N-ARYL-o-HYDROXYARYL KETIMINES
2657
2-(1-(2,4-Dimethoxyphenylimino)ethyl)phenol (17)
Yield 76%. Yellow crystals; mp 96–97 ꢀC (heptanes=CH2Cl2). 1H NMR
(CDCl3): d 15.2 (s, 1H), 7.62 (dd, 1H, J ¼ 8.1, 1.5 Hz), 7.38 (ddd, 1H, J ¼ 8.4, 7.3,
1.5 Hz), 7.03 (dd, 1H, J ¼ 8.4, 1.1 Hz), 6.88 (ddd, 1H, J ¼ 8.1, 7.3, 1.1 Hz), 6.83 (d,
1H, J ¼ 8.6 Hz), 6.56 (d, 1H, J ¼ 2.6 Hz), 6.53 (dd, 1H, J ¼ 8.6, 2.6 Hz), 3.85 (s,
3H), 3.81 (s, 3H), 2.31 (s, 3H). 13C NMR (CDCl3): d 172.2, 162.4, 158.3, 151.5,
132.7, 129.0, 128.8, 122.9, 120,1. 118.3, 117.8, 104,2. 99.5, 55.7, 55.6, 17.2. HRMS
(ESþ): m=z [M þ Na]þ calcd. for C16H17NO3Na: 294.1106. Found: 294.1104.
2-(1-(2-Aminophenylimino)ethyl)phenol (18)[19]
o-Phenylenediamine (2 equiv.) was used. Yield 100%. Yellow crystals; mp
1
102–103 ꢀC (CH2Cl2=heptanes). H NMR (DMSO-d6): d 14.99 (s, 1H), 7.75 (ddd,
1H, J ¼ 8.5, 1.7 Hz), 7.39 (ddd, 1H, J ¼ 8.4, 7.5, 1.2 Hz), 6.96–6.88 (m, 3H), 6.78
(dd, 1H, J ¼ 7.9, 1.2 Hz), 6.69 (dd, 1H, J ¼ 7.6, 1.5 Hz), 6.60 (ddd, 1H, J ¼ 7.5, 7.4,
1.2 Hz), 4.77 (s, 2H), 2.32 (s, 3H). 13C NMR (DMSO-d6): d 173.2, 161.6, 139.8,
132.8, 131.8, 129.6, 125.8, 121.3, 119.8, 117.9, 117.4, 116.2, 115.1, 17.0. HRMS
(ESþ): m=z [M þ Na]þ calcd. for C14H14N2ONa: 249.0997. Found: 249.1004.
5-Methoxy-2-(1-(4-methoxyphenylimino)ethyl)phenol (3b)
1
Yield 60%. Yellow crystals; mp 87–88 ꢀC (heptanes). H NMR (CDCl3): d
14.41 (s, 1H), 7.14 (d, 1H, J ¼ 2.7 Hz), 7.03–6.86 (m, 6H), 3.84 (s, 3H), 3.82 (s,
3H), 2.34 (s, 3H). 13C NMR (CDCl3): d 170.8, 157.0, 156.3, 151.4, 140.1, 122.6,
119.7, 119.5, 118.7, 114.3, 113.4, 56.1, 55.5, 17.0. HRMS (ESþ): m=z [M þ H]þ
calcd. for C16H18NO3: 272.1287. Found: 272.1277.
5-Fluoro-2-(1-(4-methoxyphenylimino)ethyl)phenol (3c)
Yield 86%. Yellow crystals; mp 106–107 ꢀC (CH2Cl2=heptanes). 1H NMR
(CDCl3) d 15.72 (s, 1H), 7.59 (dd, 1H, J ¼ 8.8, 6.5 Hz), 6.98–6.86 (m, 4H), 6.70
(dd, 1H, J ¼ 10.6, 2.6 Hz), 6.58 (ddd, 1H, J ¼ 8.8, 8.6, 2.6 Hz), 3.85 (s, 3H), 2.35
(s, 3H). 13C NMR (CDCl3) d 170.6, 165.5 (d, J ¼ 252 Hz), 165.1 (d, J ¼ 13.7 Hz),
157.2, 139.0, 130.6 (d, J ¼ 11.5 Hz), 122.9, 116.6, 114.4, 105.6 (d, J ¼ 22.5 Hz),
104.9 (d, J ¼ 23.0 Hz), 55.5, 16.9. HRMS (ESþ): m=z [M þ H]þ calcd. for
C15H14FNO2: 260.1087. Found: 260.1093. Anal. calcd. for C15H14FNO2: C, 69.49;
H, 5.44; N, 5.40. Found: C, 69.55; H, 5.42; N, 5.40.
2-(1-(4-Methoxyphenylimino)ethyl)-4-methylphenol (3d)[20]
1
Yield 86%. Yellow crystals; mp 125-126 ꢀC (heptanes). H NMR (CDCl3): d
14.73 (s, 1H), 7.42 (d, 1H, J ¼ 2.2 Hz), 7.19 (dd, 1H, J ¼ 8.4, 2.2 Hz), 6.97–6.86 (m,
5H), 3.85 (s, 3H), 2.36 (s, 3H), 2.34 (s, 3H). 13C NMR (CDCl3): d 171.2, 159.9,
157.0, 140.1, 133.8, 128.9, 126.9, 122.6, 119.5, 118.0, 114.3, 55.5, 20.7, 16.9. HRMS
(ESþ): m=z [M þ H]þ calcd. for C16H18NO2: 256.1338. Found: 256.1338.