Journal of Inorganic and General Chemistry
ARTICLE
Zeitschrift für anorganische und allgemeine Chemie
30:1). 1H NMR (500 MHz, CDCl3, 25 °C): δ = 7.36–7.27 (m, 2 H,
N-(2-Methyloctyl)aniline (9a):[7g] General procedure A was used to
Ar-H), 7.25–7.12 (m, 5 H, Ar-H), 6.69 (t, J = 7.3 Hz, 1 H, Ar-H), 6.59 synthesize the title compound from 1-octene and N-methylaniline (2).
(d, J = 8.1 Hz, 2 H, Ar-H), 3.16 (t, J = 7.0 Hz, 2 H, CH2), 2.74 (t, J
= 7.6 Hz, 2 H, CH2), 1.96 (p, J = 7.3 Hz, 2 H, CH2) ppm. 13C NMR
(125 MHz, DEPT, CDCl3, 25 °C): δ = 148.3 (C), 141.7 (C), 129.2
Purification by flash chromatography (PE/EtOAc, 30:1) gave the prod-
uct 9a (210 mg, 0.96 mmol, 96 %) as a colorless oil. Prior to
chromatography, the ratio of the regioisomers 9a/9b was determined
(CH), 128.4 (CH), 128.4 (CH), 126.0 (CH), 117.3 (CH), 112.8 (CH), to be Ͼ 99:1. Rf = 0.39 (PE/EtOAc, 40:1). 1H NMR (500 MHz,
43.5 (CH2), 33.4 (CH2), 31.1 (CH2) ppm.
CDCl3, 25 °C): δ = 7.20–7.17 (m, 2 H, Ar-H), 6.69 (t, J = 7.3 Hz, 1
H, Ar-H), 6.62 (d, J = 7.7 Hz, 2 H, Ar-H), 3.71 (br. s, 1 H, N-H), 3.06
(dd, J = 12.2, 5.9 Hz, 1 H, CH2), 2.89 (dd, J = 12.2, 7.3 Hz, 1 H,
2-Methyl-N-(2-phenylpropyl)aniline (7a)[7g] and 2-Methyl-N-(3-
phenylpropyl)aniline (7b):[7g] General procedure A was used to syn- CH2), 1.80–1.70 (m, 1 H, CH), 1.48–1.26 (m, 10 H, CH2), 1.24–1.14
thesize the title compounds from styrene (1) and N-methyl-ortho-tolu- (m, 1 H, CH2), 0.98 (d, J = 6.7 Hz, 3 H, CH3), 0.91 (t, J = 6.8 Hz, 3
idine. Purification by flash chromatography (PE/MTBE, 15:1) gave a
mixture of the products 7a and 7b (20 mg, 0.09 mmol, 9%) as a color-
less oil. Prior to chromatography, the ratio of the regioisomers 7a/7b
H, CH3) ppm. 13C NMR (125 MHz, DEPT, CDCl3, 25 °C): δ = 148.6
(C), 129.2 (CH), 116.9 (CH), 112.6 (CH), 50.3 (CH2), 34.8 (CH2),
32.9 (CH), 31.9 (CH2), 29.6 (CH2), 26.9 (CH2), 22.7 (CH2), 18.1
was determined to be 87:13. 7a: Rf = 0.44 (PE/MTBE, 15:1). 1H NMR (CH3), 14.1 (CH3) ppm.
(500 MHz, CDCl3, 25 °C): δ = 7.38–7.33 (m, 2 H, Ar-H), 7.28–7.23
(m, 3 H, Ar-H), 7.17–7.12 (m, 1 H, Ar-H), 7.02 (d, J = 7.2 Hz, 1 H, 4-Fluoro-N-(2-phenylpropyl)aniline (10a)[5m] and 4-Fluoro-N-(3-
Ar-H), 6.69–6.63 (m, 2 H, Ar-H), 3.44 (br. s, 1 H, N-H), 3.43 (dd, J phenylpropyl)aniline (10b):[7j] General procedure A was used to syn-
= 12.1, 6.0 Hz, 1 H, CH2), 3.24 (dd, J = 12.1, 8.5 Hz, 1 H, CH2), 3.17–
3.09 (m, 1 H, CH), 1.94 (s, 3 H, CH3), 1.39 (d, J = 6.9 Hz, 3 H, CH3)
thesize the title compounds from styrene (1) and 4-fluoro-N-methylan-
iline. Purification by flash chromatography (PE/MTBE, 20:1 with 1
ppm. 13C NMR (125 MHz, DEPT, CDCl3, 25 °C): δ = 146.0 (C), vol% Et3N) gave the products 10a (130 mg, 0.57 mmol, 57%) and 10b
144.5 (C), 130.0 (CH), 128.7 (CH), 127.2 (CH), 127.1 (CH), 126.7 (20 mg, 0.09 mmol, 9%) as colorless oils. Prior to chromatography, the
(CH), 122.0 (C), 116.8 (CH), 109.9 (CH), 50.9 (CH2), 39.0 (CH), 19.5
(CH3), 17.2 (CH3) ppm. 7b: Rf = 0.36 (PE/MTBE, 15:1). 1H NMR = 0.23 (PE/MTBE, 20:1 with 1 vol% Et3N). 1H NMR (500 MHz,
(500 MHz, CDCl3, 25 °C): δ = 7.32–7.28 (m, 2 H, Ar-H), 7.23–7.18 CDCl3, 25 °C): δ = 7.37–7.29 (m, 2 H, Ar-H), 7.28–7.21 (m, 3 H, Ar-
(m, 3 H, Ar-H), 7.12–7.09 (m, 1 H, Ar-H), 7.06–7.03 (m, 1 H, Ar-H), H), 6.91–6.84 (m, 2 H, Ar-H), 6.53–6.46 (m, 2 H, Ar-H), 3.45 (br. s,
ratio of the regioisomers 10a/10b was determined to be 87:13. 10a: Rf
6.67–6.65 (m, 1 H, Ar-H), 6.60–6.56 (m, 1 H, Ar-H), 3.20 (t, J =
7.0 Hz, 2 H, CH2), 2.77 (t, J = 7.6 Hz, 2 H, CH2), 2.09 (s, 3 H, CH3),
1 H, N-H), 3.31 (dd, J = 12.2, 6.0 Hz, 1 H, CH2), 3.20 (dd, J = 12.2,
8.4 Hz, 1 H, CH2), 3.10–3.00 (m, 1 H, CH), 1.34 (d, J = 7.0 Hz, 3 H,
2.06–1.98 (m, 2 H, CH2) ppm. 13C NMR (125 MHz, DEPT, CDCl3, CH3) ppm. 13C NMR (125 MHz, DEPT, CDCl3, 25 °C): δ = 155.7 (d,
25 °C): δ = 144.5 (C), 141.7 (C), 130.0 (CH), 128.4 (CH), 128.4 (CH),
J(C,F) = 235 Hz, C), 144.4 (C), 144.4 (C), 128.7 (CH), 127.2 (CH),
127.1 (CH), 126.0 (CH), 121.8 (C), 116.7 (CH), 109.6 (CH), 43.4 126.7 (CH), 115.6 (d, JC,F = 22 Hz, CH), 113.8 (d, JC,F = 7 Hz, CH),
(CH2), 33.5 (CH2), 31.0 (CH2), 17.4 (CH3) ppm.
51.6 (CH2), 39.2 (CH), 19.8 (CH3) ppm. 10b: Rf = 0.15 (PE/MTBE,
20:1 with 1 vol% Et3N). 1H NMR (500 MHz, CDCl3, 25 °C): δ =
7.32–7.28 (m, 2 H, Ar-H), 7.23–7.18 (m, 3 H, Ar-H), 6.90–6.84 (m, 2
H, Ar-H), 6.52–6.48 (m, 2 H, Ar-H), 3.48 (br. s, 1 H, N-H), 3.11 (t, J
= 7.0 Hz, 2 H, CH2), 2.74 (t, J = 7.6 Hz, 2 H, CH2), 1.99–1.90 (m, 2
N-(2-(2-Methylphenyl)propyl)aniline (8a) and N-(3-(2-Meth-
ylphenyl)propyl)aniline (8b): General procedure A was used to syn-
thesize the title compounds from ortho-methylstyrene and N-methylan-
iline (2). Purification by flash chromatography (PE/EtOAc, 30:1) gave H, CH2) ppm. 13C NMR (125 MHz, DEPT, CDCl3, 25 °C): δ = 155.7
the products 8a (60 mg, 0.27 mmol, 27%) and 8b (10 mg, 0.04 mmol,
4%) as colorless oils. Prior to chromatography, the ratio of the re-
(d, JC,F = 235 Hz, C), 144.7 (C), 141.6 (C), 128.4 (CH), 128.4 (CH),
126.0 (CH), 115.6 (d, JC,F = 22 Hz, CH), 113.5 (d, JC,F = 7 Hz, CH),
gioisomers 8a/8b was determined to be 91:9. 8a: Rf = 0.28 (PE/EtOAc, 44.1 (CH2), 33.4 (CH2), 31.0 ppm.
30:1). 1H NMR (500 MHz, CDCl3, 25 °C): δ = 7.29–7.13 (m, 6 H,
Ar-H), 6.76–6.70 (m, 1 H, Ar-H), 6.65–6.59 (m, 2 H, Ar-H), 3.62 (br.
s, 1 H, N-H), 3.44–3.29 (m, 3 H, CH/CH2), 2.34 (s, 3 H, CH3), 1.33
(d, J = 6.4 Hz, 3 H, CH3) ppm. 13C NMR (125 MHz, DEPT, CDCl3,
25 °C): δ = 148.2 (C), 142.6 (C), 136.1 (C), 130.5 (CH), 129.2 (CH),
126.5 (CH), 126.2 (CH), 125.3 (CH), 117.3 (CH), 112.9 (CH), 50.1
(CH2), 34.1 (CH), 19.6 (CH3), 19.5 (CH3) ppm. MS (EI, 70 eV): m/z
4-Chloro-N-(2-phenylpropyl)aniline (11a)[7g] and 4-Chloro-N-(3-
phenylpropyl)aniline (11b):[7g] General procedure A was used to syn-
thesize the title compounds from styrene (1) and 4-chloro-N-methylan-
iline. Purification by flash chromatography (PE/MTBE, 40:1) gave the
products 11a (140 mg, 0.57 mmol, 57%) and 11b (20 mg, 0.08 mmol,
8%) as slightly yellow oils. Prior to chromatography, the ratio of the
(%) = 225 (20) [M+], 106 (100) [C7H8N+], 77 (32) [C6H5+]. HRMS regioisomers 11a/11b was determined to be 88:12. 11a: Rf = 0.25 (PE/
(ESI+): calcd. (C16H20N) 226.1596; found 226.1606. IR (ATR): 1/λ = MTBE, 15:1). 1H NMR (500 MHz, CDCl3, 25 °C): δ = 7.40–7.35 (m,
3403, 3051, 3019, 2928, 2862, 1601, 1505, 1429, 1320, 1257, 1178,
2 H, Ar-H), 7.31–7.28 (m, 1 H, Ar-H), 7.27–7.23 (m, 2 H, Ar-H),
1029, 991, 865, 744, 691, 580, 552 cm–1. 8b: Rf = 0.24 (PE/EtOAc, 7.16–7.10 (m, 2 H, Ar-H), 6.57–6.51 (m, 2 H, Ar-H), 3.35 (dd, J =
30:1). 1H NMR (500 MHz, CDCl3, 25 °C): δ = 7.20–7.10 (m, 6 H,
12.4, 6.1 Hz, 1 H, CH2), 3.24 (dd, J = 12.4, 8.4 Hz, 1 H, CH2), 3.13–
Ar-H), 6.73–6.68 (m, 1 H, Ar-H), 6.63–6.58 (m, 2 H, Ar-H), 3.19 (t, 3.04 (m, 1 H, CH), 1.37 (d, J = 7.0 Hz, 3 H, CH3) ppm. 13C NMR
J = 7.0 Hz, 2 H, CH2), 2.75–2.69 (m, 2 H, CH2), 2.31 (s, 3 H, CH3), (125 MHz, DEPT, CDCl3, 25 °C): δ = 146.4 (C), 144.2 (C), 129.0
1.96–1.88 (m, 2 H, CH2) ppm. 13C NMR (125 MHz, DEPT, CDCl3, (CH), 128.7 (CH), 127.2 (CH), 126.7 (CH), 122.1 (C), 114.2 (CH),
25 °C): δ = 148.2 (C), 139.8 (C), 135.9 (C), 130.3 (CH), 129.2 (CH),
128.8 (CH), 126.1 (CH), 126.0 (CH), 117.3 (CH), 112.8 (CH), 43.8
51.1 (CH2), 39.1 (CH), 19.7 (CH3) ppm. 11b: Rf = 0.14 (PE/MTBE,
15:1). 1H NMR (500 MHz, CDCl3, 25 °C): δ = 7.33–7.28 (m, 2 H,
(CH2), 30.7 (CH2), 29.8 (CH2), 19.3 (CH3) ppm. MS (EI, 70 eV): m/z Ar-H), 7.24–7.18 (m, 3 H, Ar-H), 7.13–7.08 (m, 2 H, Ar-H), 6.52–
(%) = 225 (10) [M+], 106 (100) [C7H8N+], 77 (35) [C6H5+]. HRMS 6.46 (m, 2 H, Ar-H), 3.12 (t, J = 7.0 Hz, 2 H, CH2), 2.73 (t, J = 7.6 Hz,
(ESI+): calcd. (C16H20N) 226.1596; found 226.1597. IR (ATR): 1/λ = 2 H, CH2), 1.99–1.91 (m, 2 H, CH2) ppm. 13C NMR (125 MHz,
3415, 3050, 3020, 2963, 2926, 2868, 1601, 1504, 1458, 1430, 1378,
DEPT, CDCl3, 25 °C): δ = 146.7 (C), 141.4 (C), 129.0 (CH), 128.5
1319, 1256, 1179, 1070, 1014, 991, 866, 746, 727, 691, 580, (CH), 128.4 (CH), 126.0 (CH), 121.8 (C), 113.8 (CH), 43.5 (CH2),
552 cm–1.
33.3 (CH2), 30.8 (CH2) ppm.
Z. Anorg. Allg. Chem. 2015, 2071–2082
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