Xiao-Qiang Li et al.
FULL PAPERS
À1
1
2
543, 1451, 1231, 1156, 1079, 681 cm ; MS (APCI): m/z=
2147, 1687, 1606, 1555, 1499, 1444, 1329, 1262, 1243, 1176,
+
À1
+
13.03 (M+H ).
Heptylcarbamoyl azide (2b):
1150, 1078 cm ; MS (APCI): m/z=162.98 (M+H ).
[16i]
1
[16d]
Colorless oil; H NMR
400 MHz, CDCl ): d=5.87 (bs, 1H), 3.14 (q, J=6.7 Hz,
H), 1.43–1.46 (m, 2H), 1.20–1.22 (m, 8H), 0.80 (t, J=
.6 Hz, 3H); C NMR (100 MHz, CDCl ): d=156.35, 40.94,
1.48, 29.26, 28.68, 26.45, 22.33, 13.76; IR (KBr): n˜ =3321,
929, 2858, 2138, 1691, 1539, 1457, 1231 cm ; MS (APCI):
2-Methylphenylcarbamoyl azide (2j):
White solid; mp.
): d=7.70 (d, J=
1
(
97–998C; H NMR (400 MHz, CDCl
3
3
2
6
3
2
7.6 Hz, 1H), 7.17–6.99 (m, 3H), 6.63 (bs, 1H), 2.16 (s, 3H);
13
13
C NMR (100 MHz, CDCl ): d=154.23, 134.72, 130.53,
3
3
1
2
28.42, 126.90, 125.33, 121.92, 17.51; IR (KBr): n˜ =3277,
À1
362, 2188, 2142, 1675, 1589, 1532, 1457, 1295, 1244, 749,
À1
+
+
675 cm ; MS (APCI): m/z=176.99 (M+H ).
m/z=185.07 (M+H ).
[16i]
1
Butylcarbamoyl azide (2c):
Colorless oil; H NMR
(
400 MHz, CDCl ): d=5.12 (bs, 1H), 3.25 (q, J=6.8 Hz,
3
1
-Phenylpropan-1-one (5a); Typical Procedure for the
2
7
3
1
H), 1.46–1.54 (m, 2H), 1.30–1.40 (m, 2H), 0.92 (t, J=
13
Oxidation of Secondary Alcohols Using PhICl -NaN3
.3 Hz, 3H); C NMR (100 MHz, CDCl ): d=156.37, 40.55,
2
3
1.20, 19.56, 13.29; IR (KBr): n˜ =3313, 2960, 2152, 1689,
To a solution of 1-phenylpropan-1-ol (4a, 136 mg, 1 mmol)
in dry CH CN (10 mL) in a two-necked, 25-mL, round-bot-
tomed flask was gradually added PhICl (412 mg, 1.5 mmol)
and NaN (195 mg, 3.0 mmol) under an N atmosphere at
À1
+
232 cm ; MS (EI): m/z=142.0 [M ], 100.0, 71.0, 57.0, 27.0.
3
[16i]
Cyclohexylcarbamoyl azide (2d):
White solid; mp 105–
2
1
1
3
1
068C; H NMR (400 MHz, CDCl ): d=4.87 (bs, 1H), 3.51–
3
3
2
.53 (m, 1H), 1.84–1.88 (m, 2H), 1.62–1.66 (m, 2H), 1.53–
.57 (m, 2H), 1.18–1.33 (m, 2H), 1.07–1.10 (m, 2H);
0
8C (ice-water bath). When the reaction was completed
(
TLC), the reaction mixture was diluted with EtOAc
13
C NMR (100 MHz, CDCl ): d=155.37, 50.06, 32.90, 25.28,
3
(50 mL). Then, the resulting mixture was washed with satu-
rated aqueous Na S O . The separated aqueous phase was
extracted with EtOAc (20 mL). The combined organic layer
was washed with brine, dried over anhydrous Na SO . The
organic layer was concentrated under vacuum to afford the
crude product which was purified by flash column chroma-
tography (petroleum ether:EtOAc=49:1) to give 1-phenyl-
propan-1-one (5a);
(400 MHz, CDCl ): d=7.97(d, J=8.0 Hz, 2H), 7.53–7.57 (m,
1H), 7.46 (t, J=8.0 Hz, 2H), 3.01 (q, J=7.2 Hz, 2H), 1.23
2
2
1
4.61; IR (KBr): n˜ =3279, 3056, 2938, 2855, 2765, 2447,
2
2
3
186, 2139, 1677, 1543, 1451, 1348, 1318, 1278, 1231,
À1
+
088 cm ; MS (APCI): m/z=169.02 (M+H ).
2
4
[16i]
(
9-Chlorononyl)carbamoyl azide (2e): White solid; mp
7–498C; H NMR (400 MHz, CDCl ): d=5.06 (bs, 1H),
1
4
3
3
.54 (t, J=6.6 Hz, 2H), 3.20 (q, J=6.2 Hz, 2H), 1.73–1.80
[26]
1
(
m, 2H), 1.49–1.53 (m, 2H), 1.40–1.44 (m, 2H), 1.30 (bs,
yield: 123 mg (92%). H NMR
13
8
3
3
H); C NMR (100 MHz, CDCl ): d=156.30, 45.05, 41.07,
3
3
2.55, 29.49, 29.23, 29.01, 28.71, 26.76, 26.57; IR (KBr): n˜ =
À1
13
334, 2923, 2825, 2171, 2132, 1674, 1519, 1222 cm ; HR-MS
(t, J=7.2 Hz, 3H); C NMR: (100 MHz, CDCl
00.73, 136.82, 132.79, 128.46, 127.88, 31.70, 8.16.
): d=
3
+
2
(
ESI): m/z=269.1137, calcd. for C H ClN ONa (M+Na ):
1
0
19
4
[26]
1
4
’-Fluoroacetophenone (5c):
H NMR (400 MHz,
2
69.1140.
[
16i]
CDCl ): d=7.91 (dd, J =8.4 Hz, JH,F =5.6 Hz, 2H), 7.05
(dd, JH,H =JH,F =8.4 Hz, 2H), 2.51 (s, 3H);
9-(Azidocarbonylamino)nonyl acetate (2f):
White
3
H,H
1
3
1
C NMR
solid; mp 31–338C; H NMR (400 MHz, CDCl ): d=5.09
3
(100 MHz, CDCl ): d=196.28, 165.69 (d, J =253.2 Hz),
(
bs, 1H), 4.05 (t, J=6.7 Hz, 2H), 3.22 (q, J=6.7 Hz, 2H),
3
C,F
1
33.53 (d, JC,F =3.0 Hz), 130.85 (d, JC,F =9.2 Hz), 115.54 (d,
2
1
6
(
1
.05 (s, 3H) 1.58–1.62 (m, 2H), 1.49–1.53 (m, 2H), 1.30 (bs,
13
JC,F =21.8 Hz), 26.37.
’-Chloroacetophenone (5d):
CDCl ): d=7.90 (d, J=8.4 Hz, 2H), 7.44 (d, J=8.4 Hz, 2H),
2.60 (s, 3H); C NMR (100 MHz, CDCl
139.30, 135.30, 129.53, 128.66, 26.33.
0H); C NMR (100 MHz, CDCl ): d=170.96, 156.14,
3
[27]
1
4
H NMR (400 MHz,
4.28, 40.82, 29.16, 29.03, 28.80, 28.27, 26.35, 25.55, 20.61; IR
3
KBr): n˜ =3316, 2915, 2850, 2177, 2142, 1727, 1683, 1544,
1
3
À1
): d=196.54,
3
263, 1043, 682 cm ; HR-MS (ESI): m/z=271.1765, calcd.
+
for C H N O (M+H ): 271.1764, 293.1578, calcd. for
C H N O Na (M+Na ): 293.1584.
12
23
4
3
[26]
1
+
4’-Bromoacetophenone (5e):
H NMR (400 MHz,
1
2
22
4
3
CDCl ): d=7.82 (d, J=8.4 Hz, 2H), 7.61 (d, J=8.4 Hz, 2H),
[16i]
3
2
-Phenylethylcarbamoyl azide (2g):
White solid; mp
1
3
2
.59 (s, 3H); C NMR (100 MHz, CDCl ): d=196.90,
1
3
8
5
6
1
3
1
5–878C; H NMR (400 MHz, CDCl3): d=7.19–7.35 (m,
1
35.74, 131.80, 129.76, 128.21, 26.46.
H), 5.09 (bs, 1H), 3.50 (q, J=6.6 Hz, 2H), 2.84 (t, J=
[27]
1
4
’-Nitroacetophenone
(5f):
H NMR
(400 MHz,
13
.9 Hz, 2H);
C NMR (100 MHz, CDCl ): d=156.26,
3
CDCl ): d=8.28 (d, J=8.0 Hz, 2H), 8.09 (d, J=8.0 Hz,
3
38.01, 128.40, 128.34, 126.34, 42.00, 35.29; IR (KBr): n˜ =
13
2
1
H);
C NMR (100 MHz, CDCl ): d=196.25, 150.24,
3
286, 3062, 2930, 2443, 2177, 2142, 1703, 1673, 1545, 1496,
41.29, 129.22, 123.74, 26.88.
À1
+
463, 1285, 698 cm ; MS (APCI): m/z=191.12 (M+H ).
[26] 1
Cyclopropyl phenyl ketone (5j):
H NMR (400 MHz,
[15e]
Benzylcarbamoyl azide (2h):
White solid; mp 80–818C;
H NMR (400 MHz, CDCl ): d=7.27–7.36 (m, 5H), 5.38 (bs,
CDCl ): d=8.01 (d, J=7.3 Hz, 2H), 7.56 (t, J=7.3 Hz, 1H),
7.48 (t, J=7.6 Hz, 2H), 2.71–2.65 (m, 1H), 1.26–1.22 (m,
2H), 1.06–1.02 (m, 2H); C NMR (100 MHz, CDCl ): d=
3
1
3
1
3
1
H), 4.42 (d, J=6.0 Hz, 2H); C NMR (100 MHz, CDCl ):
13
3
3
d=156.53, 137.19, 128.78, 127.83, 127.63, 45.02; IR (KBr):
n˜ =3339, 3026, 2934, 2441, 2163, 1680, 1528, 1455, 1431,
1
H ).
Phenylcarbamoyl azide (2i):
1
2
00.59, 137.93, 132.66, 128.43, 127.94, 17.06, 11.59.
[28]
1
4
’-(3-Chloropropyl)acetophenone
(5k):
H NMR
À1
363, 1235, 1083, 1014 cm ; MS (APCI): m/z=177.01 (M+
(400 MHz, CDCl ): d=7.89 (d, J=8.0 Hz, 2H), 7.29 (d, J=
3
+
8
.0 Hz, 2H), 3.52 (t, J=6.3 Hz, 2H), 2.84 (t, J=7.3 Hz, 2H),
13
[16i]
White solid; mp 106–
2.58 (s, 3H), 2.17–1.98 (m, 2H); C NMR (100 MHz,
1
078C; H NMR (400 MHz, CDCl ): d=7.43–7.45 (m, 2H),
CDCl ): d=197.38, 146.23, 135.12, 128.52, 128.41, 43.75,
3
3
7
.32–7.36 (m, 2H), 7.12–7.16 (m, 1H), 6.82 (bs, 1H);
33.34, 32.49, 26.30.
4’-(3-Bromopropyl)acetophenone
1
3
[29]
1
C NMR (100 MHz, CDCl ): d=154.12, 136.81, 129.01,
(5l):
H NMR
3
1
24.54, 119.31; IR (KBr): n˜ =3324, 3188, 3160, 2440, 2179,
(400 MHz, CDCl ): d=7.90 (d, J=8.0 Hz, 2H), 7.29 (d, J=
3
2348
ꢁ 2009 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Adv. Synth. Catal. 2009, 351, 2342 – 2350