The Journal of Organic Chemistry
Article
5.43 (q, J = 1.3 Hz), 5.28−5.21 (m, 2H), 5.12 (q, J = 1.3 Hz, 1H), 4.31
(s, 2H), 4.06 (d, J = 4.8 Hz, 2H), 3.88 (s, 3H) ppm. 13C NMR (100
MHz, CDCl3): δ = 159.5, 148.9, 141.7, 133.9, 129.8, 129.2, 127.2,
116.5, 116.3, 114.0, 112.3, 110., 54.4, 54.2, 52.9 ppm. HRMS (ESI):
m/z calcd. for C19H22NO [M + H] 280.1696, found 280.1697.
N-Allyl-N-(2-(naphthalen-2-yl)allyl)aniline (4j). Colorless oil.
Yield: 167 mg (82%). IR (neat): 3058, 2913, 2857, 1597, 1505,
5.03 (dq, J = 8 Hz, J = 4 Hz, 1H), 4.81 (m, 1H), 3.41 (s, 2H), 3.08 (dt,
J = 4 Hz, J = 2 Hz, 2H), 2.67 (s, 2H), 2.55−2.47 (m, 1H), 1.78−1.72
(m, 4H) ppm. 13C NMR (100 MHz, CDCl3): δ = 148.4, 140.1, 138.1,
129.2, 128.1, 125.8, 115.5, 113.2, 58.4, 54.5, 52.7, 40.4, 28.7, 26.5, 26.2
ppm. HRMS (ESI): m/z calcd. for C19H28N [M + H] 270.2216, found
270.2207.
N-(2-Benzylallyl)-N-(3-methyl-2-methylenebutyl)aniline (4q).
Colorless oil. Yield: 76.9 mg (61%). IR (neat): 3062, 3027, 2960,
2924, 2870, 2854, 1649, 1597, 1506, 1494, 1453, 1432, 1391, 1363,
1234, 1190, 1162, 1054, 989,966, 899, 745 cm−1. 1H NMR (400 MHz,
CDCl3): δ = 7.36−7.23 (m, 8H), 7.18−7.14 (m, 2H), 6.66 (t, J = 8
Hz, 1H), 6.55 (d, J = 8 Hz, 2H), 3.83 (s, 2H), 3.79 (s, 2H), 3.39 (s,
2H), 2.24−2.19 (m, 1H), 1.09 (d, 6H) ppm. 13C NMR (100 MHz,
CDCl3): δ = 149.7, 148.8, 143.8, 139.0, 128.8, 128.4, 126.3, 115.8,
111.7, 111.6, 106.6, 54.5, 40.8, 31.8, 21.8 ppm. HRMS (ESI): m/z
calcd. for C22H28N [M + H] 306.2216, found 306.2236.
N-(2-Benzylallyl)-N-(2-methyleneheptyl)aniline (4r). Colorless oil.
Yield: 81.3 mg (58%). IR (neat): 3084, 3062, 3027, 2955, 2927, 2857,
1651, 1599, 1506, 1453, 1390, 1364, 1262, 1233, 1190, 1075, 1030,
989, 967, 898, 745 cm−1. 1H NMR (400 MHz, CDCl3): δ = 7.37−7.33
(m, 2H), 7.28−7.25 (m, 3H), 7.18−7.14 (m, 2H), 6.66 (t, J = 8 Hz,
2H), 3.80 (d, J = 8 Hz, 2H), 3.40 (s, 2H), 2.00 (t, J = 8 Hz, 2H), 1.48
(quin, J = 4 Hz, 2H), 1.39−1.28 (m, 4H), 0.93 (t, J = 8 Hz, 3H) ppm.
13C NMR (100 MHz, CDCl3): δ = 148.8, 144.3, 143.7, 139.0, 128.9
128.8, 128.4, 126.3, 115.9, 111.8, 111.6, 108.9, 55.1, 54.6, 40.8, 33.8,
31.7, 27.5, 22.5, 14.6 ppm. HRMS (ESI): m/z calcd. for C24H32N [M
+ H] 334.2529, found 334.2498.
3-Pentyl-1-phenyl-2,5-dihydro-1H-pyrrole (5a). Yellow solid; mp
81−83 °C. Yield: 211 mg (96%). IR (neat): 3046, 2955, 2925, 2855,
1714, 1600, 1506, 1459, 1374, 1358, 1323, 1209, 1071, 1051, 935, 752,
688 cm−1. 1H NMR (400 MHz, CDCl3): δ = 7.25 (t, J = 8.0 Hz, 2H),
6.68 (t, J = 8.1 Hz, 1H), 6.53 (d, J = 8.2 Hz, 2H), 5.55 (s, 1H), 4.09−
3.99 (m, 4H), 2.18 (t, J = 7.5 Hz, 2H), 1.58−1.44 (m, 2H), 1.40−1.25
(m, 4H), 0.92 (t, J = 6.9 Hz, 3H) ppm. 13C NMR (100 MHz, CDCl3):
δ = 147.2, 140.5, 129.4, 129.0, 118.8, 115.3, 111.1, 110.8, 56.5, 54.7,
31.6, 29.1, 27.2, 22.5, 14.0 ppm. HRMS (ESI): m/z calcd. for C15H22N
[M + H] 216.1746, found 216.1755.
3-Isopropyl-1-phenyl-2,5-dihydro-1H-pyrrole (5b). Colorless oil.
Yield: 35 mg (81%). IR (neat): 3043, 2958, 2925, 2869, 1656, 1600,
1507, 1473, 1373, 1306, 1215, 1183, 1155, 1070, 986, 802, 744, 690
cm−1. 1H NMR (400 MHz, CDCl3): δ = 7.16−7.09 (m, 2H), 6.57 (t, J
= 7.2 Hz, 1H), 6.42 (d, J = 8.4 Hz, 2H), 5.42 (d, J = 1.2 Hz, 1H), 3.96
(d, J = 3.2 Hz, 4H), 2.54 (m, 1H), 1.03 (d, J = 6.8 Hz, 6H) ppm. 13C
NMR (100 MHz, CDCl3): δ = 147.3, 146.4, 129.2, 117.0, 115.4, 111.0,
55.1, 54.7, 28.3, 21.3 ppm. HRMS (ESI): m/z calcd. for C13H18N [M
+ H] 188.1434, found 188.1435.
3-Benzyl-1-phenyl-2,5-dihydro-1H-pyrrole (5c). Yellow oil. Yield:
120 mg (89%). IR (neat): 3056, 3026, 2903, 2818, 1662, 1600, 1507,
1495, 1452, 1375, 1207, 1182, 1154, 1127, 1074, 1029, 988, 748, 703,
694 cm−1. 1H NMR (400 MHz, CDCl3): δ = 7.40−7.25 (m, 7H), 6.72
(t, J = 7.5 Hz, 1H), 6.53 (d, J = 10.4 Hz, 2H), 5.62 (t, J = 1.8 Hz, 1H),
4.16−4.12 (m, 2H), 4.02 (d, J = 3.9 Hz, 2H), 3.56 (s, 2H) ppm. 13C
NMR (100 MHz, CDCl3): δ = 147.1, 139.4, 138.5, 129.2, 128.7, 128.5,
126.4, 121.0, 115.4, 110.9, 56.2, 54.7, 35.9 ppm. HRMS (ESI): m/z
calcd. for C17H18N [M + H] 236.1434, found 236.1428.
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1391, 1345, 1234, 1184, 989, 958, 903, 857, 818, 747, 691 cm−1. H
NMR (400 MHz, CDCl3): δ = 7.91−7.85 (m, 4H), 7.70−7.68 (m,
1H), 7.56−7.50 (m, 2H), 7.29−7.24 (m, 2H), 6.81−6.74 (m, 3H),
5.98 (m, 1H), 5.64 (s, 1H), 5.30−5.18 (m, 3H), 4.45 (s, 2H), 4.09 (d,
J = 4.7, 2H) ppm. 13C NMR (100 MHz, CDCl3): δ = 148.9, 142.4,
137.0, 133.9, 133.5, 133.1, 129.3, 128.3, 128.2, 127.8, 126.4, 126.2,
124.7, 124.6, 116.6, 112.9, 112.4, 54.2, 53.1 ppm. HRMS (ESI): m/z
calcd. for C22H22N [M + H] 300.1747, found 300.1744.
N-Allyl-4-fluoro-N-(3-methyl-2-methylenebutyl)aniline (4k). Yel-
low oil. Yield: 108 mg (87%). IR (neat): 3083, 2962, 2929, 2871, 1840,
1644, 1611, 1509, 1391, 1362, 1225, 1183, 1143, 991, 960, 899, 810,
1
716 cm−1. H NMR (400 MHz, CDCl3): δ = 6.97−6.90 (m, 2H),
6.66−6.60 (m, 2H), 5.97−5.85 (m, 1H), 4.94 (s, 1H), 4.85 (s, 1H),
3.95−3.93 (m, 2H), 3.89 (s, 2H), 2.36−2.27 (m, 1H), 1.18 (d, J = 7.2
Hz, 6H) ppm. 13C NMR (100 MHz, CDCl3): δ = 155.2 (d, JCF = 240
Hz), 148.0 (d, JCF = 2.0 Hz), 133.9, 116.1, 115.3 (d, JCF = 20 Hz),
113.0 (d, JCF = 10 Hz), 107.0, 54.6, 53.4, 31.7, 21.9 ppm. HRMS
(ESI): m/z calcd. for C15H21NF [M + H] 234.1653, found 234.1658.
N-Allyl-4-chloro-N-(3-methyl-2-methylenebutyl)aniline (4l). Yel-
low oil. Yield: 124 mg (91%). IR (neat): 3085, 2961, 2928, 2871, 1855,
1644, 1596, 1497, 1463, 1439, 1390, 1361, 1234, 1184, 1096, 958, 917,
898, 805, 770 cm−1. 1H NMR (400 MHz, CDCl3): δ = 7.10 (d, J = 8.8
Hz, 2H), 6.53 (d, J = 9.2 Hz, 2H), 5.89−5.79 (m, 1H), 5.18−5.15 (m,
1H), 5.12 (s, 1H), 3.89−3.88 (m, 2H), 3.83 (s, 2H), 2.27−2.17 (m,
1H), 1.11 (d, J = 6.8 Hz, 6H) ppm. 13C NMR (100 MHz, CDCl3): δ =
150.0, 147.4, 133.3, 128.7, 120.7, 116.1, 113.0, 106.9, 54.1, 52.9, 31.7,
21.8 ppm. HRMS (ESI): m/z calcd. for C15H21NCl [M + H]
250.1357, found 250.1353.
N-Allyl-4-bromo-N-(3-methyl-2-methylenebutyl)aniline (4m).
Yellow oil. Yield: 93.7 mg (81%). IR (neat): 3085, 2960, 1926,
2870, 1854, 1644, 1590, 1495, 1463, 1390, 1361, 1234, 1183, 1082,
993, 958, 917, 898, 803, 764 cm−1. 1H NMR (400 MHz, CDCl3): δ =
7.27−7.22 (m, 2H), 6.54−6.46 (m, 2H), 5.90−5.78 (m, 1H), 5.19−
4.74 (m, 2H), 4.58 (s, 1H), 4.74 (s, 1H), 3.88 (d, J = 4.8 Hz, 2H), 3.72
(s, 2H), 2.30−2.21 (m, 1H), 1.30 (d, J = 6.9 Hz, 6H) ppm. 13C NMR
(100 MHz, CDCl3): δ = 149.7, 147.8, 133.2, 131.6, 116.1, 113.6,
107.8, 106.9, 54.0, 52.9, 31.7, 21.8 ppm. HRMS (ESI): m/z calcd. for
C15H21NBr [M + H] 294.0852, found 294.0853.
N-Allyl-4-methoxy-N-(3-methyl-2-methylenebutyl)aniline (4n).
Yellow oil. Yield: 178 mg (73%). IR (neat): 3080, 2960, 2930, 2871,
2831, 1643, 1510, 1463, 1441, 1362, 1261, 1230, 1180, 1943, 992, 959,
897, 809, 788, 708 cm−1. 1H NMR (400 MHz, CDCl3): δ = 6.80 (d, J
= 9.2 Hz, 2H), 6.60 (d, J = 8.0 Hz, 2H), 5.90−5.82 (m, 1H), 5.18 (d, J
= 8.4 Hz, 1H), 3.88 (s, 2H), 3.78 (s, 2H), 3.75 (s, 3H), 2.31−2.18 (m,
1H), 1,12 (d, J = 7.2 Hz, 6H) ppm. 13C NMR (100 MHz, CDCl3): δ =
151.1, 150.9, 143.7, 134.4, 115.9, 114.6, 113.5, 107.0, 55.8, 54.7, 53.4,
31.6, 21.9 ppm. HRMS (ESI): m/z calcd. for C16H24NO [M + H]
246.1852, found 246.1850.
N-Allyl-N,2-dibenzylprop-2-en-1-amine (4o). Colorless oil. Yield:
90.7 mg (71%). IR (neat): 3063, 3027, 2921, 2771, 1945, 1806, 1743,
1645, 1602, 1499, 1453, 1368, 1255, 1153, 1120, 1073, 1029, 994, 905,
1,3-Diphenyl-2,5-dihydro-1H-pyrrole (5d). Yellow solid; mp 85−
88 °C. Yield: 156 mg (91%). IR (neat): 3662, 2923, 1724, 1598, 1505,
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1448, 1364, 1264, 1182, 1066, 1037, 742, 689, 667 cm−1. H NMR
1
739 cm−1. H NMR (400 MHz, CDCl3): δ = 7.44−7.22 (m, 10H),
(400 MHz, CDCl3): δ = 7.59 (d, J = 6.9 Hz, 2H), 7.50−7.19 (m, 5H),
6.74 (t, J = 7.2 Hz, 1H), 6.68−6.63 (m, 3H), 4.52−4.40 (m, 2H),
4.32−4.30 (m, 2H) ppm. 13C NMR (100 MHz, CDCl3): δ = 129.6,
129.4, 128.7, 128.6, 128.0, 125.9, 125.8, 125.4, 125.2, 120.4, 120.3,
115.8, 111.1, 108.7, 55.4, 54.8 ppm. HRMS (ESI): m/z calcd. for
C16H16N [M + H] 222.1277, found 222.1273.
3-(Naphthalen-2-yl)-1-phenyl-2,5-dihydro-1H-pyrrole (5j). White
solid; mp 88−90 °C. Yield: 55.1 mg (91%). IR (neat): 3043, 2806,
1600, 1504, 1417, 1364, 1325, 1267, 1231, 1176, 1131, 995, 863, 800,
750, 740, 694 cm−1. 1H NMR (400 MHz, CDCl3): δ = 7.87−7.77 (m,
3H), 7.73−7.70 (m, 2H), 7.52−7.48 (m, 2H), 7.33 (t, J = 8.0 Hz, 2H),
6.77 (t, J = 8.0 Hz, 1H), 6.70 (d, J = 8.0 Hz, 2H), 6.46 (s, 1H), 4.63
5.98−5.88 (m, 1H), 5.27−5.20 (m, 1H), 5.18 (s, 2H), 4.95 (s, 1H),
3.62 (s, 2H), 3.51 (s, 2H), 3.12−3.09 (m, 2H), 3.03 (s, 2H) ppm. 13C
NMR (100 MHz, CDCl3): δ = 147.2, 139.7, 139.7, 135.8, 129.1,
128.8, 128.1, 126.7, 125.9, 117.2, 113.9, 58.6, 57.7, 56.2, 40.6 ppm.
HRMS (ESI): m/z calcd. for C20H24N [M + H] 278.1903, found
278.1917.
N-Allyl-N-(2-benzylallyl)cyclohexanamine (4p). Yellow oil. Yield:
102.0 mg (81%). IR (neat): 3076, 3027, 2927, 2853, 2811, 1738, 1644,
1602, 1494, 1451, 1346, 1261, 1161, 1121, 1098, 993, 913, 900, 739
1
cm−1. H NMR (400 MHz, CDCl3): δ = 7.32−7.19 (m, 5H), 5.84−
5.74 (m, 1H), 5.14 (dq, J = 16 Hz, J = 4 Hz, 1H), 5.06−5.04 (m, 1H),
H
J. Org. Chem. XXXX, XXX, XXX−XXX