N-ALKYLATION OF ANILINE AND ITS DERIVATIVES BY ALCOHOLS IN THE PRESENCE
1657
NMR spectrum, δ, ppm: 1.09 t (3H, C9H3, J 8 Hz),
1.65–1.77 m (2H, C8H2), 3.16 t (2H, C7H2, J 8 Hz),
3.71 s (1H, NH), 6.69 d (2Н, С2,6H, J 8 Hz), 6.70–6.85
m (1Н, С4H), 7.22–7.35 m (2Н, С3,5H). 13С NMR
spectrum, δ, ppm: 11.74 (С9), 22.79 (С8), 45.85 (С7),
112.78 (С2,6), 117.12 (С4), 129.30 (С3,5), 148.63 (C1).
Mass spectrum, m/z (Irel, %): 136 (5) [M]+, 135 (30),
118 (5), 106 (100), 77 (18).
117.14 (С4), 129.25 (С3,5), 148.63 (С1). Mass
spectrum, m/z (Irel, %): 163 (20) [M]+, 132 (3), 118 (5),
106 (100), 93 (7), 77 (14).
N-Hexylaniline (11). Yield 42%, light-yellow oily
liquid, bp 157–159°С (20 mmHg) {88–89°С
1
(0.1 mmHg) [15]}. Н NMR spectrum, δ, ppm: 0.91 t
(3H, C12H3, J 4 Hz), 1.25–1.45 m (6H, C9,10,11H2), 1.55
–1.65 m (2H, C8H2), 3.62 t (2H, C7H2, J 4 Hz), 3.80 s
(1H, NH), 6.62 d (2Н, С2,6H, J 8 Hz), 6.67–6.73 m
(1Н, С4H), 7.12–7.22 m (2Н, С3,5H). 13С NMR
spectrum, δ, ppm: 14.03 (C12), 22.65 (C11), 25.47 (C10),
26.87 (С9), 29.53 (С8), 44.04 (С7), 112.76 (С2,6),
117.10 (С4), 129.20 (С3,5), 148.56 (С1). Mass
spectrum, m/z (Irel, %): 177 (18) [M]+, 132 (3), 118 (3),
106 (100), 93 (5), 77 (10).
N,N-Dipropylaniline (18). Yield 8%, light-yellow
oily liquid, bp 112–114°С (10 mmHg) {62–66°С
(0.23 mmHg) [14]}. 1Н NMR spectrum, δ, ppm: 1.02 t
(3H, C9,9'H3, J 4 Hz), 1.80–1.92 m (2H, C8,8'H2), 3.30–
3.35 m (2H, C7,7'H2), 6.58–6.64 m (2Н, С2,6H), 6.65–
6.70 m (1Н, С4H), 7.05–7.20 m (2Н, С3,5H). 13С NMR
spectrum, δ, ppm: 11.55 (С9,9'), 20.49 (С8,8'), 52.94
(С7,7'), 111.77 (С2,6), 115.19 (С4), 129.08 (С3,5), 148.30
(C1). Mass spectrum, m/z (Irel, %): 177 (20) [M]+, 162
(5), 148 (100), 120 (10), 106 (72), 77 (18).
N-Cyclopentylaniline (12). Yield 71%, light-
yellow oily liquid, bp 140–142°С (15 mmHg) {137°С
1
(12 mmHg) [17]}. Н NMR spectrum, δ, ppm: 1.45–
N-Butylaniline (9). Yield 65%, light-yellow oily
liquid, bp 112–114°С (10 mmHg) {60–61°С
(0.5 mmHg) [15]}. Н NMR spectrum, δ, ppm: 0.97 t
1.55 m (2Ha, C3',4'H), 1.60–1.70 m (2Ha, C2',5'H), 1.70–
1.80 m (2He, C3',4'H), 2.00–2.10 m (2He, C2',5'H), 3.67
br.s(1Н, NH), 3.75–3.9 m (1H, C1'H), 6.63 d (2H,
С2,6H, J 8 Hz), 6.71 t (1H, C4H, J 8 Hz), 7.19 t (2H,
C3,5H, J 8 Hz). 13С NMR spectrum, δ, ppm: 24.08
(С3',4'), 33.61 (С2',5'), 54.65 (С1'), 113.16 (С2,6), 116.89
(С4), 129.19 (С3,5), 148.06 (С1). Mass spectrum, m/z
(Irel, %): 161 (50) [M]+, 133 (13), 132 (100), 119 (30),
93 (18).
1
(3H, C10H3, J 8 Hz), 1.40–1.50 m (2H, C9H2), 1.55‒
1.65 m (2H, C8H2), 3.11 t (2H, C7H2, J 4 Hz), 3.66 s
(1H, NH), 6.61 d (2Н, С2,6H, J 8 Hz), 6.65–6.70 m
(1Н, С4H), 7.15–7.20 m (2Н, С3,5H). 13С NMR
spectrum, δ, ppm: 13.89 (C10), 19.30 (С9), 31.65 (С8),
43.65 (С7), 112.64 (С2,6), 116.99 (С4), 129.18 (С3,5),
148.56 (С1). Mass spectrum, m/z (Irel, %): 150 (5) [M]+,
149 (20), 107 (10), 106 (100), 93 (3), 77 (10).
N-Cyclohexylaniline (13). Yield 23%, light-yellow
oily liquid, bp 140–142°С (10 mmHg) {92–96°С
1
N,N-Dibutylaniline (19). Yield 10%, light-yellow
oily liquid, bp 146–148°С (15 mmHg) {82–84°С
(0.23 mmHg) [14]}.1Н NMR spectrum, δ, ppm: 0.95–
1.10 m (6H, C10,10'H3), 1.40–1.60 m (3H, C9,9'H2), 1.60
–1.72 m (4H, C8,8'H2), 3.35 t (4H, C7,7'H2, J 8 Hz), 6.56
–6.60 m (2Н, С2,6H), 6.61–6.65 m (1Н, С4H), 7.05–
7.18 m (2Н, С3,5H). 13С NMR spectrum, δ, ppm: 14.02
(C10,10'), 20.40 (С9,9'), 29.40 (С8,8'), 50.84 (С7,7'), 111.35
(С2,6), 115.15 (С4), 131.61 (С3,5), 148.26 (С1). Mass
spectrum, m/z (Irel, %): 205 (34) [M]+, 162 (100), 120
(79), 106 (60), 93 (5), 77 (18).
(2 mmHg) [11]}. Н NMR spectrum, δ, ppm: 1.20–
1.50 m (2H, C4'H), 1.50–1.70 m (4H, C3',5'H), 2.00–
2.20 m (4H, C2',6'H), 3.31–3.37 m (1Н, С1'H), 3.37 s
(1Н, NH), 6.64 d (2H, С2,6H, J 8 Hz), 6.75–6.85 m
(2H, C3,5H), 7.10–7.30 m (1H, C4H). 13С NMR
spectrum, δ, ppm: 25.09 (С3',5'), 25.99 (С4'), 35.49
(С2',6'), 51.72 (С1'), 113.24 (С2,6), 117.87 (С4), 129.30
(С3,5), 147.46 (С1). Mass spectrum, m/z (Irel, %): 175
(30) [M]+, 146 (5), 132 (100), 106 (15), 93 (17).
N-Cycloheptylaniline (14). Yield 41%, light-
yellow oily liquid, bp 126–128°С (5 mmHg) {156°С
1
N-Pentylaniline (10). Yield 44%, light-yellow oily
liquid, bp 148–150°С (20 mmHg) {130°С (11 mmHg)
[16]}. 1Н NMR spectrum, δ, ppm: 0.96 t (3H, C11H3, J
4 Hz), 1.32–1.48 m (2H, C10H2), 1.32–1.48 m (2H,
C9H2), 1.55–1.68 m (2H, C8H2), 3.62 t (2H, C7H2, J
4 Hz), 3.80 s (1H, NH), 6.62 d (2Н, С2,6H, J 8 Hz),
6.67–6.73 m (1Н, С4H), 7.12–7.22 m (2Н, С3,5H). 13С
NMR spectrum, δ, ppm: 14.08 (C11), 22.56 (C10),
28.02 (С9), 32.44 (С8), 44.05 (С7), 112.86 (С2,6),
(11 mmHg) [17]}. Н NMR spectrum, δ, ppm: 1.20–
1.80 m (8H, C3'–6'H2), 2.00–2.10 m (4H, C2',7'H2), 3.44–
3.52 m (1H, C1'H), 3.65 br.s (1Н, NH), 6.59 d (2H,
С2,6H, J 8 Hz), 6.70–6.75 m (1H, C4H), 7.20 t (2H,
C3,5H, J 8 Hz). 13С NMR spectrum, δ, ppm: 24.44
(С4',5'), 28.39 (С3',6'), 34.86 (С2',7'), 54.66 (С1'), 113.23
(С2,6), 116.77 (С4), 129.29 (С3,5), 147.38 (С1). Mass
spectrum, m/z (Irel, %): 189 (38) [M]+, 160 (5), 146
(17), 132 (100), 106 (17), 93 (20), 77 (12).
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 54 No. 11 2018