RSC Advances
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5.36 (br. s, 1H), 3.78 (s, 6H), 3.71 (s, 6H); 13C NMR (101 MHz, 117.3, 112.1, 111.9, 55.9, 16.3; HRMS (ESI TOF) Calcd for
+
DOI: 10.1039/C5RA17668A
CDCl3) δ 154.5 (2C), 142.0 (2C), 137.3 (2C), 111.4 (2C), 102.2 C8H12NO (M+H) 138.0913, found 138.0913 (0.0 ppm).
(2C), 102.0 (2C) 56.2 (2C), 55.6 (2C); IR (NaCl, film, cm-1) 3411, Bis(3,4-dimethylphenyl)amine (2i):24 Colorless crystals, mp
o
2952, 2336, 1664, 1599, 1512, 1460, 1198, 991, 865; HRMS 108-110 C (EtOH), Rf 0.54 (hexane/EtOAc 3:1). Yield 54 mg
(ESI TOF) Calcd for C16H20NO4 (M+H)+ 290.1387, found (0.24 mmol, 24%). 1H NMR (400 MHz, CDCl3) δ 7.01 (d, J = 1.5
290.1392 (1.7 ppm).
Hz, 2H), 6.82 (d, J = 8.2 Hz, 2H), 6.79 (dd, J = 8.2, 1.5 Hz, 2H),
Bis(2,3-dihydrobenzo[b][1,4]dioxin-6-yl)amine (2e): Yield 208 5.27 (br. s, 1H), 2.22 (s, 6H), 2.17 (s, 6H); 13C NMR (101 MHz,
mg (0.73 mmol, 73%); colorless crystals, mp 103-105 oC CDCl3) δ 141.8 (2C), 137.3 (2C), 130.6 (2C), 129.1 (2C), 119.7
(EtOH); Rf 0.28 (hexane/EtOAc 3:1); 1H NMR (400 MHz, CDCl3) (2C), 115.5 (2C), 20.2 (2C), 19.2 (2C); HRMS (ESI TOF) Calcd for
δ 6.75 (d, J = 8.6 Hz, 2H), 6.56 (d, J = 2.6 Hz, 2H), 6.49 (dd, J = C16H20N (M+H)+ 226.1590, found 226.1594 (1.6 ppm).
8.6, 2.6 Hz, 2H), 5.26 (br. s, 1H), 4.25-4.19 (m, 8H); 13C NMR 2,2'-Azanediylbis(4-isopropylphenol) (2j): Reaction was carried
(101 MHz, CDCl3) δ 144.0 (2C), 138.4 (2C), 138.2 (2C), 117.7 out at 90 oC. Yellowish oil, Rf = 0.42 (hexane/EtOAc 1:1). Yield
1
(2C), 111.9 (2C), 107.3 (2C), 64.7 (2C), 64.4 (2C); IR (NaCl, film, 77 mg (0.27 mmol, 27%). H NMR (400 MHz, CDCl3) δ 6.59 (d, J
cm-1): 3393, 2931, 1620, 1587, 1495, 1307, 1280, 1241, 1211, = 8.0 Hz, 2H), 6.57 (d, J = 2.0 Hz, 2H), 6.47 (dd, J = 8.0, 2.0 Hz,
1063, 888, 815, 792; EA: Calcd for C16H15NO4 C 67.36, H 5.30, N 2H), 5.26 (br. s, 1H), 4.25 (br. s, 2H), 2.77 (septet, J = 6.9 Hz,
4.91; found C 67.47, H 5.26, N 4.87; HRMS (ESI TOF) Calcd for 2H), 1.12 (d, J = 6.9 Hz, 12H); 13C NMR (101 MHz, CDCl3) δ
C16H16NO4 (M+H)+ 286.1074, found 286.1084 (3.5 ppm). 2,3- 142.5 (2C), 142.2 (2C), 134.3 (2C), 117.4 (2C), 115.5 (2C), 115.3
Dihydrobenzo[b][1,4]dioxin-6-amine (3e): Yellowish oil, Rf (2C), 33.6 (2C), 24.4 (4C); IR (NaCl, film, cm-1): 3385, 3295,
0.21 (hexane/EtOAc 3:1); Yield 30 mg (0.20 mmol, 10%). 1H 2971, 2926, 2861, 1602, 1615, 1463, 1289, 1204, 810; HRMS
NMR (400 MHz, CDCl3) δ 6.67 (d, J = 8.5 Hz, 1H), 6.24 (d, J = 2.6 (ESI TOF) Calcd for C18H24NO2 (M+H)+ 286.1802, found:
Hz, 1H), 6.20 (dd, J = 8.5, 2.6 Hz, 1H), 4.24-4.16 (m, 4H); 13
C
286.1799 (0.7 ppm).
NMR (101 MHz, CDCl3) δ 144.1, 140.9, 136.6, 117.8, 108.9, Bis(2,3,5,6,8,9,11,12-octahydrobenzo[b][1,4,7,10,13]pentaox-
104.3, 64.9, 64.3; IR (NaCl, film, cm-1): 3367, 2931, 1634, 1587, acyclopentadecin-15-yl)amine (2k): Reaction was carried out
1502, 1310, 1280, 1247, 1214, 1168, 1063, 924, 891; HRMS according to the typical procedure employing commercial
calc`d for C8H10NO2 (M+H)+: 152.0706, found 152.0709 (2.0 benzo-15-crown-5 (268 mg, 1.00 mmol) and 2-nitropropane
ppm).
(182 µL, 180 mg, 2.02 mmol). Upon completion the reaction
Bis(2,4-dimethoxy-3-methylphenyl)amine (2f): Yellowish oil, Rf mixture was poured into cold water (50 mL), neutralized with
0.33 (hexane/EtOAc 3:1). Yield 187 mg (0.59 mmol, 59%). 1H aqueous ammonia and extracted with anisole (4 x 30 mL).
NMR (400 MHz, CDCl3) δ 6.90 (d, J = 8.8 Hz, 2H), 6.45 (d, J = 8.8 Combined organic phases were concentrated in vacuum and
Hz, 2H), 5.85 (br. s, 1H), 3.67 (s, 6H), 3.61 (s, 6H), 2.08 (s, 6H); residual brown amorphous solid was purified by preparative
13C NMR (101 MHz, CDCl3) δ 152.4 (2C), 149.1 (2C), 130.9 (2C), column chromatography on Silica gel, eluting with mixture
120.5 (2C), 114.2 (2C), 106.2 (2C), 60.0 (2C), 55.9 (2C), 30.9 EtOAc/EtOH 1:1. The titled compound was isolated as color-
(2C); IR (NaCl, film, cm-1) 3409, 3010, 2939, 2831, 1607, 1502, less amorphous solid, mp 281-283 oC; Rf 0.26 (EtOH). Yield 44
1468, 1130, 1037, 746; HRMS (ESI TOF) Calcd for C18H24NO4 mg (0.08 mmol, 16%). 1H NMR (400 MHz, CDCl3) δ 6.78 (d, J =
(M+H)+ 318.1700, found 318.1703 (0.9 ppm).
8.4 Hz, 2H), 6.58 (d, J = 2.4 Hz, 2H), 6.50 (dd, J = 8.4, 2.4 Hz,
Bis(4-methoxy-2-methylphenyl)amine (2g):23 Yellowish oil, Rf 2H), 4.11-4.04 (m, 8H), 3.92-3.88 (m, 8H), 3.75 (br. s, 16H); 13C
0.46 (hexane/EtOAc 3:1). Yield 108 mg (0.42 mmol, 42%). 1H NMR (101 MHz, CDCl3) δ 150.2 (2C), 143.7 (2C), 138.9 (2C),
NMR (400 MHz, CDCl3) δ 6.78 (d, J = 2.8 Hz, 2H), 6.74 (d, J = 8.6 116.3 (2C), 110.8 (2C), 105.4 (2C), 71.04 (2C), 70.98 (2C), 70.8
Hz, 2H), 6.66 (dd, J = 8.6, 2.8 Hz, 2H), 3.77 (s, 6H), 2.23 (s, 6H); (2C), 70.5 (2C), 70.2 (2C), 69.9 (2C), 69.6 (2C), 68.8 (2C); IR
13C NMR (101 MHz, CDCl3) δ 154.4 (2C), 136.6 (2C), 129.6 (2C), (NaCl, film, cm-1) 3392, 2926, 2867, 1602, 1505, 1450, 1360,
120.0 (2C), 116.5 (2C), 111.7 (2C), 55.5 (2C), 18.0 (2C); IR (NaCl, 1227, 1133, 1062, 936; HRMS (ESI TOF) Calcd for
+
film, cm-1): 3362, 2933, 2338, 1652, 1506, 1379, 1248, 1101, C28H39NNaO10 (M+Na) 572.2466, found: 572.2480 (2.4 ppm);
979; HRMS (ESI TOF) Calcd for C16H20NO2 (M+H)+ 258.1489, Calcd for C28H39NNa2O102+ (M+2Na) 595.2358, m/z = 297.6179,
found 258.1483 (2.3 ppm).
found: 297.6190 (3.7 ppm). 2,3,5,6,8,9,11,12-Octahydroben-
Bis(4-methoxy-3-methylphenyl)amine (2h): Yellowish oil, Rf zo[b][1,4,7,10,13]pentaoxacyclopentadecin-15-amine (3k):25
0.51 (hexane/EtOAc 3:1). Yield 178 mg (0.69 mmol, 69%). 1H Isolated by preparative column chromatography as colorless
NMR (400 MHz, DMSO-d6) δ 7.34 (br. s, 1H), 6.77 (m, 6H), 3.71 crystalline side product, mp 72-74 oC (n-BuOH); Rf 0.54 (EtOH).
(s, 6H), 2.09 (s, 6H); 13C NMR (101 MHz, DMSO-d6) δ 151.3 Yield 68 mg (0.24 mmol, 24%). 1H NMR (400 MHz, DMSO-d6) δ
(2С), 138.1 (2C), 126.5 (2C), 120.3 (2C), 115.3 (2C), 111.6 (2C), 6.64 (d, J = 8.4 Hz, 1H), 6.22 (d, J = 2.4 Hz, 1H), 6.05 (dd, J = 8.4,
55.8 (2C), 16.5 (2C); IR (NaCl, film, cm-1) 3366, 2945, 2337, 2.4 Hz, 1H), 4.68 (br. s, 2H), 3.94 (m, 2H), 3.89 (m, 2H), 3.76-
1654, 1505, 1379, 1247, 1101, 988; HRMS (ESI TOF) Calcd for 3.70 (m, 4H), 3.60 (br. s, 8H); 13C NMR (101 MHz, DMSO-d6) δ
C16H20NO2 (M+H)+ 258.1489, found 258.1489 (0.0 ppm). 4- 150.0, 144.0, 139.4, 117.5, 105.6, 101.0, 70.3, 70.18, 70.17,
Methoxy-3-methylaniline (3h): yellowish oil, Rf 0.42 (hexane/ 70.1, 69.7, 69.3, 68.9, 67.8; HRMS (ESI TOF) Calcd for
EtOAc 3:1); Yield 21 mg (0.15 mmol, 8%). 1H NMR (400 MHz, C14H21NNaO5+ (M+Na) 306.1312, found: 306.1319 (2.2 ppm);
DMSO-d6) δ 6.67 (d, J = 8.4 Hz, 1H), 6.45 (d, J = 2.1 Hz, 1H),
6.41 (d, J = 8.4, 2.1 Hz, 1H), 4.57 (br. s, 2H), 3.69 (s, 3H), 2.08 (s,
3H); 13C NMR (101 MHz, DMSO-d6) δ 149.1, 142.2, 126.1,
Acknowledgements
This journal is © The Royal Society of Chemistry 20xx
J. Name., 2013, 00, 1-3 | 5
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