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weighed (28 mg, 96%). NMR (CDCl
3
): d 9.48 (dd, J ¼ 8.1, 1.1 Hz, Hz, 2H), 3.63 (t, 2H), 3.36 (t, J ¼ 5.3 Hz, 2H), 3.22 (m, 8H), 3.06 (s,
+
1
H), 8.98 (dd, J ¼ 2.4, 0.5 Hz, 1H), 8.82 (dd, J ¼ 9.4, 0.5 Hz, 1H), 12H), 1.08 (t, J ¼ 7.1 Hz, 12H). HRMS-FAB [M + H] (calcd with M
.26 (dd, J ¼ 9.4, 2.4 Hz, 1H), 8.18 (dd, J ¼ 7.6, 1.7 Hz, 1H), 7.69 as C H N O ): 748.4339; found, 748.4349. The product was
8
4
7
53 7 2
(m, 2H), 7.15 (s, 1H), 3.06 (s, 6H), 2.37 (s, 3H). The product was a yellow solid. It was soluble in dimethylformamide and CH Cl
2
2,
a brown solid. It was soluble in dimethylformamide and CH
and insoluble in H O and hexanes.
-Dimethylamino-9-aminobenz(a)acridine, 33. Under H
2
Cl
2
,
and insoluble in H
9-Ethanolamino-3,6-bis(dimethylamino)acridine, 38.
mixture of 5 (63 mg), ethanolamine (78 mg) and CH
2
O and hexanes.
2
A
5
2
,
3
OH (5 mL)
a suspension of 32 (28 mg), Raney Ni (100 mg) and CH
3
OH (15 was heated (reux) for 73 h, and evaporated to dryness by rotary
ꢁ
mL) was stirred for 48 h, ltered, and evaporated to dryness by evaporation (40 C). The solid was washed (aqueous NaOH, 2 N)
ꢁ
rotary evaporation (40 C). The solid was chromatographed until the washings were pH >8, further washed (H O), vacuum
2
ꢁ ꢁ
basic Al O III, CH Cl ), vacuum dried (40 C) and weighed (5 dried (40 C), and weighed (65 mg, 95% based on 5). NMR
2 3 2 2
(
mg, 26%). NMR (CDCl ): d 9.12 (s, 1H), 8.67 (dd, J ¼ 8.1, 1.3 Hz, (CDCl ): d 7.93 (d, J ¼ 9.3 Hz, 2H), 6.95 (s, 2H), 6.93 (d, 2H), 3.85
3
3
1
H), 8.26 (dd, J ¼ 8.1, 1.2 Hz, 1H), 7.86 (d, J ¼ 8.8 Hz, 1H), 7.65 (t, J ¼ 5.1 Hz, 2H), 3.81 (t, J ¼ 4.6 Hz, 2H), 3.05 (s, 12H). The
(
2
m, 2H), 7.45 (s, 1H), 7.28 (d, J ¼ 2.2 Hz, 1H), 7.01 (dd, J ¼ 8.8, product was a yellow solid. It was soluble in dimethylformamide
.2 Hz, 1H), 3.02 (s, 6H). The product was an orange solid. It was and CH
2
Cl
2
, slightly soluble in H
2
O, and insoluble in hexanes.
ꢁ
soluble in dimethylformamide and CH
O and hexanes.
2
Cl
2
, and insoluble in
Ester conjugate of 38 and rhodamine B, 39. At 0 C, a mixture
of 38 (44 mg), 4-dimethylaminopyridine (3 mg), N,N-diisopro-
H
2
5
,9-Bis(dimethylamino)benz(a)acridine, 34. A solution of pylcarbodiimide (15 mg) and CH Cl (5 mL) was treated slowly
2 2
aqueous formaldehyde (37%, 56 mg) and sulfuric acid (6%, with rhodamine B (30 mg), stirred for 96 h, and evaporated to
ꢁ
0
.032 mL) was treated with a suspension of 33 (5 mg), NaBH (8 dryness by rotary evaporation (40 C). The solid was chroma-
4
mg) and tetrahydrofuran (2 mL), treated with aqueous NaOH (2 tographed (silica gel, CH
N) until the pH was >9 and extracted with ether (20 mL). The dried (40 C) and weighed (16 mg, 22%). UV-vis (CH
extract was evaporated to dryness by rotary evaporation (room nm (log 3): 418, 556 (4.0, 4.4). NMR (CDCl
2
Cl
2
–CH
3
OH solution, 10 : 1), vacuum
OH) lmax
): d 8.25 (d, J ¼ 9.8 Hz,
2H), 8.16 (d, J ¼ 8.4 Hz, 1H), 7.70 (d, J ¼ 3.5 Hz, 2H), 7.26 (s, 2H),
ꢁ
3
,
3
temperature), and the solid was chromatographed (basic Al
2
O
3
ꢁ
III, CH
2
Cl
2
), vacuum dried (40 C) and weighed (2.8 mg, 45%). 7.16 (d, J ¼ 8.7 Hz, 1H), 6.95 (d, J ¼ 9.4 Hz, 2H), 6.69 (m, 4H),
UV-vis (CH OH) l , nm (log 3): 495 (3.8). NMR (CDCl ): d 9.11 6.47 (d, J ¼ 2.1 Hz, 2H), 4.58 (t, 2H), 4.08 (t, 2H), 3.57 (m, 8H),
3
max
3
+
(
1
¼
s, 1H), 8.67 (dd, J ¼ 8.1, 1.3 Hz, 1H), 8.26 (dd, J ¼ 8.2, 1.3 Hz, 3.13 (s, 12H), 1.26 (t, J ¼ 7.1 Hz, 12H). HRMS-FAB [M + H] (calcd
H), 7.89 (d, J ¼ 9.1 Hz, 1H), 7.64 (m, 2H), 7.45 (s, 1H), 7.24 (d, J with M as C H N O ): 750.4257; found, 750.4243. The product
4
7
53 6 3
2 2
6.6 Hz, 1H), 7.20 (s, 1H), 3.18 (s, 6H), 3.01 (s, 6H). HRMS-FAB was a red solid. It was soluble in dimethylformamide, CH Cl
+
[
M + H] (calcd with M as C21
H
21
N
3
): 316.1814; found, and H
2
O, and insoluble in hexanes.
316.1805. The product was a yellow solid. It was soluble in
NAO, 3,6-bis(dimethylamino)-10-nonylacridinium bromide
dimethylformamide and CH
hexanes.
2
Cl
2
, and insoluble in H
2
O and (acridine orange 10-nonyl bromide), 40. A mixture of acridine
orange (69 mg, 0.26 mmol), 1-bromononane (0.99 g, 4.8 mmol)
Rhodamine B, 35. 35 was purchased from Sigma-Aldrich.
and toluene (5 mL) was heated (reux) for 4 h and evaporated
0
0
ꢁ
2
-Aminoethyl-3 ,6 -bis(dimethylamino)-spiro[1H-isoindole- nearly to dryness by rotary evaporation (40 C). The wet solid
0
1
,9 -[9H]xanthen]-3(2H)-one, 36. In a sealed pressure tube, was chromatographed (basic Al O III, CH Cl –ethanol solu-
2
3
2
2
ꢁ
a mixture of 35 (311 mg) and ethylenediamine (2.10 g) was tion, 80 : 1), washed (ether), vacuum dried (40 C) and weighed
stirred at room temperature for 24 h, diluted with CH Cl (20 (81 mg, 65%). UV-vis (CH OH) lmax, nm (log 3): 495 (5.1). NMR
): d 8.80 (s, 1H), 7.96 (d, J ¼ 9.5 Hz, 2H), 7.05 (dd, J ¼ 9.3,
2
2
3
mL) and ltered. The ltrate was evaporated to dryness by rotary (CDCl
3
ꢁ
evaporation (room temperature), vacuum dried (40 C), and 2.1 Hz, 2H), 6.62 (d, J ¼ 2.0 Hz, 2H), 4.83 (t, J ¼ 9.0, 7.7 Hz, 2H),
weighed (300 mg, 85%). NMR (CDCl
3
): d 7.90 (dd, J ¼ 6.0, 2.9 Hz, 3.34 (s, 12H), 1.95 (m, 2H), 1.62 (m, 2H), 1.40 (m, 2H), 1.26 (m,
H), 7.44 (dd, J ¼ 5.6, 3.1 Hz, 2H), 7.09 (dd, J ¼ 5.6, 2.6 Hz, 1H), 8H), 0.86 (t, J ¼ 7.2, 7.2 Hz, 3H). The product was a brown solid.
.43 (d, J ¼ 8.8 Hz, 2H), 6.37 (d, J ¼ 2.6 Hz, 2H), 6.27 (dd, J ¼ 8.9, It was soluble in dimethylformamide and CH Cl , slightly
1
6
2
2
2
.6 Hz, 2H), 3.33 (q, J ¼ 7.1 Hz, 8H), 3.18 (t, J ¼ 6.7 Hz, 2H), 2.40 soluble in H O, and insoluble in hexanes.
2
(
t, J ¼ 6.7 Hz, 2H), 1.16 (t, J ¼ 7.1 Hz, 12H). The product was
9-Methylmercapto-3,6-bis(dimethylamino)-10-hexylacridinium
, and insoluble in dime- bromide(9-methylmercaptoacridine orange 10-hexyl bromide),
41. A mixture of acridine 3 (133 mg, 0.427 mmol), 1-bromohexane
2 2
a pink solid. It was soluble in CH Cl
2
thylformamide, H O and hexanes.
3
Lactam conjugate of 36 and acridine, 37. A solution of 5 (31 (1.20 g, 7.27 mmol) and CHCl (3 mL) was heated (reux) for 10
mg) and lactam 36 (54 mg) and 2-butanol (5 mL) was heated days and evaporated nearly to dryness by rotary evaporation (40
ꢁ
(
reux) for 6.5 h, and evaporated to dryness by rotary evapora-
C). The product was chromatographed (basic Al O III, CH Cl –
2 3 2 2
ꢁ
tion (40 C). The solid was chromatographed (silica gel, CH Cl – ethanol solution, 30 : 1), and the solid obtained was washed
CH OH solution, 10 : 1), washed with aqueous NaOH (2 N), (ether), vacuum dried (40 C), and weighed (49 mg, 23%). UV-vis
2
2
ꢁ
3
ꢁ
ltered, vacuum dried (40 C) and weighed (38 mg, 50% based (CH
3
OH) lmax, nm (log 3): 523 (4.8). NMR (CDCl
): 9.7 Hz, 2H), 7.19 (dd, J ¼ 9.7, 5.0 Hz, 2H), 6.68 (d, J ¼ 2.1 Hz, 2H),
d 8.00 (m, 1H), 7.84 (d, J ¼ 9.5 Hz, 2H), 7.44 (m, 2H), 7.06 (m, 4.88 (t, J ¼ 9.2, 8.0 Hz, 2H), 3.38 (s, 12H), 2.52 (s, 3H), 1.99 (m, 2H),
3
):d 8.58 (d, J ¼
3 3
on 5). UV-vis (CH OH) lmax, nm (log 3): 424 (4.5). NMR (CDCl
1
(
H), 6.91 (d, J ¼ 2.6 Hz, 2H), 6.83 (dd, J ¼ 9.5, 2.7 Hz, 2H), 6.31 1.70 (m, 2H), 1.40 (m, 4H), 0.91 (t, J ¼ 7.8, 7.2 Hz, 3H). HRMS-FAB
+
d, J ¼ 2.6 Hz, 2H), 6.25 (d, J ¼ 8.9 Hz, 2H), 5.90 (dd, J ¼ 8.9, 2.6 [M ꢂ Br] (calcd with M as C24
34 3
H N SBr): 396.2473; found,
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RSC Adv., 2016, 6, 29391–29403 | 29395