10.1002/ejoc.201900707
European Journal of Organic Chemistry
FULL PAPER
2H), 7.10 (d, J=1.8 Hz, 2H), 6.72 (d, J=9.2 Hz, 2H), 6.22 (d, J=9.2 Hz,
2H), 1.60 (br s, 2H), 1.38 (br s, 6H), 1.26 (br s, 8H), 0.81 (br s, 2H) −0.01
(br s, 2H); 13C NMR (75 MHz, CDCl3) δ 146.44, 133.32, 131.27, 130.68,
130.37, 130.05, 128.00, 127.78, 127.26, 126.93, 125.23, 125.09, 124.58,
124.44, 122.77, 122.31, 122.12, 46.02, 38.26, 30.88, 27.85, 26.35;
LCMS (CI-(+)) m/z (rel. int.) 570 (3), 569 (13), 568 (48), 567 (100,
[M+H]+); HRMS (APPI) calc’d for C44H38 [M]+ 566.2974, found 566.2945.
min a solution of 1,5-bis(7-tert-butylpyren-1-yl)-1,5-pentanedione (40)
(0.540 g, 0.882 mmol) in THF (20 mL) was added. The reaction mixture
was heated at 70 ºC for a further 2 h and then poured without significant
cooling into chloroform (50 mL). The resulting mixture was concentrated
under reduced pressure and adsorbed onto silica gel in preparation for
column chromatography. Aqueous work-up for this reaction is not
recommended as layer separation can be problematic and the yields are
typically lower. The preadsorbed sample was subjected to column
chromatography (20×3.5 cm; 1:9 dichloromethane / hexanes) to yield
1,2-bis(7-tert-butylpyren-1-yl)cyclopentene (41) as a light green oil (0.487
g, 95%): Rf = 0.34 (1:9 dichloromethane / hexanes); 1H NMR (500 MHz,
CDCl3) δ 8.47 (d, J=9.2 Hz, 2H), 8.22 (d, J=1.8 Hz, 2H), 8.18 (d, J=1.8
Hz, 2H), 8.04 (d, J=9.2 Hz, 2H), 7.94 (d, J=8.9 Hz, 2H), 7.87–7.85 (m,
4H), 7.80 (d, J=7.9 Hz, 2H), 3.43 (t, J=7.4 Hz, 4H) 2.57 (quint, J=7.4 Hz,
2H), 1.60 (s, 18H); 13C NMR (125.77 MHz, CDCl3) δ 148.93, 141.49,
134.64, 131.28, 130.92, 130.01, 128.48, 127.19, 127.15, 126.53, 125.55,
125.53, 124.54, 123.26, 122.18, 122.11, 122.09 41.24, 35.32, 32.10,
24.33; LCMS (APCI-positive) m/z (rel. int.) 583 (11), 582 (49), 581 (100,
[M+H]+); HRMS (EI) calc’d for C45H40 [M]+ 580.3130, found 580.3129.
(Z)-11,20-Diformyl-1,1,6,6-tetramethyl[6.2](7,1)pyrenophane-17-ene
(39a):
To
a
stirred
0
°C
solution
of
(Z)-1,1,6,6-
tetramethyl[6,2](7.1)pyrenophane-17-ene (38a) (80 mg, 0.14 mmol) and
dichloromethyl methyl ether (0.03 mL, 0.4 mmol) in dichloromethane (7
mL) was added titanium(IV) chloride (0.04 mL, 0.4 mmol). The ice bath
was removed and the reaction mixture was stirred at room temperature
for 2 h. The reaction mixture was poured into ice-cold water (20 mL) and
the organic layer was separated. The aqueous layer was extracted with
dichloromethane (2×15 mL) and the combined organic layers were
washed with brine (20 mL), dried over Na2SO4, filtered and the solvent
was removed under reduced pressure. The residue was subjected to
column chromatography (10.0×2.5 cm, dichloromethane) to afford (Z)-
11,20-diformyl-1,1,6,6-tetramethyl[6.2](7,1)pyrenophane-17-ene (39a) as
a bright yellow solid (58 mg, 66%): Rf=0.30 (dichloromethane); m.p. >300
°C, 1H NMR (500 MHz, CDCl3) δ 10.88 (s, 2H), 9.41 (br d, J=9.2 Hz, 2H),
8.54 (br s, 2H), 8.19 (d, J=9.2 Hz, 2H), 7.96 (s, 2H), 7.66 (s, 2H), 7.15 (br
s, 2H), 7.12 (br d, J=8.0 Hz, 2H), 6.34 (br d, J=8.3 Hz, 2H), 1.66 (br s,
2H), 1.35 (br s, 6H), 1.25 (br s, 8H), 0.71 (br s, 2H), 0.07 (br s, 2H); 13C
NMR (125 MHz, CDCl3) δ 193.14, 147.37, 132.37, 132.37, 131.32,
130.97, 129.99, 129.53, 129.44, 128.35, 126.82, 124.64, 124.62, 124.52,
124.00, 122.39, 121.39, 45.58, 38.05, 29.95, 28.00, 26.14 (22 of 23
expected signals observed); LC-MS (CI-(+)) m/z (rel. int.) 625 (18), 624
(35), 623 (100, [M+H]+); HRMS (APPI) calcd for C46H38O2 ([M]+)
622.2872, found 622.2876.
1,1,8,8-Tetramethyl-20-thia[8.3](7,1)pyrenophane (43): Na2S/Al2O3
(0.198 g, 0.497 mmol) was added in three equal portions to a stirred
room temperature solution of 2,9-bis(6-(bromomethyl)pyren-2-yl)-2,9-
dimethyldecane (42) (0.250 g, 0.331 mmol) in 1:9 (v/v)
EtOH/dichloromethane (75 mL) over a 20 min period. The resulting
slurry was stirred vigorously for 12 h and then was suction filtered. The
filtrate was concentrated under reduced pressure and the residue was
subjected to column chromatography (25×3 cm; 2:5 dichloromethane /
hexanes) to yield 43 as a light yellow oil (0.184 g, 89%); Rf=0.62 (2:5
dichloromethane / hexanes); 1H NMR (500 MHz, CDCl3) δ 8.06 (s, 2H),
8.01 (d, J=7.9 Hz, 2H), 7.98–7.94 (m, 24), 7.96 (d, J=7.7 Hz, 2H), 7.71 (s,
2H) 6.82 (s, 4H), 4.41 (s, 4H), 1.73–1.69 (m, 4H) 1.54 (s, 12H), 1.20–
1.17 (m, 4H), 0.91–0.87 (m, 4H); 13C NMR (125.77 MHz, CDCl3) δ
146.94, 131.33, 131.08, 130.99, 130.41, 128.80, 127.78, 127.63, 127.34,
127.28, 125.42, 123.97, 123.36, 122.95, 122.88, 122.85, 45.36, 38.36,
34.13, 30.30, 30.11, 24.05; LCMS (APCI-positive), m/z (rel. int.) 631 (12),
630 (51), 629 (100, [M+H]+); HRMS (EI) calc’d for C46H44S [M]+ 628.3164,
found 628.3162.
1,5-Bis(7-tert-butylpyren-1-yl)-1,5-pentanedione
(40):
Aluminum
chloride (3.20 g, 24.0 mmol) was added to a stirred 0 °C solution of
glutaryl dichloride (0.99 g, 5.9 mmol) and 2-tert-butylpyrene (22) (3.02 g,
11.7 mmol) in dichloromethane (20 mL). After 1 h, the reaction mixture
was poured into ice water (100 mL) and the layers were separated. The
aqueous layer was extracted with dichloromethane (3×30 mL) and the
combined organic extracts were washed with brine (50 mL), dried over
MgSO4, filtered and concentrated under reduced pressure. The brown
residue was subjected to column chromatography (45×4 cm;
dichloromethane) to yield 1,5-bis(7-tert-butylpyren-1-yl)-1,5-pentanedione
1,1,8,8-Tetramethyl-20-thia[8.3](7,1)pyrenophane-S,S-dioxide (44): 3-
Chloroperoxybenzoic acid (0.066 g, 0.381 mmol) and sodium
bicarbonate (0.107 g, 1.27 mmol) were added to a stirred 0 °C solution of
thiacyclophane 43 (0.080 g, 0.127 mmol) in dichloromethane (6 mL).
The reaction mixture was allowed to warm slowly to room temperature
and then stirred for 12 h. The reaction mixture was poured into water (20
mL) and the layers were separated. The aqueous layer was extracted
with dichloromethane (2×20 mL). The combined organic extracts were
washed with water (20 mL), washed with brine (20 mL), dried over
MgSO4, filtered and concentrated under reduced pressure to give an
orange residue, which was directly subjected to chromatography (15×2
cm, dichloromethane) to afford 44 as a light orange oil (0.042 g, 50%);
Rf=0.28 (dichloromethane); 1H NMR (500 MHz, CDCl3) δ 8.16–8.13 (m,
4H), 8.09 (d, J=1.4 Hz, 2H), 8.06 (d, J=8.9 Hz, 2H), 8.01 (d, J=8.9 Hz,
2H), 7.63 (d, J=1.4 Hz, 2H), 6.80 (d, J=9.3 Hz, 2H), 6.62 (d, J=9.3 Hz,
2H), 5.07 (s, 4H), 1.70–1.67 (m, 4H), 1.46 (s, 12H), 1.16–1.14 (m, 4H),
0.81–0.78 (m, 4H); 13C NMR (125.77 MHz, CDCl3) δ 147.57, 132.25,
131.22, 130.58, 130.41, 129.05, 128.95, 128.38, 127.28, 125.34, 125.03,
123.97, 123.79, 122.72, 122.42, 121.60, 56.71, 45.51, 38.63, 30.43,
30.18, 24.20; LCMS (APCI-positive), m/z (rel. int.) 663 (11), 662 (49),
661 (100, [M+H]+); HRMS (EI) calc’d for C46H44SO2 660.3062 ([M]+),
found 660.3058.
(40) as
a pale yellow solid (1.36 g, 38%): m.p. 231–233 °C
(dichloromethane); Rf=0.35 (dichloromethane); 1H NMR (500 MHz,
CDCl3) δ 8.95 (d, J=9.4 Hz, 2H), 8.33 (d, J=8.0 Hz, 2H), 8.29 (br s, 4H),
8.18 (d, J=9.4 Hz, 2H), 8.13 (d, J=8.9 Hz, 2H), 8.09 (d, J=8.0 Hz, 2H),
7.99 (d, J=8.9 Hz, 2H), 3.46 (t, J=7.0 Hz, 4H), 2.49 (quint, J=7.0 Hz, 2H),
1.60 (s, 18H); 13C NMR (125.77 MHz, CDCl3) δ 204.65, 149.79, 133.83,
132.18, 131.14, 130.60, 129.89, 129.78, 129.39, 127.09, 126.24, 125.12,
124.86, 124.03, 123.79, 123.44, 122.75, 41.25, 35.45, 32.10, 20.51;
LCMS (APCI-positive) m/z (rel. int.) 615 (13), 614 (51), 613 (100, [M+H]+),
355 (12); HRMS (EI) calc’d for C45H40O2 [M]+ 612.3028, found 612.3018.
Also obtained from this reaction was 6-(7-tert-butylpyren-1-yl)-3,4-
dihydro-2H-pyran-2-one as a light brown oil (1.45 g, 35%): Rf = 0.32
(dichloromethane); 1H NMR (500 MHz, CDCl3) δ 8.39 (d, J=9.3 Hz, 1H),
8.27 (s, 2H), 8.13–8.08 (m, 3H), 8.04–8.01 (m, 2H), 5.71 (t, J=4.7 Hz,
1H), 2.91–2.88 (m, 2H), 2.70–2.66 (m, 2H), 1.59 (s, 9H); 13C NMR
(125.77 MHz, CDCl3) δ 169.14, 151.96, 149.59, 131.94, 131.35, 130.82,
128.80, 128.65, 128.56, 128.35, 127.32, 126.51, 124.96, 124.57, 124.49,
123.16, 123.09, 122.93, 101.44, 36.48, 32.16, 28.81, 20.04; IR (neat) ν =
3102, 2953, 2889, 1752, 1594, 1546, 1460; LCMS (APCI-positive) m/z
(rel. int.) 388 (27), 387 (100, [M+Na]+), 356 (17), 355 (62, [M+H]+); HRMS
(EI) calc’d for C25H22O2 [M]+ 354.1620, found 354.1622.
(Z)-1,1,8,8-Tetramethyl[8.2](7,1)pyrenophanemonoene
(Z)-38c:
Potassium hydroxide (0.048 g, 1.21 mmol) was added to a stirred room
temperature solution of sulfone 44 (0.040 g, 0.061 mmol) in a mixture of
carbon tetrachloride (2.5 mL), water (1 mL) and tert-butanol (2.5 mL).
The resulting mixture was heated at 80 °C for 4 d, until all of the starting
material had been consumed (TLC analysis). The reaction was cooled to
room temperature, poured into water (25 mL) and extracted with
dichloromethane (3×15 mL). The combined organic extracts were
1,2-Bis(7-tert-butylpyren-1-yl)cyclopentene (41): Titanium(IV) chloride
(1.34 g, 7.22 mmol) was added to a stirred 0 °C slurry of zinc dust (0.461
g, 7.05 mmol) in THF (45 mL). After the addition was complete, the
reaction mixture was heated at 70 °C for 1 h, at which point a dark black
color persisted. Pyridine (0.2 mL) was added to the mixture and after 10
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