The Journal of Organic Chemistry
Article
pentacene-2,3,9,10-tetracarboxylic acid tetra alkyl ester (0.008 mmol)
was taken in a 10 mL round-bottomed flask. The solvent was slowly
evaporated under reduced pressure to form a film at the bottom. The
flask was then heated at 160 °C under high vacuum for 30−75 min.
The crude product of compounds 10c and 10h were purified by
column chromatography on silica gel (CH2Cl2−E.A, 100:1 to 50:1) as
eluent, but yields of the other products are calculated by calibration
with 1,4-dimethoxybenzene as an internal standard.
Octabutyl-6,7,14,15-tetrahydro-6,15:7,14-bis([2,3]naphthaleno)-
cycloocta[1,2-b:5,6-b′]dinaphthalen-2,3,10,11,21,22,29,30-octacar-
boxylate (10a). Yield 72%. IR (Neat, ν) 2960, 2928, 2868, 1723, 1679,
1455, 1382, 1262, 1215, 1122, 1015, 941, 801 cm−1. 1H NMR (CDCl3,
500 MHz, ppm): δ 7.91 (s, 8H), 7.54 (s, 8H), 5.20 (s, 4H), 4.27−4.19
(m, 16H), 1.73−1.62 (m, 16H), 1.43−1.36 (m, 16H), 0.91 (t, J = 7.2
Hz, 24H); HRMALDIMS m/z 1379.6284 ([M + Na]+, calcd for
C84H92O16Na 1379.6283).
Octahexyl-6,7,14,15-tetrahydro-6,15:7,14-bis([2,3]naphthaleno)-
cycloocta[1,2-b:5,6-b′]dinaphthalen-2,3,10,11,21,22,29,30-octacar-
boxylate (10b). Yield 72%. IR (Neat, ν) 2956, 2925, 2851, 1727, 1679,
1454, 1380, 1262, 1119, 1096, 1017, 924, 799 cm−1. 1H NMR (CDCl3,
400 MHz, ppm): δ 7.91 (s, 8H), 7.53 (s, 8H), 5.20 (s, 4H), 4.25−4.19
(m, 16H), 1.73−1.61 (m, 16H), 1.33−1.19 (m, 48H), 0.86 (t, J = 6.6
Hz, 24H); HRMALDIMS m/z 1603.8790 ([M + Na]+, calcd for
C100H124O16Na 1603.8787).
Octaheptyl-6,7,14,15-tetrahydro-6,15:7,14-bis([2,3]-
naphthaleno)cycloocta[1, 2-b:5, 6-b′]dinaphthalen-
2,3,10,11,21,22,29,30-octacarboxylate (10c). White solid (10 mg,
74%). IR (Neat, ν) 2956, 2925, 2851, 1723, 1679, 1455, 1380, 1263,
1215, 1122, 1017, 924, 801 cm−1. 1H NMR (CDCl3, 400 MHz, ppm):
δ 7.91 (s, 8H), 7.53 (s, 8H), 5.20 (s, 4H), 4.27−4.17 (m, 16H), 1.71−
1.61 (m, 16H), 1.35−1.19 (m, 64H), 0.85 (t, J = 6.6 Hz, 24H). 13C
NMR (CDCl3, 100 MHz, ppm): δ 167.7, 142.1, 132.1, 129.4, 128.9,
126.6, 65.9, 53.6, 31.7, 28.9, 28.5, 25.9, 22.6, 14.0; HRMALDIMS m/z
1716.0042 ([M + Na]+, calcd for C108H140O16Na 1716.0039).
Octaoctyl-6,7,14,15-tetrahydro-6,15:7,14-bis([2,3]naphthaleno)-
cycloocta[1,2-b:5,6-b′]dinaphthalen-2,3,10,11,21,22,29,30-octacar-
boxylate (10d). Yield 73%. IR (Neat, ν) 2956, 2925, 2855, 1728, 1679,
1456, 1377, 1271, 1215, 1124, 1047, 954, 802 cm−1. 1H NMR (CDCl3,
400 MHz, ppm): δ 7.91 (s, 8H), 7.53 (s, 8H), 5.19 (s, 4H), 4.26−4.18
(m, 16H), 1.71−1.61 (m, 16H), 1.35−1.21 (m, 80H), 0.85 (t, J = 6.6
Hz, 24H); HRESIMS m/z 1806.1466 ([M + H]+, calcd for
C116H157O16 1806.1461).
Octanonyl-6,7,14,15-tetrahydro-6,15:7,14-bis([2,3]naphthaleno)-
cycloocta[1,2-b:5,6-b′]dinaphthalen-2,3,10,11,21,22,29,30-octacar-
boxylate (10e). Yield 73%. IR (Neat, ν) 2956, 2924, 2854, 1727, 1679,
1456, 1380, 1271, 1124, 1091, 1017, 924, 801 cm−1. 1H NMR (CDCl3,
500 MHz, ppm): δ 7.91 (s, 8H), 7.53 (s, 8H), 5.19 (s, 4H), 4.24−4.19
(m, 16H), 1.72−1.61 (m, 16H), 1.38−1.21 (m, 96H), 0.85 (t, J = 6.3
Hz, 24H); HRMALDIMS m/z 1940.2548 ([M + Na]+, calcd for
C124H172O16Na 1940.2543).
Octadecyl-6,7,14,15-tetrahydro-6,15:7,14-bis([2,3]naphthaleno)-
cycloocta[1,2-b:5,6-b′]dinaphthalen-2,3,10,11,21,22,29,30-octacar-
boxylate (10f). Yield 73%. IR (Neat, ν) 2956, 2922, 2851, 1728, 1679,
1454, 1377, 1267, 1122, 1094, 1017, 798 cm−1. 1H NMR (CDCl3, 500
MHz, ppm): δ 7.91 (s, 8H), 7.53 (s, 8H), 5.19 (s, 4H), 4.25−4.18 (m,
16H), 1.72−1.63 (m, 16H), 1.44−1.21 (m, 112H), 0.85 (t, J = 6.7 Hz,
24H); HRMALDIMS m/z 2052.3796 ([M + Na]+, calcd for
C132H188O16Na 2052.3795).
Octaundecyl-6,7,14,15-tetrahydro-6,15:7,14-bis([2,3]-
naphthaleno)cycloocta[1, 2-b:5, 6-b′]dinaphthalen-
2,3,10,11,21,22,29,30-octacarboxylate (10g). Yield 74%. IR (Neat,
ν) 2956, 2922, 2846, 1725, 1679, 1454, 1380, 1263, 1122, 1094, 1015,
798 cm−1. 1H NMR (CDCl3, 400 MHz, ppm): δ 7.91 (s, 8H), 7.53 (s,
8H), 5.19 (s, 4H), 4.25−4.18 (m, 16H), 1.72−1.61 (m, 16H), 1.44−
1.21 (m, 128H), 0.86 (t, J = 6.2 Hz, 24H); HRMALDIMS m/z
2164.5049 ([M + Na]+, calcd for C140H204O16Na 2164.5047).
Octadodecyl-6,7,14,15-tetrahydro-6,15:7,14-bis([2,3]-
naphthaleno)cycloocta[1, 2-b:5, 6-b′]dinaphthalen-
2,3,10,11,21,22,29,30-octacarboxylate (10h). White solid (13.7 mg,
76%). IR (Neat, ν) 2954, 2923, 2853, 1727, 1674, 1455, 1378, 1274,
1213, 1124, 1049, 925, 802 cm−1. 1H NMR (CDCl3, 500 MHz, ppm):
δ 7.91 (s, 8H), 7.53 (s, 8H), 5.19 (s, 4H), 4.26−4.17 (m, 16H), 1.73−
1.63 (m, 16H), 1.37−1.21 (m, 144H), 0.86 (t, J = 6.7 Hz, 24H). 13C
NMR (CDCl3, 100 MHz, ppm): δ 167.7, 142.1, 132.1, 129.4, 128.9,
126.6, 65.9, 53.4, 31.9, 29.7, 29.6, 29.5, 29.4, 29.3, 28.5, 25.9, 22.7,
14.1; HRFABMS m/z 2251.6196 ([M − 2H]+, calcd for C148H218O16
2251.6225).
General Procedure for the Solid State Reaction of
Pentacene-9,10-dicyano-2,3-dicarboxylic Acid Dialkyl Ester. A
CH2Cl2 solution of pentacene-9,10-dicyano-2,3-dicarboxylic acid
dialkyl ester (0.008 mmol) was taken in a 10 mL round-bottom
flask. The solvent was slowly evaporated under reduced pressure to
make a film of unified thickness. After that, the flask was heated at 160
°C under high vacuum for 4−6 h to afford the title compound as a
white solid. The crude product of compounds 11a, 11d, and 11e were
purified by column chromatography on silica gel (hexane−E.A., 1:1 to
1:3). However, yields of the other products are calculated by
calibration with 1,4-dimethoxybenzene as an internal standard.
Tetrabutyl-21,22,29,30-tetracyano-6,7,14,15-tetrahydro-
6,15:7,14-bis([2,3]naphtha-aleno)cycloocta[1,2-b:5,6-b′]-
dinaphthalene-2,3,10,11-tetracarboxylate (11a). White solid (7.5
mg, 90%). IR (Neat, ν) 2958, 2928, 2868, 2234, 1724, 1632, 1453,
1
1377, 1282, 1212, 1123, 1059, 927, 750 cm−1. H NMR (CDCl3, 400
MHz, ppm): δ 8.03 (s, 4H), 7.91 (s, 4H), 7.60 (s, 4H), 7.57 (s, 4H),
5.27 (s, 4H), 4.25 (t, J = 6.6 Hz, 8H), 1.73−1.61 (m, 8H), 1.46−1.32
(m, 8H), 0.93 (t, J = 7.4 Hz, 12H). 13C NMR (CDCl3, 125 MHz,
ppm): δ 167.4, 144.4, 140.8, 135.1, 132.2, 132.0, 129.5, 129.3, 126.9,
126.6, 115.6, 110.6, 65.8, 53.5, 30.6, 19.2, 13.7; FABMS m/z 1057
[M+]; HRFABMS m/z 1057.4175 ([M+], calcd for C68H57O8N4
1057.4176).
Tetrahexyl-21,22,29,30-tetracyano-6,7,14,15-tetrahydro-
6,15:7,14-bis([2,3]naphtha-aleno)cycloocta[1,2-b:5,6-b′]-
dinaphthalene-2,3,10,11-tetracarboxylate (11b). Yield 89%. IR
(Neat, ν) 2956, 2926, 2855, 2233, 1724, 1673, 1453, 1374, 1261,
1
1122, 1089, 1018, 800 cm−1. H NMR (CDCl3, 400 MHz, ppm): δ
8.03 (s, 4H), 7.91 (s, 4H), 7.60 (s, 4H), 7.57 (s, 4H), 5.27 (s, 4H),
4.24 (t, J = 6.8 Hz, 8H), 1.77−1.64 (m, 8H), 1.44−1.21 (m, 24H),
0.87 (t, J = 6.6 Hz, 12H); FABMS m/z 1169 [M + H]+; HRFABMS
m/z 1169.5428 ([M + H]+, calcd for C76H73O8N4 1169.5408).
Tetraoctyl-21,22,29,30-tetracyano-6,7,14,15-tetrahydro-
6,15:7,14-bis([2,3]naphtha-aleno)cycloocta[1,2-b:5,6-b′]-
dinaphthalene-2,3,10,11-tetracarboxylate (11c). Yield 92%. IR
(Neat, ν) 2956, 2924, 2854, 2234, 1725, 1679, 1453, 1377, 1262,
1
1122, 1089, 1018, 800 cm−1. H NMR (CDCl3, 400 MHz, ppm): δ
8.03 (s, 4H), 7.91 (s, 4H), 7.60 (s, 4H), 7.57 (s, 4H), 5.26 (s, 4H),
4.24 (t, J = 6.8 Hz, 8H), 1.74−1.62 (m, 8H), 1.41−1.21 (m, 40H),
0.86 (t, J = 6.8 Hz, 12H); FABMS m/z 1281 [M + H]+; HRFABMS
m/z 1281.6698 ([M + H]+, calcd for C84H89O8N4 1281.6680).
Tetradecyl-21,22,29,30-tetracyano-6,7,14,15-tetrahydro-
6,15:7,14-bis([2,3]naph-thaleno)cycloocta[1,2-b:5,6-b′]-
dinaphthalene-2,3,10,11-tetracarboxylate (11d). White solid (10.5
mg, 95%). IR (Neat, ν) 2961, 2922, 2853, 2233, 1723, 1678, 1454,
1399, 1261, 1212, 1091, 1019, 800 cm−1. 1H NMR (CDCl3, 400 MHz,
ppm): δ 8.03 (s, 4H), 7.91 (s, 4H), 7.60 (s, 4H), 7.57 (s, 4H), 5.26 (s,
4H), 4.24 (t, J = 6.8 Hz, 8H), 1.73−1.62 (m, 8H), 1.40−1.22 (m,
56H), 0.86 (t, J = 6.6 Hz, 12H). 13C NMR (CDCl3, 100 MHz, ppm):
δ 167.5, 144.4, 140.7, 135.1, 132.2, 132.0, 129.4, 129.3, 126.9, 126.6,
115.4, 111.0, 66.1, 53.4, 31.9, 29.7, 29.5, 29.3, 28.5, 25.9, 22.7, 14.1;
FABMS m/z 1393 [M + H]+; HRFABMS m/z 1393.7913 ([M + H]+,
calcd for C92H105O8N4 1393.7932).
Tetradodecyl-21,22,29,30-tetracyano-6,7,14,15-tetrahydro-
6,15:7,14-bis([2,3]napht-haleno)cycloocta[1,2-b:5,6-b′]-
dinaphthalene-2,3,10,11-tetracarboxylate (11e). White solid (11.3
mg, 94%). IR (Neat, ν) 2959, 2923, 2853, 2234, 1725, 1633, 1453,
1402, 1261, 1211, 1092, 1015, 799 cm−1. 1H NMR (CDCl3, 400 MHz,
ppm): δ 8.03 (s, 4H), 7.91 (s, 4H), 7.60 (s, 4H), 7.57 (s, 4H), 5.26 (s,
4H), 4.24 (t, J = 6.6 Hz, 8H), 1.74−1.62 (m, 8H), 1.42−1.22 (m,
72H), 0.85 (t, J = 6.6 Hz, 12H). 13C NMR (CDCl3, 125 MHz, ppm):
δ 167.4, 144.4, 140.7, 135.1, 132.2, 132.0, 129.4, 129.3, 126.9, 126.6,
115.6, 110.6, 66.1, 53.5, 31.9, 29.6, 29.5, 29.33, 29.29, 28.6, 25.9, 22.7,
14.1; FABMS m/z 1504 [M+]; HRFABMS m/z 1504.9111 ([M+],
calcd for C100H120O8N4 1504.9106).
K
J. Org. Chem. XXXX, XXX, XXX−XXX