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DOI: 10.1055/s-0029-1218535
Novel Rhodamine Dyes via Suzuki Coupling of Xanthone Triflates with Arylboroxins
Publikationsverlauf
Publikationsdatum:
02. Dezember 2009 (online)
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Abstract
Novel rhodamine dyes were prepared from xanthone precursors in a ‘one-pot’ procedure via reaction of the xanthone with trifluoromethanesulfonic anhydride followed by Pd-mediated Suzuki coupling between the xanthone triflate and an arylboroxin. Rhodamines with 9-(3- or 4-carboxyphenyl) and 9-(3-nitrophenyl) substituents were prepared by this procedure. The procedure also works well with thio- and selenoxanthones, but not with telluroxanthones.
Key words
Suzuki coupling - arylations - palladium - rhodamine dyes - arylboroxins
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References and Notes
Trifluoromethanesulfonic anhydride
(61.7 µL, 0.367 mmol, 1.1 equiv) was added to 3,6-dimethylaminoxanth-9-one 1-E (1.0 equiv 0.334 mmol) in MeCN (15
mL). The resulting solution was stirred for 20 min at ambient temperature. PdCl2(PPh3)2 (23
mg, 0.033 mmol, 0.1 equiv), Na2CO3 (106 mg,
1.00 mmol, 3.0 equiv), and arylboroxin 4 (0.334
mmol, 1.0 equiv) were added, and the temperature was increased to 55 ˚C.
The reaction was monitored by visible spectroscopy for the appearance
of the dye chromophore and disappear-ance of the chromophore of
triflate 2-E (20 min for 7-S to
4.5
h for 8-S). The reaction mixture was cooled
to ambient temperature, and H2O (15 mL) was added. The
dye was extracted with CH2Cl2 (5 × 20
mL), and the combined extracts were concentrated onto SiO2 and
dry loaded onto
a column of SiO2. A gradient
elution system (10% Et2O-CH2Cl2,
40% Et2O-CH2Cl2,
5% MeOH-CH2Cl2, and 10% MeOH-CH2Cl2)
separated recovered starting material from rhodamine/rosamine
dye isolated as a mixture of triflate and boronate salts. The dye
was dissolved in AcOH (3 mL), and 30% HPF6 or
concentrated HCl was added dropwise until the characteristic color
of the rhodamine/rosamine faded. The reaction mixture was
poured into stirring ice H2O, and the dye was collected
by filtration. The ion exchange was repeated for a total of 3 times.
The success of the ion exchange was confirmed by elemental analysis
(±0.4% in C, H, N).
Analytical Data
for 8-O
Mp >260 ˚C. ¹H
NMR (500 MHz, CD2Cl2): δ = 8.35
(d, 2 H, J = 8.0
Hz), 7.47 (d, 2 H, J = 8.0
Hz), 7.41 (d, 2 H, J = 9.5 Hz),
6.96 (dd, 2 H, J = 2.0,
9.5 Hz), 6.82 (d, 2 H, J = 2.0
Hz), 3.31 (s, 12 H). ¹³C NMR (75.5
MHz, CD3OD): δ = 168.7, 159.2, 159.0,
158.1, 137.9, 133.8, 132.5, 131.1, 131.0, 115.8, 114.3, 97.7, 41.0.
UV/vis: λmax (CH2Cl2) = 568
nm (ε 1.10˙105 M-¹ cm-¹).
ESI-HRMS: m/z calcd for C24H23N2O3
+: 387.1703;
found: 387.1720.
Analytical Data for
8-S
Mp >260 ˚C. ¹H
NMR (500 MHz, CD3OD): δ = 8.17 (d,
2 H, J = 7.0
Hz), 7.36 (d, 2 H, J = 7.0
Hz), 7.28 (d, 2 H, J = 9.5 Hz),
7.24 (d, 2 H, J = 2.5
Hz), 7.01 (dd, 2 H, J = 2.5,
9.5 Hz), 3.19 (s, 12 H). ¹³C NMR (75.5
MHz, CD3OD): δ = 160.3, 154.2, 144.9,
139.3, 136.9, 130.5 (br, 2 C), 129.7, 119.4, 115.9, 106.0, 40.8.
UV/vis: λmax (MeOH) = 582
nm (ε 7.91˙104 M-¹ cm-¹).
ESI-HRMS: m/z calcd for C24H23N2O2S+:
403.1475; found: 403.1468.
Analytical
Data for 9-O
Mp >260 ˚C. ¹H
NMR (500 MHz, CD3OD): δ = 8.24 (d,
1 H, J = 8.0
Hz), 8.00 (s, 1 H), 7.72 (t, 1 H, J = 7.5
Hz), 7.62 (d, 1 H, J = 7.5
Hz), 7.26 (d, 2 H, J = 9.0
Hz), 7.03 (dd, 2 H, J = 2.0,
9.0 Hz), 6.91 (d, 2 H, J = 2.0
Hz), 3.23 (s, 12 H). ¹³C NMR (75.5
MHz, CD2Cl2/CD3OD): δ = 168.4,
159.0, 158.6, 158.0, 134.5, 133.4, 132.3, 132.2, 131.4, 131.2, 130.1, 115.4,
114.4, 97.5, 41.0. UV/vis: λmax (MeOH) = 562
nm (ε 1.03˙106 M-¹ cm-¹).
ESI-HRMS: m/z calcd for C24H23N2O3
+: 387.1703;
found: 387.1704.
Analytical Data for
9-S
¹H NMR (500 MHz, CD3CO2D/CD2Cl2): δ = 8.31
(d, 1 H, J = 7.5
Hz), 8.02 (s, 1 H), 7.74 (t, 1 H, J = 7.5
Hz), 7.60 (d, 1 H, J = 7.5
Hz), 7.32 (d, 2 H, J = 9.5
Hz), 7.20 (d, 2 H, J = 2.0
Hz), 6.95 (dd, 2 H, J = 2.0,
9.5 Hz), 3.25 (s, 12 H). ¹³C NMR (75.5
MHz, CD3OD): δ = 160.6, 154.7, 145.4, 137.2,
136.5, 132.9, 131.4, 131.2, 129.5, 119.9, 116.3, 106.5, 40.8. UV/vis: λmax (MeOH) = 579
nm (ε 7.26˙104
M-¹ cm-¹).
ESI-HRMS: m/z calcd for C24H23N2O2S+: 403.1475;
found: 403.1467.
Analytical Data for
10-O
¹H NMR (500 MHz, CD2Cl2): δ = 8.53
(dd, 1 H, J = 2.0,
8.0 Hz), 8.28 (t, 1 H, J = 2.0
Hz), 7.91 (t, 1 H, J = 8.0
Hz), 7.81 (d, 1 H, J = 8.0
Hz), 7.27 (d, 2 H, J = 9.0
Hz), 6.98 (dd, 2 H, J = 2.0,
9.0 Hz), 6.88 (d, 2 H, J = 2.0
Hz), 3.32 (s, 12 H). ¹³C NMR (75.5
MHz, CD2Cl2): δ = 158.1,
157.8, 154.8, 148.7, 135.9, 131.4, 131.0, 125.4, 124.6, 115.1, 113.7,
97.2, 41.3. UV/vis: λmax (CH2Cl2) = 574
nm (ε 6.77˙104 M-¹ cm-¹).
ESI-HRMS: m/z calcd for C23H22N3O3
+:
388.1656; found: 388.1660.
Analytical
Data for 10-S
Mp >260 ˚C. ¹H
NMR (500 MHz, CD2Cl2): δ = 8.50
(dt, 1 H, J = 1.0,
8.0 Hz), 8.20 (s, 1 H), 7.90 (t, 1 H, J = 8.0
Hz), 7.73 (d, 1 H, J = 8.0
Hz), 7.28 (d, 2 H, J = 9.0
Hz), 7.17 (d, 2 H, J = 2.0
Hz), 6.97 (dd, 2 H, J = 2.0,
9.0 Hz), 3.29 (s, 12 H). ¹³C NMR (75.5
MHz, CD2Cl2): δ = 156.5,
153.9, 148.6, 144.7, 137.5, 136.0, 135.8, 130.8, 124.7, 124.4, 119.0, 116.1,
106.2, 41.0. UV/vis: λmax (CH2Cl2) = 593
nm
(ε 1.02˙105 M-¹ cm-¹).
ESI-HRMS: m/z calcd for C23H22N3O2S+:
404.1427; found: 404.1420.