Full Papers
doi.org/10.1002/ejoc.202100108
149.77, 149.26, 148.91, 148.33, 141.77, 128.62, 125.09, 124.75,
128.88, 128.69, 124.41, 124.19, 116.54, 113.99, 108.58, 107.72,
107.22, 106.96, 70.23, 69.76, 69.67, 69.51, 46.78, 31.92, 31.88, 29.68,
29.59, 29.56, 29.54, 29.53, 29.52, 29.37, 28.75, 26.26, 26.24, 22.71,
14.12. HRMS m/z (100%) (MALDI): [M]+ calcd for C103H154O8
1520.1677; Found 1520.1668. Elemental analysis: Calcd. for
1
2
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4
5
6
7
8
9
124.15, 123.21, 123.13, 122.36, 114.60, 108.60, 108.24, 107.73,
107.39, 100.33, 70.20, 70.06, 69.82, 69.62, 31.92, 31.81, 29.79, 29.77,
29.74, 29.72, 29.70, 29.68, 29.65, 29.61, 29.60, 29.58, 29.51, 29.43,
29.37, 29.29, 28.62, 27.51, 26.29, 26.25 22.68, 22.61, 14.09, 14.01.
*
HRMS m/s (MALDI): [M]+ Calcd. for C156H261NO8: 2278.0081; Found:
C103H154O8: C 81.37%, H 10.21%. Found: C 80.96%, H 10.18%.
2278.0078. Elemental analysis: Calcd. for C156H261NO8: C 82.22%, H
11.55%, N 0.61%; Found: C 81.98%, 11.22%, N, 0.30%.
(LTP10) 2,3,6,7,12,13,16,17-Octakis(decyloxy)-20,20-dimethyl-20H-
cyclopenta[1,2-b:3,4-b’]ditriphenylene. As above. 4g (0.22 g,
0.13 mmol), FeCl3 (0.10 g, 0.63 mmol) in chloroform (60 mL) and
nitromethane (5 mL). Silica gel column chromatography (dichloro-
methane/petroleum ether=1:2 v/v). Recrystallization from ethyl
acetate and ethanol gave a white solid LTP10 (0.19 g, 88%). 1H
NMR (CDCl3, TMS, 400 MHz) δ (ppm): 9.00 (s, 2H, ArH), 8.52 (s, 2H,
ArH), 8.30 (s, 2H, ArH), 8.12 (s, 2H, ArH), 7.88 (s, 4H, ArH), 4.27–4.40
(m, 16H, OCH2), 1.95–2.06 (m, 16H, CH2), 1.83 (s, 6H, CH3), 1.60–1.68
(m, 16H, CH2), 1.30–1.55 (m, 96H, CH2), 0.88 (t, J=5.6 Hz, 24H, CH3).
13C NMR (CDCl3, TMS, 100 MHz) δ (ppm): 152.11, 149.58, 149.41,
148.96, 148.81, 137.60, 128.82, 128.66, 124.34, 124.24, 124.08,
116.49, 113.94, 108.39, 107.39, 107.09, 106.63, 70.15, 69.63, 69.36,
(FTP10)
2,3,6,7,12,13,16,17-Octakis(decyloxy)-20H-cyclopenta[1,2-
b:3,4-b’]ditriphenylen-20-one. As above. 4c (0.11 g, 0.07 mmol),
FeCl3 (0.06 g, 0.39 mmol), in chloroform (60 mL) and nitromethane
(5 mL). Silica gel column chromatography (toluene/petroleum
ether=1:2 v/v). Recrystallization toluene and petroleum ether gave
10
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16
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18
19
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24
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27
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32
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an orange-yellow solid FTP10 (0.09 g, 80%). H NMR (CDCl3, TMS,
400 MHz) δ (ppm): 8.35 (s, 2H, ArH), 8.18 (s, 2H, ArH), 7.91 (s, 2H,
ArH), 7.56 (s, 2H, ArH), 7.43 (s, 2H, ArH), 7.41 (s, 2H, ArH), 4.36 (t, J=
8.0 Hz, 4H, OCH2), 4.10 (t, J=4.0 Hz, 12H, OCH2), 1.92–2.07 (m, 16H,
CH2), 1.62–1.72 (m, 10H, CH2), 1.25–1,48 (m, 102H, CH2), 0.90 (t, J=
*
8.0 Hz, 24H, CH3). HRMS m/s (MALDI): [M]+ Calcd. for C117H180O9:
1730.3661; Found: 1730.3660. Elemental analysis: Calcd. for
C117H180O9: C 81.20%, H 10.48%; Found: C 80.96%, H 10.59%.
46.76, 31.99, 29.78, 29.70, 29.65, 29.63, 29.60, 29.55, 29.48, 29.46,
*
28.82, 26.30, 22.76, 14.18, 14.16. HRMS m/s (MALDI): [M]+ Calcd. for
C
119H186O8: 1744.4181; Found: 1744.4180. Elemental analysis: Calcd.
(FTP12) 2,3,6,7,12,13,16,17-Octakis(dodecyloxy)-20H-cyclopenta[1,2-
b:3,4-b’]ditriphenylen-20-one. As above. 4d (0.14 g, 0.07 mmol),
FeCl3 (0.07 g, 0.43 mmol) in chloroform (60 mL) and nitromethane
(5 mL). Silica gel column chromatography (toluene/petroleum
ether=1:2 v/v). Recrystallization from ethyl acetate and ethanol
(toluene and petroleum ether) gave an orange-yellow solid FTP12
for C119H186O8: C 81.92%, H 10.75%; Found: C 81.94%, H 10.51%.
(LTP12) 2,3,6,7,12,13,16,17-Octakis(dodecyloxy)-20,20-dimethyl-
20H-cyclopenta[1,2-b:3,4-b’]ditriphenylene. As above. 4h (0.18 g,
0.09 mmol), FeCl3 (0.07 g, 0.46 mmol) in chloroform (60 mL) and
nitromethane (5 mL). Silica gel column chromatography (dichloro-
methane/petroleum ether=1:2 v/v). Recrystallization from ethyl
acetate and ethanol gave a white solid LTP12 (0.12 g, 66%). 1H
NMR (CDCl3, TMS, 400 MHz) δ (ppm): 9.00 (s, 2H, ArH), 8.52 (s, 2H,
ArH), 8.29 (s, 2H, ArH), 8.12 (s, 2H, ArH), 7.87 (s, 4H, ArH), 4.28–4.40
(m, 16H, OCH2), 1.93–2.05 (m, 16H, CH2), 1.83 (s, 6H, CH3), 1.25–1.64
(m, 144H, CH2), 0.86 (t, J=6.4 Hz, 24H, CH3). 13C NMR (CDCl3, TMS,
100 MHz) δ (ppm): 149.62, 147.05, 146.90, 146.41, 146.30, 135.05,
126.28, 126.10, 121.79, 121.73, 121.54, 113.96, 111.40, 105.85,
104.95, 104.52, 104.19, 67.59, 67.09, 67.05, 66.86, 44.20, 29.40, 27.25,
1
(0.07 g, 47%). H NMR (CDCl3, TMS, 400 MHz) δ (ppm): 8.41 (s, 2H,
ArH), 8.24 (s, 2H, ArH), 7.94 (s, 2H, ArH), 7.61 (s, 2H, ArH), 7.47 (s, 2H,
ArH), 7.45 (s, 2H, ArH), 4.37 (t, J=8.0 Hz, 4H, OCH2), 4.09–4.15 (m,
12H, OCH2), 1.94–2.05 (m, 16H, CH2), 1.61–1.70 (m, 16H, CH2), 1.30–
1,45 (m, 128H,CH2), 0.89 (t, J=8.0 Hz, 24H, CH3). HRMS m/s (MALDI):
*
[M+H]+ Calcd. for C133H212O9: 1955.6243; Found 1955.6264.
Elemental analysis: Calcd. for C133H212O9: C 81.71%, H 10.93%;
Found: C 82.06%, H 11.23%.
(LTP5) 2,3,6,7,12,13,16,17-Octakis(pentyloxy)-20,20-dimethyl-20H-
cyclopenta[1,2-b:3,4-b’]ditriphenylene. As above. 4e (0.1 g,
0.08 mmol), dichloromethane (40 mL), nitromethane (4 mL), FeCl3
(0.70 g, 0.42 mmol). Silica gel column chromatography (dichloro-
methane/petroleum ether=1:1 v/v) and recrystallization with
ethanol and ethyl acetate to obtain LTP5 as a white solid (0.095 g,
27.22, 27.20, 27.16, 27.13, 27.06, 27.04, 27.01, 26.95, 26.86, 26.21,
*
23.73, 23.71, 20.17, 11.60, 11.58. HRMS m/s (MALDI): [M]+ Calcd. for
C
135H218O8: 1968.6685; Found: 1968.6686. Elemental analysis: Calcd.
for C135H218O8: C 82.34%, H 11.16%; Found: C 82.43%, H 11.30%.
(LTP58) 2,3,6,7,12,13,16,17-Octakis(pentyloxy)-20,20-dioctyl-20H-cy-
clopenta[1,2-b:3,4-b’]ditriphenylene. As above. 4i (0.18 g,
0.13 mmol), dichloromethane (50 mL), nitromethane (5 mL), FeCl3
(0.11 g, 0.65 mmol). Silica gel column (dichloromethane/petroleum
ether=1:1.5 v/v) and recrystallization with ethanol and ethyl
acetate gave LTP58 as a white solid (0.14 g, 80.0%). 1H NMR (CDCl3,
TMS, 400 MHz) δ (ppm): 9.00 (s, 2H, ArH), 8.41 (s, 2H, ArH), 8.30 (s,
2H, ArH), 8.12 (s, 2H, ArH), 7.89 (s, 4H, ArH), 4.31 (t, J=6.8 Hz, 16H,
OCH2), 2.28 (t, J=7.2 Hz, 4H, 2CH2), 1.94–2.05 (m, 16H, CH2), 1.48–
1.62 (m, 40H, CH2), 1.01–1.08 (m, 16H, CH2), 0.99 (t, J=1.2 Hz, 24H,
CH3), 0.70 (t, J=2.8 Hz, 6H, CH3). 13C NMR (CDCl3, TMS, 100 MHz) δ
(ppm): 149.69, 149.64, 149.39, 149.08, 149.04, 139.66, 128.87,
128.58, 124.47, 124.35, 124.26, 116.59, 113.69, 108.42, 108.03,
107.40, 107.09, 70.12, 70.10, 69.85, 69.75, 69.57, 55.10, 41.75, 31.74,
30.06, 29.56, 29.50, 29.25, 29.21, 29.20, 29.16, 29.12, 28.42, 28.40,
28.38, 28.37, 25.92, 25.89, 23.98, 22.70, 22.65, 22.63, 22.59, 22.57,
22.48, 14.15, 14.12, 14.08, 13.96. HRMS m/z (100%) (MALDI): [M]+
calcd for C93H134O8 1380.0112; Found 1380.0090. Elemental analysis:
Calcd. for C93H134O8 :C 80.94%, H 9.79%. Found: C 80.58%, H 9.86%.
1
93.8%). H NMR (CDCl3, TMS, 400 MHz) δ (ppm): 9.00 (s, 2H, ArH),
8.52 (s, 2H, ArH), 8.29 (s, 2H, ArH), 8.11 (s, 2H, ArH), 7.87 (s, 4H, ArH),
4.39 (t, J=5.6 Hz, 4H, OCH2), 4.29 (t, J=3.6 Hz, 12H, OCH2), 1.97–
2.07 (m, 16H, CH2), 1.84 (s, 6H, 2CH3), 1.49–1.62 (m, 32H, CH2), 1.00
(t, J=1.6 Hz, 24H, CH3). 13C NMR (CDCl3, TMS, 100 MHz) δ (ppm):
152.28, 152.20, 149.75, 149.61, 148.93, 137.75, 137.69, 137.62,
128.75, 124.17, 116.53, 113.98, 108.56, 107.59, 107.36, 106.98,
106.84, 70.22, 69.64, 69.43, 46.82, 29.32, 29.21, 29.17, 28.79, 28.43,
28.41, 22.64, 22.63, 22.61, 14.16, 14.14. HRMS m/z (100%) (MALDI):
[M]+ calcd for C79H106O8 1182.7888; Found 1182.7888. Elemental
analysis: Calcd. for C79H106O8: C 80.16%, H 9.03%. Found: C 79.80%,
H 8.70%.
(LTP8) 2,3,6,7,12,13,16,17-Octakis(octyloxy)-20,20-dimethyl-20H-cy-
clopenta[1,2-b:3,4-b’]ditriphenylene. As above. 4f (0.20 g,
0.13 mmol), dichloromethane (60 mL), nitromethane (5 mL), FeCl3
(0.11 g, 0.66 mmol). Silica gel column (dichloromethane/petroleum
ether=1:2 v/v) and recrystallization with ethanol and ethyl acetate
gave LTP8 as a white solid (0.16 g, 80.4%). 1H NMR (CDCl3, TMS,
400 MHz) δ (ppm): 9.00 (s, 2H, ArH), 8.52 (s, 2H, ArH), 8.30 (s, 2H,
ArH), 8.12 (s, 2H, ArH), 7.88 (s, 4H, ArH), 4.32 (t, J=6.4 Hz, 16H,
OCH2), 1.94–2.04 (m, 16H, CH2), 1.84 (s, 6H, 2CH3), 1.33–1.66 (m,
80H, CH2), 0.91 (t, J=8 Hz, 24H, CH3). 13C NMR (CDCl3, TMS,
100 MHz) δ (ppm): 152.25, 149.68, 149.56, 149.04, 148.96, 137.63,
(LTP88) 2,3,6,7,12,13,16,17-Octakis(octyloxy)-20,20-dioctyl-20H-cy-
clopenta[1,2-b:3,4-b’]ditriphenylene. As above. 4j (0.25 g,
0.15 mmol), dichloromethane (70 mL), nitromethane (5 mL), FeCl3
(0.12 g, 0.73 mmol). Silica gel column (dichloromethane/petroleum
ether=1:2 v/v) and recrystallization from ethanol and ethyl acetate
Eur. J. Org. Chem. 2021, 1989–2002
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