107 (10), 91 (39), 77 (23) and 51 (5); m/z (CI) 272 (Mϩ ϩ NH4,
(t) and 29.2 (t); m/z (EI) 294 (Mϩ, 2%), 147 (100), 119 (20), 91
8%), 255 (MHϩ, 100) and 135 (35).
(60), 65 (60) and 51 (12); m/z (CI) 312 (Mϩ ϩ NH4, 80%), 295
(MHϩ, 100) and 147 (25).
1-(2,3-Dihydrobenzofuran-5-yl)propan-1-one 4a. Mp 58–59
ЊC, δH(CDCl3) 7.87 (d, J 1.9, 1 H), 7.82 (dd, J 1.9, 8.4, 1 H), 6.81
(d, J 8.4, 1 H), 4.67 (t, J 8.8, 2 H), 3.26 (t, J 8.8, 2 H), 2.95 (q,
J 7.3, 2 H) and 1.22 (t, J 7.3, 3 H); δC(CDCl3) 199.4 (s), 164.1
(s), 130.4 (s), 129.8 (d), 127.6 (s), 125.3 (d), 108.9 (d), 72.1 (t),
31.4 (t), 29.0 (t) and 8.6 (q); m/z (EI) 176 (Mϩ, 16%), 147 (100),
119 (21), 91 (82), 77 (13), 65 (85) and 51 (28); m/z (CI) 194
(Mϩ ϩ NH4, 8%) and 177 (MHϩ, 100).
Ethyl tris(2,3-dihydrobenzofuran-5-yl)ethanoate 8. Oil,
δH(CDCl3) 7.00 (d, J 1.2, 3 H), 6.88 (dd, J 1.2, 8.5, 3 H), 6.67 (d,
J 8.5, 3 H), 4.56 (t, J 8.7, 6 H), 4.30 (q, J 7.1, 2 H), 3.15 (t, J 8.7,
6 H) and 1.22 (t, J 7.1, 3 H); δC(CDCl3) 174.5 (s), 158.7 (s),
136.0 (s), 130.2 (d), 126.8 (d), 126.2 (s), 108.1 (d), 71.4 (t), 66.1
(s), 61.5 (t), 29.8 (t) and 14.0 (q); m/z (EI) 442 (Mϩ, 2%) and 369
(100); m/z (CI) 460 (Mϩ ϩ NH4, 2%), 369 (40) and 323 (100).
1-(2,3-Dihydrobenzofuran-5-yl)-2-methylpropan-1-one
4b.
Acknowledgements
Oil, δH(CDCl3) 7.86 (d, J 1.9, 1 H), 7.81 (dd, J 1.9, 8.4, 1 H),
6.81 (d, J 8.4, 1 H), 4.65 (t, J 8.7, 2 H), 3.50 (septet, J 6.8, 1 H),
3.25 (t, J 8.7, 2 H) and 1.20 (t, J 6.8, 6 H); δC(CDCl3) 203.0 (s),
164.1 (s), 130.1 (d), 129.5 (s), 127.7 (s), 125.6 (d), 109.0 (d), 72.1
(t), 34.9 (d), 29.1 (t) and 19.4 (q); m/z (EI) 190 (Mϩ, 12%), 147
(100), 119 (21), 91 (86), 77 (13), 65 (92) and 51 (24); m/z (CI) 208
(Mϩ ϩ NH4, 10%), 191 (MHϩ, 100) and 147 (20).
We thank the University of Wales Swansea, Pfizer Central
Research and the EPSRC for financial support, and the EPSRC
Mass Spectrometry Centre at Swansea for mass spectra. We
also thank the EPSRC, the Higher Education Funding
Council for Wales (ELWa-HEFCW) and the University of
Wales Swansea for grants that enabled the purchase and
upgrading of NMR equipment used in the course of this work,
and Zeolyst International for gifts of zeolites. G. A. El-Hiti
thanks the Royal Society of Chemistry for an international
author grant.
1-(2,3-Dihydrobenzofuran-5-yl)-2,2-dimethylpropan-1-one 4c.
Oil, δH(CDCl3) 7.73 (m, 2 H), 6.77 (d, J 8.3, 1 H), 4.64 (t, J 8.8,
2 H), 3.25 (t, J 8.8, 2 H) and 1.38 (s, 9 H); δC(CDCl3) 206.3 (s),
162.8 (s), 130.3 (s), 130.2 (d), 127.0 (s), 126.2 (d), 108.4 (d), 71.9
(t), 43.8 (s), 29.2 (t) and 28.5 (q); m/z (EI) 204 (Mϩ, 5%), 147
(100), 119 (12), 91 (28), 77 (3), 65 (18) and 51 (12); m/z (CI) 222
(Mϩ ϩ NH4, 3%), 205 (MHϩ, 100) and 147 (15).
References
1 Friedel–Crafts Chemistry, ed. G. A. Olah, Wiley-Interscience,
New York, 1973.
2 K. Smith and S. D. Roberts, Catal. Today, 2000, 60, 227; K. Smith,
S. D. Roberts and G. A. El-Hiti, Org. Biomol. Chem., 2003, 1, 1552.
3 K. Smith and G. Pollaud, J. Chem. Soc., Perkin Trans. 1, 1994, 3519.
4 K. Smith and D. Bahzad, Chem. Commun., 1996, 467; K. Smith,
G. A. El-Hiti, M. E. W. Hammond, D. Bahzad, Z. Li and C. Siquet,
J. Chem. Soc., Perkin Trans. 1, 2000, 2745.
5 K. Smith, P. He and A. Taylor, Green Chem., 1999, 1, 35.
6 K. Smith, M. Butters and B. Nay, Synthesis, 1985, 1157.
7 K. Smith, M. Butters, W. E. Paget, D. Goubet, E. Fromentin and
B. Nay, Green Chem., 1999, 1, 83.
1-(2,3-Dihydrobenzofuran-5-yl)phenylmethanone 4d. Oil,
δH(CDCl3) 7.74 (m, 3 H), 7.65 (dd, J 1.8, 8.4, 1 H), 7.55 (d,
J 1.8, 1 H), 7.46 (t, J 7.5, 2 H), 6.82 (d, J 8.4, 1 H), 4.67 (t, J 8.8,
2 H) and 3.26 (t, J 8.8, 2 H); δC(CDCl3) 195.6 (s), 164.2 (s),
138.6 (s), 132.5 (d), 131.7 (d), 130.4 (s), 129.6 (d), 128.2 (d),
127.6 (s), 127.5 (d), 108.8 (d), 72.2 (t) and 29.0 (t); m/z (EI) 224
(Mϩ, 3%), 147 (10), 119 (3), 105 (88), 77 (100) and 51 (50); m/z
(CI) 242 (Mϩ ϩ NH4, 2%), 225 (MHϩ, 100) and 147 (10).
8 K. Smith, G. M. Ewart and K. R. Randles, J. Chem. Soc., Perkin
Trans. 1, 1997, 1085.
9 K. Smith, K. Fry, M. Butters and B. Nay, Tetrahedron Lett., 1989,
30, 5333.
10 K. Smith, A. Musson and G. A. DeBoss, J. Org. Chem., 1998, 63,
8448.
11 K. Smith, T. Gibbins, R. W. Millar and R. P. Claridge, J. Chem. Soc.,
Perkin Trans. 1, 2000, 2753.
12 K. Smith, S. Almeer and S. J. Black, Chem. Commun., 2000, 1571.
13 K. Smith, S. Almeer and C. Peters, Chem. Commun., 2001, 2748.
14 K. Smith, S. Almeer, S. J. Black and C. Peters, J. Mater. Chem., 2002,
12, 3285.
15 M. Butters, in Solid Supports and Catalysts in Organic Synthesis,
ed. K. Smith, Ellis Horwood, Chichester, 1992, pp. 130–170.
16 J. H. Clark, S. R. Cullen, S. J. Barlow and T. W. Bastock, J. Chem.
Soc., Perkin Trans. 2, 1994, 1117.
17 See for example: C. Gauthier, B. Chiche, A. Finiels and P. Geneste,
J. Mol. Catal., 1989, 50, 219; D. E. Akporiaye, K. Daasvatn,
J. Solberg and M. Stöcker, Stud. Surf. Sci. Catal., 1993, 78,
521; I. Neves, F. Jayat, P. Magnoux, G. Pérot, F. R. Ribeiro,
M. Gubelmann and M. Guisnet, J. Mol. Catal., 1994, 93, 169;
K. Gaare and D. E. Akporiaye, J. Mol. Catal., 1996, 109, 177;
J. M. Escola and M. E. Davis, Appl. Catal., A, 2001, 214, 111;
A. E. W. Beers, T. A. Nijhuis, F. Kapteijn and J. A. Moulijn,
Micropor. Mesopor. Mater., 2001, 48, 279; C. Castro, A. Corma
and J. Primo, J. Mol. Catal. A: Chem., 2002, 177, 273; C. P.
Bezouhanova, Appl. Catal. A, 2002, 229, 127.
18 M. Spagnol, L. Gilbert, R. Jacquot, H. Guillot, P. J. Tirel and A.-M.
Le Govic, Abstract P1, pp. 91–92, in the Book of Abstracts of the
Fourth International Symposium on Heterogeneous Catalysis and
Fine Chemicals, Basel, Switzerland, September 8–12, 1996;
M. Spagnol, E. Benazzi and C. Marcilly, US Patent 1998, 5,817,878.
19 K. Smith, Z. Zhenhua and P. K. G. Hodgson, J. Mol. Catal. A:
Chem., 1998, 134, 121; K. Smith, Z. Zhenhua, L. Delaude and P. K.
G. Hodgson, Abstract O18, pp. 62–63, in the Book of Abstracts of
the Fourth International Symposium on Heterogeneous Catalysis and
Fine Chemicals, Basel, Switzerland, September 8–12, 1996.
20 K. Smith, G. A. El-Hiti, A. J. Jayne and M. Butters, Org. Biomol.
Chem., 2003, 1, 1560.
2-Chloro-1-(2,3-dihydrobenzofuran-5-yl)ethanone 4e. Mp 73–
74 ЊC, δH(CDCl3) 7.82 (m, 2 H), 6.83 (d, J 8.4, 1 H), 4.68 (t,
J 8.8, 2 H), 4.64 (s, 2 H) and 3.27 (t, J 8.8, 2 H); δC(CDCl3) 189.5
(s), 165.2 (s), 130.7 (d), 128.2 (s), 127.4 (s), 126.0 (d), 109.4 (d),
72.4 (t), 45.8 (t) and 20.3 (t); m/z (EI) 198 (Mϩ37Cl, 1%), 196
(Mϩ35Cl, 3), 147 (100), 119 (12), 91 (46), 86 (20), 84 (31), 77 (24),
65 (36) and 51 (52); m/z (CI) 216 (Mϩ37Cl ϩ NH4, 1%),
214 (Mϩ35Cl ϩ NH4, 3), 199 (MHϩ37Cl, 3), 197 (MHϩ35Cl, 9)
and 147 (100) (Found: C, 60.8; H, 4.8. Calc. for C10H9ClO2: C,
61.08; H, 4.61%).
Ethyl
(2,3-dihydrobenzofuran-5-yl)glyoxylate
5.
Oil,
δH(CDCl3) 7.89 (d, J 1.9, 1 H), 7.85 (dd, J 1.9, 8.4, 1 H), 6.85 (d,
J 8.4, 1 H), 4.70 (t, J 8.8, 2 H), 4.43 (q, J 7.2, 2 H), 3.27 (t, J 8.8,
2 H) and 1.42 (t, J 7.2, 3 H); δC(CDCl3) 184.9 (s), 166.1 (s),
164.4 (s), 132.8 (d), 128.4 (s), 127.2 (d), 125.8 (s), 109.7 (d), 72.6
(t), 62.1 (t), 28.7 (t) and 14.1 (q); m/z (EI) 220 (Mϩ, 2%),
147 (100), 119 (12), 91 (22), 65 (16) and 49 (25); m/z (CI) 238
(Mϩ ϩ NH4, 18%), 221 (MHϩ, 100) and 147 (10).
Ethyl bis(2,3-dihydrobenzofuran-5-yl)ethanoate 6. Oil,
δH(CDCl3) 7.14 (d, J 1.5, 2 H), 7.03 (dd, J 1.5, 8.2, 2 H), 6.72 (d,
J 8.2, 2 H), 4.87 (s, 1 H), 4.54 (t, J 8.7, 4 H), 4.19 (q, J 7.1, 2 H),
3.17 (t, J 8.7, 4 H) and 1.25 (t, J 7.1, 3 H); δC(CDCl3) 173.3 (s),
159.2 (s), 131.3 (s), 128.2 (d), 127.4 (s), 125.0 (d), 109.1 (d), 71.3
(t), 61.0 (t), 55.9 (d), 29.7 (t) and 14.2 (q); m/z (EI) 324 (Mϩ,
5%), 251 (100) and 147 (47); m/z (CI) 342 (Mϩ ϩ NH4, 15%),
325 (MHϩ, 8), 251 (35) and 205 (100).
Bis(2,3-dihydrobenzofuran-5-yl)ethanedione 7. Oil, δH(CDCl3)
7.70 (d, J 1.3, 2 H), 7.60 (dd, J 1.3, 8.3, 2 H), 6.81 (d, J 8.3, 2 H),
4.66 (t, J 8.7, 4 H), 3.26 (t, J 8.7, 4 H); δC(CDCl3) 194.7 (s),
163.7 (s), 131.9 (d), 131.2 (s), 127.3 (s), 127.2 (d), 108.6 (d), 72.1
O r g . B i o m o l . C h e m . , 2 0 0 3 , 1, 2 3 2 1 – 2 3 2 5
2325