Liu, Wang & Zou
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135.1, 134.7, 130.0, 129.5, 114.6, 60.5, 57.5, 55.8.
3H, ArH), 6.45 (d, J=11.0 Hz, 1H, CH), 5.51 (d, J=
11.0, 1H, CH); 13C NMR (CDCl3, 100 MHz) δ: 192.9,
151.3, 149.8, 137.8, 137.6, 129.8, 129.2, 128.8, 128.7,
124.1, 60.5, 55.5. HRMS: m/z (%), calcd for
C14H1135Cl2NO (M+) 279.0218, found 279.0228 (M+,
0.06).
+
HRMS: m/z (%), calcd for C16H1435Cl2O2 (M
)
308.0371, found 308.0366 (M+, 0.45).
2d: Yield 84%, m.p. 157—158 ℃ (lit.7 155—157
1
℃). H NMR (CDCl3, 400 MHz) δ: 8.03 (d, J=8.3 Hz,
2H, ArH), 7.54—7.51 (m, 4H, ArH), 7.46—7.41 (m, 3H,
ArH), 5.48—5.41 (m, 2H, 2CH); 13C NMR (CDCl3, 100
MHz) δ: 190.6, 141.4, 137.3, 133.3, 130.8, 129.9, 129.3,
128.7, 60.4, 5+7.4. HRMS: m/z (%), calc+d for
C15H1135Cl3O (M ) 311.9875, found 278.0067 (M -Cl,
6.62).
2k: Yield 85%, m.p. 91—92 ℃ (lit.10 92—93 ℃).
1H NMR (CDCl3, 400 MHz) δ: 7.42—7.40 (m, 5H,
ArH), 5.15 (d, J=10.5 Hz, 1H, CH), 4.60 (d, J=10.5
Hz, 1H, CH), 2.44 (s, 3H, CH3); 13C NMR (CDCl3, 100
MHz) δ: 199.5, 136.7, 129.7, 129.0, 128.5, 63.6, 60.4,
27.2.
2e: Yield 85%, m.p. 167—168 ℃ (lit.8 167—168
1
℃). H NMR (CDCl3, 400 MHz) δ: 8.08 (d, J=7.3 Hz,
2H, ArH), 7.68—7.66 (m, 1H, ArH), 7.58—7.54 (m, 2H,
ArH), 7.48—7.41 (dd, J=7.7, 19.6 Hz, 4H, ArH), 5.46
(s, 2H, 2CH); 13C NMR (DMSO-d6, 100 MHz) δ: 192.1,
137.0, 135.5, 134.5, 134.4, 131.5, 129.9, 129.8, 129.3,
59.8, 55.9. HRMS: m/z (%), calcd for C15H1135Cl3O (M+)
311.9875, found 311.9908 (M+, 0.01).
Results and discussion
At the initial stage, the chlorination of 1,3-diphenyl-
propenone (chalcone) with Mn(OAc)3/HCl(aqueous)
was explored (Eq. 1), fortunately, a major product was
isolated and its structure was characterized to be
2,3-dichloro-1,3-diphenylpropanone (Table 1, Entry 1).
Solvent scanning was then conducted with CH2Cl2,
CH3CN, EtOH and MeOH, which indicated that HOAc
was the best medium (Table 1, Entries 2—5). Increasing
reaction temperature reduced the reaction time without
improving the yields (Table 1, Entries 6—7). Based on
the experimental results obtained, the optimal reaction
conditions were determined to be that 1,3-diphenyl-
propenone (1 mmol) and Mn(OAc)3•2H2O (2 mmol)
were reacted in the mixture of HOAc (2 mL) and 36%
aq. HCl (1 mL) at 25 ℃, and this was used for other
chalcones.
1
2f: Yield 80%, m.p. 96—97 ℃. H NMR (CDCl3,
400 MHz) δ: 8.10 (d, J=7.2 Hz, 2H, ArH), 7.66 (t, J=
7.4 Hz, 1H, ArH), 7.55 (t, J=7.7 Hz, 2H, ArH), 7.48
(dd, J=1.4, 7.6 Hz, 1H, ArH), 7.41—7.36 (m, 1H, ArH),
7.04 (t, J=7.5 Hz, 1H, ArH), 6.98 (d, J=8.3 Hz, 1H,
ArH), 5.93—5.87 (m, 2H, 2CH), 3.95 (s, 3H, CH3); 13C
NMR (CDCl3, 100 MHz) δ: 190.5, 156.5, 133.8, 133.1,
129.6, 128.7, 128.0, 127.9, 124.0, 119.8, 110.4, 54.+8,
54.6. HRMS: m/z (%), calcd for C16H1435Cl2O2 (M )
308.0371, found 308.0372 (M+, 0.87).
2g: Yield 66%, m.p. 117—119 ℃ (lit.7 108—114
1
℃). H NMR (CDCl3, 400 MHz) δ: 8.31 (d, J=8.6 Hz,
2H, ArH ), 8.09 (d, J=7.9 Hz, 2H, ArH), 7.74—7.68 (m,
3H, ArH), 7.58 (t, J=7.7 Hz, 2H, ArH), 5.57 (d, J=
10.3 Hz, 1H, CH), 5.46 (d, J=10.4 Hz, 1H, CH); 13C
NMR (CDCl3, 100 MHz) δ: 189.4, 147.2, 142.9, 133.6,
133.1, 128.5, 128.1, 128.0, 127.7, 122.9, 57.3, 55+.4.
O
O
Cl
Mn(OAc)3/aq. HCl
HOAc, r.t.
(1)
Cl
1
2a
HRMS: m/z (%), calcd for C15H1135Cl2NO3 (M
323.0116, found 287.0344 (M+-Cl, 6.64).
)
2h: Yield 78%, m.p. 139—141 ℃. 1H NMR (CDCl3,
400 MHz) δ: 8.08 (d, J=8.8 Hz, 2H, ArH ), 7.45 (d J=
8.6 Hz, 2H, ArH), 7.02 (d, J=8.8 Hz, 2H, ArH), 6.95 (d,
J=8.6 Hz, 2H, ArH), 5.46 (s, 2H, 2CH), 3.91 (s, 3H,
CH3), 3.84 (s, 3H, CH3); 13C NMR (CDCl3, 100 MHz) δ:
188.8, 163.4, 159.1, 130.4, 128.5, 128.2, 126.4, 113.2,
113.0, 59.1, 55.9, +54.6, 54.3. HRMS: m/z (%), calcd for
C17H1635Cl2O3 (M ) 338.0476, found 338.0482 (M+,
0.10).
Table 1 Effects of solvent and temperature on the chlorination
Entrya
Solvent
HOAc
CH2Cl2
CH3CN
EtOH
Temp./℃
Time/h
Yieldb/%
1
2
3
4
5
6
7
25
25
25
25
25
40
60
1
1
82
complicated
1
43
50
45
82
81
1
MeOH
HOAc
HOAc
1
0.5
0.4
2i: Yield 73%, m.p. 140—141 ℃ (lit.9 142—144
1
℃). H NMR (CDCl3, 100 MHz) δ: 11.78 (s, 1H, OH),
a
1,3-Diphenylpropenone (1 mmol), Mn(OAc)3•2H2O (2 mmol)
7.85 (d, J=8.3 Hz, 1H, ArH), 7.58 (t, J=7.8 Hz, 1H,
ArH), 7.45 (d, J=8.6 Hz, 2H, ArH), 7.08 (d, J=8.5 Hz,
1H, ArH), 7.03—6.99 (m, 1H, ArH), 6.96 (d, J=8.7 Hz,
2H, ArH), 5.55—5.40 (m, 2H, 2CH), 3.85 (s, 3H,
OCH3).
were reacted in the mixture of HOAc (2 mL) and 36% aq. HCl (1
ml ). b Isolated yields.
Chlorination results for a series of conjugated ke-
tones are summarized in Table 2, which showed that all
the reactions were completed in 1 h to afford the desired
products in moderate to good yields (66%—85%) ex-
cept for substrate bearing NO2 group (Table 2, Entry 7).
2j: Yield 71%, m.p. 116—118 ℃. 1H NMR (CDCl3,
400 MHz) δ: 8.79 (d, J=4.7 Hz, 1H, pyridine-H), 8.23
(d, J=7.0 Hz, 1H, pyridine-H), 8.00—7.92 (m, 1H,
pyridine-H), 7.60—7.56 (m, 3H, ArH), 7.46—7.40 (m,
2098
© 2011 SIOC, CAS, Shanghai, & WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Chin. J. Chem. 2011, 29, 2097— 2100