1
378
A. B. Shivarkar et al.
LETTER
was seen after 70% formation of mono-amino alcohol. It
shows that bis-amino alcohol formation is also dependant on
the concentration of mono-amino alcohol.
MHz, CDCl ): d = 1.74 (br s, 1 H, OH), 2.96 (s, 3 H, NCH ),
3
3
3.47 (t, J = 5.6 Hz, 2 H, NCH ), 3.81 (t, J = 5.6 Hz, 2 H,
2
OCH ), 6.72–6.83 (m, 3 H, Ar), 7.21–7.29 (m, 2 H, Ar).
2
1
3
(
23) Typical Procedure The reaction was conducted in a 50-mL
round-bottom flask under a nitrogen atmosphere. Aniline
C NMR (100 MHz, CDCl ): d = 38.68 (NCH ), 55.32
3
3
(NCH ), 59.90 (OCH ), 112.93 (Ar-CH), 117.07 (Ar-CH),
2
2
(
(
0.0107 mol), cyclic carbonate (0.013 mol), triglyme
0.0155 mol), and Na-Y zeolite (0.250 g, activated at 500 °C
129.11 (Ar-CH), 149.94 (Ar-C). GC-MS (EI, 70 eV): m/z
+
+
(%) = 151 (17) [M] , 120 (100) [C H N(CH )=CH ] ,
6 5 3 2
for 6 h) were added. The reaction mixture was stirred at 160
C for 0.5 h. After cooling to r.t., the reaction mixture was
filtered to separate the catalyst and the reaction mass
filtrate) was quantitatively analyzed by GC. Then H O (15–
105(11), 91 (5), 77 (15), 65(1), 51 (5).
2-Phenylamino-1-phenylethanol (10b)
°
IR (CHCl ): 3610 (OH), 3433 (NH), 2927 (CH), 1604 (Ar-
3
–
1
(
C=C), 1505 (Ar-C=C), 1316 (Ar-CN), 1060, 790 cm .
2
1
2
0 mL) was added and extracted with Et O (3 × 20 mL). The
H NMR (200 MHz, CDCl ): d = 1.61 (br s, 2 H, NH, OH),
2
3
combined organic layer was dried over Na SO , filtered, and
3.32 (dd, J = 8.5, 13.1 Hz, 1 H, NCH ), 3.48 (dd, J = 4.0,
2
4
2
concentrated. The residue was purified by flash
13.1 Hz, 1 H, NCH ), 4.96 (dd, J = 4.0, 8.5 Hz, 1 H, OCH),
2
chromatography (4 g RediSep column normal phase silica,
hexane–EtOAc). Liquid chromatography was performed
using CombiFlash Companion, supplied by Teledyne ISCO,
USA. N-Phenylethanolamine was thus isolated in pure form
in 94% yield.
6.68 (d, J = 7.6 Hz, 2 H, Ar), 6.76 (t, J = 7.3 Hz, 1 H, Ar),
7.20 (t, J = 7.5 Hz, 2 H, Ar), 7.30–7.42 (m, 5 H, Ar). GC-MS
+
(EI, 70 eV): m/z (%) = 213 (8) [M] , 194 (13), 182 (10),
+
165 (2), 106 (100) [C H NH=CH ] , 91 (7), 77 (33), 65 (3),
6
5
2
51 (9).
2-Phenylamino-2-phenylethanol (11b)
IR (film): 3396 (OH, NH), 2927 (CH), 1602 (Ar-C=C), 1504
3
,25
After completion of the reaction, the reaction mixture was
filtered (sartorius-393 grade filter paper) to separate the
catalyst, which was washed with acetone to remove organic
impurities. Then the catalyst was calcined at 500 °C for 6 h
in air. This catalyst was re-used affording 3a in 100% yield.
The catalyst was recycled five times retaining up to 99% of
its original activity and selectivity.
–
1 1
(Ar-C=C), 1317 (Ar-CN), 1066, 750 cm . H NMR (200
MHz, CDCl ): d = 2.71 (br s, 2 H, NH, OH), 3.76 (dd,
3
J = 7.0, 11.1 Hz, 1 H, OCH ), 3.96 (dd, J = 4.2, 11.1 Hz,
2
1 H, OCH ), 4.50 (dd, J = 4.2, 7.0 Hz, 1 H, NCH) 6.55 (d,
2
J = 7.5 Hz, 2 H, Ar), 6.88 (t, J = 7.3 Hz, 1 H, Ar), 7.11 (t,
2
4
13
N-Phenylethanolamine (3a)
IR (film): 3392 (OH, NH), 2943 (CH), 1602 (Ar-C=C), 1506
J = 7.4 Hz, 2 H, Ar), 7.30–7.36 (m, 5 H, Ar). C NMR (50
MHz, CDCl ): d = 59.83 (NCH), 67.33 (OCH ), 113.82 (Ar-
3
2
–
1 1
(
Ar-C=C), 1323 (Ar-CN), 1058, 752 cm . H NMR (200
CH), 117.86 (Ar-CH), 126.70 (Ar-CH), 127.58 (Ar-CH),
128.80 (Ar-CH), 129.13 (Ar-CH), 140.10 (Ar-C), 147.20
MHz, CDCl ): d = 2.86 (br s, 2 H, NH, OH), 3.27 (t, J = 5.4
3
+
Hz, 2 H, NCH ), 3.80 (t, J = 5.4 Hz, 2 H, OCH ), 6.63–6.77
(Ar-C). GC-MS (EI, 70 eV): m/z (%) = 213 (7) [M] , 182
2
2
1
3
+
(
m, 3 H, Ar-CH), 7.14–7.22 (m, 2 H, Ar-CH). C NMR (50
(100) [C H NH=CHPh] , 104 (17), 91 (4), 77 (23), 65 (2),
6
5
MHz, CDCl ): d = 45.99 (NCH ), 60.97 (OCH ), 113.20
51(5).
3
2
2
(
Ar-CH), 117.84 (Ar-CH), 129.21 (Ar-CH), 148.00 (Ar-C).
3-(Phenylamino)propan-1-ol (12)
IR (film): 3381 (OH, NH), 2935 (CH), 1602 (Ar-C=C), 1506
(Ar-C=C), 1321 (Ar-CN), 1064, 752 cm . H NMR (200
+
GC-MS (EI, 70 eV): m/z (%) = 137 (23) [M] , 106 (100)
[
+
–1 1
C H NH=CH ] , 91 (2), 77 (23), 65 (3), 51 (8).
6
5
2
N-Phenyldiethanolamine (4a)
MHz, CDCl ): d = 1.87 (quin, J = 5.9, 6.4 Hz, 2 H, CH ),
3
2
IR (film): 3382 (OH, NH), 2952 (CH), 1598 (Ar-C=C), 1504
2.79 (br s, 2 H, NH, OH), 3.27 (t, J = 6.4 Hz, 2 H, NCH2),
–
1 1
(
Ar-C=C), 1355 (Ar-CN), 1062, 750 cm . H NMR (200
3.80 (t, J = 5.9 Hz, 2 H, OCH ), 6.62–6.76 (m, 3 H, Ar),
2
1
3
MHz, CDCl ): d = 3.49 (t, J = 4.9 Hz, 4 H, NCH ), 3.75 (t,
7.14–7.22 (m, 2 H, Ar). C NMR (50 MHz, CDCl ):
3
2
3
J = 4.9 Hz, 4 H, OCH ), 6.63–6.75 (m, 3 H, Ar), 7.17–7.25
d = 31.85 (CH ), 41.89 (NCH ), 61.55 (OCH ), 113.10 (Ar-
2
2
2
2
(
m, 2 H, Ar). 13C NMR (50 MHz, CDCl ): d = 55.21
CH), 117.63 (Ar-CH), 129.22 (Ar-CH), 148.28 (Ar-C). GC-
3
+
(
NCH ), 60.48 (OCH ), 112.41 (Ar-CH), 116.75 (Ar-CH),
MS (EI, 70 eV): m/z (%) = 151 (27) [M] , 132 (1), 118 (2),
2
2
+
1
29.20 (Ar-CH), 147.62 (Ar-C). GC-MS (EI, 70 eV): m/z
106 (100) [C H NH=CH ] , 93 (5), 77 (15), 65 (4), 51 (4).
6
5
2
+
+
(%) = 181 (16) [M] , 150 (100) [C H N(C H OH)=CH ] ,
(24) Lu, Z.; Twieg, R. J. Tetrahedron Lett. 2005, 46, 2997.
(25) (a) Rampalli, S.; Chaudhari, S. S.; Akamanchi, G. Synthesis
2000, 78. (b) De, S. K.; Gibbs, R. A. Synth. Commun. 2005,
35, 2675.
6
5
2
4
2
106 (56), 91 (7), 77 (16), 65 (1), 52 (4), 45 (7).
2-[Methyl(phenyl)amino]ethanol (7)
IR (film): 3344 (OH, NH), 2906 (CH), 1596 (Ar-C=C), 1505
–
1 1
(
Ar-C=C), 1340 (Ar-CN), 1056, 746 cm . H NMR (200
Synlett 2006, No. 9, 1374–1378 © Thieme Stuttgart · New York