The Journal of Organic Chemistry
Article
under reduced pressure through a short pad of silica gel to withhold
the catalyst with the aid of ethyl acetate (∼15 mL) for separating the
catalyst from the reaction mixture. After solvent evaporation under a
vacuum, the residue was purified with column chromatography using
a gradient mixture of hexane−EtOAc (10:1 to 1:5), and the
corresponding amine 4b was isolated in 85% yield (39 mg).
MHz, CDCl3): 7.85 (d, J = 8.5 Hz, 2H), 6.63 (d, J = 8.5 Hz, 2H),
4.07 (s, 2H), 3.85 (s, 3H). 13C{H} NMR (125 MHz, CDCl3): 167.3,
150.9, 131.7, 119.9, 113.9, 51.7.15a
1-(4-Aminophenyl)ethenone (13b). The compound was isolated
using a gradient mixture of hexane−EtOAc (10:1 to 1:8) as a yellow
1
solid. Mp: 106−108 °C (28 mg, 89% yield). H NMR (500 MHz,
CDCl3): 7.81 (d, J = 8.2 Hz, 2H), 6.66 (d, J = 8.2 Hz, 2H), 4.31 (br s,
2H), 2.50 (s, 3H); 13C{H} NMR (125 MHz, CDCl3): 196.6, 151.0,
130.9, 128.2, 114.0, 26.2.15a
Characterization and Spectroscopic Data of Compounds
15a
1b−19b.
p-Toluidine (1b). The compound was isolated using a gradient
mixture of hexane−EtOAc (10:1 to 1:4) as a brown solid. Mp: 41−43
°C (20 mg, 92% yield). 1H NMR (500 MHz, CDCl3): 6.97 (d, J = 7.6
Hz, 2H), 6.62 (d, J = 7.6 Hz, 2H), 3.56 (br s, 2H), 2.25 (s, 3H).
13C{H} NMR (125 MHz, CDCl3): 143.9, 129.9, 127.9, 115.4, 20.6.
m-Toluidine (2b). The compound was isolated using a gradient
mixture of hexane−EtOAc (10:1 to 1:4) as a light yellow liquid: 19
mg, 91% yield. 1H NMR (500 MHz, CDCl3): 7.10 (t, J = 7.6 Hz, 1H),
6.65 (d, J = 7.5 Hz, 1H), 6.58−6.52 (m, 2H), 3.54 (s, 2H), 2.32 (s,
3H). 13C{H} NMR (125 MHz, CDCl3): 146.3, 139.1, 129.2, 119.5,
116.0, 112.3, 21.5.3
p-Aminobenzonitrile (14b). The compound was isolated using a
gradient mixture of hexane−EtOAc (10:1) as a dark-yellow solid. Mp:
84−86 °C (20 mg, 85% yield). 1H NMR (500 MHz, CDCl3): 7.39 (d,
J = 8.5 Hz, 2H), 6.63 (d, J = 8.5 Hz, 2H), 4.20 (br s, 2H). 13C{H}
NMR (125 MHz, CDCl3): 153.0, 133.5, 121.0, 113.0, 95.5.11
m-Aminobenzonitrile (15b). The compound was isolated using a
gradient mixture of hexane−EtOAc (10:1) as a brown solid. Mp: 51−
53 °C (23 mg, 89% yield). 1H NMR (500 MHz, CDCl3): 7.21 (t, J =
7.9 Hz, 1H), 7.00 (d, J = 7.4 Hz, 1H), 6.89 (s, 1H), 6.86 (d, J = 7.9
Hz, 1H), 3.88 (br s, 2H). 13C{H} NMR (125 MHz, CDCl3): 147.1,
130.2, 122.1, 119.3(2C), 117.5, 113.0.15a
3,5-Dimethylaniline (3b). The compound was isolated using a
gradient mixture of hexane−EtOAc (15:1 to 1:4) as a light-yellow
(3-Aminophenyl)sulfonamide (16b). The compound was isolated
using a gradient mixture of hexane−EtOAc (5:1) as a yellow solid (31
1
liquid (22 mg, 91% yield). H NMR (500 MHz, CDCl3): 6.43 (s,
1
1H), 6.34 (s, 2H), 3.48 (br s, 2H), 2.23 (s, 6H). 13C{H} NMR (125
mg, 91% yield). H NMR (500 MHz, CD3OD): 7.24 (d, J = 7.8 Hz,
MHz, CDCl3): 146.5, 139.1, 120.6, 113.2, 21.4.32
1H), 7.22, (s, 1H), 7.18 (d, J = 7.5 Hz, 1H), 6.89 (d, J = 7.8 Hz, 1H).
13C{H} NMR (125 MHz, CD3OD): 149.8, 145.2, 130.6, 119.3, 115.5,
112.7.33
Aniline (4b). The compound was isolated using a gradient mixture
of hexane−EtOAc (10:1 to 1:5) as a light-yellow liquid (16 mg, 88%
yield). 1H NMR (500 MHz, CDCl3) 7.16 (t, J = 7.8 Hz, 2H), 6.77 (t,
J = 7.3 Hz, 1H), 6.70 (d, J = 7.8 Hz, 2H). 13C{H} NMR (125 MHz,
CDCl3) 129.3, 126.7, 118.7, 115.2.15a
6-Aminoisobenzofuran-1(3H)-one (17b). The compound was
isolated using a gradient mixture of hexane−EtOAc (5:1) as a yellow
1
solid. Mp: 178−180 °C (26 mg, 89% yield). H NMR (500 MHz,
p-Anisidine (5b). The compound was isolated using a gradient
mixture of hexane−EtOAc (10:1 to 1:7) as a brown solid. Mp: 57−59
°C (22 mg, 91% yield). 1H NMR (500 MHz, CDCl3): 6.75 (d, J = 8.7
Hz, 2H), 6.65 (d, J = 8.7 Hz, 2H), 3.74 (s, 3H), 3.41 (br s, 2H).
13C{H} NMR (125 MHz, CDCl3): 153.0, 139.9, 116.6, 114.9, 55.9.15a
m-Anisidine (6b). The compound was isolated using a gradient
mixture of hexane−EtOAc (10:1 to 1:5) as a light-yellow liquid (22
CD3OD): 7.29 (d, J = 7.6 Hz, 1H), 7.11- 7.04 (m, 2H), 5.23 (s, 2H).
13C{H} NMR (125 MHz, CD3OD): 174.3, 150.7, 137.3, 127.3, 123.8,
123.2, 109.7, 71.3.15c
1H-Benzo[d]imidazol-5-amine (18b). The compound was isolated
using a gradient mixture of hexane−EtOAc (5:1) as a brown solid.
Mp: 107−110 °C (24 mg, 86% yield). 1H NMR (500 MHz,
CD3OD): 7.99 (s, 1H), 7.36 (d, J = 8.6 Hz, 1H), 6.92 (s, 1H), 6.77
(d, J = 8.6 Hz, 1H). 13C{H} NMR (125 MHz, CD3OD): 144.9,
140.9, 139.7, 117.2, 114.8(2C), 100.4.34
1H-Indazol-6-amine (19b). The compound was isolated using a
gradient mixture of hexane−EtOAc (5:1) as a yellow liquid (23 mg,
85% yield). 1H NMR (500 MHz, CD3OD): 7.78 (s, 1H), 7.45 (d, J =
8.6 Hz, 1H), 6.69 (d, J = 1.8 Hz, 1H), 6.63 (dd, J = 8.6, 1.8 Hz, 1H).
13C{H} NMR (125 MHz, CD3OD): 147.3, 142.1, 133.2, 120.7, 116.5,
113.2, 91.9.15a
1
mg, 90% yield). H NMR (500 MHz, CDCl3): 7.06 (t, J = 8.0 Hz,
1H), 6.33 (d, J = 8.0 Hz, 1H), 6.30 (d, J = 7.7 Hz, 1H), 6.25 (s, 1H),
3.76 (s, 3H), 3.68 (br s, 2H). 13C{H} NMR (125 MHz, CDCl3):
160.9, 147.9, 130.2, 108.0, 104.1, 101.2, 55.2.15a
4-(Benzyloxy)aniline (7b). The compound was isolated using a
gradient mixture of hexane−EtOAc (15:1 to 1:5) as a white solid:
1
Mp: 55−57 °C (35 mg, 89% yield). H NMR (500 MHz, CDCl3):
7.53−7.32 (m, 4H), 7.34 (s, 1H), 6.84 (d, J = 8.6 Hz, 2H), 6.65 (d, J
= 8.6 Hz, 2H), 5.00 (s, 2H), 3.50 (br s, 2H). 13C{H} NMR (125
MHz, CDCl3): 152.1, 140.2, 137.6, 128.6, 127.9, 127.6, 116.5, 116.1,
70.8.15c
ASSOCIATED CONTENT
■
sı
* Supporting Information
p-Phenylenediamine (8b). The compound was isolated using a
gradient mixture of hexane−EtOAc (10:1) as a yellow-brown liquid
(20 mg, 92% yield). 1H NMR (500 MHz, CDCl3): 6.56 (s, 4H), 3.25
(s, 4H). 13C{H} NMR (125 MHz, CDCl3): 138.7, 116.8.15a
p-Chloroaniline (9b). The compound was isolated using a gradient
mixture of hexane−EtOAc (10:1 to 1:5) as a light-yellow solid. Mp:
69−72 °C (23 mg, 91% yield). 1H NMR (500 MHz, CDCl3): 7.09 (d,
J = 8.1 Hz, 2H), 6.60 (d, J = 8.1 Hz, 2H), 3.68 (s, 2H). 13C{H} NMR
(125 MHz, CDCl3): 145.1, 129.2, 123.3, 116.4.15a
The Supporting Information is available free of charge at
Detailed experimental procedures, compound character-
ization data, and mechanistic analysis experiments
Accession Codes
3-Amino-4-chloroanisole (10b). The compound was isolated
using a gradient mixture of hexane−EtOAc (10:1 to 1:7) as a
brown liquid−solid (28 mg, 90% yield). 1H NMR (500 MHz,
CDCl3): 7.11 (d, J = 8.6 Hz, 1H), 6.31 (s, 1H), 6.27 (d, J = 8.6 Hz,
1H), 4.01 (s, 2H), 3.73 (br s, 2H). 13C{H} NMR (125 MHz,
CDCl3): 159.5, 143.8, 129.9, 111.5, 105.0, 101.5, 55.5.15a
CCDC 1995930 contains the supplementary crystallographic
data for this paper. These data can be obtained free of charge
bridge Crystallographic Data Centre, 12 Union Road,
Cambridge CB2 1EZ, UK; fax: +44 1223 336033.
p-Bromoanisole (11b). The compound was isolated using a
gradient mixture of hexane−EtOAc (10:1 to 1:5) as a brown liquid
1
(30 mg, 88% yield). H NMR (500 MHz, CDCl3): 7.23 (d, J = 7.9
AUTHOR INFORMATION
■
Hz, 2H), 6.56 (d, J = 7.9 Hz, 2H), 3.63 (br s, 2H). 13C{H} NMR
Corresponding Authors
(125 MHz, CDCl3): 145.6, 132.1, 116.8, 110.3.15a
Panagiotis A. Angaridis − Department of Chemistry, Aristotle
University of Thessaloniki, Thessaloniki 54124, Greece;
Methyl 4-Aminobenzoate (12b). The compound was isolated
using a gradient mixture of hexane−EtOAc (10:1 to 1:7) as a light-
1
yellow solid. Mp: 110−112 °C (24 mg, 80% yield). H NMR (500
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J. Org. Chem. 2021, 86, 2895−2906