Page 7 of 11
The Journal of Organic Chemistry
3-Ethyl-N-Methylaniline (scheme 2 entry 2).new It is
= 3.4 Hz), 67.69, 51.95, 31.32; HRMS (ESI-TOF) m/z:
[M+H]+ calcd for C11H15FN2O, 211.1241; found: 211.1252.
N-Methylpyridin-3-amine (scheme 2 entry 10).30 It is
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obtained as colorless liquid (54.67mg, 81%) after purification
by column chromatography (n-hexane/EtOAc : 95:5). 1H
NMR (500 MHz, CDCl3) δ 7.15 – 7.07 (m, 1H), 6.68 (m, 1H),
6.45 (d, J = 9.0 Hz, 2H), 3.46 (s, 1H), 2.83 (s, 3H), 2.73 (q,
2H), 1.25 – 1.19 (t, 3H). 13C{1H} NMR (126 MHz, CDCl3) δ
149.45, 145.44, 129.17, 117.04, 112.12, 109.84, 30.70, 29.08,
15.63; HRMS (ESI-TOF) m/z: [M+H]+ calcd for C9H14N,
136.1126; found: 136.1130.
N1,N1,N3-Trimethylbenzene-1,3-diamine (scheme 2 entry
3).30 It is obtained as colorless semi solid (65.25 mg, 87%)
after purification by column chromatography (n-
hexane/EtOAc : 90:10). 1H NMR (500 MHz, CDCl3) δ 6.93 (t,
1H), 6.02 (m, 1H), 5.89 (m, 1H), 5.84 (t, 1H), 3.48 (s, 1H),
2.79 (s, 6H), 2.74 (s, 3H). 13C{1H} NMR (126 MHz, CDCl3) δ
151.68, 149.98, 129.58, 102.77, 101.85, 96.98, 39.95.
obtained as
a colorless liquid (48.60mg, 90%) after
purification by column chromatography (n-hexane/EtOAc :
8:1): 1H NMR (500 MHz, CDCl3) δ 7.93 (d, J = 47.0 Hz, 2H),
7.04 (dt, J = 31.1, 15.6 Hz, 1H), 6.82 (dd, J = 8.2, 1.4 Hz, 1H),
3.72 (s, 1H, NH), 2.79 (s, 3H). 13C{1H} NMR (126 MHz,
CDCl3) δ 144.23, 137.11, 134.39, 122.81, 117.33, 29.39.
N-Methylquinolin-8-amine (scheme 2 entry 11).30 It is
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obtained as a black solid (71.10mg, 90%) after purification by
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column chromatography (n-hexane/EtOAc : 98:2): H NMR
(500 MHz) δ 8.71 (d, 1H), 8.12 (d, 1H), 7.38 (m, 2H), 7.10 (d,
1H), 6.63 (d, 1H), 6.12 (s, 1H, NH), 3.03 (s, 3H). 13C{1H}
NMR (126 MHz) δ 146.89, 146.06, 138.31, 136.20, 129.09,
121.82, 113.65, 104.27, 30.06.
N-Methylbenzo[d][1,3]dioxol-5-amine (scheme 2 entry
4).30 It is obtained as dark brown solid (71.78 mg, 95%) after
purification by column chromatography (n-hexane/EtOAc:
N-(4-(Methylamino)-2-
phenoxyphenyl)methanesulfonamide (scheme 2 entry 12).12e
It is obtained as a colorless (134.32 mg, 92%) after
purification by column chromatography (n-hexane/EtOAc :
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98:2). H NMR (400 MHz) δ 6.72 – 6.60 (m, 1H), 6.24 (d, J =
2.6 Hz, 1H), 5.99 (s, 1H), 5.87 – 5.82 (s, 2H), 3.41 (s, 1H, NH
2.78 (s, 3H). 13C{1H} NMR (126 MHz, CDCl3): δ 149.22,
146.7, 141.5, 109.26, 104.75, 101.28, 96.64, 32.45, 31.65.
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85:15): H NMR (500 MHz, CDCl3) δ 7.41(m, 3H), 7.15 (t, J
= 7.4 Hz, 2H), 7.00 (d, J = 7.8 Hz, 2H), 6.36 (d, J = 10.5, 5.2
Hz, 1H), 6.26 (s, 1H), 6.10 (d, 1H), 3.84 (s, 1H, NH), 2.91 (s,
3H), 2.74 (s, 3H). 13C{1H} NMR (126 MHz, CDCl3) δ 156.31,
150.74, 149.50, 130.33, 127.91, 124.04, 118.85, 116.60,
108.03, 102.02, 38.64, 30.57.
N-Methyl-2,3-dihydrobenzo[b][1,4]dioxin-6-amine
(scheme 2 entry 5).20 It is obtained as brown solid (64.42mg,
78%) after purification by column chromatography (n-
hexane/EtOAc : 98:2): 1H NMR (500 MHz, CDCl3) δ 6.64 (d,
J = 8.4 Hz, 1H), 6.09 (dd, J = 11.7, 2.8 Hz, 2H), 4.16 (dd, J =
5.2, 2.6 Hz, 2H), 4.11 (dd, J = 5.3, 2.5 Hz, 2H), 2.70 (s, 3H).
13C{1H} NMR (126 MHz, CDCl3) δ 143.54, 143.00, 134.52,
116.56, 105.43, 100.03, 63.86, 63.16, 30.44.
4-(Methylamino)phenol (scheme 2 entry 6)12e It is obtained
as colorless liquid (36.91, 60%) after purification by column
chromatography (n-hexane/EtOAc : 98:2): 1H NMR (500
MHz, CDCl3) δ 7.52 – 6.98 (m, 4H), 5.67 (s, 1H), 3.01 (s, 1H),
2.93 (s, 3H). 13C{1H} NMR (126 MHz, CDCl3) δ 147.99,
142.98, 117.06, 117.03, 30.44.
Nimesulide ND3 (scheme 2 entry 13):new It is obtained as
bluish semi solid (133.50 mg, 89%) after purification by
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column chromatography (n-hexane/EtOAc : 85:15): H NMR
(400 MHz) δ 7.45 (d, 2H), 7.15 (t, J = 7.4 Hz, 1H), 7.00 d, J
= 7.8 Hz, 2H), 6.38 (d, 1H), 6.26 (s, 1H), 6.11 (d, 1H).
13C{1H} NMR (101 MHz) δ 156.00, 150.56, 149.22, 130.01,
127.55, 124.04, 116.61, 108.14, 102.07. HRMS (ESI-TOF)
m/z: [M]+ calcd for C14H8D8N2O3S, 300.1384; found:
300.1390.
N,N-Dimethylaniline (scheme 4 entry 14): It is obtained as
colorless liquid (55.05mg, 91%) after purification by column
chromatography (n-hexane/EtOAc : 85:15): 1H NMR (400
MHz) δ 7.48 (d, 2H), 7.01 (d, 2H), 3.06 (s, 6H). 13C{1H} NMR
(126 MHz) δ 150.58, 129.59, 116.81, 112.69, 104.07, 40.89.
N,N,4-Trimethylaniline (scheme 4 entry 15):12a It is
obtained as a brown liquid (57.37 mg, 85%) after purification
by column chromatography (n-hexane/EtOAc : 98:2). 1H
NMR (500 MHz, CDCl3) δ 7.13 (d, 2H), 6.78 (d, 2H), 2.87 (s,
6H), 2.25 (s, 3H). 13C{1H} NMR (126 MHz, CDCl3) δ 148.81,
129.56, 126.17, 113.19, 41.03, 20.40.
4-Methoxy-N,N-dimethylaniline (scheme 4 entry 16).12a It
is obtained as a colorless liquid (41.52mg, 55%) after
purification by column chromatography (n-hexane/EtOAc :
98:2). 1H NMR (500 MHz, CDCl3) δ 7.10 – 6.88 (m, 1H), 6.26
– 6.08 (m, 3H), 3.66 (s, 3H), 2.79 (s, 6H). 13C{1H} NMR (126
MHz, CDCl3) δ 160.81, 152.11, 129.86, 105.84, 101.51,
99.20, 55.14, 40.65.
4-Methoxy-N-Methylaniline (scheme 2 entry 7).30 It is
obtained as a colorless liquid (65.16 mg, 95%) after
purification by column chromatography (n-hexane/EtOAc :
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9:1) H NMR (500 MHz, CDCl3) δ 6.85 – 6.75 (d, 2H), 6.62
(d, J = 6.1 Hz, 2H), 3.76 (s, 3H), 3.41 – 3.11 (s, 1H), 2.81 (s,
3H). 13C{1H} NMR (126 MHz, CDCl3) δ 152.30, 143.09,
114.90, 113.97, 55.53, 31.85.
N-Methyl-4-morpholinoaniline (scheme 2 entry 8).30 It is
obtained as a white solid (81.71 mg, 85%) after purification by
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column chromatography (n-hexane/EtOAc : 99:1) H NMR
(500 MHz, CDCl3): 6.82 (m, 2H), 6.76 (m, 2H), 3.8 (m, 4H),
2.99 (m, 4H), 2, 78 (s, CH3). 13C{1H} NMR (126 MHz,
CDCl3) δ 143.81, 143.55, 118.70, 113.72, 67.09, 51.35, 31.59.
3-Fluoro-N-methyl-4-morpholinoaniline (scheme 2 entry
9).new It is obtained as a light bluish solid (107.44 mg, 95%)
after purification by column chromatography (n-
hexane/EtOAc : 8:1) 1H NMR (500 MHz, CDCl3) δ 6.85 (t, J
= 9.0 Hz, 1H), 6.47 – 6.26 (m, 2H), 3.95 – 3.78 (t, 4H), 3.05,
(s, 1H), 3.04 – 2.90 (t, 4H), 2.79 (s, 3H). 13C{1H} NMR (126
MHz, CDCl3) δ 158.4 (1JCF = 243 Hz), 146 (2JCF = 10.5), 130
(3JCF = 9.9 Hz), 101 (2JCF = 24 Hz), 120 (3JCF = 5.5), 108 (4JC-F
1-(3-(Dimethylamino)phenyl)ethanone (scheme 4 entry
17).12a It is obtained as a semi solid (39.12 mg, 48%) after
purification by column chromatography (n-hexane/EtOAc :
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20:80). H NMR (500 MHz, CDCl3) δ 7.41 (d, 3H), 6.69 (s,
1H), 3.03 (s, 6H), 2.62 (s, 3H). 13C{1H} NMR (126 MHz,
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