M. Barbero, S. Bazzi, S. Cadamuro, S. Dughera, G. Ghigo
FULL PAPER
Representative Procedure for the Disproportionation Reaction. Syn-
thesis of Bis(4-methoxyphenyl)methane (6a): o-Benzenedisulfon-
imide (1; 10 mol-%; 0.11 g, 0.5 mmol) was added to a mixture of
bis(4-methoxyphenyl)methanol (2a; 1.22 g, 5 mmol) and propan-2-
ol (8c, 0.30 g, 5.5 mmol). The mixture was stirred at 80 °C. The
reaction was monitored by GC and GC/MS; after 15 min, 2a had
disappeared, and both isopropyl bis(4-methoxyphenyl)methyl ether
(9c; m/z = 286 [M]+) and the title compound 6a (m/z = 228 [M]+)
were observed. As the reaction progressed, GC and GC/MS analy-
ses showed that 9c decreased and 6a increased. After 3 h, 6a re-
mained, and acetone (10c; m/z = 58 [M]+) could also be observed.
The reaction mixture was poured into diethyl ether/water (1:1,
100 mL). The aqueous layer was separated and extracted with di-
ethyl ether (2ϫ50 mL). The combined organic extracts were
washed with water (2ϫ50 mL), dried with Na2SO4, and concen-
trated under reduced pressure. The crude residue (1.14 g, 100%
yield) was virtually pure 6a (GC, GC/MS, 1H NMR). The aqueous
layer and aqueous washings were collected and concentrated under
reduced pressure. After removal of water, virtually pure (1H NMR)
o-benzenedisulfonimide (1) was recovered [0.10 g, 91% yield; m.p.
192–194 °C (toluene; ref.[19] m.p. 192–194 °C)].
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[8]
(4-Fluorophenyl)(4-hydroxyphenyl)methane (6i): Colorless oil. 1H
NMR (200 MHz, CDCl3, 25 °C): δ = 8.78 (br. s, 1 H) 7.70–7.67
and 7.08–7.03 (2 m, 1:1, 4 H), 7.62 and 6.84 (2 d, 1:1, J = 8.75 Hz,
4 H), 3.95 (s, 2 H) ppm. 13C NMR (50 MHz, CDCl3, 25 °C): δ =
1
4
[9]
165.1 (d, JCF = 251.5 Hz), 161.2, 134.6 (d, JCF = 3.0 Hz), 132.8,
3
2
132.3 (d, JCF = 9.0 Hz), 129.1, 115.5, 115.3 (d, JCF = 15.5 Hz),
46.6 ppm. MS (EI): m/z = 202 [M]+. C13H11FO (202.23): calcd. C
77.21, H 5.48, F 9.39; found C 77.22, H 5.51, F 9.44.
[10]
Hydrolysis of 6d: As reported in the literature,[14] Fe(NO3)3·9H2O
(0.40 g, 1.0 mmol) was added to a solution of 6d (0.56 g, 2.0 mmol)
in MeOH (10 mL). The reaction mixture was stirred at room tem-
perature for 24 h. The solvent was then removed under reduced
pressure, and the crude residue was poured into diethyl ether/water
(1:1, 100 mL). The aqueous layer was separated and extracted with
diethyl ether (2ϫ50 mL). The combined organic extracts were
washed with water (2ϫ50 mL), dried with Na2SO4, and concen-
trated under reduced pressure. The residue was virtually pure (GC,
GC/MS, 1H NMR) bis(4-aminophenyl)methane (6m, 0.35 g, 88%
yield). M.p. 90–92 °C (MeOH). MS (EI): m/z = 198 [M]+, identical
to a commercial sample (Sigma–Aldrich).
[11]
[12]
[13]
[14]
[15]
Theoretical Methods: The theoretical study was performed by using
density functional theory (DFT)[23] making use of the mPWB1K
functional.[24] This functional was developed by Truhlar and co-
workers for the accurate evaluation of energy barriers. All geome-
tries were fully optimized with the 6-311+G(d,p) basis set[25a,25b]
and characterized by vibrational frequency analysis.[26] Single-point
energy calculations were performed with the 6-311+(3df,2p) basis
set,[25b,25c] including the electrostatic and nonelectrostatic solvent
effects with the polarized continuum method.[27] Finally, these data
were combined with the gas-phase zero-point energy corrections.
All energy values are reported in the Supporting Information. Cal-
culations were performed by using the Gaussian 03 program.[28]
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[18]
[19]
Supporting Information (see footnote on the first page of this arti-
cle): Total (in a.u.) and relative (in kcalmol–1) energies and nuclear
coordinates (in Å).
[20]
[21]
[22]
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Acknowledgments
This work was supported by the Ministero dell’Università e della
Ricerca and by the University of Torino.
[23]
R. G. Parr, W. Yang, Density Functional Theory of Atoms and
Molecules, Oxford University Press, New York, 1989.
4350
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Eur. J. Org. Chem. 2009, 4346–4351