(1.8 g, 23 mmol), following the procedure for compound 5 to give
0.21 g (20%) 19. dH (400 MHz, D2O/CD3OD, CH3OH) 8.18 (1H,
d, J = 7.96 Hz), 7.95 (1H, d, J = 7.32 Hz), 7.87 (1H, m), 7.80 (1H,
m), 2.73 (3H, s); dC 202.1, 140.3, 137.8, 137.1, 134.9, 132.5, 120.8,
110.5, 28.4; nmax/cm-1 1686.5 (C O).
then ice water with HCl was added. The mixture was extracted
with CH2Cl2, dried over MgSO4, and concentrated to give 0.25 g
(94%) 24. dH (400 MHz, D2O/CD3OD, CH3OH) 7.99 (1H, m),
7.70 (1H, m), 7.48 (1H, m), 7.25 (1H, m), 2.63 (3H, s), 2.38 (3H,
s); dC 204.4, 174.6, 149.4, 136.1, 132.4, 131.3, 128.4, 125.0, 30.0,
21.8; nmax/cm-1 1682.6 (C O).
meta-Cyano acetophenone (11)29. Compound 11 was prepared
from meta-amino acetophenone (20, 1.0 g, 7 mmol) and KCN
(1.8 g, 23 mmol), following the procedure for compound 5 to give
0.35 g (24%) 11. dH (400 MHz, D2O/CD3OD, CH3OH) 8.41 (1H,
m), 8.30 (1H, d, J = 7.27 Hz), 8.05 (1H, d, J = 7.78 Hz), 7.75 (1H,
m), 2.72 (3H, s); dC 202.8, 138.4, 137.9, 134.5, 133.9, 131.8, 120.4,
112.7, 26.3; nmax/cm-1 1686.8 (C O).
para-Acetoxy acetophenone (25)35. Compound 25 was pre-
pared from para-hydroxy acetophenone (18, 0.5 g, 38 mmol),
following the procedure for compound 24 to give 0.62 g (92%) 25.
dH (400 MHz, D2O/CD3OD, CH3OH) 8.09 (2H, d, J = 8.80 Hz),
7.31 (2H, d, J = 8.80 Hz), 2.69 (3H, s), 2.39 (3H, s); dC 204.0,
174.1, 155.8, 136.0, 131.9 (2C), 123.5 (2C), 27.7, 21.9; nmax/cm-1
1680.1 (C O).
ortho-Nitro acetophenone (13)33. A solution of ortho-amino
acetophenone (19, 1.0 g, 7.4 mmol) in 20 mL CHCl3 was added
to a refluxing solution of meta-chloro perbenzoic acid (5.1 g, 30
mmol) in CHCl3 and refluxed for 2 h. The mixture was filtrated,
washed with 20 mL NaOH solution (1 N), dried over MgSO4, and
concentrated. The residue was purified by flash chromatography
on silica gel with CH2Cl2 to afford 0.42 g (43%) 13. dH (400 MHz,
D2O/CD3OD, CH3OH) 8.21 (1H, m), 7.88 (1H, m), 7.76 (1H, m),
7.65 (1H, m), 2.67 (3H, s); dC 207.1, 146.5, 137.1, 136.4, 133.0,
128.9, 126.0, 31.1; nmax/cm-1 1702.5 (C O).
meta-Acetamino acetophenone (26)35. Compound 26 was pre-
pared from meta-amino acetophenone (20) (1.0 g, 7 mmol),
following the procedure for compound 24 to give 1.14 g (92%)
26. dH (400 MHz, D2O/CD3OD, CH3OH) 8.02 (1H, s), 7.83 (1H,
d, J = 7.80 Hz), 7.69 (1H, d, J = 9.04 Hz), 7.56 (1H, m), 2.67 (3H,
s), 2.22 (3H, s); dC 204.6, 174.5, 138.9, 138.6, 131.0, 128.4, 126.9,
122.7, 27.7, 24.3; nmax/cm-1 1668.8 (C O).
ortho-Chloro acetophenone (1). dH (400 MHz, D2O/CD3OD,
CH3OH) 7.72 (1H, d, J = 6.96 Hz), 7.56 (2H, m), 7.48 (1H, m),
2.72 (3H, s); dC 207.7, 139.2, 134.3, 132.2, 131.8, 130.9, 128.7, 31.4;
meta-Nitro acetophenone (14)33. Compound 14 was prepared
from meta-amino acetophenone (20, 1.0 g, 7.4 mmol), following
the procedure for compound 13 to give 0.66 g (55%) 14. dH
(400 MHz, D2O/CD3OD, CH3OH) 8.83 (1H, s), 8.53 (1H, d,
J = 8.76 Hz), 8.41 (1H, d, J = 7.76 Hz), 7.82 (1H, m), 2.77 (3H,
s); dC 202.1, 138.2, 135.6, 131.2, 128.9, 124.2, 27.3, one 13C n.d.;32
n
max/cm-1 1695.2 (C O).
meta-Chloro acetophenone (2). dH (400 MHz, D2O/CD3OD,
CH3OH) 8.03 (1H, s), 7.94 (1H, m), 7.72 (1H, m), 7.55 (1H, m),
2.68 (3H, s); dC 203.9, 139.5, 135.8, 135.1, 131.7, 128.7, 128.4, 27.8;
n
max/cm-1 1686.8 (C O).
n
max/cm-1 1689.9 (C O).
para-Chloro acetophenone (3). dH (400 MHz, D2O/CD3OD,
para-Nitro acetophenone (15)33. Compound 15 was prepared
CH3OH) 7.99 (2H, d, J = 8.56 Hz), 7.59 (2H, d, J = 8.56 Hz),
2.68 (3H, s); dC 204.16, 141.2, 136.4, 131.6 (2C), 130.3 (2C), 27.6;
from para-amino acetophenone (21, 1.0 g, 7.4 mmol), following the
procedure for compound 13 to give 0.68 g (56%) 15. dH (400 MHz,
D2O/CD3OD, CH3OH) 8.40 (2H, d, J = 8.90 Hz), 8.22 (2H, d,
J = 8.90 Hz), 2,77 (3H, s); dC 196.5, 150.5, 141.5, 129.9 (2C), 124.2
(2C), 27.0; nmax/cm-1 1692.0 (C O).
n
max/cm-1 1682.4 (C O).
ortho-Fluoro acetophenone (9). dH (400 MHz, D2O/CD3OD,
CH3OH) 7.86 (1H, m), 7.69 (1H, m), 7.35 (1H, m), 7.29 (1H, m),
2.70 (3H, d, J = 3.68 Hz); dC 203.2, 163.2, 137.2, 131.8, 126.6,
126.0, 118.3, 31.6; nmax/cm-1 1683.3 (C O).
ortho-Methoxy acetophenone (22)34. MeI (0.8 mL, 12.5 mmol)
was added to a solution of ortho-hydroxy acetophenone (16,
0.2 g, 15 mmol) and K2CO3 (1.0 g, 75 mmol) in 150 mL acetone
and refluxed for 12 h. After filtration of the precipitated salt
the mixture was concentrated. The residue was purified by flash
chromatography on silica gel with CH2Cl2 to afford 0.2 g (98%) 22.
dH (400 MHz, D2O/CD3OD, CH3OH) 7.78 (1H, d, J = 6.90 Hz),
7.70 (1H, m), 7.26 (1H, d, J = 7.77 Hz), 7.17 (1H, m), 3.99 (3H,
s), 2.71 (3H, s); dC 205.7, 158.9, 135.3, 130.6, 127.3, 120.9, 112.9,
55.9, 30.6; nmax/cm-1 1680.4 (C O).
para-Cyano acetophenone (12). dH (400 MHz, D2O/CD3OD,
CH3OH) 8.13 (2H, d, J = 8.44 Hz), 7.94 (2H, d, J = 8.44 Hz),
2.73 (3H, s); dC 203.5, 141.3, 134.3 (2C), 130.2 (2C), 120.2, 117.1,
27.92; nmax/cm-1 1686.8 (C O).
ortho-Hydroxy
acetophenone
(16). dH
(400
MHz,
D2O/CD3OD, CH3OH) 7.97 (1H, d, J = 8.04 Hz), 7.62
(1H, m), 7.08 (1H, m), 7.02 (1H, d, J = 8.56 Hz), 2.70 (3H, s);
dC 208.8, 161.1, 138.5, 133.3, 121.3, 120.4, 118.9, 27.7; nmax/cm-1
1637.5 (C O).
para-Methoxy acetophenone (23)34. Compound 23 was pre-
pared from para-hydroxy acetophenone (18, 0.2 g, 15 mmol)
following the procedure for compound 22 to give 0.2 g (98%)
product 23. dH (400 MHz, D2O/CD3OD, CH3OH) 8.01 (2H, d,
J = 8.96 Hz), 7.09 (2H, d, J = 8.96 Hz), 3.90 (3H, s); 2.69 (3H, s);
dC 204.0, 165.2, 132.6 (2C), 131.0, 115.5 (2C), 56.0, 31.7; nmax/cm-1
1666.6 (C O).
meta-Hydroxy
acetophenone
(17). dH
(400
MHz,
D2O/CD3OD, CH3OH) 7.57 (1H, d, J = 7.76 Hz), 7.44
(1H, m), 7.10 (1H, s), 7.18 (1H, m), 2.64 (3H, s); dC 205.0, 157.3,
139.5, 133.7, 122.5, 122.4, 116.0, 27.7; nmax/cm-1 1661.6 (C O).
para-Hydroxy
acetophenone
(18). dH
(400
MHz,
ortho-Acetoxy acetophenone (24)35. A solution of ortho-
hydroxy acetophenone (16, 0.2 g, 15 mmol) and acetic anhydride
(0.94 g, 92 mmol) in 14 mL pyridine was heated for 30 min and
D2O/CD3OD, CH3OH) 7.87 (2H, d, J = 8.82 Hz), 6.91
(2H, d, J = 8.82 Hz), 2.55 (3H, s); dC 203.8, 163.0, 132.9 (2C),
130.3, 116.8 (2C), 27.1; nmax/cm-1 1659.1 (C O).
5868 | Org. Biomol. Chem., 2011, 9, 5863–5870
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The Royal Society of Chemistry 2011
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