1
118 Zheng et al.
Asian J. Chem.
(8.56 g, 80 mmol), xylene 80 mL in dry round flask refluxed
for 2 h. The reaction was cooled to room temperature and for
MHz, CDCl ): δ = 146.75, 138.54, 121.33, 116.09, 109.35,
3
+
55.40, 43.42, 31.68, 20.42, 13.98; ESI-MS: m/z 180.04 [M+H] .
1
3
formation of crystals, filtered to afford the product N ,N -
1
N-Butyl-3-methoxyaniline (Table-4, entry 7): H NMR
1
dibutylmalonamide and N ,N -dibenzylmalonamide .
3
27
3
(400 MHz, CDCl ): δ = 7.06 (t, J = 8.1 Hz, 1H), 6.26-6.20 (m,
All reactions were carried out under a nitrogen atmosphere
2H), 6.15 (s, 1H), 3.76 (s, 3H), 3.09 (t, J = 7.1 Hz, 2H), 1.63-
13
1.55 (m, 2H), 1.46-1.39 (m, 2H), 0.95 (t, J = 7.3 Hz, 3H); C
1
3
1
3
with N ,N -dibutylmalonamide or N ,N -dibenzylmalonamide
2 mmol) and aryl halides (1 mmol) were allowed to react
with CuI (9.5 mg, 0.05 mmol), KOt-Bu (0.34 g, 3 mmol),
O (90 mg, 5 mmol), DMSO 4 mL at 160 ºC for 8 h in PTFE
(
3
NMR (100 MHz, CDCl ): δ = 160.88, 149.94, 129.94, 105.96,
102.19, 98.63, 55.07, 43.70, 31.64, 20.31, 13.92; ESI-MS:
+
m/z 180.04 [M+H] .
H
2
1
N-Butyl-4-methoxyaniline (Table-4, entry 8): H NMR
airtight reaction. The reaction mixture was filtered and washed
with 30 mL ethyl acetate after the reaction finished, the filtrate
(400 MHz, CDCl ): δ = 6.78 (d, J = 8.2 Hz, 2H), 6.58 (d, J =
3
8.3 Hz, 2H), 3.74 (s, 3H), 3.06 (t, J = 7.0 Hz, 2H), 1.62-1.55
2 4
was washed with water and dried over Na SO , concentrated
13
in vacuo. The residue was purified by silica gel chromato-
graphy to provide the desired product.
(m, 2H), 1.47-1.37 (m, 2H), 0.95 (t, J = 7.3 Hz, 3H); C NMR
(100 MHz, CDCl ): δ = 152.01, 142.83, 114.92, 55.85, 44.76,
1.79, 29.72, 20.34, 13.95; ESI-MS: m/z 180.02 [M+H] .
3
+
3
Spectral data of product
1
N-Butylnaphthalen-1-amine (Table-4, entry 9): H
NMR (400 MHz, CDCl ): δ = 7.79 (dd, J = 8.7, 6.1 Hz, 2H),
7.39-7.34 (m, 2H), 7.32 (t, J = 7.9 Hz, 1H), 7.24-7.21 (m, 1H),
1
3
1
N ,N -Dibutylmalonamide (I): H NMR (400 MHz,
CDCl ): δ = 3.24 (dd, J = 14.0, 7.9 Hz, 6H), 1.54-1.40 (m,
H), 1.38-1.30 (m, 4H), 0.92 (t, J = 7.4 Hz, 6H); C NMR
100 MHz, CDCl ): δ = 167.67, 43.09, 39.30, 31.28, 21.01,
3.65; ESI-MS: m/z 451.58 [2M+Na] .
3
3
13
4
6.62 (d, J = 7.5 Hz, 1H), 3.27 (t, J = 7.1 Hz, 2H), 1.80-1.72
13
(
3
(m, 2H), 1.53-1.47 (m, 2H), 1.00 (t, J = 7.4 Hz, 3H); C NMR
(100 MHz, CDCl ): δ = 143.55, 134.33, 128.69, 126.68,
125.67, 124.62, 123.36, 119.80, 117.17, 104.33, 44.02, 31.53,
+
1
3
1
3
1
N ,N -Dibenzylmalonamide(II): H NMR (400 MHz,
CDCl ): δ = 7.64 (s, 2H), 7.26 (ddd, J = 17.4, 7.0 Hz, 10H),
+
3
20.53, 14.00; ESI-MS: m/z 200.14 [M+H] .
N-Benzylaniline (Table-4, entry 10, 11, 12): H NMR
13
1
4
.36 (d, J = 5.7 Hz, 4H), 3.20 (s, 2H); C NMR (100 MHz,
CDCl ): δ = 167.41, 137.80, 128.67, 127.55, 43.54, 42.98;
3
(400 MHz, CDCl ): δ = 7.28-7.24 (m, 4H), 7.19-7.16 (m, 1H),
3
7.16-7.14 (m, 2H), 6.71 (t, J = 7.3 Hz, 1H), 6.62 (d, J = 7.7
+
ESI-MS: m/z 587.26 [2M+Na] .
N-Butylaniline (Table-4, entry 1 and 2): H NMR (400
MHz, CDCl ): δ = 7.18 (dd, J = 22.0, 14.3 Hz), 6.68 (t, J =
.3 Hz, 1H), 6.60 (d, J = 7.8 Hz, 2H), 3.59 (s, 1H), 3.10 (t, J
1
13
Hz, 2H), 4.30 (s, 2H); C NMR (100 MHz, CDCl ): δ = 148.15,
3
3
139.46, 129.33, 128.70, 127.58, 127.30, 117.66, 112.94, 48.38;
+
ESI-MS: m/z 183.84 [M+H] .
7
1
N-Benzyl-2-methylaniline (Table-4, entry 13): H NMR
=
7.1 Hz, 2H), 1.64-1.56 (m, 2H), 1.47-1.38 (m, 2H), 0.95 (t,
13
J = 7.3 Hz, 3H); C NMR (100 MHz, CDCl ): δ = 148.55,
3
3
(400 MHz, CDCl ): δ = 7.36 (dt, J = 14.8, 7.4 Hz, 4H), 7.27
1
29.24, 117.10, 112.71, 43.70, 31.70, 20.33, 13.94; ESI-MS:
(dd, J = 15.2, 8.3 Hz, 1H), 7.09 (dd, J = 12.8, 7.2 Hz, 2H),
13
6.78-6.61 (m, 2H), 4.37 (s, 2H), 2.17 (s, 3H); C NMR (100
+
m/z 150.12 [M+H] .
N-Butyl-2-methylaniline (Table-4, entry 3): H NMR
400 MHz, CDCl ): δ = 7.12 (t, J = 7.6 Hz, 1H), 7.04 (d, J =
.1 Hz, 1H), 6.64 (dd, J = 12.1, 7.7 Hz, 2H), 3.15 (t, J = 7.1
Hz, 2H), 2.13 (s, 3H), 1.67-1.62 (m, 2H), 1.48-1.41 (m, 2H),
1
MHz, CDCl ): δ = 145.99, 139.44, 130.10, 128.68, 127.60,
3
127.29, 127.18, 122.02, 117.28, 110.09, 48.38, 17.58; ESI-
(
3
+
MS: m/z 197.92 [M+H] .
7
1
N-Benzyl-3-methylaniline (Table-4, entry 14): H NMR
13
0
1
2
.97 (t, J = 7.3 Hz, 3H); C NMR (100 MHz, CDCl ): δ =
3
3
(400 MHz, CDCl ): δ = 7.29 (ddd, J = 26.5, 13.2, 3.7 Hz,
46.28, 130.04, 127.15, 112.80, 116.76, 109.79, 43.75, 31.69,
+
0.40, 17.47, 13.96; ESI-MS: m/z 164.02 [M+H] .
5H), 7.05 (dd, J = 12.4, 7.6 Hz, 1H), 6.56-6.53 (m, 1H), 6.45
(d, J = 7.3 Hz, 2H), 4.30 (d, J = 4.5 Hz, 2H), 3.97 (s, 1H),
13
2.26 (d, J = 4.5 Hz, 3H); C NMR (100 MHz, CDCl ): δ =
3
1
N-Butyl-3-methylaniline (Table-4, entry 4): H NMR
(
400 MHz, CDCl
3
): δ = 7.05 (t, J = 7.7 Hz, 1H), 6.51 (d, J =
.4 Hz, 1H), 6.41 (d, J = 7.4 Hz, 2H), 3.53 (s, 1H), 3.09 (t, J
7.1 Hz, 2H), 2.27 (s, 3H), 1.59-1.55 (m, 2H), 1.47-1.37 (m,
148.23, 139.57, 139.09, 129.20, 128.67, 127.60, 127.26,
118.62, 113.72, 110.05, 48.42, 21.69; ESI-MS: m/z 197.97
7
+
[M+H] .
=
13
1
N-Benzyl-4-methylaniline (Table-4, entry 15): H NMR
2
H), 0.95 (t, J = 7.3 Hz, 3H); C NMR (100 MHz, CDCl
3
): δ
148.60, 138.99, 129.11, 118.06, 113.50, 109.90, 43.73,
=
(400 MHz, CDCl ): δ = 7.37-7.30 (m, 4H), 7.26 (dd, J = 14.8,
3
+
1.74, 21.65, 20.33, 13.94; ESI-MS: m/z 164.02 [M+H] .
3
7.9 Hz, 1H), 6.97 (d, J = 8.2 Hz, 2H), 6.55 (d, J = 8.3 Hz,
13
2H), 4.29 (s, 2H), 2.23 (s, 3H); C NMR (100 MHz, CDCl ):
3
1
N-Butyl-4-methylaniline (Table-4, entry 5): H NMR
(
400 MHz, CDCl
3
): δ = 6.98 (d, J = 8.2 Hz, 2H), 6.53 (d, J =
.3 Hz, 2H), 3.39 (s, 1H), 3.09-3.06 (m, 2H), 2.23 (s, 3H),
δ = 145.88, 139.65, 129.79, 128.64, 127.56, 127.20, 126.85,
+
113.09, 48.71, 20.44; ESI-MS: m/z 197.93 [M+H] .
8
1
N-Benzyl-2-methoxyaniline (Table-2, entry 16): H
1
.58-1.55 (m, 2H), 1.46-1.37 (m, 2H), 0.94(t, J = 7.3 Hz, 3H);
13
C NMR (100 MHz, CDCl ): δ = 146.32, 129.73, 126.32,
3
12.95, 44.11, 31.76, 20.40, 20.37, 13.96; ESI-MS: m/z 164.05
NMR (400 MHz, CDCl ): δ = 7.36-7.31 (m, 5H), 6.84-6.76
3
1
(m, 2H), 6.67 (t, J = 7.7 Hz, 1H), 6.59 (d, J = 7.8 Hz, 1H),
13
4.33 (s, 2H), 3.82 (s, 3H); C NMR (100 MHz, CDCl ): δ =
3
+
[
M+H] .
N-Butyl-2-methoxyaniline (Table-4, entry 6): H NMR
400 MHz, CDCl ): δ = 6.88-6.80 (m, 1H), 6.75 (dd, J = 7.8,
.9 Hz, 1H), 6.63 (ddd, J = 11.3, 8.3, 1.2 Hz, 2H), 4.16 (s, 1H),
.83 (s, 3H), 3.11 (m, 2H), 1.67-1.60 (m, 2H), 1.44 (dd, J =
1
146.86, 139.61, 138.13, 129.95, 128.63, 127.57, 127.17,
121.33, 116.73, 110.18, 109.46, 55.45, 48.11; ESI-MS: m/z
(
3
+
213.92 [M+H] .
0
3
1
1
N-Benzyl-3-methoxyaniline (Table-4, entry 17): H
13
5.1, 7.4 Hz, 2H), 0.95 (t, J = 7.4 Hz, 3H); C NMR (100
3
NMR (400 MHz, CDCl ): δ = 7.34 (q, J = 7.8 Hz, 4H), 7.26