PAPER
An Efficient Method for the a-Acetoxylation of Ketones
1167
1
1
H NMR (300 MHz, CDCl ): d = 8.01 (d, J = 7.2 Hz, 2 H), 7.61 (t,
H NMR (300 MHz, CDCl ): d = 8.73 (s, 1 H), 8.47 (d, J = 8.1 Hz,
3
3
J = 6.6 Hz, 1 H), 7.50 (dd, J = 7.2, 6.6 Hz, 2 H), 6.33 (s, 1 H), 4.25
1 H), 8.26 (d, J = 7.8 Hz, 1 H), 7.75 (dd, J = 8.1, 7.8 Hz, 1 H), 5.37
(
q, J = 6.3 Hz, 2 H), 2.22 (s, 3 H), 1.21 (t, J = 6.3 Hz, 3 H).
(s, 2 H), 2.24 (s, 3 H).
1
3
13
C NMR (75 MHz, CDCl ): d = 189.65, 169.52, 165.13, 134.19,
C NMR (75 MHz, CDCl ): d = 190.45, 170.21, 148.37, 135.27,
3
3
1
29.17, 128.75, 128.45, 74.46, 62.47, 20.48, 13.86.
133.29, 130.20, 128.00, 122.61, 65.90, 20.34.
+
+
MS (EI): m/z = 250 [M ], 205, 105, 77.
MS (EI): m/z = 223 [M ], 181, 163, 150, 104, 92, 76.
Anal. Calcd for C H O : C, 62.39; H, 5.64; Found: C, 62.51; H,
Anal. Calcd for C H NO : C, 53.82; H, 4.06; N, 6.28. Found: C,
13
14
5
10
9
5
5
.44.
53.70; H, 3.98; N: 6.43.
2
-Acetoxy-4¢-chloroacetophenone
2-Acetoxy-4¢-methylacetophenone
Light yellow solid; mp 82 °C.
5
White solid; mp 68 °C (Lit. 73 °C).
–
1
IR (KBr): 1748, 1696 cm–1.
IR (KBr): 1745, 1694 cm .
1
1
H NMR (300 MHz, CDCl ): d = 7.84 (d, J = 9.0 Hz, 2 H), 7.45 (d,
H NMR (300 MHz, CDCl ): d = 7.80 (d, J = 8.1 Hz, 2 H), 7.27 (d,
3
3
J = 9.0 Hz, 2 H), 5.27 (s, 2 H), 2.21 (s, 3 H).
J = 8.1 Hz, 2 H), 5.31 (s, 2 H), 2.41 (s, 3 H), 2.22 (s, 3 H).
1
3
13
C NMR (75 MHz, CDCl ): d = 191.05, 170.28, 140.33, 132.47,
C NMR (75 MHz, CDCl ): d = 191.69, 170.40, 144.80, 131.68,
3
3
1
29.18, 129.12, 65.79, 20.45.
129.47, 127.80, 65.90, 21.69, 20.54.
+
+
MS (EI): m/z = 212 [M ], 141, 139, 113, 111.
MS (EI): m/z = 192 [M ], 119, 91, 65.
Anal. Calcd for C H ClO : C, 56.49; H, 4.27. Found: C, 56.23; H,
Anal. Calcd for C H O : C, 68.74; H, 6.29. Found: C, 69.31; H,
10
9
3
11 12
3
3
.87.
5.86.
2
-Acetoxy-4¢-bromoacetophenone
2-Acetoxy-4¢-phenylacetophenone
Light yellow solid; mp 109 °C.
White solid; mp 83 °C.
–
1
IR (KBr): 1750, 1702 cm–1.
IR (KBr): 1744, 1693 cm .
1
1
H NMR (300 MHz, CDCl ): d = 7.77 (d, J = 8.1 Hz, 2 H), 7.63 (d,
H NMR (300 MHz, CDCl ): d = 7.99 (d, J = 8.4 Hz, 2 H), 7.71 (d,
3
3
J = 8.1 Hz, 2 H), 5.29 (s, 2 H), 2.22 (s, 3 H).
J = 8.4 Hz, 2 H), 7.62 (d, J = 6.6 Hz, 2 H), 7.48 (m, 3 H), 5.37 (s, 2
1
3
H), 2.25 (s, 3 H).
C NMR (75 MHz, CDCl ): d = 191.27, 182.74, 170.38, 132.80,
3
1
3
1
32.20, 129.20, 65.80, 20.53.
C NMR (75 MHz, CDCl ): d = 191.72, 170.40, 146.56, 139.58,
3
+
132.86, 128.97, 128.40, 128.32, 127.43, 127.24, 65.99, 20.55.
MS (EI): m/z = 258 [M ], 256, 185, 183, 157, 155, 76, 75.
+
MS (EI): m/z = 254 [M ], 181, 153, 152.
Anal. Calcd for C H BrO : C, 46.72; H, 3.53. Found: C, 47.19; H,
10
9
3
3
.14.
Anal. Calcd for C H O : C, 75.57; H, 5.55. Found: C, 75.86; H,
1
6
14
3
5
.22.
2
-Acetoxy-4¢-iodoacetophenone
White solid; mp 113 °C.
2-Acetoxyacetonaphthone
–
1
Red oil.
IR (KBr): 1744, 1692 cm .
–
1
1
IR (neat): 1747, 1696 cm .
1
H NMR (300 MHz, CDCl ): d = 7.86 (d, J = 7.5 Hz, 2 H), 7.62 (d,
3
J = 7.5 Hz, 2 H), 5.28 (s, 2 H), 2.23 (s, 3 H).
1
H NMR (300 MHz, CDCl ): d = 8.63 (m, 1 H), 8.01 (m, 1 H), 7.85
(m, 2 H), 7.56 (m, 3 H), 5.31 (s, 2 H), 2.25 (s, 3 H).
3
3
C NMR (75 MHz, CDCl ): d = 191.58, 170.29, 138.16, 133.38,
3
1
3
1
29.00, 101.93, 65.73, 20.49.
C NMR (75 MHz, CDCl ): d = 196.02, 170.43, 133.87, 133.43,
3
+
132.29, 130.14, 128.40, 128.26, 127.38, 126.70, 125.47, 124.15,
7.42, 20.50.
MS (EI): m/z = 304 [M ], 231, 202.
6
Anal. Calcd for C H IO : C, 39.50; H, 2.98. Found: C, 40.18; H,
1
0
9
3
+
MS (EI): m/z = 228 [M ], 155, 127.
2
.62.
Anal. Calcd for C H O : C, 73.67; H, 5.30. Found: C, 74.06; H,
1
4
12
3
2
-Acetoxy-4¢-nitroacetophenone
5.03.
5
Yellow solid; mp 121 °C (Lit. 123.8 °C).
–
1
2-Acetoxy-3,4-dihydronaphthalen-1(2H)-one
Red solid; mp 69–70 °C.
IR (KBr): 1740, 1698 cm–1.
IR (KBr): 1748, 1703 cm .
1
H NMR (300 MHz, CDCl ): d = 8.32 (d, J = 8.1 Hz, 2 H), 8.07 (d,
J = 8.1 Hz, 2 H), 5.32 (s, 2 H), 2.20 (s, 3 H).
3
1H NMR (300 MHz, CDCl
J = 7.5, 7.8 Hz, 1 H), 7.33 (dd, J = 7.5, 7.8 Hz, 1 H), 7.28 (d, J = 7.5
): d = 8.03 (d, J = 7.5 Hz, 1 H), 7.51 (dd,
1
3
3
C NMR (75 MHz, CDCl ): d = 191.07, 170.20, 150.64, 138.57,
28.86, 124.01, 66.02, 20.36.
3
1
Hz, 1 H), 5.56 (m, 1 H), 3.21 (m, 2 H), 2.39 (m, 2 H), 2.23 (s, 3 H).
+
MS (EI): m/z = 223 [M ], 181, 163, 150, 104, 92, 76.
1
3
C NMR (75 MHz, CDCl ): d = 192.96, 170.20, 143.03, 133.89,
3
Anal. Calcd for C H NO : C, 53.82; H, 4.06; N, 6.28. Found: C,
10
9
5
131.52, 128.61, 127.79, 126.93, 74.55, 29.11, 27.92, 20.84.
5
3.85; H, 3.97; N: 6.35.
+
MS (EI): m/z = 204 [M ], 162, 144.
2
-Acetoxy-3¢-nitroacetophenone
Anal. Calcd for C H O : C, 70.57; H, 5.92. Found: C, 71.03; H,
5.54.
1
2
12
3
Yellow oil.
–
1
IR (neat): 1746, 1706 cm .
1
-Acetoxy-3,3-dimethylbutan-2-one
Colorless oil.
Synthesis 2007, No. 8, 1165–1168 © Thieme Stuttgart · New York