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J. Teichgraber, U. Holzgrabe / Tetrahedron 59 (2003) 8697–8703
8701
(DMSO-d6) d: 173.62 (COOH), 173.55 (COOH), 137.56
(Cquat., aromat.), 137.53 (Cquat., aromat.), 137.48
(2£Cquat., aromat.), 136.24 (Cquat., aromat.), 136.00
(Cquat., aromat.), 132.44 (Cquat., aromat.), 132.36
(Cquat., aromat.), 131.79 (2£Cquat., aromat.), 130.08
(4£C-aromat.), 127.80 (2£C-aromat.), 127.63 (C-aromat.),
127.52 (2£C-aromat.), 127.37 (C-aromat.), 126.27
(C-aromat.), 126.19 (C-aromat.), 125.79 (C-aromat.),
125.66 (C-aromat.), 125.26 (C-aromat.), 125.21
(C-aromat.), 35.08 (CH2), 34.87 (CH2), 28.98 (CH2),
28.72 ppm (CH2). MS (EI); m/z (%): 474 (Mþ, 100.0),
428 (68.85), 414 (7.47), 369 (13.78), 355 (39.84), 339
(27.51), 177 (77.87). IR (ATR): 3200–2400 (COO–H, br,
carboxylic acid), 1697 (CvO, carboxylic acid), 1507,
carbamoyl)-ethyl]-5,6,500,600-dibenzo-[1,10;40,100]ter-
phenyl-2-yl}-propionamide 7b. Oxalylchloride (1.67 g,
13.17 mmol) and a catalytic amount of DMF was added to
6 (2.50 g, 5.27 mmol) dissolved in dry THF (120.0 mL) and
the mixture was stirred 12 h at 258C. The THF was
evaporated in vacuo. The residue was dissolved in toluene
(2£30.0 mL) and evaporated in vacuo twice, in order to
remove the excess of oxalylchloride. The residue was
dissolved in dry THF (80.0 mL), an excess of 2-methoxy-
ethylamine (7.71 g, 105.36 mmol) was added and the
mixture was stirred for 12 h at 258C. 10% HCl was added
until the solution had adopted pH,4 and the solvent was
evaporated in vacuo. The aqueous layer was extracted twice
with chloroform (200.0 mL). The organic solvent was
washed with brine (100 mL) and dried with Na2SO4 and
evaporated in vacuo. The resulting residue can be
recrystallised from methanol. Yield: 1.84 g (74%), mp
199.58C. 1H NMR (CDCl3) d: 7.90–7.84 (4H, m,
H-aromat.), 7.66–7.42 (12H, m, H-aromat.), 6.60 (1H, s,
NH), 5.70 (0.5H, s, NH), 3.41–3.34 (8H, m, CH2), 3.21–
3.18 (6H, m, CH3), 3.11–3.00 (4H, m, CH2), 2.48–
2.41 ppm (4H, m, CH2). 13C NMR (CDCl3) d: 172.85
(CvO, amide), 172.12 (CvO, amide), 138.25 (Cquat.,
aromat.), 138.19 (Cquat., aromat.), 138.07 (2£Cquat.,
aromat.), 136.35 (Cquat., aromat.), 136.17 (Cquat.,
aromat.), 133.22 (Cquat., aromat.), 133.06 (Cquat.,
aromat.), 132.43 (Cquat., aromat.), 132.38 (Cquat.,
aromat.), 130.48 (2£C-aromat.), 130.44 (2£C-aromat.),
128.11 (C-aromat.), 128.05 (C-aromat.), 128.00
(C-aromat.), 127.89 (2£C-aromat.), 127.54 (C-aromat.),
126.62 (C-aromat.), 126.52 (C-aromat.), 126.35
(C-aromat.), 126.20 (C-aromat.), 125.43 (2£C-aromat.),
71.22 (CH2), 71.11 (CH2), 58.74 (OCH3), 58.72 (OCH3),
39.50 (CH2), 39.29 (CH2), 38.12 (CH2), 37.98 (CH2), 30.43
(CH2), 30.05 ppm (CH2). IR (ATR): 3265 (N–H, amide),
2924 (CH2), 2870 (CH2), 1639 (CvO, amide), 1534 (N–
CvO, amide), 1123 (C–O–C, ether), 1093 (C–O–C,
ether), 1020, 820, 748, 680. MS (EI); m/z (%): 588 (Mþ,
100), 555 (12.60), 514 (16.82), 485 (12.80), 471 (17.38),
368 (28.09), 353 (41.17), 339 (18.61), 76 (79.96). Anal.
calcd for C38H40N2O4: C, 77.5; H, 6.85; N, 4.76; found C,
77.3; H, 6.89; N, 4.61.
1210, 945, 822, 751, 679 cm21
. Anal. calcd for
C32H26O4£0.5H2O: C, 79.5; H, 5.63; found C, 79.7; H,
5.62.
4.1.5. N-Cyclohexyl-3-[200-(2-cyclohexylcarbamoyl-
ethyl)-5,6,500,600-dibenzo-[1,10;40,100]terphenyl-2-yl]-pro-
pionamide 7a. Oxalylchloride (1.67 g, 13.17 mmol) and a
catalytic amount of DMF was added to 6 (2.50 g,
5.27 mmol) dissolved in dry THF (80.0 mL) and the mixture
was stirred 12 h at 258C. The THF was evaporated in vacuo.
The residue was dissolved in toluene (2£30.0 mL) and
evaporated in vacuo twice in order to remove the excess of
oxalylchloride. The residue was dissolved in dry THF
(80.0 mL), an excess of cyclohexylamine (10.45 g,
105.36 mmol) was added and the mixture was stirred for
12 h at 258C. 10% HCl was added until the solution had
adopted pH,4 and the solvent was evaporated in vacuo.
The aqueous layer was extracted twice with chloroform
(300.0 mL). The solvent was evaporated in vacuo. The
resulting residue was purified by means of column
chromatography (silica gel/chloroform) to obtain pale
yellow crystals which can be recrystallised from chloro-
1
form/petroleum ether. Yield: 0.6 g (18%), mp 263.48C. H
NMR (CDCl3) d: 7.89–7.85 (4H, m, H-aromat.), 7.66–7.41
(12H, m, H-aromat.), 6.6 (1H, s, NH), 3.66–3.77 (2H, m,
CH), 3.08–2.99 (4H, m, CH2), 2.44–2.39 (4H, m, CH2),
1.87–1.78 (4H, m, CH2), 1.67–1.56 (6H, m, CH2), 1.34–
1.23 (4H, m, CH2), 1.13–1.02 ppm (6H, m, CH2). 13C NMR
(CDCl3) d: 171.93 (CvO, amide), 171.15 (CvO, amide),
138.29 (Cquat., aromat.), 138.16 (Cquat., aromat.), 138.06
(Cquat., aromat.), 137.98 (Cquat., aromat.), 136.42 (Cquat.,
aromat.), 136.38 (Cquat., aromat.), 133.20 (Cquat.,
aromat.), 133.02 (Cquat., aromat.), 132.46 (Cquat.,
aromat.), 132.39 (Cquat., aromat.), 130.47 (4£C-aromat.),
128.09 (4£C-aromat.), 128.02 (2£C-aromat.), 127.57
(C-aromat.), 126.63 (C-aromat.), 126.45 (C-aromat.),
126.31 (C-aromat.), 126.19 (C-aromat.), 125.43
(C-aromat.), 48.93 (CH), 48.33 (CH), 38.65 (CH2), 37.89
(CH2), 33.31 (2£CH2), 32.99 (2£CH2), 30.41 (CH2), 30.24
(CH2), 25.56 (2£CH2), 25.06 (2£CH2), 24.97 ppm
(2£CH2). IR (ATR): 3306 (N–H, amide), 2932 (CH2),
2849 (CH2), 1631 (CvO, amide), 1549 (N–CvO, amide),
852, 804, 744, 694, 654 cm21. MS (EI); m/z (%): 636 (Mþ,
63.71), 537 (4.71), 510 (9.56), 495 (11.23), 369 (19.19),
353 (29.00), 98 (100.0). Anal. calcd for
C44H48N2O2£0.75H2O: C, 81.3; H, 7.67; N, 4.31; found
C, 81.2; H, 7.53; N, 4.28.
4.1.7. Cyclohexyl-{3-[200-(3-cyclohexyl-propyl-
ammonium)-5,6,500,600-dibenzo-[1,10;40,100]terphenyl-2-
yl]propyl}-ammonium dihydrochloride 8a. 1.0 M
Diborane–THF solution (25 mL, 25 mmol) was added to
7a (2.50 g, 3.93 mmol) dissolved in dry THF, and the
mixture was stirred for 12 h at 258C and additionally 1 h at
608C. The reaction was quenched carefully with 10% HCl
and afterwards refluxed for 1 h. 10% NaOH was added until
the solution had adopted pH,7. The aqueous layer was
extracted with chloroform (2£100 mL). The organic solvent
was washed with brine (100 mL) and dried with Na2SO4 and
evaporated in vacuo. The resulting residue was dissolved in
ethanolic HCl and the solvent was evaporated in vacuo. The
resulting residue can be recrystallised from methanol. Yield:
1
0.930 g (35%), mp .2908C (dec.). H NMR (CDCl3) d:
9.30 (3H, s), 7.90–7.32 (16H, m), 2.83–2.72 (8H, m), 2.27
(2H, s), 2.15–2.02 (8H, m), 1.79–1.78 (4H, m), 1.59–1.48
(6H, m), 1.26–1.19 ppm (6H, m). 13C NMR (CDCl3) d:
139.08 (2£Cquat., aromat.), 137.59 (2£Cquat., aromat.),
134.91 (2£Cquat., aromat.), 133.30 (2£Cquat., aromat.),
4.1.6. N-(2-Methoxy-ethyl)-3-{200-[2-(2-methoxy-ethyl-