V.E. Shershov et al. / Dyes and Pigments 97 (2013) 353e360
355
2.4. General procedure for the synthesis of cyanine dyes (10aed)
and (11aec)
2.4.5. 1-(5-carboxypentyl)-10-ethyl-3,3,30,30-tetramethyl-50-
sulfoindotricarbocyanine (11a)
Yield 35 mg (29%), dark-green powder. MS (MALDI-TOF) m/z:
A solution of indolenine 5, 7aec (for compounds 10aed) or
calcd. for C35H42N2O5S 602.78; found 602.3 [M]þ. 1H NMR (DMSO-
indolenine 7a, d (for compounds 11aec) (0.2 mmol) and gluta-
conaldehyde dianil monohydrochloride 8 (0.25 mmol) in a mix-
ture of acetic anhydride (2 mL) and acetic acid (0.7 mL) was
heated at 118 ꢀC for 3 h. The indolenine 5, 7aec (for compounds
10aed) or indolenine 7b, e (for compounds 11aec) (0.3 mmol),
anhydrous potassium acetate (0.2 g, 2 mmol), acetic anhydride
(2 mL) and acetic acid (1 mL) were added to the reaction mixture,
and heated at 80 ꢀC for an additional 5 h. The solvent was
evaporated, and the cyanine dyes were purified using reversed-
phase (C18) chromatography. The cyanine dye was dissolved in
0.1 M triethylammonium acetate buffer (TEAA), and loaded onto
the column. Elution of the dye was carried out using a linear
gradient from 0.1 M TEAA to 50% acetonitrile in 0.1 M TEAA. The
pure dye obtained as a triethylammonium salt was converted into
its sodium salt in the following fashion: the solution of dye in
Milli-Q water was loaded onto the C18-RP column, washed with
0.1 M NaCl and Milli-Q water, and eluted with an acetonitrilee
Milli-Q water mixture.
d6)
d
: 7.86 (m, 2H,
b
,
b
0-CH), 7.73 (m, 1H,
d
-CH), 7.72, 7.56, 7.31 (3m,
a,a
7H, ArH), 6.55 (m, 2H,
g,
g
0-CH), 6.33 (d, 2H, 0-CH, J 13.5 Hz), 4.14
(m, 4H, CH2CH3, CH2CH2CH2CH2CH2COOH), 1.57 [s, 12H, CH3(3,3),
CH3(3,30)], 2.14, 1.71, 1.52, 1.34 (4m, 8H, CH2CH2CH2CH2CH2COOH),
1.25 (t, 3H, CH2CH3, J 7.0 Hz). Anal. Calcd. for C35H42N2O5S (%): C,
69.74; H, 7.02; N, 4.65. Found: C, 69.51; H, 7.26; N, 4.71.
2.4.6. Sodium salt of 1-(5-carboxypentyl)-10-ethyl-3,3,30,30-
tetramethyl-5,50-disulfoindotricarbocyanine (11b)
Yield 30 mg (21%), dark-green powder. MS (MALDI-TOF) m/z:
calcd. for C35H41N2O8S2ˉ 681.84; found 681.4 [M]þ. 1H NMR (DMSO-
d6)
d
: 7.88 (m, 2H,
b
,
b
0-CH), 7.74 (m, 1H,
0-CH), 6.35 (d, 2H,
a,a
d
-CH), 7.74, 7.63, 7.28 (3m,
6H, ArH), 6.57 (m, 2H,
g
,g
0-CH, J 13.5 Hz), 4.11
(m, 4H, CH2CH3, CH2CH2CH2CH2CH2COOH), 1.63 [s, 12H, CH3(3,3),
CH3(3,30)], 2.16, 1.72, 1.54, 1.38 (4m, 8H, CH2CH2CH2CH2CH2COOH),
1.27 (t, 3H, CH2CH3, J 7.0 Hz). Anal. Calcd. for C35H41N2NaO8S2 (%): C,
59.64; H, 5.86; N, 3.97. Found: C, 59.93; H, 5.98; N, 3.91.
2.4.7. Disodium salt of 1-(5-carboxypenthyl)-3,3,30,30-tetramethyl-
10-(4-sulfonatobuthyl)-5,50-disulfoindotricarbocyanine (11c)
Yield 27 mg (16%), dark-green powder. MS (MALDI-TOF) m/z:
calcd. for C37H44N2O11S32ˉ 788.95; found 788.4 [M]þ. 1H NMR
2.4.1. Trisodium salt of 5,50-disulfo-1,10-di(4-sulfonatobutyl)-
3,3,30,30-tetramethylindotricarbocyanine (10a)
Yield 93 mg (53%), dark-green powder. MS (MALDI-TOF) m/z:
calcd. for C35H41N2O12S43ˉ 809.97; found 810.5 [M]þ. 1H NMR
(DMSO-d6)
6H, ArH), 6.55 (m, 2H,
d
: 7.85 (m, 2H, -CH), 7.18e7.76 (m,
b
,
b
0-CH), 7.78 (m,1H,
d
(DMSO-d6)
7.23e7.63 (m, 6H, ArH), 6.55 (t, 2H,
2H,
0-CH), 4.12 (m, 4H, CH2CH2CH2CH2SO3), 2.56 (m, 4H,
d
: 7.86 (t, 2H,
b,
b
0-CH, J 12.0 Hz), 7.72 (m, 1H,
d-CH),
g,
g
0-CH), 6.33 (d, 2H, 0-CH, J 13.5 Hz), 4.09
a,a
g,g
0-CH, J 12.0 Hz), 6.34 (m,
(m, 4H, CH2CH2CH2CH2SO3, CH2CH2CH2CH2CH2COOH), 2.51, 1.76
(2m, 6H, CH2CH2CH2CH2SO3), 1.65 [s, 12H, CH3(3,3), CH3(3,30)], 2.14,
1.7, 1.51, 1.36 (4m, 8H, CH2CH2CH2CH2CH2COOH). Anal. Calcd. for
C37H44N2Na2O11S3 (%): C, 53.23; H, 5.31; N, 3.36. Found: C, 53.36; H,
5.08; N, 3.28.
a,a
CH2CH2CH2CH2SO3), 1.73 (m, 8H, CH2CH2CH2CH2SO3), 1.61 [s, 12H,
CH3(3,3), CH3(3,30)]. Anal. Calcd. for C35H41N2Na3O12S4 (%): C, 47.83;
H, 4.70; N, 3.19. Found: C, 47.49; H, 4.89; N, 3.28.
2.4.2. Sodium salt of 5,50-disulfo-1,10-di(5-carboxypentyl)-3,3,30,30-
tetramethylindotricarbocyanine (10b)
2.5. General procedure for the synthesis of cyanine dyes (13aec)
Yield 68 mg (43%), dark-green powder. MS (MALDI-TOF) m/z:
A mixture of dye 10b (0.036 mmol), diaminoalkane dihydro-
chloride 12aec (0.18 mmol) and O-(benzotriazol-1-yl)-N,N,N0,N0-
tetramethyluronium hexafluorophosphate (HBTU) (1.8 mmol) was
dissolved in anhydrous DMF (6 mL) in the presence of N,N-diiso-
propylethylamine (DIPEA) (0.45 mL), and stirred at room temper-
ature for 3 h. The mixture was diluted with 0.1 M TEAA (15 mL), and
purified as described for dyes 10aed.
calcd. for C39H47N2O10S2ˉ 767.93; found 767.4 [M]þ. 1H NMR
(DMSO-d6)
7.17e7.52 (m, 6H, ArH), 6.54 (t, 2H,
2H, a,a
0-CH), 4.1 (m, 4H, CH2CH2CH2CH2CH2COOH), 1.63 [s, 12H,
d
: 7.86 (t, 2H,
b
,b
0-CH, J 12.0 Hz), 7.71 (m, 1H,
d-CH),
g,g
0-CH, J 12.0 Hz), 6.32 (m,
CH3(3,3), CH3(3,30)], 2.13, 1.74, 1.52, 1.36 (4m, 16H, CH2CH2CH2
CH2CH2COOH). Anal. Calcd. for C39H47N2NaO10S2 (%): C, 59.22; H,
5.99; N, 3.54. Found: C, 59.48; H, 5.74; N, 3.42.
2.5.1. Sodium salt of 1,10-(7,10-diaza-6,11-diketohexadecane-1,16-
diyl)-3,3,30,30-tetramethyl-5,50-disulfoindotricarbocyanine (13a)
Yield 25 mg (61%), dark-green powder. MS (MALDI-TOF) m/z:
calcd. for C41H51N4O8S2ˉ 792.00; found 793.1 [M]þ. 1H NMR (DMSO-
2.4.3. Sodium salt of 5,50-disulfo-1,10-dibenzyl-3,3,30,30-
tetramethylindotricarbocyanine (10c)
Yield 41 mg (36%), dark-green powder. MS (MALDI-TOF) m/z:
calcd. for C41H39N2O6S2ˉ 719.89; found 720.8 [M]þ. 1H NMR
d6)
d
: 7.85 (m, 2H,
b
,
b
0-CH), 7.71 (m, 1H,
-CH), 7.19e7.57 (m, 6H,
a,a
0-CH), 6.33 (d, 2H, 0-CH, J 13.5 Hz), 4.09 [m,
d
(DMSO-d6)
d
: 7.83 (m, 2H,
b
,
b
0-CH), 7.71 (m, 1H,
d
-CH), 7.83.
ArH), 6.53 (m, 2H,
g
,g
7.68, 7.08 (3m, 6H, ArH), 7.83, 7.21, (2m, 10H, CH2Ph), 6.13 (m,
4H, CH2(1), CH2(16)], 1.6 [s, 12H, CH3(3,3), CH3(3,30)], 3.42, 2.12, 1.71,
1.57, 1.41 [5m, 20H, CH2(2), CH2(3), CH2(4), CH2(5), CH2(8),
CH2(9), CH2(12), CH2(13), CH2(14), CH2(15)]. Anal. Calcd. for
C41H51N4NaO8S2 (%): C, 60.42; H, 6.31; N, 6.87. Found: C, 60.21; H,
6.56; N, 6.75.
2H,
g
,
g
0-CH), 6.08 (d, 2H,
a,a
0-CH, J 13.5 Hz), 5.46 (m, 4H,
CH2Ph), 1.64 [s, 12H, CH3(3,3), CH3(3,30)]. Anal. Calcd. for
C41H39N2NaO6S2 (%): C, 66.29; H, 5.29; N, 3.77. Found: C, 66.64;
H, 5.42; N, 3.68.
2.4.4. Trisodium salt of 5,50-disulfo-1,10-di(4-sulfonatophenyl)-
3,3,30,30-tetramethylindotricarbocyanine (10d)
2.5.2. Sodium salt of 1,10-(7,12-diaza-6,13-diketooktadecane-1,18-
diyl)-3,3,30,30-tetramethyl-5,50-disulfoindotricarbocyanine (13b)
Yield 18 mg (53%), dark-green powder. MS (MALDI-TOF) m/z:
calcd. for C43H55N4O8S2ˉ 820.05; found 821.2 [M]þ. 1H NMR (DMSO-
Yield 53 mg (29%), dark-green powder. MS (MALDI-TOF) m/z:
calcd. for C39H33N2O12S43ˉ 849.95; found 850.3 [M]þ. 1H NMR
(DMSO-d6)
7.03 (3m, 14H, NPh, ArH), 6.49 (m, 2H,
d
: 7.85 (m, 2H,
b
,
b
0-CH), 7.68 (m,1H,
0-CH), 6.31 (d, 2H,
d
-CH), 7.8, 7.56, 7.18,
d6)
d: 7.82 (m, 2H,
b
,b
0-CH), 7.73 (m, 1H,
0-CH, J 13.5 Hz), 4.13 [m, 4H,
d-CH), 7.2e7.6 (m, 6H, ArH),
g,
g
a,
a
0-CH,
6.55 (m, 2H,
g,
g
0-CH), 6.32 (d, 2H,
a,a
J 13.5 Hz), 1.62 [s, 12H, CH3(3,3), CH3(3,30)]. Anal. Calcd. for
C39H33N2Na3O12S4 (%): C, 50.97; H, 3.62; N, 3.05. Found: C, 50.65; H,
3.38; N, 3.13.
CH2(1), CH2(18)], 1.62 [s, 12H, CH3(3,3), CH3(3,30)], 3.46, 2.19, 1.75,
1.58, 1.36 [5m, 24H, CH2(2), CH2(3), CH2(4), CH2(5), CH2(8), CH2(9),
CH2(10), CH2(11), CH2(14), CH2(15), CH2(16), CH2(17)]. Anal. Calcd.