U. Maitra, K. Rissanen et al.
FULL PAPER
À1
7
l
1%) as a yellow solid; m.p. 60 ± 618C; UV/Vis (1% CHCl
3
/EtOH v/v):
(Nujol): nÄ 1250 cm ; 1H NMR (300 MHz, CDCl
): d 8.47(d, J
3
max (loge) 354.5 (4.33), 282 (4.56), 242 (4.68), 232.5 nm (4.70); IR (thin
9.0 Hz, 1H), 8.16 ± 7.86 (m, J 7.0 Hz. 7 H), 7.53 (d,J 8.4 Hz, 1H), 4.31
(t, J 6.5 Hz, 2H), 2.06 (quintet, J 6.7Hz, 2H), 1.84 (m, 2H), 1.26 (m,
À1
1
film): nÄ 1670, 1600 cm
;
H NMR (300 MHz, CDCl
3
): d 8.85 (d, J
1
3
9
6
.6 Hz, 1H) 8.30 ± 8.01 (m, 8H), 3.19 (t, J 7.5Hz, 2H), 1.85 (quintet, J
20H), 0.88 ppm (t, J 6.0 Hz, 3H); C NMR (75 MHz, CDCl ): d 153.27,
3
1
3
.9, J 7.5 Hz, 2H), 1.47 (m, 24H), 0.88 ppm (t,J 6.6 Hz, 3H); C NMR
131.76, 131.73, 127.26, 126.24, 126.04, 125.49, 125.09, 124.99, 124.86, 124.15,
124.06, 121.32, 120.43, 109.14, 60.01, 31.94, 29.71, 29.69, 29.66, 29.64, 29.51,
(
75 MHz, CDCl
3
): d 205.49, 133.55, 133.03, 131.11, 130.59, 129.44, 129.34,
1
3
27.09, 126.35, 126.15, 125.96, 125.93, 125.04, 124.83, 124.38, 123.99, 42.73,
29.48, 29.37, 26.28, 22.70, 14.13 ppm; LRMS:m/z (%): 414 [M] ; elemen-
tal analysis calcd (%) for C30
1.93, 29.69, 29.66, 29.62, 29.52, 29.50, 29.44, 29.36, 25.03, 22.70, 14.12 ppm;
H38O: C 86.90, H 9.24; found: C 86.76,
LRMS: m/z (%): 440 [M] , 229 (100); elemental analysis calcd (%) for
H 9.34.
C
32
H
40O: C 87.23, H 9.15; found: C 87.24, H 9.30.
-Dodecanoyl-1-pyrene: This compound was made from 1-dodecanoic acid
and pyrene in 70% yield, m.p. 56 ± 578C; UV/Vis (1% CHCl /EtOH): lmax
loge) 356 (4.34), 282 (4.39), 242 (4.61), 233.5 (4.61), 209.5 nm (4.46); IR
1
-Pyrenyl-1-hexadecylcarboxylate (9): 1-Hexadecylcarboxylic acid
1
(160 mg, 0.62 mmol) was converted to the corresponding acid chloride by
treating with oxalyl chloride (0.16 mL, 1.85 mmol) and DMF (4 mL) in dry
toluene (1.4 mL). After the reaction mixture had been stirred at 458C for
1 h, volatiles were removed in vacuo. The crude acid chloride obtained was
dissolved in toluene (1.5 mL), and treated with pyridine (0.6 mL) and
pyrenol (146 mg, 0.63 mmol) in toluene (1 mL) and heated at 1008C for
14 h. The reaction mixture was extracted with EtOAc and the organic
extract was washed with dilute HCl, saturated NaHCO solution, water and
3
brine. The crude product obtained on evaporation of the solvent was
purified on a silica gel column (3 ± 5% EtOAc/hexanes) to yield 9 (185 mg;
3
(
(
À1
1
thin film): nÄ 1668, 1595 cm ; H NMR (300 MHz, CDCl ): d 8.86 (d,
3
J 9.6 Hz, 1H), 8.31 (d, J 8.1 Hz, 1H), 8.26 ± 8.01 (m, 6H), 8.06 (d, J
9
1
1
1
2
.6 Hz, 1H), 3.12 (t, J 7.2 Hz, 2H), 1.86 (q, J 7.3 Hz, 2H), 1.47- 1.25 (m,
13
6H), 0.87ppm (t, J 6.6 Hz, 3H); C NMR (75 MHz, CDCl ): d 205.57,
3
33.54, 133.00, 131.10, 130.57, 129.44, 129.35, 129.21, 127.09, 126.36, 126.15,
25.96, 125.93, 125.02, 124.80, 124.37, 123.99, 59.55, 42.73, 31.90, 29.60,
9.49, 29.42, 29.33, 25.02, 22.68, 14.11 ppm; LRMS: m/z (%): 384 [M] , 229
100%); elemental analysis calcd (%) for C28 32O: C 87.45, H 8.38; found:
À1
1
(
H
65%). IR (neat): nÄ 3045, 2923, 2852, 1760, 1599 cm
;
H
NMR
): d 8.2 ± 8.07(m, 8H), .78 1 (d, J 8.4 Hz, 1H), 2.84
t, J 7.4 Hz, 2H), 1.92 (quintet, J 7.5 Hz, 2H), 1.27 (m, 26H), 0.89 ppm
C 87.69, H 8.52.
(300 MHz, CDCl
3
(
(
1
-Hexadecyl-1-pyrene (7a): In a 35-mL test tube fitted with a reflux
1
3
t, J 6.8 Hz, 3H); C NMR (75 MHz, CDCl
3
): d 172.69, 144.36, 131.14,
condenser, 1-hexadecanoyl-1-pyrene (0.15 g, 0.34 mmol), hydrazine mono-
hydrate (0.14 mL, 2.88 mmol), and KOH (0.10 g, 1.78 mmol) in digol
1
1
2
30.97, 129.23, 128.07, 127.09, 127.02, 126.26, 125.60, 125.44, 125.17, 125.0,
24.57, 123.14, 120.24, 119.77, 34.54, 31.93, 29.71, 29.69, 29.63, 29.52, 29.37,
9.33, 29.28, 26.20, 22.70, 14.13 ppm; LRMS: m/z (%): 456 [M] .
(
1.5 mL, 12.40 mmol) was heated at 1258C in a sand bath for 2 h, and then
water was removed from the reaction mixture by distilling at 2058C. The
General procedure for the preparation of alkyl amides of pyrene: An
aliphatic acid (0.70 mmol) was converted to the corresponding acid
chloride by stirring with oxalyl chloride (2.25 mmol) and DMF (5 mL) in
dry toluene (1 mL) at RT. After 5 h, the volatiles were removed in vacuo
reaction mixture was cooled to RT, extracted with CHCl
washed with water and brine, and dried over anhydrous Na SO
3
(2 Â 5 mL),
2
4
. The crude
product was purified on a silica gel column (1.2 cm  15 cm, hexane) to give
a (0.12 g; 80%). M.p. 79 ± 808C; UV/Vis (1% CHCl /EtOH v/v): lmax
loge) 342.5 (4.60), 326 (4.44), 313 (4.04), 276 (4.65), 265 (4.39), 255
7
3
2 2
and the resulting oil was dissolved in dry CH Cl (6 mL) and treated with
(
(
(
À1
1
1-aminopyrene (0.69 mmol) and Et N (1.0 mmol). A buff colored precip-
4.13), 243 (4.82), 210 nm (4.36); IR (Nujol): nÄ 1465, 850 cm ; H NMR
300 MHz, CDCl
): d 8.27(d, J 9.3Hz, 1H), 8.16 ± 8.08 (m, 4H), 8.02 ±
.98 (m, 3H), 7.88 (d,J 7.8 Hz, 1H), 3.33 (t,J 7.7 Hz, 2H), 1.53 (quintet,
3
itate resulted. After the mixture had been stirred for 15 h, the precipitate
was filtered and washed with EtOH. The solid obtained was then dissolved
3
7
1
3
in hot 40% EtOH/CHCl and decolorized (charcoal). The white precipitate
J 7.5 Hz, 2H), 1.25 (m, 26H), 0.88 ppm (t, J 6.9 Hz, 3H); C NMR
3
formed on cooling the filtrate was collected by filtration and dried.
(
1
3
75 MHz, CDCl
3
): d 137.37, 131.43, 130.92, 129.65, 128.58, 127.52, 127.23,
27.04, 126.44, 125.72, 125.05, 124.75, 124.73, 124.57, 123.53, 33.62, 31.96,
1-Octadecanoyl-1-pyrene amide (10a): Yield 73%; m.p. 1538C; UV/Vis
1.92, 29.83, 29.69, 29.67, 29.63, 29.59, 29.36, 22.69, 14.12 ppm; LRMS: m/z
(CHCl ): l
(loge) 245.8 (4.54), 278.8 (4.36), 343.4 (4.33), 380.0 nm
3
max
À1 1
(
%): 426 [M] ; elemental analysis calcd (%) for C32
H
42: C 90.08, H 9.92;
(3.13); IR (Nujol): nÄ 3240, 1650 cm ; H NMR (300 MHz, CDCl ): d
3
found: C 90.49, H 10.12.
8.34 ± 8.00 (m, 9H), 7.80 (s, 1H), 2.59 (t,J 7.5 Hz, 2H), 1.88 (q,J 7.5 Hz,
2
H), 1.26 (m, 28H), 0.90 ppm (t, 3H); LRMS: m/z (%): 483 (19) [M] ;
1
7
-Dodecyl-1-pyrene (7b): A similar procedure gave 7b in 62% yield; m.p.
2 ± 738C; UV/Vis (1% CHCl
/EtOH v/v): lmax (loge) 342.5 (4.65), 326.5
elemental analysis calcd (%) for C34H45NO: C 84.42, H 9.38, N 2.89; found:
3
C 84.19, H 9.6, N 2.52.
(
1
8
1
4.49), 312 (408), 276 (4.69), 265 (4.42), 255 nm (4.15); IR (thin film): nÄ
À1
1
465, 840 cm ; H NMR (300 MHz, CDCl
.17(m, 5H), 8.02 (m, 2H), 7. 87(d, J 7.8 Hz, 1H), 3.33 (t,J 7.7 Hz, 2H),
.37(quintet, J 7.5 Hz, 2H), 1.49 (m, 2H), 1.37 ± 1.26 (m, 16H), 0.88 ppm
3
): d 8.29 (d, J 9.3 Hz, 1H),
1-Dodecanoyl-1-pyrene amide (10b): Yield 85%; m.p. 149 ± 1498C; UV/
Vis (CHCl
): lmax (loge) 245.8 (4.52), 278.8 (4.35), 343.4 (4.3) 389.0 nm
3
À1
1
(3.12); IR (Nujol): nÄ 3240, 1640 cm ; H NMR (300 MHz, CDCl ): d
3
1
3
(
1
1
t, J 6.8 Hz, 3H); C NMR (75 MHz, CDCl
3
): d 137.39, 131.47, 130.96,
8.40 (s, 1H), 8.20 ± 8.02 (m, 8H), 7.78 (s, 1H), 2.60 (t,J 7.5 Hz, 2H), 1.89
29.68, 127.54, 127.25, 127.07, 126.46, 125.74, 125.08, 124.77, 124.76, 124.59,
23.55, 33.64, 31.98, 31.93, 29.85, 29.68, 29.65, 29.61, 29.36, 22.07, 14.13 ppm;
(q, 2H), 1.51 ± 1.11 (m, 16H), 0.88 ppm (t, 3H); LRMS: m/z (%): 399 [M] ;
elemental analysis calcd (%) for C28
C 84.17, H 8.41, N 3.2.
H33NO: C 84.16, H 8.33, N 3.51; found:
LRMS: m/z (%): 384 [M] ; elemental analysis calcd (%) for C28
H
34: C
9
0.75, H 9.25; found: C 90.95, H 9.33.
1
-Octanoyl-1-pyrene amide (10c): Yield 81%; IR (Nujol): nÄ 3240, 1650,
À1 1
1
590, 1560, 1530, 1465 cm ; H NMR (300 MHz, CDCl
3
): d 8.36 (s, J
1
-Ethylpyrene (7c): 1-Ethylpyrene was prepared following the procedure
1
8.1 Hz, 1H), 8.33 ± 8.05 (m, 8H), 7.82 (s, 1H), 2.59(t,J 7.5Hz, 2H), 1.88 (q,
for 7b in 98% yield; m.p. 94 ± 958C; H NMR (300 MHz, CDCl
3
): d 8.26
2
H), 1.5 ± 1.11 (m, 8H), 0.88 ppm (t, 3H); LRMS: m/z (%): 343 [M] ;
(
6
(
d, J 9.3Hz, 1H), 8.14 ± 8.05 (m, 4H), 7.99 ± 7.91 (m, 3H), 7.86 (d,J
1
3
elemental analysis calcd (%) for C H NO: C 83.92, H 7.34, N 4.08; found:
C 83.47, H 7.28, N 3.75.
.9 Hz, 1H), 3.35 (q, J 7.5 Hz, 2H), 1.45 ppm (t,J 6.3 Hz, 3H); C NMR
24 25
75, MHz, CDCl
3
): d 138.57, 131.43, 130.92, 129.66, 128.36, 127.51, 127.12,
1
1
26.46, 126.35, 125.72, 125.05, 124.93, 124.75, 124.61, 123.33, 26.56,
6.12 ppm; LRMS m/z (%): 230 [M] ; elemental analysis calcd (%) for
General procedure for the synthesis of alkyl carbamates derived from
1-aminopyrene: To a stirred solution of the alcohol (0.62 mmol) in CHCl3
(3 mL), bis(trichloromethyl) carbonate (0.20 mmol) was added and the
mixture was cooled in an ice bath. Pyridine (0.62 mmol) was added slowly
over a period of 5 min. After 2 h, a solution of 1-aminopyrene (0.6 mmol)
C
18
H
14: C 93.87, H 6.13; found: C 94.12, H 6.22.
1
-Tetradecyl-1-pyrenyl ether (8): In a 5-mL round-bottomed flask fitted
with a reflux condenser, 1-pyrenol (0.021 g, 0.095 mmol) and 1-tetradecyl-
bromide (28 mL, 0.094 mmol) in dry acetone (1.0 mL) were placed under an
Ar atmosphere and K CO (0.014 g, 0.10 mmol) was added. The reaction
2 3
and pyridine (0.7mmol) in CHCl
0 min. After 1 h, the reaction mixture was diluted with CHCl
washed with 1n HCl, water, aqueous NaHCO , and dried over anhydrous
Na SO . The crude product was chromatographed on a silica gel column
50% CHCl /hexanes).
3
(2 mL) was added over a period of
1
3
(5 mL) and
mixture was refluxed for 7.5 h. The solvent was removed in vacuo, extracted
with EtOAc (4 mL), washed with brine, and then the solvent was removed
in vacuo. The crude product was purified by column chromatography on
silica gel (1.0 cm  14 cm, hexane) to give 8 (21 mg; 54%). M.p. 74 ± 758C;
3
2
4
(
3
Pyren-1-yl-carbamic acid hexadecyl ester (11a): 1-Hexadecanol (0.150 mg)
was converted to the carbamate in 83% yield; m.p. 113 ± 1148C; UV/Vis
(0.5% CHCl
UV/Vis (1% CHCl
3
/EtOH v/v): lmax (loge) 382.5 (3.96), 363 (4.14), 351
(
4.40), 346 (4.42), 337(4.33), 2 77. 5 (4.61), 267(4.31), 241.5 nm (4. 78 ); IR
3
/CH
3
CN): lmax (loge) 383 (3.26), 340 (4.44), 277(4.51), 269
1930
¹ 2003 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.chemeurj.org Chem. Eur. J. 2003, 9, 1922 ± 1932