6.3, a-CH2 EZ), 3.37 (t, J 6.3, a-CH2 EZ), 3.30 (t, J 6.3, a-CH2
ZZ), 2.83 (s, CH3NCO EE), 2.82 (s, CH3NCO EZ), 2.80 (t, J
6.3, b-CH2 EZ), 2.75 (t, J 6.3, b-CH2 ZZ), 2.72 (s, CH3NCO
ZZ), 2.63 (t, J 6.3, b-CH2 EE), 2.60 (s, CH3NCO EZ), 2.55 (t,
J 6.3, b-CH2 EZ), 2.07 (s, CH3N EE), 2.03 (s, CH3N EZ), 1.58
(s, CH3N EZ), 1.51 (s, CH3N ZZ); [EE/EZ/ZZ (NMR) =
reaction mixture was stirred for another 48 h and then more 9-
bromomethylanthracene (100 mg, 0.37 mmol) was added. After
24 h of stirring, a last addition of NaH (13 mg, 0.33 mmol)
and 9-bromomethylanthracene (110 mg, 0.4 mmol) was
performed and the reaction was stirred at rt for another 24 h.
After quenching with water, the solvent was removed under a
high vacuum. The crude product thus obtained was purified
by silica gel flash column chromatography using hexane–ethyl
acetate (1 : 1, v/v) as the initial eluent. The ethyl acetate content
was gradually increasing up to 100% to give pure product
(124 mg, 20%) as a yellow–brown solid, mp (AcOEt) 109 ◦C.
(Found C, 85.29; H, 5.11; N, 4.42. C44H32N2O2 requires C,
85.14; H, 5.20; N, 4.51%); IR (KBr), mmax/cm−1 3050, 2922, 2853,
1724, 1622, 1591, 1524 and 1446; dH (300 MHz; CDCl3) 8.67
(2H, s, 10-H Anthr), 8.43 (4H, d, J 8.6, 1-H, 8-H Anthr), 8.17
(2H, d, J 8.4, 4-H, 7-H), 8.00 (4H, d, J3–4 8.6, 4-H, 5-H Anthr),
7.82 (2H, d, J 8.4, 3-H, 8-H), 7.71 (2H, s, 5-H, 6-H), 7.56–7.41
(8H, m, H-2, H-7, H-3, H-6 Anthr), 5.96 (4H, s, CH2Anthr),
5.25 (4H, s, CH2Phen); dC (75 MHz, CDCl3) 159.2 (C-2, C-9),
144.3 (C-10a, C-10b), 136.6 (C-4, C-7), 131.1 (C-4a, C-10a
Anthr), 130.7 (C-8a, C-9a Anthr), 128.7 (C-4, C-5 Anthr), 128.3
(C-10 Anthr), 128.1 (C-9 Anthr), 127.7 (C-4a, C-6a), 126.0
(C-2, C-7 Anthr), 125.8 (C-5, C-6), 124.7 (C-3, C-6 Anthr),
124.0 (C-1, C-8 Anthr), 121.0 (C-3, C-8), 73.9 (CH2Phen), 65.2
(CH2Anthr); m/z (FAB) 621 [M + H]+ (C44H32N2O2 requires
620).
=
15/41/44]; dC (125 MHz, C6D6) 169.1 and 168.7 (C O), 155.3
(C-2, C-9), 149.7 and 149.4 (C-4a, C-10a Acr), 144.3 (C-10a,
C-10b), 141.2 and 141.1 (C-9 Acr), 136.50 (C-4, C-7), 131.1
(C-4, C-5 Acr), 129.6, 129.5 and 129.2 (C-4a, C-6a and C-3,
C-6 Acr), 126.8 and 126.4 (C-5, C-6), 126.0, 125.9 and 125.7
(C-2, C-7 Acr), 125.3 (C-1, C-8 Acr), 123.8, 123.7, 123.4 and
123.1 (C-3, C-8 and C-8a, C-9a Acr), 57.4 (CH2-b EZ), 57.3
(CH2-b ZZ), 55.3 (CH2-b EE), 54.9 (CH2-b EZ), 54.3 (CH2Acr
EZ), 54.2 (CH2Acr ZZ), 53.7 (CH2Acr EE + EZ), 49.2 (CH2-a
EZ + ZZ), 46.6 (CH2-a EE), 45.9 (CH2-a EZ), 41.9 (CH3N
EE + EZ), 41.2 (CH3N EZ + ZZ), 37.7 (CH3NCO EE), 37.3
(CH3NCO EZ), 34.9 (CH3NCO EZ), 34.5 (CH3NCO ZZ); m/z
(FAB) 791 [M + H]+ (C50H46N8O2 requires 790).
N,Nꢀ-Bis[2-[(9-anthracenylmethyl)methylamino]-ethyl]-N,Nꢀ-
dimethyl-[1,10-phenanthroline]-2,9-dicarboxamide (4). To
a
solution of amide 2 (106 mg, 0.26 mmol) in acetonitrile (10 mL)
under argon, K2CO3 (170 mg, 1.23 mmol) was added, followed
by dropwise addition of 9-bromomethylanthracene (145 mg,
0.53 mmol) in dry acetonitrile (25 mL). The reaction was stirred
at rt for 16 h, after which the solvent was removed under a
reduced pressure. The crude product was purified by flash
column chromatography using 0.1% Ca enriched silica gel and
ethyl acetate as eluent to give the product (107 mg, 52%) as a
yellow foam, mp (AcOEt) 104 ◦C. (Found C, 79.29; H, 6.09;
N, 10.51. C52H48N6O2 requires C, 79.16; H, 6.13; N, 10.65%);
IR (KBr), mmax/cm−1 3048, 2934, 2846 and 1632; dH (500 MHz;
C6D6) 8.48 (m, 1-H, 8-H Anthr EE + EZ + ZZ), 8.15 and 8.12
(s, 10-H Anthr EE + EZ + ZZ), 7.78 (m, 4-H, 5-H Anthr and
3-H, 8-H), 7.66 (d, J 8.3, 3-H, 8-H), 7.54 (d, J 8.3, 4-H, 7-H),
7.43 (m, 2-H, 7-H Anthr), 7.38 (d, J 8.3, 4-H, 7-H), 7.32 (d, J
8.3, 4-H, 7-H), 7.26 (m, 3-H, 6-H Anthr), 7.09, 7.07 and 7.02
(s, 5-H, 6-H), 4.29 (s, CH2 Anthr EE), 4.28 (s, CH2 Anthr EZ),
4.26 (s, CH2 Anthr EZ), 4.24 (s, CH2 Anthr ZZ), 3.58 and 3.56
(2t overlapped, J 6.3, a-CH2 EE + EZ), 3.52 (t, J 6.3, a-CH2
EZ), 3.44 (t, J 6.1, a-CH2 ZZ), 2.84 (s, CH3NCO EE), 2.81
(s, CH3NCO EZ), 2.80 (m, b-CH2), 2.78 (s, CH3NCO ZZ),
2.71 (m, b-CH2), 2.71 (s, CH3NCO EZ), 2.21 (s, CH3N EE),
2.17 (s, CH3N EZ), 1.68 (s, CH3N EZ), 1.64 (s, CH3N ZZ);
[EE/EZ/ZZ (NMR) = 11/45/44]; dC (125 MHz, C6D6) 169.2,
2,9-Bis[(phenylmethoxy)methyl]-1,10-phenanthroline (7). To
a suspension of crushed KOH (450 mg, 8.0 mmol) in an-
hydrous dimethylsulfoxide (2 mL), a solution of the 2,9-
bis(hydroxymethyl)-1,10-phenanthroline (200 mg, 0.83 mmol)
in dimethylsulfoxide (10 mL) was added dropwise. The mixture
was stirred at rt for 30 min, after which benzyl bromide (568 mg,
0.4 mL, 3.32 mmol) was slowly added. The reaction was stirred
at rt for 1.5 h and quenched with water (2 mL). The solvent was
evaporated under a vacuum and the crude product was dissolved
in dichloromethane (20 mL) and washed with brine (2 ×
10 mL). The organic phase was dried with MgSO4, concentrated
and purified by flash column chromatography in silica gel
using hexane–ethyl acetate (1 : 1) as eluent to give the desired
product (82 mg, 23%) as a yellow solid, mp (AcOEt) 115 ◦C.
dH (300 MHz; CDCl3) 8.25 (2H, d, J 8.4, 4-H, 7-H), 7.93 (2H,
d, J 8.4, 3-H, 8-H), 7.75 (2H, s, 5-H, 6-H), 7.47–7.31 (10H, m,
Ph), 5.14 (4H, s, CH2Ph or CH2Phen), 4.74 (4H, s, CH2Ph or
CH2Phen); dC (75 MHz, CDCl3) 159.7 (C-2, C-9), 145.1 (C-10a,
C-10b), 138.1 (C-4ipso Ph), 136.7 (C-4, C-7), 128.3 (CO Ph), 128.0
(C-4a, C-6a), 129.8 (Cm Ph), 127.7 (Cp Ph), 126.0 (C-5, C-6),
120.8 (C-3, C-8), 73.8 (CH2), 73.1 (CH2); m/z (APCI) 421 (M+ +
H) (C28H24N2O2 requires 420).
=
168.8, 168.2 and 167.8 (C O), 155.5, 155.3 and 155.0 (C-2,
C-9), 144.8 and 144.4 (C-10a, C-10b), 136.4 and 136.3 (C-4,
C-7), 131.9, 131.8 and 131.7 (C-4a, C-10a, C-8a, C-9a Anthr),
129.2 and 129.1 (C-4, C-5 Anthr), 128.8 and 128.7 (C-4a, C-6a),
128.1 (C-9 Anthr solvent overlap), 127.5 (C-10 Anthr), 127.1,
126.9 and 126.8 (C-5, C-6), 126.0 and 125.9 (C-2, C-7 Anthr),
125.8 and 125.7 (C-1, C-8 Anthr), 125.2 and 125.1 (C-3, C-6
Anthr), 123.9 (C-3, C-8 EZ + EE), 123.7 (C-3, C-8 ZZ), 123.3
(C-3, C-8 EZ), 56.9 and 56.8 (CH2-b), 54.8, 54.7, 54.5 and 54.4
(CH2-b + CH2Anthr), 49.1 (CH2-a EZ + ZZ), 46.5 (CH2-a
EE), 46.0 (CH2-a EZ), 41.8 (CH3N EE), 41.6 (CH3N EZ),
41.0 (CH3N EZ), 40.9 (CH3N ZZ), 37.4 (CH3NCO EE), 37.2
(CH3NCO EZ), 34.5 (CH3NCO EZ), 34.3 (CH3NCO ZZ); m/z
(FAB) 789 [M + H]+ (C52H48N6O2 requires 788).
2,9-Bis[(2-naphthalenylmethoxy)methyl]-1,10-phenanthroline
(8). To a suspension of NaH (80% dispersion in mineral oil;
66 mg, 2.2 mmol) in anhydrous dimethylformamide (5 mL),
a
solution of 2,9-bis(hydroxymethyl)-1,10-phenanthroline
(240 mg, 1 mmol) in dimethylformamide (17 mL) was added
dropwise. The mixture was stirred at rt for 30 min, after which
a solution of 2-bromomethylnaphthalene (460 mg, 2 mmol)
in dimethylformamide (3 mL) was slowly added. The reaction
was stirred at rt for 24 h and quenched with water (2 mL). The
solvent was evaporated in vacuo and the crude product thus
obtained was purified by flash column chromatography in silica
gel using hexane–ethyl acetate (1 : 1, v/v) as eluent to give the
desired product (110 mg, 21%) as a white solid mp, (AcOEt)
109–111 ◦C. (Found C, 82.90; H, 5.36; N, 5.56. C36H28N2O2
requires C, 83.05; H, 5.42; N, 5.38%); IR (KBr), mmax/cm−1
3051, 2888, 1593, 1507 and 1450; dH (300 MHz; CDCl3) 8.28
(2H, d, J 8.4, 4-H, 7-H), 7.97 (2H, d, J 8.4, 3-H, 6-H), 7.90 (2H,
br s, 1-H Naph), 7.89–7.83 (6H, m, 4-H, 5-H, 8-H Naph), 7.78
(2H, s, 5-H, 6-H), 7.57 (2H, dd, J 8.4 and 1.8, 3-H Naph), 7.48
(4H, m, 6-H, 7-H Naph), 5.20 (4H, s, CH2), 4.91 (4H, s, CH2);
dC (75 MHz, CDCl3) 159.7 (C-2, C-9), 145.1 (C-10a, C-10b),
2,9-Bis[(9-anthracenylmethoxy)methyl]-1,10-phenanthroline
(6). Sodium hydride (90 mg, 2.25 mmol; 60% dispersion
in mineral oil) was added to
a suspension of 2,9-
bis(hydroxymethyl)-1,10-phenanthroline (240 mg, 1 mmol) in
anhydrous dimethylformamide (30 mL) and stirred for 30 min
at rt. Then, a solution of 9-bromomethylanthracene (600 mg,
2.2 mmol) in dimethylformamide (15 mL) was added dropwise.
The reaction was stirred for 24 h, after which additional amounts
of NaH (60% dispersion in mineral oil; 14 mg, 0.35 mmol) and
9-bromomethylanthracene (110 mg, 0.4 mmol) were added. The
O r g . B i o m o l . C h e m . , 2 0 0 5 , 3 , 1 8 5 6 – 1 8 6 2
1 8 6 1