Y. Yamamoto et al. / Tetrahedron xxx (2017) 1e6
5
1365 (m), 1330 (m), 1253 (m), 1215 (m) cmꢁ1
500 MHz):
(s, 2H), 9.01 (s, 2H), 9.44 (s, 2H), 9.44 (s, 2H); 13C NMR (CDCl3,
125 MHz): 31.72, 31.98, 35.81, 35.92, 123.13, 124.16, 124.23, 127.42,
;
1H NMR (CDCl3,
Table 2
The results of TD-DFT calculations of 7, 8, 10a and 11a.
d
1.60 (s, 18H), 1.64 (s, 18H), 7.14 (s, 2H), 8.00 (s, 2H), 8.01
Absorption/nm
(Oscillator strength: f) (ratios of contribution)
Assignments
HOMO (eV) LUMO (eV)
d
129.05, 129.38, 132.02, 134.22, 134.34, 139.01, 140.42, 141.16, 150.50,
151.85, 187,48; HRMS (FAB, NBA) m/z calcd. for C46H46O2 [M]þ
630.3498, found: 630.3499.
7
8
482 (0.12)
439 (0.0016)
415 (0.45)
344 (0.00)
HOMO /LUMO (68%)
HOMO/LUMOþ1 (68%)
HOMO/LUMO (70%)
HOMOe1/LUMO (50%)
ꢁ5.19
ꢁ5.12
ꢁ2.18
ꢁ1.86
ꢁ1.87
ꢁ2.96
10a 408 (0.053)
398 (0.0009)
11a 495 (0.022)
493 (0.020)
HOMO / LUMO (61%) ꢁ5.47
4.2.3. Reaction of 1a and p-benzoquinone
HOMOe1/LUMO (68%)
HOMOe1/LUMO (69%) ꢁ6.00
HOMO/LUMO (69%)
A solution of 1a (166 mg, 0.50 mmol) and p-benzoquinone
(435 mg, 4.0 mmol) in 10 mL of nitrobenzene was stirred at 200 ꢀC
for 2 days. The reaction mixture was cooled to rt. After removing
the solvent in a vacuum, the resulting solid was dissolved in ethyl
acetate. After removing insoluble material by filtration and the
solvent by evaporator, resulting crude products were purified by
silica gel column chromatography (hexane: chloroform ¼ 1:1) to
give 10a (40 mg, 0.13 mmol) in 25% yield.
trichloroacetic acid (196 mg, 1.2 mmol) in 15 mL of DME was stirred
in an ice bath. Isoamyl nitrite (3 mL, 20.6 mmol) was added to the
solution, and the reaction mixture was allowed to warm at rt. After
stirring 0.5 h at rt, the resulting white solid (o-benzenediazonium
carboxylate 12) was filtered off, and washed with DME. A suspen-
sion of 12 and 1a (86.3 mg, 0.26 mmol) in DME was heated at reflux
for 1 day. The reaction mixture was cooled to rt. After removing the
solvent, the crude products were purified by silica gel column
chromatography (hexane:toluene ¼ 7:3) to give the mixture of 7
and 8. These compounds were separated by gel permeation chro-
matography (CHCl3) to give 7 (45.7 mg, 0.12 mmol) as pale orange
solids in 47% yield and 8 (13.5 mg, 0.03 mmol) as pale yellow solids
10a; Mp 240.0e240.5 ꢀC; IR (KBr):
2345 (w), 2359 (m), 1438 (m), 1421 (m), 1261 (m), 1096 (m), 802 (s),
759 (s); 1H NMR (CDCl3, 500 MHz):
y
/cmꢁ1 3040 (w), 2925 (w),
d
7.69 (dd, J ¼ 6.9, 8.1 Hz, 2H),
7.80 (dd, J ¼ 7.1, 8.1 Hz, 2H), 7.89 (d, J ¼ 8.1 Hz, 2H), 7.94 (d,
J ¼ 8.1 Hz, 2H), 7.99 (s, 2H), 8.01 (d, J ¼ 6.9 Hz, 2H), 8.65 (d, J ¼ 7.1 Hz,
2H); 13C NMR (CDCl3, 125 MHz):
d 119.52, 120.30, 123.98, 126.63,
126.97, 127.96, 127.99, 130.16, 133.16, 135.27, 13þ7.17, 137.34, 140.22;
HRMS (FAB, NBA) m/z calcd. for C26H14 [M]
326.1096, found:
in 11% yield. 7; Mp 280.0e281.0 ꢀC; IR (KBr)
1441 (w), 1417 (m), 1257 (m), 1150 (m), 1128 (m), 957 (m), 921 (m),
881 (m), 734 (s) cmꢁ1; 1H NMR (CDCl3, 500 MHz):
7.60e7.62 (m,
y 3065 (w), 3008 (w),
326.1092.
d
4.3. X-ray crystallography
JAA'xx’, 2H), 7.73e7.78 (m, 4H), 7.91 (d, J ¼ 8.1 Hz, 2H), 7.93 (d,
J ¼ 8.1 Hz, 2H), 8.53 (d, J ¼ 7.1 Hz, 2H), 8.75 (d, J ¼ 7.1 Hz, 2H),
Single crystals of 8 and 11b suitable for X-ray analysis were
obtained by slow evaporation from a toluene solution. X-ray
diffraction data were collected on a Rigaku Rapid Auto diffrac-
8.89e8.87 (m, JAA'xx’, 2H); 13C NMR (CDCl3, 125 MHz):
d 124.21,
124.67, 125.33, 126.41, 127.08, 127.62, 127.73, 128.11, 129.83, 130.68,
132.62, 134.36, 135.60, 137.21, 137.98; HRMS (FAB, NBA) m/z calcd.
for C30H16 [M] þ 376.1252, found: 376.1246.
tometer with graphite-monochromated MoK
a
(l
¼ 0.71070 Å) ra-
diation, and scans to a maximum 2
F
u
q
value of 55.0ꢀ. The
8; Mp > 300 ꢀC; IR (KBr)
y
3065 (w), 3008 (w), 1441 (w), 1417
(m), 1257 (m), 1150 (m), 1128 (m), 957 (m), 921 (m), 881 (w), 734
(s) cmꢁ1 1H NMR (CDCl3, 500 MHz):
6.99e7.01 (m, JAA'xx’, 4H),
structures were solved by a direct method using SIR-2004.15 All
non-hydrogen atoms were refined anisotropically by full-matrix
least-squares on F2 using SHELXL2014.16 Hydrogen atoms of 8 and
11b were positioned geometrically and refined using a riding
model. All calculations were performed using the WinGX program
package.17
;
d
7.30e7.32 (m, JAA'xx’, 4H), 7.70 (dd, J ¼ 7.1, 8.2 Hz, 2H), 7.87 (d,
J ¼ 8.2 Hz, 2H), 7.94 (t, J ¼ 7.1 Hz, 2H), 8.00 (d, J ¼ 7.1 Hz, 4H), 8.09 (d,
J ¼ 6.6 Hz, 2H); 13C NMR (CDCl3, 125 MHz):
d 67.73, 121.30, 122.30,
123.28, 125.01, 125.23, 125.28, 127.79, 128.64, 132.45, 134.97, 137.40,
141.59, 145.56, 146.13; HRMS (FAB, NBA) m/z calcd. for C36H20 [M]þ
452.1565, found: 452.1566.
8: Crystal System ¼ monoclinic, P21/n, a ¼ 13.5571 (14) Å,
b ¼ 8.1842 (8) Å, c ¼ 20.27 (2) Å,
a
¼ 90ꢀ,
b
¼ 92.578ꢀ,
g
¼ 90ꢀ,
V ¼ 2247 (2) Å3, Z ¼ 4, dcalc ¼ 1.338 mg/m3, Total refs. 20850, Unique
refs. 5141, R1 [I > 2
s
(I)] ¼ 0.0524, wR2 (all) ¼ 0.1688.
11b: Crystal System ¼ monoclinic, C2/c, a ¼ 29.1510(17) Å,
b ¼ 17.2488(12) Å, c ¼ 21.2879(13) Å,
a
¼
g
¼ 90ꢀ,
b
¼ 96.515(7)º,
4.2.2. Reaction of 1b and p-benzoquinone
V ¼ 10634.9(12) Å3, Z ¼ 12, dcalc ¼ 1.182 mg/m3, Total refs. 47306,
A solution of 1b (167 mg, 0.30 mmol) and 1,4-benzoquinone
(648 mg, 6.0 mmol) in 10 mL of nitrobenzene was stirred at 200 ꢀC
for 2 days. The reaction mixture was cooled to rt. After removing
the solvent in a vacuum, the resulting solid was dissolved in ethyl
acetate. After removing insoluble material by filtration and evap-
orating the solvent, crude products were purified by silica gel col-
umn chromatography (hexane:toluene ¼ 4:1) to give the mixture of
10b (103 mg, 0.19 mmol, 62%) and 11b (17 mg, 0.027 mmol, 9%),
respectively.
Unique refs. 4056, R1 [I > 2
s
(I)] ¼ 0.0825, wR2 (all) ¼ 0.1832.
Acknowledgments
This study was supported in Japan by Hyogo prefecture and a
JSPS Grant-in-Aid for Scientific Research (C) (JP16K05896 and JSPS
KAKENHI grant No. JP15H00959). We special thank Dr. Akihito
Konishi (Osaka University) for the measurement of HRMS
spectrum.
10b; Mp > 300 ꢀC; IR (KBr):
(m), 2341 (m), 1626 (m), 1476 (m), 1457 (m), 1364 (s), 1250 (m),
1209 (m), 875 (s), 828 (m), 646 (m) cmꢁ1 1H NMR (CDCl3,
500 MHz): 1.53 (s, 18H), 1.64 (s, 18H), 7.83 (s, 2H), 7.88 (s, 2H), 8.01
(s, 2H), 8.07 (s, 2H), 8.80 (s, 2H); 13C NMR (CDCl3, 125 MHz):
31.75,
y 2960 (s), 2904 (m), 2866 (m), 2359
;
Appendix A. Supplementary data
d
d
Supplementary data related to this article can be found at http://
31.95, 35.61, 35.83, 117.64, 119.98, 121.80, 122.08, 122.42, 129.42,
130.46, 135.85, 136.73, 136.82, 140.64, 151.19, 151.45; HRMS (FAB,
NBA) m/z calcd. for C42H46 [M]þ 550.3600, found: 550.3595.
References
11b; Mp > 300 ꢀC; IR (KBr):
y
2954 (s), 2925 (s), 2868 (m), 2362
(m), 2336 (m), 1697 (m), 1662 (m), 1623 (m), 1443 (s), 1394 (m),
Please cite this article in press as: Yamamoto Y, et al., Construction of new fluorophores by Diels-Alder reaction of diacenaphthothiophenes,