H. Langhals, L. Flamigni et al.
1.19–1.38 (m, 16H; CH2), 1.85–1.91 (m, 2H; b-CH2), 2.22–2.29 (m, 2H;
b-CH2), 2.43 (ddd, 3J=7.9 Hz, 3J=10.3 Hz, 2J=12.2 Hz, 1H; CH2), 3.14
(ddd, 3J=5.7 Hz, 3J=7.9 Hz, 2J=12.2 Hz, 1H; CH2), 4.88 (t, 3J=7.9 Hz,
9.2 Hz, 1H; CH), 4.38 (qd, 3J
(H,H)=5.9 Hz, 3J
ACHUTGTNRENNGU ACHTUNGTNER(NUGN H,H)=9.2 Hz, 1H; CH),
5.10 (d, 3J
AHCTUNGTRENNUNG
(m, 5H; CHAromat), 7.53 (dd, 3J
ACHTUNGTRNEN(UG H,H)=6.2 Hz, 4H; CHAromat), 8.63–
3
1H; CH), 5.14 (dd, 3J=5.7 Hz, J=10.3 Hz, 1H; CH), 5.16–5.21 (m, 1H;
8.73 ppm (m, 8H; CHPerylene); 13C NMR (151 MHz, CDCl3, 258C): d=
a-CH), 5.39 (d, 1H; N-CH2), 5.42 (d, 1H; N-CH2), 6.88–6.91 (m, 1H;
Haryl), 7.01 (d, 3J=1.0 Hz, 2H; Haryl), 7.02 (d, 3J=1.0 Hz, 2H; Haryl), 7.21
(d, 3J=7.4 Hz, 2H; Haryl), 7.23 (d, 3J=7.4 Hz, 2H; Haryl), 7.28–7.30 (m,
14.3, 22.8, 27.1, 29.4, 29.9, 32.0, 32.6, 55.0, 122.4, 123.8, 126.7, 129.1, 129.8,
˜
131.9, 135.2, 136.7, 163.7 ppm; IR (ATR): n=2935.4 (w), 2923.6 (m),
2853.9 (m), 1736.0 (w), 1693.4 (s), 1654 (s), 1592.7 (s), 1577.5 (m), 1507.3
(w), 1486.1 (w), 1434.1 (m), 1403.2 (m), 1376.9 (w), 1331.6 (s), 1247.3
(m), 1216.2 (w), 1169.3 (w), 1124.5 (w), 1105.0 (w), 1020.8 (w), 987.5 (w),
851.8 (w), 808.8 (m), 744.0 (m), 694.4 cmꢁ1 (w); UV/Vis (CHCl3): lmax
(e)=459 (21500), 490 (52400), 527 nm (84700); HRMS: m/z calcd for
C56H56N3O5: 882.408; found: 882.409; D=1 mmu; elemental analysis
calcd (%) for C56H55N3O5 (882.1): C 76.25, H 6.28, N 4.76; found: C
75.84, H 6.16, N 4.58.
3
1H; Haryl), 7.32–7.35 (m, 2H; Haryl), 7.39–7.41 (m, 2H; Haryl), 7.52 (d, J=
3
8.4 Hz, 2H; Haryl), 7.61 (d, J=8.4 Hz, 2H; Haryl), 8.52–8.65 ppm (m, 8H;
Hperylene); minor diastereomer: 1H NMR (600 MHz, CDCl3, 258C): d=
0.82 (t, 3J=7.0 Hz, 3H; CH3), 1.19–1.38 (m, 16H; CH2), 1.85–1.91 (m,
3
3
2H; b-CH2), 2.22–2.29 (m, 2H; b-CH2), 2.61 (ddd, J=4.5 Hz, J=6.5 Hz,
2J=12.0 Hz, 1H; CH2), 2.74 (td, 3J=9.1 Hz, 2J=12.0 Hz, 1H; CH2), 4.66
3
3
(dd, J=4.5 Hz, J=9.1 Hz, 1H; CH), 5.16–5.21 (m, 1H; a-CH), 5.31 (dd,
3J=6.5 Hz, 3J=9.1 Hz, 1H; CH), 5.39 (d, 1H; N-CH2), 5.42 (d, 1H; N-
CH2), 6.88–6.91 (m, 1H; Haryl), 6.96 (d, 3J=1.0 Hz, 2H; Haryl), 6.97 (d,
N-(1-Hexylheptyl)-N’-4-(5-phenyl-2-phenylisoxazolidine-3-yl)biphenyl-
methyl-perylene-3,4:9,10-tetracarboxylic bisimide (12): Compound 10
(100 mg, 0.130 mmol) was dissolved in styrene (5 mL). The resulting solu-
tion was treated with N-phenyl hydroxylamine (142 mg, 1.30 mmol),
stirred at 858C for 25 h and then stirred at room temperature for a fur-
ther 40 h. The solution was then evaporated in vacuo and the resulting
residue was dissolved in dichloromethane, added to silica on a column
for separation and eluted with dichloromethane/methanol 70:1 (first,
non-fluorescent fraction). The first fraction was dissolved in the minimal
amount of dichloromethane, precipitated with methanol, collected by
vacuum filtration, and dried in air at 1108C (two diastereomers, de=
28% by 1H NMR). Yield 34 mg (27%) red solid; Rf (silica gel, chloro-
form/ethanol=60:1)=0.28; m.p.> 3008C; major diastereomer: 1H NMR
(600 Hz, CDCl3, 258C): d=0.82 (t, 3JH,H =7.0 Hz, 6H; CH3), 1.21–1.36
(m, 16H; CH2), 1.84–1.90 (m, 2H; b-CH2), 2.20–2.28 (m, 2H; b-CH2),
2.50 (ddd, 3JH,H =7.7 Hz, 3JH,H =10.2 Hz, 2JH,H =12.2 Hz, 1H; CH2), 3.20
(ddd, 3JH,H =5.8 Hz, 3JH,H =8.0 Hz, 2JH,H =12.2 Hz, 1H; CH2), 4.95 (dd,
3JH,H =7.8 Hz, 1H; CH), 5.16–5.21 (m, 2H; a-CH, CH), 5.46 (s, 2H; CH2-
N), 6.93–7.72 (m, 18H; Harom), 8.63–8.73 ppm (m, 8H; Hperylene); minor
3
3
3J=1.0 Hz, 2H; Haryl), 7.15 (d, J=7.4 Hz, 2H; Haryl), 7.17 (d, J=7.4 Hz,
2H; Haryl), 7.28–7.30 (m, 1H; Haryl), 7.32–7.35 (m, 2H; Haryl), 7.39–7.41
(m, 2H; Haryl), 7.52 (d, 3J=8.4 Hz, 2H; Haryl), 7.61 (d, 3J=8.4 Hz, 2H;
Haryl), 8.52–8.65 ppm (m, 8H; Hperylene); 13C NMR (150 MHz, CDCl3,
258C): d=14.0, 22.6, 26.9, 29.2, 31.8, 32.4, 43.4, 47.2, 48.8, 54.8, 69.4, 71.4,
80.5, 113.9 ,115.8 ,122.9, 123.2, 126.5, 126.8, 128.5, 128.9, 129.6, 129.7,
131.0, 131.8, 134.2, 134.8, 136.2, 137.7, 142.4, 152.5, 163.4 ppm; IR (ATR):
n˜ =3604.9 (w), 3036.7 (w), 2954.5 (m), 2924.2 (m), 2855.3 (m), 1691.5 (s),
1655.3 (s), 1593.0 (m), 1577.8 (s), 1508.3 (w), 1484.6 (w), 1436.1 (m),
1403.7 (s), 1351.8 (s), 1332.5 (s), 1300.6 (m), 1249.1 (s), 1251.8 (w), 1169.9
(m), 1127.1 (w), 1104.9 (w), 1082.7 (w), 1020.7 (w), 983.9 (w), 924.9 (w),
854.54 (w), 810.2 (s), 796.1 (w), 771.8 (m), 748.3 (s), 696.2 cmꢁ1 (s); UV/
Vis (CHCl3): lmax (e)=459 (18800), 491 (52100), 527 nm (85700);
HRMS: m/z calcd for C59H56N3O5: 886.426; found: 886.430; D=4 mmu;
elemental analysis calcd (%) for C59H55N3O5·H2O (885.4): C 78.38, H
6.35, N 4.65; found: C 78.17, H 6.70, N 4.34.
N-(1-Hexylheptyl)-N’-4-(5-cyano-2-phenylisoxazolidine-3-yl)benzylpery-
lene-3,4:9,10-tetracarboxylic bisimide (8) and N-(1-Hexylheptyl)-N’-4-(4-
cyano-2-phenyl-isoxazolidine-3-yl)benzylperylene-3,4:9,10-tetracarboxylic
bisimide (9): Compound 4 (110 mg, 153 mmol) was disperged in acryloni-
trile (50 mL), heated under reflux for 1 h, allowed to cool, evaporated in
vacuo, and purified by column separation (silica gel, CH2Cl2/methanol
1
3
diastereomer (36%): H NMR (600 Hz, CDCl3, 258C): d=0.82 (t, JH,H
=
7.0 Hz, 6H; CH3), 1.21–1.36 (m, 16 , CH2), 1.84–1.90 (m, 2 , b-CH2),
2
2.20–2.28 (m, 2 , b-CH2), 2.69 (ddd, 3JH,H =4.6 Hz, 3JH,H =6.6 Hz, JH,H
=
3
12.0, 1H; CH), 2.78–2.83 (m, 1H; CH), 4.72 (dd, 3JH,H =4.6 Hz, JH,H
=
6.6 Hz, 1H; CH), 5.16–5.21(m, 1H; a-CH), 5.34–5.39 (m, 1H; CH), 5.46
(s, 2H; CH2-N), 6.93–7.72 (m, 18H; Harom), 8.63–8.73 ppm (m, 8H;
Hperylene); 13C NMR (150 MHz, CDCl3, 258C): d=14.0, 22.6, 26.9, 29.2,
29.7, 31.8, 32.4, 43.5, 48.7, 54.8, 71.5, 80.8, 114.0, 121.4, 123.0, 126.7, 126.9,
127.2, 127.5, 128.6, 129.0, 129.5, 131.8, 135.0, 136.1, 137.8, 139.9, 140.2,
142.0, 152.5, 163.5 ppm; IR (ATR): n˜ =3066.9 (w), 2952.0 (m), 2923.4
(m), 2854.1 (m), 1691.8 (s), 1646.1 (s), 1592.0 (s), 1575.4 (m), 1483.0 (w),
1457.9 (w), 1435.6 (w), 1402.6 (m), 1334.8 (s), 1249.0 (m), 1170.8 (m),
1125.9 (w), 1108.1 (w), 1069.6 (w), 1022.9 (w), 987.3 (w), 892.3 (w), 850.5
(w), 832.3 (w), 809.6 (m), 763.0 (w), 684.9 (w), 660.6 (w), 622.5 cmꢁ1 (w);
UV/Vis (CHCl3): lmax (Erel)=459 (0.21), 490 (0.60), 527 nm (1.0);
HRMS: m/z calcd for C65H60N3O5: 962.456; found: 962.459; D=3 mmu.
4-(1,3-Dioxolane-2-yl)-4-methylbenzonitrile:[26] 4-Cyano acetophenon
(5.0 g, 34.4 mmol) was dissolved in toluene (50 mL). The resulting mix-
ture was treated dropwise with ethylene glycol (3.4 g, 55.1 mmol) and
BF3 etherate (0.5 mL), heated under reflux for 12 h at a water separator,
allowed to cool at room temperature (yellow mixture), treated with 5%
aqueous sodium hydrogen carbonate (40 mL), extracted with diethyl
ether, washed with brine, dried with MgSO4 and filtered. The filtrate was
evaporated in vacuo and the residue crystallised from diethyl ether/n-
pentane (1:1). Yield 2.2 g (34%) colourless solid; m.p. 708C; 1H NMR
(200 MHz, CDCl3, 258C): d=1.62 (s, 3H; CH3), 3.72–3.75 (m, 2H; CH2),
4.02–4.08 (m, 2H; CH2), 7.57–7.64 ppm (m, 4H; Haryl); HRMS: m/z calcd
for C11H12NO2: 190.086; found: 190.087; D=1 mmu.
1
45:1, mixture of two diastereomers, de=52% by H NMR spectroscopy).
Yield 94 mg (73%); Rf (silica gel, CH2Cl2/methanol 20:1)=0.79; m.p.>
3008C; major diastereomer: 1H NMR (600 MHz, CDCl3, 258C): d=0.82
3
(t, J=7.0 Hz, 3H; CH3), 1.19–1.38 (m, 16H; CH2), 1.85–1.91 (m, 2H; b-
CH2), 2.22–2.29 (m, 2H; b-CH2), 2.47 (ddd, 3J=3.9 Hz, 3J=5.9 Hz, 2J=
12.8 Hz, 1H; CH2), 3.15 (ddd, 3J=3.9 Hz, 3J=9.0 Hz, 2J=12.8 Hz, 1H;
CH2), 4.47 (dd, 3J=5.9 Hz, 3J=9.0 Hz, 1H; CH), 4.95 (dd, 3J=3.9 Hz,
3J=9.0 Hz, 1H; CH), 5.16–5.21 (m, 1H; a-CH), 5.41 (s, 2H; N-CH2),
6.94–6.95 (m, 3H; Haryl), 7.18–7.24 (m, 2H; Haryl), 7.49 (d, 3J=8.3 Hz,
2H; Haryl), 7.61 (d, 3J=8.3 Hz, 2H; Haryl), 8.55–8.66 ppm (m, 8H;
Hperylene); minor diastereomer: 1H NMR (600 MHz, CDCl3, 258C): d=
0.82 (t, 3J=7.0 Hz, 3H; CH3), 1.19–1.38 (m, 16H; CH2), 1.85–1.91 (m,
3
3
2H; b-CH2), 2.22–2.29 (m, 2H; b-CH2), 2.77 (ddd, J=6.1 Hz, J=7.6 Hz,
2J=12.5 Hz, 1H; CH2), 2.98 (ddd, 3J=5.2 Hz, 3J=7.6 Hz, 2J=12.5 Hz,
1H; CH2), 4.87 (dd, 3J=5.2 Hz, 3J=7.6 Hz, 1H; CH), 4.95–4.97 (m, 1H;
CH), 5.16–5.21 (m, 1H; a-CH), 5.41 (s, 2H; N-CH2), 6.94–6.95 (m, 3H;
Haryl), 7.18–7.24 (m, 2H; Haryl), 7.49 (d, 3J=8.3 Hz, 2H; Haryl), 7.61 (d,
3J=8.3 Hz, 2H; Haryl), 8.55–8.66 ppm (m, 8H; Hperylene); elemental analy-
sis calcd (%) for C54H50N4O5 (834.4): C 77.67, H 6.04, N 6.71; found: C
77.30, H 5.89, N 6.31.
N-(1-Hexylheptyl)-N’-4-(4-methyloxycarbonyl-5-methyl-2-phenylisoxazo-
lidine-3-yl)benzylperylene-3,4:9,10-tetracarboxylic bisimide (7): Com-
pound 4 (120 mg, 0.15 mmol) was disperged in methyl crotonate (20 mL),
heated at 658C for 6 h (reflux), evaporated in vacuo, purified by column
separation (silica gel, dichloromethane/methanol 50:1, non-fluorescent
fraction), dissolved in a minimal amount of chloroform, and precipitated
with methanol. Yield 80 mg (62.6%), bright red solid; Rf (silica gel, di-
chloromethane/methanol 30:1)=0.82; m.p.> 3008C; 1H NMR (600 MHz,
4-(1,3-Dioxolane-2-yl)-4-methylbenzylamine:[26] 4-(1,3-Dioxolane-2-yl)-4-
methylbenzonitrile (2.00 g, 10.6 mmol) in diethyl ether (10 mL) was
added cautiously dropwise at 08C under argon to a dispersion of lithium
aluminium hydride (800 mg, 21.1 mmol) in diethyl ether (20 mL) over a
period of 15 min. The resulting mixture was stirred at 08C for 2 h and
then at room temperature for a further 16 h; it was then hydrolysed by
cautiously adding dropwise aqueous NaOH (2 n, 20 mL), extracted with
CDCl3, 258C): d=0.82 (t, 3J
G
3
16H; 8ꢂCH2), 1.46 (d, J
U
CH2), 2.21–2.27 (m, 2H; b-CH2), 3.12 (dd, 3J
12742
ꢁ 2009 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Chem. Eur. J. 2009, 15, 12733 – 12744