P. Langer, M. Döring, D. Seyferth, H. Görls
FULL PAPER
are uncorrected and were measured on a Büchi apparatus. Elemen-
tal analyses: Microanalytical laboratory of the University of Hann-
over.
1695 (m), 1599 (m), 1494 (m), 1480 (m), 1443 (m), 1363 (m), 1203
(m), 1078 (w). MS (EI): m/z (%) ϭ 442 [Mϩ] (14), 441 [M Ϫ 1]ϩ
(50), 440 [M Ϫ 2]ϩ (100), 385 (76).
2-[2,4-Bis(4-methylphenyl)imidazol-5-yl]-1-(4-methylphenyl)-3,3-di-
phenylpropen-1-imine (7c): From 1 (1.80 g, 5.60 mmol), 7c was iso-
lated by column chromatography (silica gel, diethyl ether/petroleum
ether, 3:1) as an orange solid (851 mg, 28%), m.p. 152Ϫ157 °C. 1H
NMR ([D8]THF, 200 MHz): δ ϭ 2.21 ppm, 2.28, 2.32 (s, 9 H, Tol-
CH3), 6.75Ϫ7.85 (m, 22 H, Ar), 11.20 (br., 1 H, NH). 13C NMR
([D8]THF, 50 MHz): δc ϭ 125.89 ppm, 127.79, 128.25, 128.68,
128.91, 129.19, 129.27, 129.55, 129.89, 130.92, 131.01, 131.47 (CH,
Ph, Tol), 132.57, 133.00, 134.90, 135.92, 136.81, 137.23, 138.23,
139.01 (C, Ph, Tol, CϭCPh2), 139.52, 142.11, 143.17, 144.50 (C,
Tol-C to CNH, CϭCN, CPh2), 162.82 (C, CN2), 178.21 (C, Cϭ
NH). IR (KBr): ν˜ ϭ 3429 cmϪ1 (m), 3027 (m), 2921 (m), 1598 (m),
1558 (m), 1506 (s), 1444 (m); 1362 (m), 1183 (m), 1078 (w), 1033
(w), 823 (s), 698 (s). MS (CI, H2O): m/z (%) ϭ 544 [M ϩ 1]ϩ (100).
C39H33N3 (543.693): calcd. C 86.16, H 6.12, N 7.72; found C, 85.25,
H 6.27, N 8.45.
General Procedure for the Generation of 1,1-Dilithio-3,3-diphenylal-
lene (2) and Its Reaction with Nitriles: A THF solution of LDA,
prepared by addition of nBuLi (1.6 solution in hexane) to a THF
solution (20 mL) of diisopropylamine (3.3 equiv.), was added at 0
°C to a THF solution (40 mL) of silyl enol ether 1 (1.80 g,
5.60 mmol). The solution was stirred at 20 °C for 6 h, during which
it became deep red. A THF solution (10 mL) of benzonitrile
(2.58 mL, 4.5 equiv.), pivalonitrile (1.61 g) or p-tolunitrile (2.26 g)
was then added at 0 °C by syringe. After the mixture had been
stirred for 10 h at 20 °C, water (20 mL) was added. The colour of
the solution changed from deep purple to yellow. The reaction mix-
ture was extracted (diethyl ether/THF, 1:1) and the combined or-
ganic layers were dried (MgSO4) and filtered, and the solvent was
removed in vacuo to give the crude product, which was purified
as indicated.
5-(2,4-Diphenylimidazol-5-yl)-2,4,4,6-tetraphenyl-1,4-dihydro-
pyrimidine (8a): From 1 (1.80 g, 5.60 mmol), 8a was isolated by
chromatography (silica gel, diethyl ether/petroleum ether, 1:1) as a
colourless solid (1.73 g, 51%), m.p. 146Ϫ150 °C. Imidazole 7a was
isolated as a second product in 12% yield (spectroscopic data: see
below). 1H NMR ([D8]THF, 200 MHz): δ ϭ 6.75Ϫ8.20 ppm (m,
30 H, Ar), 8.75 (br., 1 H, NH), 10.68 (br., 1 H, NH). 13C NMR
([D8]THF, 50 MHz): δc ϭ 107.20 ppm (C, CPh2), 125.27, 125.76,
125.87, 126.06, 126.26, 127.12, 127.30, 127.50, 128.02, 128.08,
128.17, 128.30, 128.68, 128.90, 129.21, 129.76 129.92, 130.86 (CH,
Ph), 132.15, 132.19, 136.43, 136.73, 137.37, 138.19 (C, Ph, ϭ
CCPh2), 145.67, 148.50, 148.78 (C, CϭCN), 150.65, 150.78 (C,
CN2). IR (KBr): ν˜ ϭ 3495 cmϪ1 (br), 3395 (br), 3060 (m), 3029
(m), 2923 (w), 1640 (s), 1598 (m), 1578 (m), 1524 (s), 1496 (m),
5-(2Ј,2Ј-Diphenylethenyl)-2,4-bis(3-methylphenyl)imidazole
(6d):
From 1 (1.80 g, 5.60 mmol), 6d was isolated by chromatography
(silica gel, diethyl ether/petroleum ether, 3:1) as an orange solid
(954 mg, 40%). In addition, 5d was isolated as an orange solid
1
(550 mg, 28%). H NMR (CDCl3, 250 MHz): δ ϭ 2.35 ppm, 2.48
(2 ϫ s, 2 ϫ 3 H, 2 ϫ CH3), 7.05Ϫ7.75 (m, 19 H, Ar, ϭCHϪ), 8.23
(br., 1 H, NH). 13C NMR (CDCl3, 75 MHz): δc ϭ 21.22 ppm,
21.49 (CH3), 114.61, 121.58 (CH), 125.49 (C), 125.60, 125.64,
126.67, 127.35, 128.05, 128.28, 128.30, 128.34, 128.55, 129.09 (CH),
129.24 (C), 129.43, 129.71, 129.90 (CH), 134.43, 137.86, 138.11,
138.38, 140.33, 141.21, 144.20, 145.64 (C). MS (EI): m/z (%) ϭ 426
(100) [Mϩ], 349 (6).
1,3,5-Tris(3-methylphenyl)triazine (5d): Yield: 550 mg (28%). 1H
1446 (m), 1395 (s), 1370 (m), 1178 (m), 1072 (m), 1028 (m), 697 NMR (CDCl3, 250 MHz): δ ϭ 2.60 ppm (s, 9 H, CH3), 7.30Ϫ7.60
(s). MS (FAB): m/z (%) ϭ 605 [M ϩ 1]ϩ (100). C43H32N4 (604.729):
calcd. C 85.41, H 5.33, N 9.26; found calcd. C 85.17, H 5.61, N
9.62.
(m, 9 H, Ar), 8.58 (s, 3 H, Ar). 13C NMR (CDCl3, 75 MHz): δc ϭ
42.30 ppm (CH3), 126.14, 128.40, 129.29, 133.14 (CH), 136.16,
138.12 (C), 171.50 (CN2). MS (EI): m/z (%) ϭ 351 [Mϩ] (100), 119
(22). MS (CI, H2O): m/z (%) ϭ 703 [2M ϩ 1]ϩ (6), 352 [M ϩ
1]ϩ (100).
2-(2,4-Diphenylimidazol-5-yl)-1,3,3-triphenyl-2-propen-1-one (7a):
From 1 (1.80 g, 5.60 mmol), 7a was isolated by chromatography
(silica gel, diethyl ether/petroleum ether, 3:1, more polar fraction)
as an orange solid (337 mg, 12%), m.p. 160Ϫ163 °C. 1H NMR
(CDCl3, 200 MHz): δ ϭ 6.80Ϫ7.70 ppm (m, 25 H, Ar), 9.10 (br.,
1 H, NH), 9.30 (br., 1 H, NH). 13C NMR (CDCl3, 50 MHz): δc ϭ
125.26 ppm, 125.32, 125.90, 126.83, 127.60, 127.62, 127.78, 128.06,
128.18, 128.38, 128.60, 128.99, 129.60, 130.02, 130.14 (CH, Ph),
132.00, 134.11, 137.40, 137.45, 138.22 (C, Ph, CϭCPh2), 141.51,
142.24, 146.81, 147.55 (C, Ph-C to CNH, CϭCN, CPh2), 160.0 (C,
CN2), 177.11 (C, CϭNH). IR (KBr): ν˜ ϭ 3430 cmϪ1 (m), 3133
(m), 3060 (s), 3029 (s), 2925 (m), 1593 (s), 1565 (s), 1494 (s), 1459
(s); 1446 (s), 1365 (s), 1190 (m), 1159 (m), 1073 (m), 1028 (m), 693
(s). MS (CI, H2O): m/z (%) ϭ 502 [M ϩ 1]ϩ (100).
Crystal Structure Determinations: The intensity data for the com-
pounds were collected on a Nonius CAD4 diffractometer (graph-
ite-monochromated Mo-Kα radiation). Data were corrected for Lo-
rentz and polarization effects, but not for absorption.[16] The struc-
tures were solved by direct methods (SHELXS)[17] and refined by
full-matrix, least-squares techniques against F2o (SHELXL-97).[18]
For the imine nitrogen N2 and for the water-molecule of 7b the
hydrogen atoms were located by difference Fourier synthesis and
refined isotropically. The other hydrogen atoms were included at
calculated positions with fixed thermal parameters. All non-hydro-
gen atoms were refined anisotropically.[19] XP (SIEMENS Analyti-
cal X-ray Instruments, Inc.) was used for structure representations.
Crystal Data for 7a:[19] C36H24N2O·H2O, Mr ϭ 518.59 g·molϪ1
colourless prism, size 0.40 ϫ 0.38 ϫ 0.36 mm, triclinic, space group
,
1-(tert-Butyl)-2-[2,4-di(tert-butyl)imidazol-5-yl]-3,3-diphenyl-2-
propen-1-one (7b): From 1 (1.80 g, 5.60 mmol), 7b was isolated by
crystallization of the crude product (from ether) and subsequent
washing of the crystals (ether) as colourless crystals (1.63 g, 66%),
˚
¯
P1, a ϭ 11.415(2), b ϭ 11.551(2), c ϭ 11.655(2) A, α ϭ 72.77(3),
3
˚
β ϭ 87.02(3), γ ϭ 85.88(3)°, V ϭ 1463.2(4) A , T ϭ 20 °C, Z ϭ 2,
ρ
calcd. ϭ 1.177 g·cmϪ3, µ(Mo-Kα) ϭ 0.73 cmϪ1, F(000) ϭ 544, 3660
1
m.p. 171Ϫ172 °C. H NMR ([D8]THF, 200 MHz): δ ϭ 1.00 ppm
reflections in h(Ϫ12/0), k(Ϫ12/12), l(Ϫ12/12), measured in the
range 6.88° Յ Θ Յ 21.97°, completeness Θ ϭ 96.8%, 3457
(s, 9 H, CH3), 1.05 (s, 9 H, CH3), 1.36 (s, 9 H, CH3), 7.01 (m, 3 H,
Ph), 7.24 (m, 3 H, Ph), 9.65 (br., 1 H, NH). 13C NMR ([D8]THF,
50 MHz): δc ϭ 126.93 ppm, 127.38, 127.72, 128.26, 131.86, 132.45
(CH, Ph), 132.93, 133.95, 137.64 (C, Ph, CϭCPh2), 140.29, 143.84,
max
independent reflections, Rint ϭ 0.090, 2333 reflections with Fo Ͼ
4σ(Fo), 357 parameters, 0 restraints.
144.28 (C, CϭCN, CPh2), 154.21 (C, CN2), 191.71 (C, CϭO). IR Crystal Data for 8a:[19] C43H32N4, Mr ϭ 604.73 g·molϪ1, colourless
(KBr): ν˜ ϭ 3455 cmϪ1 (m), 3060 (m), 3028 (m), 2959 (s), 2928 (m),
prism, size 0.40 ϫ 0.38 ϫ 0.36 mm, triclinic, space group P1, a ϭ
¯
1952
2003 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Eur. J. Org. Chem. 2003, 1948Ϫ1953