m/z 649 (Mϩ, 100%).
N,N,NЈ,NЈ-Tetra-4-tolyl-4,5-dimethyl-o-phenylenediamine 10
General procedure as for compound 1. 4,5-Dimethyl-1,2-
phenylenediamine (1.00 g, 7.35 mmol), 4-iodotoluene (14.4 g,
66.2 mmol), copper powder (2.12 g, 33.1 mmol), K2CO3 (9.13 g,
66.2 mmol), 18-crown-6 (0.50 g) and o-dichlorobenzene
(20 ml were heated to 180 ЊC for 18 h. Yield 63%; colourless
solid, mp 219–220 ЊC (from dichloromethane–light petroleum)
(Found: C, 86.9; H, 7.1; N, 5.4. C36H36N2 requires C, 87.1; H,
7.3; N, 5.6%); λmax (CH2Cl2)/nm 303 (log ε 4.69); νmax (KBr)/
cmϪ1 3019m, 2918m, 2859m, 1605s, 1579w, 1506s, 1450m,
1396m, 1313s, 1296m, 1262m, 1220m, 1108m, 1017w, 877w,
813s, 783w, 754w, 711m and 619w; δH (250 MHz; CDCl3) 2.13
(6H, s, Me), 2.21 (12H, s, Me), 6.60–6.64 (8H, d, J 8.0, Ar)
and 6.85–6.88 (10H, d, J 9.0, Ar); δC (62.9 MHz; CDCl3) 19.8,
21.7, 122.8, 129.0, 130.1, 130.9, 133.4, 141.5 and 145.6; m/z 496
(Mϩ, 100%).
N,N-Bis{4-[N-(2,4-dimethylphenyl)-N-phenylamino]phenyl}-
tolylamine 6
General procedure as for compound 1. N,N-Bis(4-iodophenyl)-
tolylamine 13 (1.20 g, 2.31 mmol), N-(2,4-dimethylphenyl)-N-
phenylamine (1.00 g, 5.10 mmol), copper powder (0.14 g, 2.30
mmol), K2CO3 (0.70 g, 5.10 mmol), 18-crown-6 (0.40 g) and
o-dichlorobenzene (30 ml) were heated at 180 ЊC for 72 h.
Yield 43%; yellow crystalline solid, mp 263–264 ЊC (from cyclo-
hexane); λmax (CH2Cl2)/nm 327 (log ε 6.19); νmax (KBr)/cmϪ1
3094w, 3034m, 2915m, 2855w, 1594m, 1502s, 1383w, 1309m,
1265s, 1232m, 1110w, 879w, 816m, 749m, 693m, 587w, 549w
and 512m; δH (250 MHz; C6D6) 2.21 (6H, s, Me), 2.24 (3H, s,
Me), 2.28 (6H, s, Me), 6.89–7.11 (6H, m, Ar) and 7.18 (22H, m,
Ar); δC (62.9 MHz; C6D6) 19.1, 21.2, 21.4, 121.2, 121.4, 124.0,
124.6, 125.5, 129.8, 130.2, 130.6, 132.2, 133.2, 136.0, 136.8,
143.2, 143.3, 143.8, 146.7 and 148.8 (one overlapping peak);
m/z 649 (Mϩ, 100%). Acc. mass: calc. 649.3457, found 649.3450.
N,N,NЈ,NЈ-Tetra-4-tolyl-p-phenylenediamine 11
General procedure as for compound 1. 1,4-Phenylenediamine
(1.00 g, 9.26 mmol), 4-iodotoluene (16.2 g, 74.0 mmol), copper
powder (2.33 g, 37.0 mmol), K2CO3 (10.2 g, 74.0 mmol), 18-
crown-6 (0.50 g) and o-dichlorobenzene (20 ml) were heated to
180 ЊC for 12 h. Yield 35%; colourless solid, mp 271–272 ЊC
(from dichloromethane–light petroleum) (Found: C, 87.4;
H, 6.7; N, 5.85. C34H32N2 requires C, 87.1; H, 6.9; N, 6.0%);
λmax (CH2Cl2)/nm 313 (log ε 4.62); νmax (KBr)/cmϪ1 3022m,
2915m, 2858w, 1607m, 1579w, 1501s, 1383w, 1318m, 1270s,
1110m, 838m, 815s and 713m; δH (250 MHz; C6D6) 2.24 (12H,
s, Me), 7.03–7.07 (8H, d, J 8.0, Ar), 7.23–7.27 (8H, d, J 8.0, Ar)
and 7.31 (4H, s, Ar); δC (62.9 MHz; C6D6) 21.2, 124.9, 125.5,
130.6, 132.4, 143.9 and 146.7; m/z 468 (Mϩ, 100%).
N,N,NЈ,NЈ-Tetraphenyl-o-phenylenediamine 7
General procedure as for compound 1. N-Phenyl-o-phenylene-
diamine (5.00 g, 27.3 mmol), iodobenzene (100 g, 480 mmol),
copper powder (5.00 g, 82.0 mmol), K2CO3 (20.0 g, 164 mmol)
and 18-crown-6 (0.50 g) were refluxed at 188 ЊC for 6 h. Yield
63%, as a colourless solid, mp 175–176 ЊC (from dichloro-
methane–light petroleum) (lit.11c 168 ЊC) (Found: C, 87.1; H,
5.65; N, 6.6. C30H24N2 requires C, 87.35; H, 5.9; N, 6.8%);
λmax (CH2Cl2)/nm 299 (log ε 5.97); νmax (KBr)/cmϪ1 3063m,
3033m, 1586s, 1518w, 1487s, 1438m, 1313s, 1266s, 1169m,
1075m, 1026w, 833w, 831w, 749s, 692s, 632m, 546w and 499m;
δH (250 MHz; CDCl3) 6.72–7.29 (24H, m, Ar); δC (62.9 MHz;
CDCl3) 122.3, 123.0, 125.3, 128.5, 129.5, 143.7 and 147.4;
m/z 412 (Mϩ, 100%).
4,4Ј-Bis[N-(2,4-dimethylphenyl)-N-phenylamino]biphenyl 15
N,NЈ-Diphenylbenzidine (78.0 g, 213 mmol), 2,4-dimethyl-
iodobenzene (154.0 g, 664 mmol), copper powder (40.0 g,
635 mmol), K2CO3 (142 g, 1.02 mol) and 18-crown-6 (10.0 g)
with o-dichlorobenzene (200 ml) as solvent were heated at
J. Chem. Soc., Perkin Trans. 1, 2001, 2548–2552
2551