References
1a
Olah GA.
Friedel-Crafts
Chemistry
Wiley-Interscience;
London:
1973.
1b
Heaney H. In Comprehensive
Organic Synthesis
Vol. 2:
Trost BM.
Fleming I.
Pergamon
Press;
Oxford:
1991.
p.733
2a
Kawada A.
Mitamura S.
Kobayashi S.
J. Chem. Soc., Chem. Commun.
1993,
1157
2b
Kawada A.
Mitamura S.
Kobayashi S.
Synlett
1994,
545
2c
Hachiya I.
Moriwaki M.
Kobayshi S.
Bull.
Chem. Soc. Jpn.
1995,
68:
2053
2d
Kobayashi S.
Iwamoto S.
Tetrahedron Lett.
1998,
39:
4697
3a
Desmur JR.
Labrouillere M.
Le Roux C.
Gaspard H.
Laporterie A.
Dubac J.
Tetrahedron
Lett.
1997,
38:
8871
3b
Repichet S.
LeRoux C.
Dubac J.
Desmurs JR.
Eur. J. Org. Chem.
1998,
2743
4
Mikami K.
Kotera O.
Motoyama Y.
Sakaguchi H.
Maruta M.
Synlett
1996,
171
5
Fürstner A.
Voightlander D.
Schrader W.
Giebel D.
Reetz MT.
Org.
Lett.
2001,
3:
417
6
Waller FJ.
Barrett AGM.
Braddock DC.
Ramprasad D.
McKinnell RM.
White JP.
Williams DJ.
Ducray R.
J.
Org. Chem.
1999,
64:
2910
7
Barrett AGM.
Braddock DC.
Ducray R.
McKinnell RM.
Waller FJ.
Synlett
2000,
57
8a
Barrett AGM.
Braddock DC.
Catterick D.
Chadwick D.
Henschke JP.
McKinnell RM.
Synlett
2000,
847
8b
Barrett AGM.
Bouloc N.
Braddock DC.
Catterick D.
Chadwick D.
White AJP.
Williams DJ.
Tetrahedron
2002,
58:
3835
9 Catalytic Compounds and Processes.
UK Patent Application No 9919583.6.
10a
Mikami K.
Mikami Y.
Matsumoto Y.
Nishikido J.
Yamamoto F.
Nakajimi H.
Tetrahedron
Lett.
2001,
42:
289
10b
Mikami K.
Mikami Y.
Matsuzawa H.
Matsumoto Y.
Nishikido J.
Yamamoto F.
Nakajima H.
Tetrahedron
2002,
58:
4015
11 For experimental details for the
preparation of these complexes see: Barrett AGM.
Bouloc N.
Braddock DC.
Catterick D.
Chadwick D.
White AJP.
Williams DJ.
Tetrahedron
2002,
58:
3835
12 These plots were obtained using a
Mettler-Toledo REACT-IR 4000 system with a dicomp probe scanning
every 60 s
(25 °C, 50 °C) or 45 s (70 °C)
for the first two hours followed by one scan every five min for
the remaining time. The profiles are generated by following the
peak area between 1672 and 1685 wave numbers to a constant baseline
point.
13
General Experimental
Procedure: A stirred solution of arene (0.6 mmol), anhydride
(1.2 mL) and catalyst 1 (16 mg, 0.006 mmol)
in PhCF3 (1.2 mL) was heated to 150 °C in a sealed
tube for 20 h. The resulting mixture was allowed to cool, diluted
with Et2O (10 mL), washed with water (2 × 10 mL),
sat. aq sodium hydrogen carbonate solution (2 × 10 mL),
sat. aq sodium chloride solution (2 × 10 mL), dried (MgSO4),
concentrated in vacuo and chromatographed.
14
IR and
¹
H NMR
for Friedel-Crafts Acylation Products: 4-Methoxyacetophenone:
IR (KBr): 1676 cm-1. 1H
NMR (300 MHz, CDCl3): δ = 2.58 (s,
3 H), 3.84 (s, 3 H), 6.96 (d, 2 H, J = 9.0
Hz), 7.95 (d, 2 H, J = 9.0
Hz). 4-Methoxy-isobutyrophenone: IR (KBr):
1675 cm-1. 1H NMR
(300 MHz, CDCl3): δ = 1.20 (d, 6 H, J = 7.0 Hz),
3.53 (septet, 1 H, J = 7.0
Hz), 3.87 (s, 3 H), 6.94 (d, 2 H, J = 8.5
Hz), 7.95 (d, 2 H, J = 8.5
Hz). 4-Methoxybenzophenone: IR (KBr): 1650
cm-1. 1H NMR (300
MHz, CDCl3): δ = 3.91 (s, 3 H), 6.98
(d, 2 H, J = 8.0
Hz), 7.47-7.59 (m, 3 H), 7.78 (d, 2 H, 7.0 Hz), 7.85 (d,
2 H, J = 8.0
Hz). 4-Thiomethylace-tophenone: IR (KBr):
1673 cm-1. 1H NMR
(300 MHz, CDCl3): δ = 2.55 (s, 3 H),
2.59 (s, 3 H), 7.28 (d, 2 H, J = 8.0 Hz),
7.89 (d, 2 H, J = 8.0
Hz). 4-Thiomethyl-isobutyro-phenone: IR
(KBr): 1670 cm-1. 1H
NMR (300 MHz, CDCl3): δ = 1.21 (d,
6 H, J = 7.0
Hz), 2.53 (s, 3 H), 3.51 (septet, 1 H, J = 7.0
Hz), 7.27 (d, 2 H, J = 8.5
Hz), 7.87 (d, 2 H, J = 8.5
Hz). 4-Thiomethylbenzophenone: IR (KBr): 1649
cm-1. 1H NMR (300
MHz, CDCl3): δ = 2.56 (s, 3 H), 7.28-7.32
(2 H, m), 7.48-7.65 (3 H, m), 7.72-7.80 (m, 4 H). 2-Acetylthiophene: IR (KBr): 1662 cm-1. 1H
NMR (270 MHz, CDCl3): δ = 2.59 (s,
3 H), 7.15 (1 H, t, J = 4.0
Hz) 7.65 (d, 1 H, J = 4.0
Hz), 7.71 (d, 1 H, J = 4.0
Hz). 2-Isobutyryl-thiophene: IR (KBr):
1662 cm-1. 1H NMR
(300 MHz, CDCl3): δ = 1.27 (d, 6 H, J = 7.0 Hz),
3.41 (septet, 1 H, J = 7.0
Hz) 7.15 (t, 1 H, J = 4.5
Hz) 7.65 (d, 1 H, J = 5.0
Hz), 7.75 (d, 1 H, J = 4.5
Hz). 2-Benzoylthiophene: IR (KBr): 1632
cm-1. 1H NMR (300
MHz, CDCl3): δ = 7.19 (t, 1 H, J = 3.5 Hz),
7.52-7.68 (m, 6 H), 7.87 (d, 2 H, J = 3.0
Hz). 5-Acetyl-3-methylthiophene: IR (KBr):
1662 cm-1. 1H NMR (270
MHz, CDCl3): δ = 2.29 (s, 3 H), 2.53
(s, 3 H), 7.22 (d, 1 H, J = 1.0 Hz), 7.49 (d,
1 H, J = 1.0
Hz). 2-Acetyl-3-methylthiophene: IR (KBr):
1662 cm-1. 1H NMR
(270 MHz, CDCl3): δ = 2.29 (s, 3 H),
2.55 (s, 3 H), 6.93 (d, 1 H, J = 5.0 Hz), 7.39 (d,
1 H, J = 5.0
Hz). 2- and 5-Isobutyryl-3-methylthiophene:
IR (KBr): 1660 cm-1. 1H
NMR (300 MHz, CDCl3): δ = 1.23 (d,
6 H, J = 7.0
Hz), 2.13 (s, 1.05 H), 2.59 (s, 1.95 H), 3.32 (m, 1 H), 6.97 (d,
0.65 H, J = 5.0
Hz), 7.38 (s, 0.35 H), 7.40 (d, 0.65 H, J = 5.0
Hz), 7.55 (s, 0.35 H). 2- and 5-Benzoyl-3-methylthiophene:
IR (KBr): 1633 cm-1. 1H
NMR (300 MHz, CDCl3): δ = 2.34 (s,
1.2 H), 2.51 (s, 1.8 H), 7.03 (d, 0.6 H, J = 5.0
Hz), 7.34 (s, 0.4 H), 7.46-7.61 (m, 4 H), 7.86 (m, 2 H). 9-Benzoylanthracene: IR (KBr): 1656 cm-1. 1H
NMR (300 MHz, CDCl3): δ = 7.39-7.61
(m, 7 H), 7.74 (d, 2 H, J = 8.5
Hz), 7.84 (d, 2 H, J = 7.0 Hz),
8.09 (d, 2 H, J = 8.5
Hz), 8.56 (s, 1 H). α- and β-
Benz-oylnaphthalene: IR (KBr): 1659 cm-1. 1H
NMR (300 MHz, CDCl3): δ = 7.46-7.65
(m, 7 H), 7.88-8.05 (m, 4 H), 8.11 (d, 0.65 H, J = 7.5 Hz),
8.29 (s, 0.35 H). 2,4-Dimethyl-benzophenone:
IR (KBr): 1662 cm-1. 1H
NMR (300 MHz, CDCl3): δ = 2.35 (s,
3 H), 2.41 (s, 3 H), 7.07 (d, 1 H, J = 7.0 Hz),
7.13 (s, 1 H), 7.25 (d, 1 H, J = 7.5
Hz), 7.47 (m, 2 H), 7.58 (m, 1 H), 7.81 (d, 2 H, J = 7.0
Hz). 2- and 4-Methyl-benzophenone: IR (KBr):
1658 cm-1. 1H NMR
(300 MHz, CDCl3): δ = 2.36 (s, 0.4
H, 2-CH3), 2.45 (s, 2.6 H, 4-CH3), 7.29-7.82
(m, 9 H).