4
380 J. Phys. Chem. B, Vol. 109, No. 10, 2005
Bag and Bharadwaj
a pale yellow solid, which crystallizes from MeCN or DCM as
pale yellow blocks.
129.4, 128.8, 127.0, 126.7, 125.3, 123.7, 104.9, 55.4, 44.6, 43.5,
43.2; FAB-MS (m/z) 400 (70%) [M] . Anal. Calcd for
C H N O : C, 71.98; H, 6.04; N, 13.99. Found: C, 71.51;
24 24 4 2
H, 6.29; N, 13.91.
+
1
Yield 70(%); mp 165 °C; H NMR (400 MHz, CDCl3, 25
°
C, TMS, δ) 1.95 (s, 6H, 2×CH3), 2.25 (t, J ) 6.95 Hz, 2H,
CH2), 3.12 (t, J ) 6.95 Hz, 2H, CH2), 5.09 (s, 2H, An-CH2),
7
7
N,N-Dimethyl-N′-(2,4-dinitrophenyl)ethylenediamine, 5: To
a stirring solution of N,N-dimethylethylenediamine (0.55 mL;
5 mmol) in ethanol (40 mL) was added anhydrous K2CO3 (0.83
g; 6 mmol) followed by dropwise addition of an ethanolic
solution of 1-chloro 2,4-dinitrobenzene (1.0 g; 5 mmol). The
mixture was heated to reflux for 16 h whereupon orange solids
were precipitated out. The reaction mixture, after cooling to
room temperature, was filtered off and the residue stirred with
water for 1 h to remove K2CO3. The orange solid thus obtained
was recrystallized from ethanol to obtain the desired product
as orange rectangular parallelepiped crystals suitable for single-
crystal X-ray diffraction.
.25 (d, J ) 9.51 Hz, 1H, Ph-H6), 7.46 (m, 4H, An-H2,3,6,7),
.89 (d, J ) 9.03 Hz, 2H, An-H4,5), 7.99 (d, J ) 7.55 Hz, 2H,
An-H1,8), 8.24 (dd, J ) 2.68 Hz, J ) 9.27 Hz, 1H, Ph-H5),
.45 (s, 1H, An-H10), 8.8 (s, 1H, Ph-H3); 13C NMR (100 MHz,
CDCl3, 25 °C, TMS, δ) 149.38, 137.66, 131.2, 129.3, 127.15,
8
1
4
27.76, 125.43, 124.38, 123.14, 119.60, 57.12, 49.77, 47.09,
5.08; FAB-MS (m/z) 444.489 (65%) [M] . Anal. Calcd for
+
C25H24N4O4: C, 67.56; H, 5.44; N, 12.61. Found: C, 67.38;
H, 5.59; N, 12.53.
N,N-Dimethyl[N′-(9-methylanthracenyl)-N′-(4-nitrophenyl)]-
ethylenediamine, 3: To a completely dissolved solution of 1
1
(
0.54 g; 2 mmol) in DMSO was added K2CO3 (0.33 g; 2.4
mmol) with stirring for 15 min at room temperature. Neat
-fluoro-1-nitrobenzene (0.2 mL; 2 mmol) was added and the
Yield 91(%); mp 66 °C; H NMR (400 MHz, CDCl3, 25 °C,
TMS, δ) 2.29 (s, 6H, 2 × CH3), 2.64 (t, J ) 6.12 Hz, 2H,
CH2), 3.39 (q, J ) 4.88 Hz, 2H, CH2), 6.85 (d, J ) 9.51 Hz,
1H, Ph-H6), 8.20 (dd, J ) 2.28 Hz, J ) 9.51 Hz, 1H, Ph-H5),
4
solution was allowed to react for 48 h at 70 °C with constant
stirring. A yellow precipitate was deposited at the bottom,
collected by filtration, and washed with plenty of water. The
compound was dissolved in CHCl3 and the CHCl3 layer was
washed six times with water. The organic layer after, drying
over anhydrous Na2SO4, was evaporated to dryness to obtain a
brown semisolid, which was further purified by passing through
a column (100-200 mesh silica gel) with an ethyl acetate and
dichloromethane mixture (30:70 v/v) as the eluent. The desired
product was obtained as yellow crystals from acetonitrile.
1
3
8.94 (br, s, 1H, NH), 9.05 (s, 1H, Ph-H3), C NMR (100 MHz,
CDCl3, 25 °C, TMS, δ) 40.83, 44.96, 56.52, 114.14, 124.17,
+
130.13, 135.64, 148.06. FAB-MS (m/z) 254 (100%) [M] . Anal.
Calcd for C10H14N4O4: C, 47.24; H, 5.55; N, 22.04. Found:
C, 47.15; H, 5.59; N, 21.91.
9,10-Bis(chloromethyl)anthracene, 6a: This compound was
1
8
prepared as per the procedure reported earlier by Miller et al.
The yellow solid obtained was recrystallized from toluene.
1
Yield 92 (%); mp 254-256 °C; H NMR (400 MHz, d6-
1
Yield 79(%); mp 181 °C; H NMR (400 MHz, CDCl3, 25
acetone, 25 °C, TMS, δ) 5.70(s, 4H, 2 × CH ), 7.60 (m, 4H,
2
°
C, TMS, δ) 1.65 (s, 6H, 2×CH3), 2.01 (t, J ) 7.93 Hz, 2H,
An-H
,3,6,7
), 8.40 (m, 4H, An-H
1,4,5,8 16 12
). Anal. Calcd for C H -
2
CH2), 3.11 (t, J ) 7.91 Hz, 2H, CH2), 5.32 (s, 2H, An-CH2),
2
Cl : C, 69.84; H, 4.40. Found: C, 69.69; H, 4.29.
6
8
8
.92 (d, J ) 9.51 Hz, 2H, Ph-H2,6), 7.52 (m, 4H, An-H2,3,6,7),
.03 (m, 4H, An-H1,4,5,8), 8.21 (d, J ) 7.31 Hz, 2H, Ph-H3,5),
.5 (s, 1H, An-H10); 13C NMR (100 MHz, CDCl3, 25 °C, TMS,
9
,10-Bisaminomethyl[N,N-dimethyl-N′-(2,4-dinitrophenyl)-
aminoethyl)]anthracene, 6: To a stirring solution of 5 (1.0 g; 4
mmol) in toluene (40 mL) was added triethylamine (0.56 mL;
mmol) and the solution was warmed at 50 °C for 30 min. A
δ) 153.22,137.52, 131.37, 131.24, 129.41, 128.99, 127.05,
4
1
4
26.45, 125.72, 125.28, 123.55, 110.91, 55.74, 45.51, 44.97,
4.44; FAB-MS (m/z) 400 (65%) [M] . Anal. Calcd for
solution of 9,10-bis(chloromethyl)anthracene (0.55 g; 2 mmol)
in toluene (30 mL) was added dropwise and then heated to reflux
for 48 h. The solvent was removed under reduced pressure and
the solid remaining was stirred with water (50 mL) and then
extracted with ethyl acetate. The organic layer, after drying over
Na SO , was evaporated to dryness to obtain the desired product
+
C25H25N3O2: C, 75.16; H, 6.31; N, 10.52. Found: C, 75.01;
H, 6.39; N, 10.48.
N,N-Dimethyl[N′-(9-methylanthracenyl)-N′-(5-nitropyridyl)]-
ethylenediamine, 4: To a solution of 1 (0.54 g; 2 mmol) in dry
N-methyl-2-pyrolidone (NMP, 20 mL) was added triethylamine
2
4
1
as a brown solid. Yield 86(%); mp 161 °C; H NMR (400 MHz,
DMSO-d , 25 °C, TMS, δ) 3.05 (s, 12H, 4×CH ), 4.14 (br, s,
(0.42 mL; 3 mmol) over a period of 15 min with constant
6
3
stirring. A solution of 2-chloro-5-nitropyridine (0.32 g; 2 mmol)
in NMP (10 mL) was added dropwise for 1 h and then allowed
to react for 36 h at 70° C with constant stirring. The reaction
mixture, after bringing it back to room temperature, was poured
into cold water. A pale yellow solid crushed out, which was
collected by filtration. The solid was washed with plenty of
water and dried, then further purified by passing through a
column (100-200 mesh silica gel) with an ethyl acetate and
dichloromethane mixture (7:93 v/v) as the eluent. The desired
product thus obtained easily crystallizes from ethyl acetate
solution as yellow needles suitable for single-crystal X-ray
diffraction.
4H, 2×CH ), 4.21 (br, s, 4H, 2×CH ), 5.93 (s, 4H, 2×An-
2 6 2,3,6,7
2
2
CH ), 7.45 (d, 2H, 2×Ph-H ), 7.72 (m, 4H, An-H
), 8.24
(d, 2H, 2×Ph-H ), 8.85 (d, 2H, An-H ), 8.90 (d, 2H, An-H ),
5
4,5
1,8
1
3
9.04 (d, 2H, 2×Ph-H ); C NMR (100 MHz, DMSO-d , 25
3
6
°C, TMS, δ) 147.66, 135.43, 132,71,130.57, 129.92, 127.09,
125.80, 124.11, 123.46, 115.89, 62.76, 58.63, 49.80, 37.17;
+
FAB-MS (m/z) 747 (77%) [M + 1.2H O] . Anal. Calcd for
2
C H N O : C, 60.84; H, 5.39; N, 15.77. Found: C, 60.75;
3
6
38
8
8
H, 5.67; N, 15.69.
N-(9-Methylanthracenyl)ethylenediamine, 7a: To a stirring
solution of anthracene 9-carbaldehyde (1.0 g; 5 mmol) in ethanol
70 mL) was added ethylenediamine (1.7 mL; 25 mmol) and
the solution was allowed to react for 36 h at room temperature
with constant stirring. The Schiff base thus formed was reduced
by adding solid NaBH4 (excess) to it. The mixture was further
heated at 50 °C for 2 h to ensure a complete reduction of the
imine formed. The solvent was distilled off under reduced
pressure, the solid was stirred with 50 mL of water, and the
product was extracted with CHCl3 (3 × 30 mL). The organic
layer, after drying over anhydrous Na2SO4, was evaporated to
(
1
Yield 75(%); mp 189 °C; H NMR (400 MHz, CDCl3, 25
°
C, TMS, δ) 1.79 (s, 6H, 2 × CH3), 2.01 (t, J ) 7.79 Hz, 2H,
CH2), 3.33 (t, J ) 7.79 Hz, 2H, CH2), 5.92 (s, 2H, An-CH2),
6
8
.71 (d, J ) 9.51 Hz, 1H, Ph-H3), 7.50 (m, 4H, An-H2,3,6,7),
.03 (d, J ) 9.47 Hz, 2H, An-H4, 5), 8.20(d, J ) 8.51 Hz, 2H,
An-H1,8), 8.28 (dd, J ) 2.68 Hz, J ) 9.39 Hz, 1H, Ph-H4),
.50 (s, 1H, An-H10), 9.23(s, 1H, Ph-H6); 13C NMR (100 MHz,
CDCl3, 25 °C, TMS, δ) 160.0, 146.6, 135.4, 133.3, 131.4 (d),
8