10
S. van der Wal et al. / Dyes and Pigments 132 (2016) 7e19
found 1397.75; [M þ 2H]2þ calculated 350.12, found 350.29.
(t, 2H) (CH2CH2COOH), 4.39 (t, 4H, 2 CH2CH2CH2SO3), 6.42 and 7.26
(2d, 2 ꢀ 2H, 2 ꢀ 2 vinylic CH), 7.21 and 7.54 (2 d, 2 ꢀ 2H,
PhCH2CH2COOH), 7.44 (t, 2H), 7.58e7.63 (m, 2H), 7.76 (d, 2H),
7.99e8.03 (m, 4H) and 8.08 (d, 2H) (6 ꢀ CH benz[e]indolenine).
2.2.7. 2-((E)-2-((E)-2-chloro-3-(2-((E)-1,3,3-trimethyl-5-
sulfonatoindolin-2-ylidene)ethylidene)cyclohex-1-en-1-yl)vinyl)-
1,3,3-trimethyl-3H-indol-1-ium-5-sulfonate (8)
13C NMR (DMSO-d6, 150 MHz)
d
¼ 21.12, 23.59, 24.23, 25.44,
Compound 4 (99 mg, 0.24 mmol), compound 1 (42 mg,
0.118 mmol) and sodium acetate (29 mg, 0.354 mmol) were dis-
solved in EtOH (10 mL). The mixture was refluxed for 11 h. After
cooling of the mixture, it was added dropwise to 80 mL of Et2O to
precipitate the product. The green suspension was centrifuged
(5 min, 4500 rpm, 2 tubes) and decanted. To every tube 40 mL of
Et2O was added and the pellets were resuspended. Tubes were
centrifuged (5 min, 4500 rpm) and decanted. The product was
dried overnight in a desiccator yielding a black solid in quantitative
yield. MS: [M þ H]þ calculated 643.17, found 643.17.
26.60, 30.37, 36.41, 40.06, 42.64, 47.84, 49.89, 99.92, 111.56, 122.12,
124.51, 127.45, 127.55, 128.64, 129.11, 129.83, 130.25, 131.16, 132.70,
136.49, 138.44, 139.85, 141.22, 146.50, 161.12, 172.43, 173.62.
2.2.10. 3-((E)-2-((E)-2-(40-(2-carboxyethyl)-6-((E)-2-(3,3-
dimethyl-1-(3-sulfonatopropyl)-3H-indol-1-ium-2-yl)vinyl)-4,5-
dihydro-[1,10-biphenyl]-2(3H)-ylidene)ethylidene)-3,3-
dimethylindolin-1-yl)propane-1-sulfonate (11)
Compound 7 (82 mg, 0.12 mmol) and 4-(2-carboxyethyl)ben-
zeneboronic acid (39 mg, 0.20 mmol) were dissolved in dioxane
(2 mL) and H2O (2 mL). Et3N (84 mL, 0.60 mmol) was added and the
2.2.8. 2-((E)-2-((E)-2-chloro-3-(2-((E)-3,3-dimethyl-5-sulfonato-
1-(3-sulfonatopropyl)indolin-2-ylidene)ethylidene)cyclohex-1-en-
1-yl)vinyl)-3,3-dimethyl-1-(3-sulfonatopropyl)-3H-indol-1-ium-5-
sulfonate (9)
Compound 5 (1.00 g, 2.0 mmol), compound 1 (359 mg,
1.0 mmol) and sodium acetate (246 mg, 3.0 mmol) were dissolved
in EtOH (100 mL). The mixture was refluxed for 117 h. After cooling
of the mixture, it was added dropwise to 400 mL of EtOAc to pre-
cipitate the product. The suspension was filtered and the product
was washed on the filter with EtOAc. The product was dried over-
night in a desiccator yielding a purple/blue solid in quantitative
yield. MS: [M þ H]þ calculated 859.15, found 859.08.
solution was stirred under nitrogen. Pd(PPh3)4 (5 mg) was added
under a nitrogen atmosphere and the mixture was stirred at 90 ꢁC
for 2.5 h. The solution was added dropwise to 40 mL of EtOAc/EtOH/
formic acid (400:100:0.5) and the product precipitated. The sus-
pension was centrifuged in a plastic tube (5 min, 4500 rpm) and
decanted. The product was dried overnight in a desiccator yielding
a green solid.
The crude product was dissolved in DMSO (1 mL), H2O/CH3CN/
TFA (75:25:0.1) (0.5 mL), CH3CN (0.5 mL) and 1 M KCl (2 mL) to
obtain potassium counterions of the sulfonate groups. The dis-
solved product was purified by preparative HPLC using a gradient of
H2O/CH3CN/TFA 80:20:0.1 to H2O/CH3CN/TFA 50:50:0.1 in 30 min.
After pooling and lyophilization of the appropriate fractions the
product was obtained as a green fluffy solid. MS: [M þ H]þ calcu-
lated 813.32, found 813.19; [M þ 2H]2þ calculated 407.17, found
406.75.
2.2.9. 3-(2-((E)-2-((E)-40-(2-carboxyethyl)-6-((E)-2-(1,1-dimethyl-
3-(3-sulfonatopropyl)-1,3-dihydro-2H-benzo[e]indol-2-ylidene)
ethylidene)-3,4,5,6-tetrahydro-[1,10-biphenyl]-2-yl)vinyl)-1,1-
dimethyl-1H-benzo[e]indol-3-ium-3-yl)propane-1-sulfonate (10)
Compound 6 (1.00 g, 1.25 mmol) and 4-(2-carboxyethyl)ben-
zeneboronic acid (291 mg, 1.5 mmol) were dissolved in dioxane
HRMS: [M ꢂ H]ꢂ calculated 811.30923 for C45H51N2O8S2, found
811.31005.
The dye (4.76 mg) was dissolved in 4 mM ethylene carbonate
(20 mL) and H2O (15 mL). Et3N (700
solution was stirred under nitrogen. Pd(PPh3)4 (30 mg) was added
under a nitrogen atmosphere and the mixture was stirred at 90 ꢁ
m
L, 5 mmol) was added and the
(internal standard for NMR) in DMSO-d6 (1398
solution, which was used for NMR and as a stock solution.
1H NMR (DMSO-d6, 300 MHz)
(m, 6H, 1 CH2 cyclohexene, 2 CH2CH2CH2SO3), 2.54 (t, 4H, 2
CH2CH2CH2SO3), 2.66e2.70 (m, 4H, 2 CH2 cyclohexene), 2.66e2.70
mL) to afford a 4 mM
C
d
¼ 1.10 (s, 12H, 4 CH3), 1.94e1.98
for 2.5 h. The solution was added dropwise to 160 mL of EtOAc/
EtOH/formic acid (400:100:0.5) and the product precipitated. The
suspension was centrifuged in 4 50 mL plastic tubes (5 min,
4500 rpm) and decanted. To every tube 30 mL of EtOAc/EtOH/for-
mic acid (400:100:0.5) was added and the pellets were resus-
pended. Tubes were centrifuged (5 min, 4500 rpm) and decanted.
To every tube 10 mL EtOH was added to dissolve the product and
then 40 mL of EtOAc was added to each tube and the product
precipitated. Tubes were centrifuged (5 min, 4500 rpm), decanted
and the product was dried overnight in a desiccator yielding
570 mg (0.62 mmol, 50%) of a green solid.
The crude product (50 mg) was dissolved in DMSO (3 mL), H2O/
CH3CN/TFA (75:25:0.1) (0.5 mL) and 1 M KCl (1 mL) to obtain po-
tassium counterions of the sulfonate groups. The dissolved product
was purified by preparative HPLC using a gradient of H2O/CH3CN/
TFA 70:30:0.1 to H2O/CH3CN/TFA 50:50:0.1 in 28 min. After pooling
and lyophilization of the appropriate fractions the product was
obtained as a green fluffy solid. MS: [M þ H]þ calculated 913.36,
found 913.23; [M þ 2H]2þ calculated 457.18, found 456.69.
HRMS: [M ꢂ H]ꢂ calculated 911.34053 for C53H55N2O8S2, found
911.34117.
(m, 2H) and 2.98 (t, 2H) (CH2CH2COOH), 4.25 (t, 4H,
2
CH2CH2CH2SO3), 6.37 and 7.11e7.17 (d and m, 2 ꢀ 2H, 2 ꢀ 2 vinylic
CH), 7.11e7.17 and 7.31e7.49 (2m, 12H, Ar).
13C NMR (DMSO-d6, 150 MHz)
30.13, 35.71, 40.06, 42.45, 47.86, 48.13, 100.28, 110.96, 122.28,
124.35, 128.41, 128.55, 129.04, 131.10, 136.40, 140.69, 141.02, 142.18,
147.51, 161.65, 171.20, 173.50.
d
¼ 21.03, 23.31, 24.17, 27.09,
2.2.11. 2-((E)-2-((E)-40-(2-carboxyethyl)-6-(2-((E)-1,3,3-trimethyl-
5-sulfonatoindolin-2-ylidene)ethylidene)-3,4,5,6-tetrahydro-[1,10-
biphenyl]-2-yl)vinyl)-1,3,3-trimethyl-3H-indol-1-ium-5-sulfonate
(12)
Compound 8 (97 mg, 0.15 mmol) and 4-(2-carboxyethyl)ben-
zeneboronic acid (50 mg, 0.30 mmol) were dissolved in dioxane
(2 mL) and H2O (2 mL). Et3N (146 mL, 1.05 mmol) was added and the
solution was stirred under nitrogen. Pd(PPh3)4 (5 mg) was added
under a nitrogen atmosphere and the mixture was stirred at 90 ꢁC
for 2.5 h. The solution was added dropwise to 80 mL of EtOAc/EtOH/
formic acid (175:25:0.1) and the product precipitated. The sus-
pension was centrifuged in 2 50 mL plastic tubes (5 min, 4500 rpm)
and decanted. To every tube 5 mL EtOH was added to dissolve the
product and then 20 mL of EtOAc was added to each tube and the
product precipitated. Tubes were centrifuged (5 min, 4500 rpm),
decanted and the product was dried overnight in a desiccator
yielding 57 mg (0.075 mmol, 50%) of a brown solid.
The dye (5.14 mg) was dissolved in 4 mM ethylene carbonate
(internal standard for NMR) in DMSO-d6 (1350
solution, which was used for NMR and as a stock solution. 1H NMR
(DMSO-d6, 300 MHz)
mL) to afford a 4 mM
d
¼ 1.42 (s, 12H, 4 CH3), 1.90e2.10 (m, 6H, 1
CH2 cyclohexene, 2 CH2CH2CH2SO3), 2.56 (t, 4H, 2 CH2CH2CH2SO3),
2.76e2.80 (m, 4H, 2 CH2 cyclohexene), 2.76e2.80 (m, 2H) and 3.10