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R. M. Kellogg et al.
FEATURE ARTICLE
Synthesis of Sulfonates 18; General procedure
The chalcone 17 (90 mmol) was dissolved in 96% EtOH (150 mL).
NaHSO3 (90 mmol) was dissolved in H2O (100 mL) and added to
the chalcone solution. The reaction mixture was heated to reflux.
The reaction was usually complete within 3.5 h, but can convenient-
ly be refluxed overnight. After cooling to r.t., the reaction mixture
was concentrated in vacuo to give the end product 18. If precipita-
tion occurred after cooling, the product 18 was removed by filtra-
tion under suction.
trate was passed over Amberlite IR-120. The column was eluted
with H2O. The eluent was concentrated in vacuo and stripped with
toluene to obtain 50 mg of free sulfonic acid, which still contained
some H2O.
Synthesis of Chalcones 17a–e; General Procedure
Acetophenone (4.2 g, 0.43 mol) was dissolved in 96% EtOH (100
mL) and H2O (200 mL). NaOH (21.8 g) was added. The reaction
mixture was cooled in ice and benzaldehyde (4.1 g, 0.43 mol) was
added dropwise within 5 min. The reaction mixture was stirred at r.t.
overnight. The solid formed was removed by filtration under suc-
tion. If precipitation did not occur, the reaction mixture was extract-
ed with Et2O (3 × 100 mL). The combined ether layers were washed
with brine, dried over Na2SO4, and concentrated in vacuo to yield
the desired products.
Sodium 1,3-Diphenyl-3-oxo-propanesulfonate (18a)
Yield: 71%; white solid; mp 119.9–132.5 °C (lit.15 135 ºC).
1H NMR (DMSO-d6): = 3.61 (dd, J = 17.2, 9.9 Hz, 1 H), 3.83 (dd,
J = 4.0, 17.2 Hz, 1 H), 4.20 (dd, J = 9.9, 4.0 Hz, 1 H), 7.12–7.24 (m,
3 H), 7.35 (d, J = 7.0 Hz, 2 H), 7.50–7.91 (m, 3 H), 7.92 (d, J = 7.3
Hz, 2 H).
13C NMR (DMSO-d6): = 40.2 (t), 60.2 (d), 125.2 (d), 126.3 (d),
126.8 (d), 127.6 (d), 128.2 (d), 132.0 (d), 135.7 (s), 137.9 (s), 196.9
(s).
Chalcone 17a
Yield: 94%; yellow solid; mp 56.7–58.2 ºC (lit.23 55–57 ºC).
1H NMR (CDCl3): = 7.35–7.62 (m, 9 H), 7.76 (d, J = 15.7 Hz, 1
H), 7.97 (d, J = 7.3 Hz, 2 H).
13C NMR (CDCl3): = 119.6 (d), 125.6 (d), 125.9 (d), 126.0 (d),
126.1 (d), 126.5 (d), 128.1 (d), 130.3 (d), 132.4 (s), 135.7 (s), 142.3
(d), 188.2 (s).
Sodium 1-(p-Methylphenyl)-3-phenyl-3-oxo-propanesulfonate
(18b)
Yield: 87%; white solid; mp 94.6–97.5 °C.
HRMS: m/z calcd for C15H12O, 208.089; found, 208.089.
1H NMR (DMSO-d6): = 2.20 (s, 3 H), 3.53 (dd, J = 21.6, 9.8 Hz,
1 H), 3.76 (dd, J = 21.6, 4.2 Hz, 1 H), 4.12 (dd, J = 9.8, 4.2 Hz, 1
H), 6.96 (d, J = 8.1 Hz, 2 H), 7.18 (d, J = 8.1 Hz, 2 H), 7.43–7.59
(m, 3 H), 7.87 (d, J = 6.8 Hz, 2 H).
p-Methylchalcone 17b
Yield: 99%; yellow solid, mp 93.2 ºC (decomp.) (lit.24 84–86 ºC).
1H NMR (CDCl3): = 2.35 (s, 3 H), 7.17 (d, J = 8.1 Hz, 2 H), 7.42–
7.56 (m, 6 H), 7.75 (d, J = 15.8 Hz, 1 H), 7.97 (d, J = 7.0 Hz, 2 H).
13C NMR (CDCl3): = 21.3 (q), 121.0 (d), 128.3 (d), 128.5 (d),
13C NMR (DMSO-d6): = 20.8 (q), 41.4 (t), 61.1 (d), 128.2 (d),
128.3 (d), 129.0 (d), 129.4 (d), 133.4 (d), 135.5 (s), 136.1 (s), 137.0
(s), 198.3 (s).
129.6 (d), 132.0 (d), 132.5 (d), 138.2 (s), 141.0 (s), 144.8 (d), 190.6
(s).
Sodium 1-(p-Methoxyphenyl)-3-phenyl-3-oxo-propane-
sulfonate (18c)
Yield: 99%; white solid.
HRMS: m/z calcd for C16H14O, 222.104; found, 222.106.
1H NMR (DMSO-d6): = 3.54 (dd, J = 17.2, 9.9 Hz, 1 H), 3.70 (s,
3 H), 3.79 (dd, J =16.8, 4.0 Hz, 1 H), 4.13 (dd, J = 9.3, 3.7 Hz, 1 H),
6.76 (d, J = 8.8 Hz, 2 H), 7.24 (d, J = 8.8 Hz, 2 H), 7.48–7.89 (m, 3
H), 7.91 (d, J = 7.0 Hz, 2 H).
13C NMR (DMSO-d6): = 41.6 (t), 55.1 (q), 60.7 (d), 113.1 (d),
128.2 (d), 129.0 (d), 130.4 (d), 131.4 (s), 133.3 (d), 137.1 (s), 158.2
(s), 195.6 (s).
p-Methoxychalcone 17c
Yield: 98%; yellow solid; mp 73.1–75.3 ºC (lit.25 73–74 ºC).
1H NMR (CDCl3): = 3.78 (s, 3 H), 6.87 (d, J = 8.8 Hz, 2 H), 7.34–
7.56 (m, 6 H), 7.74 (d, J = 15.4 Hz, 1 H), 7.95 (d, J = 7.0 Hz, 2 H).
13C NMR (CDCl3): = 55.2 (q), 114.3 (d), 119.6 (d), 127.5 (s),
128.3 (d), 128.2 (d), 130.1 (d), 132.4 (d), 138.4 (s), 144.6 (d), 190.4
(s).
Sodium 1-Phenyl-3-(p-methylphenyl)-3-oxo-propanesulfonate
(18d)
HRMS: m/z calcd for C16H14O2, 238.099; found, 238.100.
Yield: 87%; white solid; mp 88.9–95.7 °C.
p -Methylchalcone 17d
Yield: 89%; yellow solid; mp 69.5–75.9 ºC (lit.25 96–97 °C)
1H NMR (DMSO-d6): = 2.42 (s, 3 H), 3.64 (dd, J = 9.5, 17.2 Hz,
1 H), 3.84 (dd, J = 4.0, 16.8 Hz, 1 H), 4.24 (dd, J = 4.0, 9.9 Hz, 1
H), 7.19–7.42 (m, 7 H), 7.87 (d, 2 H).
13C NMR (DMSO-d6): = 21.8 (q), 41.4 (t), 62.1 (d), 126.9 (d),
128.0 (d), 128.6 (d), 129.9 (d), 134.9 (s), 139.6 (s), 144.1 (s), 191.0
(s).
1H NMR (CDCl3): = 2.52 (s, 3 H), 7.34–8.04 (m, 11 H).
13C NMR (CDCl3): = 21.7 (q), 122.1 (d), 128.4 (d), 128.7 (d),
129.0 (d), 129.4 (d), 130.5 (d), 135.0 (s), 135.6 (s), 143.7 (s), 144.5
(d), 190.1 (s).
HRMS: m/z calcd for C16H14O, 222.104; found, 222.105.
Sodium 1-Phenyl-3-(p-methoxyphenyl)-3-oxo-propane-
sulfonate (18e)
Yield: 80%; white solid; mp 122.5–124.5 °C.
1H NMR (DMSO-d6): = 3.46–3.40 (dd, J = 9.9, 17.0 Hz, 1 H),
3.68–3.78 (2 dd, J = 4.0, 16.9 Hz, 2 H), 3.89 (s, 3 H), 4.26 (dd, J =
3.7, 9.5 Hz, 1 H), 7.05–7.42 (m, 7 H), 7.95 (d, 2 H).
13C NMR (DMSO-d6): 41.4 (t), 56.1 (q), 62.0 (d), 126.9 (d), 128.0
(d), 129.9 (d), 130.3 (d), 130.8 (d), 139.6 (s), 161.9 (s), 163.7 (s),
196 (s).
p -Methoxychalcone 17e
Yield: 77%; yellow solid; mp 96.1 ºC (decomp.) (lit.25 106-107 °C).
1H NMR (CDCl3): = 3.97 (s, 3 H), 7.06 (d, 2 H), 7.48–8.15 (m, 9
H).
13C NMR (CDCl3): = 55.5 (q), 113.9 (d), 121.9 (d), 128.4 (d),
129.0 (d), 130.3 (d), 130.8 (d), 131.1 (d), 135.1 (s), 144.0 (s), 163.5
(s), 188.7 (s).
HRMS: m/z calcd for C16H14O2, 238.099; found, 238.100.
Synthesis 2003, No. 10, 1626–1638 © Thieme Stuttgart · New York