PAPER
MoCl5-Mediated Coupling Reaction
95
Anal. Calcd for C20H24Cl2O4 (399.31): C, 60.16; H, 6.06. Found: C,
59.93; H, 6.35.
Acknowledgement
This work was supported by the Deutsche Forschungsgemeinschaft
(DFG) and the European Graduate College ‘Template Directed
Chemical Synthesis’. The gift of MoCl5 by H.C. Starck (Goslar,
Germany) was very helpful.
4,5,4 ,5 -Tetrakis-(2-chloroethoxy)-2,2 -dimethylbiphenyl (2k)
Mp 93–94 °C (from MeOH).
1H NMR (300 MHz, CDCl3): = 1.91 (s, 6 H, ArCH3), 3.71–3.79
(m, 8 H, CH2Cl), 4.15 (m, 8 H, CH2O), 6.63 (s, 2 H, 3-H), 6.76 (s,
2 H, 6-H).
13C NMR (75 MHz, CDCl3): = 19.2 (ArCH3), 41.9 (CH2Cl), 42.2
(CH2Cl), 70.1 (CH2O), 70.3 (CH2O), 117.8; 117.9 (C-3, C-6), 130.4
(C-2), 135.0 (C-1), 146.2 (C-5), 147.6 (C-4).
References
(1) (a) Waldvogel, S. R.; Fröhlich, R.; Schalley, C. A. Angew.
Chem. Int. Ed. 2000, 39, 2472. (b) Waldvogel, S. R.;
Wartini, A. R.; Rasmussen, P. H.; Rebek, J. Jr. Tetrahedron
Lett. 1999, 40, 3515.
(2) Kramer, B.; Averhoff, A.; Waldvogel, S. R. Angew. Chem.
Int. Ed. 2002, 41: in press.
(3) Waldvogel, S. R.; Aits, E.; Holst, C.; Fröhlich, R. Chem.
Commun. 2002, 1278.
(4) Waldvogel, S. R. Synlett 2002, 622.
MS (EI, 70 eV): m/z (%) = 494.0; 496.0; 498.0 (76, 100, 50) [M+],
63.0 (31) [CHCH2Cl+].
Anal. Calcd for C22H26Cl4O4 (496.25): C, 53.25; H, 5.28. Found: C,
52.79; H, 5.16 (Calcd for C22H26Cl4O4 0.25 CH3OH (504.25.): C,
53.00; H, 5.40).
(5) Kumar, S.; Manickham, M. Chem. Commun. 1997, 1615.
(6) Green, T. W.; Wuts, G. M. In Protective Groups in Organic
Synthesis; Wiley-Interscience: New York, 1999.
(7) Takada, T.; Arisawa, M.; Gyoten, M.; Hamada, R.; Tohma,
H.; Kita, Y. J. Org. Chem. 1998, 63, 7698.
(8) Ogura, K.; Tsuchihashi, G. Tetrahedron Lett. 1971, 12,
3151.
(9) Weertunga, G.; Jaworska-Sobiesiak, A.; Horne, S.; Russell,
R. Can. J. Chem. 1987, 65, 2019.
(10) Benigni, J. D.; Minnis, R. L. J. Heterocycl. Chem. 1965, 2,
307.
(11) Arcoleo, A.; Garofano, T. Ann. Chim. (Rome, Italy) 1957,
47, 1142.
(12) Srikishna, A.; Rao, M. S. Tetrahedron Lett. 2001, 42, 5781.
(13) Larock, R. C.; Babu, S. Tetrahedron 1987, 43, 2013.
(14) (a) Nelson, T. D.; Crouch, R. D. Synthesis 1996, 1031.
(b) Davies, J. S.; Higginbotham, C. L.; Tremeer, E. J.;
Brown, C.; Treadgold, R. C. J. Chem. Soc., Perkin Trans. 1
1992, 3043.
(15) Laatsch, H. Liebigs Ann. Chem. 1980, 140.
(16) Laatsch, H. Z. Naturforsch., B: Chem. Sci. 1985, 40, 534.
(17) X-ray crystal structure analysis of 4: formula C26H30O6
M = 438.50 colorless crystal 0.35 0.30 0.10 mm
a = 11.923(2) b = 12.352(2) c = 16.974(2) Å = 96.80(1)
= 92.64(2) = 112.76(1)° V = 2277.4(6) Å3 calc = 1.279
gcm–3 = 7.34 cm–1 empirical absorption correction via
2,3-Bis-(5-hydroxy-4-methoxy-2-methylbenzyl)-6-methoxy-4-
methylphenol Hemihydrate (4)18
Mp 200–202 °C (from hexane).
1H NMR (600 MHz, CDCl3): = 1.64 (s, 1 H, 0.5 H2O), 2.11 (s, 3
H, 7-H), 2.16 (s, 3 H, 8 -H), 2.17 (s, 3 H, 8 -H), 3.54 (s, 2 H, 1 -H),
3.67 (s, 2 H, 1 -H), 3.82 (s, 3 H, 9 -H), 3.83 (s, 3 H, 9 -H), 3.89 (s,
3 H, 8-H), 5.31 (s, 2 H, 4 -OH; 4 -OH), 5.54 (s, 1 H, 1-OH), 6.18
(s, 1 H, 3 -H), 6.33 (s, 1 H, 3 -H), 6.63 (s, 1 H, 6 -H), 6.65 (s, 1 H,
6 -H), 6.66 (s, 1 H, 3-H).
13C NMR (150 MHz, CDCl3): = 19.2 (C-8 ), 19.3 (C-8 ), 19.8 (C-
7), 28.5 (C-1 ), 31.3 (C-1 ), 55.9 (C-8; C-9 ; C-9 ), 111.2 (C-3),
112.5 (C-6’), 112.6 (C-6 ), 113.4 (C-3 ), 113.6 (C-3 ), 125.2 (C-6),
127.2 (C-7 ), 127.3 (C-7 ), 128.2 (C-4), 130.1 (C-5), 131.4 (C-2 ),
131.6 (C-2 ), 142.3 (C-1), 143.3 (C-4 ), 143.4 (C-4 ), 144.1 (C-5 ;
C-5 ), 144.6 (C-2).
GCOSY (600 MHz / 600 MHz, CDCl3): (13C) / (1H) = 2.11 (7-
H) / 6.66 (3-H), 2.16 (8 -H) / 3.54 (1 -H) / 6.65 (6 -H), 2.17 (8 -H)
/ 3.67 (1 -H) / 6.63 (6 -H), 2.16 (8 -H) / 3.54 (1 -H) / 6.18 (3 -H),
2.17 (8 -H) / 3.67 (1 -H) / 6.33 (3 -H).
GHSQC (150 MHz / 600 MHz, CDCl3): (13C) / (1H) = 19.2 /
2.16 (C-8 / 8 -H), 19.3 / 2.17 (C-8 / 8 -H), 19.8 / 2.11 (C-7 / 7-H),
28.5 / 3.67 (C-1 / 1 -H), 31.3 / 3.54 (C-1 / 1 -H), 55.9 / 3.82 (C-8,
C-9 , C-9 / 9 -H), 55.9 / 3.83 (C-8, C-9 , C-9 / 9 -H), 55.9 (C-8,
C-9 , C-9 / 8-H), 111.2 / 6.66 (C-3 / 3-H), 112.5 / 6.65 (C-6 / 6 -
H), 112.57 / 6.61 (C-6 / 6 -H), 113.4 / 6.18 (C-3 / 3 -H), 113.61 /
6.33 (C-3 / 3 -H).
scan data (0.783
T
0.930) Z = 4 triclinic space group
P1bar (No. 2) = 1.54178 Å T = 223 K /2 scans 9478
reflections collected (+h k l) [(sin )/ ] = 0.62 Å-1 9040
independent (Rint = 0.026) and 7595 observed reflections [I
GHMBC (50 MHz / 600 MHz, CDCl3): (13C) / (1H) = 28.5 (C-
1 ); 127.3 (C-7 ); 143.3 (C-4 ); 144.1 (C-5 ; C-5 ) / 6.33 (3 -H),
31.3 (C-1 ); 127.2 (C-7 ); 143.4 (C-4 ); 144.1 (C-5 ; C-5 ) / 6.18 (3 -
H), 125.2 (C-6); 127.2 (C-7 ); 128.2 (C-4); 130.1 (C-5); 131.4 (C-
2 ) / 3.54 (1 -H), 125.2 (C-6); 127.3 (C-7 ), 130.1 (C-5), 131.6 (C-
2 ) / 3.67 (1 -H), 125.2 (C-6) / 5.54 (1-OH), 127.2 (C-7 ) / 6.18 (3 -
H), 127.3 (C-7 ) / 6.33 (3 -H), 128.2 (C-4); 130.1.(C-5) / 2.11 (7-
H), 143.3 (C-4 ); 144.1 (C-5 C-5 ) / 6,33 (3 -H), 143.4 (C-4 );
144.1 (C-5 ; C-5 ) / 6.18 (3 -H).
2
(I)] 595 refined parameters R = 0.047 wR2 = 0.134
max. residual electron density 0.30 (–0.24) e Å–3 two
independent molecules in the asymmetric unit hydrogens
calculated and refined as riding atoms.
Data set was collected with an Enraf Nonius CAD4
diffractometer. Programs used: data collection Express
(Nonius B.V. 1994) data reduction MolEN (K. Fair 1990)
structure soln SHELXS-97 (Sheldrick, G. M. Acta Cryst.
1990, A46, 467) structure refinement SHELXL-97
(Sheldrick, G. M. Universität Göttingen, 1997) graphics
POV-Ray 3.2.
Crystallographic data (excluding structure factors) for the
structure reported in this paper have been deposited with the
Cambridge Crystallographic Data Centre as supplementary
publication CCDC 191456. Copies of the data can be
obtained free of charge on application to The Director
CCDC 12 Union Road CambridgeCB2 1EZ UK [fax:
+44(1223)336033 e-mail: deposit@ccdc.cam.ac.uk].
1D-NOE (600 MHz, CDCl3): Irradiation at = 2.11 (7-H), NOE-
signal at 3.54 (1 -H), 6.18 (3 -H), 6.66 (3-H); irradiation at = 3.53
(1 -H), NOE-signal at 2.11 (7-H), 2.16 (8 -H), 3.67 (1 -H), 6.18 (3 -
H), 6.33 (3 -H); irradiation at = 3.66 (1 -H), NOE-signal at 2.17
(8 -H), 3.54 (1 -H), 6.18 (3 -H), 6.33 (3 -H); irradiation at = 3.89
(8-H), NOE-signal at 6.66 (3-H).
MS (EI, 70 eV): m/z (%) = 438.2 (100) [M+], 285.1 (86) [M+ –
+
C9H13O2], 151.1 (37) [C9H12O2 ].
Anal. Calcd for C26H30O6 0.5 H2O (447.52): C, 69.78; H, 6.98.
Found: C, 70.02; H, 6.74.
Synthesis 2003, No. 1, 91–96 ISSN 0039-7881 © Thieme Stuttgart · New York