D. Yildirim et al. / Journal of Molecular Catalysis B: Enzymatic 100 (2014) 91–103
95
NCH3), 3.60 (s, 1H, OH), 4.67 (dd, 1H, J = 2.32 Hz, J = 2.16 Hz,
2.7.7. 2-(Ethylamino)-1-phenylethyl acetate
ArCHOH), 7.29–7.32 (m, 5H, HAr ).
(C10H15NO): Brown liquid, purity 96% (HPLC).
13C NMR ı (ppm): 39.8 ( NCH3), 56.5 ( NCH2 ), 70.2 ( HCOH),
127.7–138.7 (ArC).
1H NMR ı (ppm): 1.90 (t, 3H, J = 12.50 Hz, CH2CH3), 2.02 (s,
3H,
O C CH3), 2.11 (q, 2H, J = 12.09 Hz, CH2CH3), 2.58 (s, 1H,
HPLC: Retention times of (S)-1a and (R)-1a are 5.27 and
9.10 min, respectively.
NHCH2 CH3), 3.20 (d, 1H, J = 5.57 Hz, CHHNH CH2), 3.22 (t,
1H, J = 6.0 Hz, CHHNH CH2 ), 5.37 (dd, 1H, dd, 1H, J = 4.60 Hz,
J = 4.50 Hz, ArCHO ), 7.36–7.38 (m, 5H, HAr ).
IR (film) cm−1: 4056, 3244, 3086, 2881, 1952, 1885, 1758, 1659,
1555, 1493, 1338, 1268, 1201, 1091, 1026.
13C NMR
ı
(ppm): 14.0
HNCH2 CH3), 50.6 ( CH2NHCH2), 73.6 ( COH), 128.2–149.7
(ArC), 172.7 ( O).
( CH3), 21.3 (O C CH3), 44.4
(
C
2.7.3. 2-(Ethylamino)-1-phenylethanol
HPLC: Retention time of (R)-2b is 6.93 min.
(C10H15NO): Pale yellow solid, purity 99% (HPLC).
1H NMR ı (ppm): 1.0 (t, 3H, J = 12.50 Hz, CH2CH3), 2.58 (q, 2H,
J = 12.09 Hz, CH2CH3), 2.60 (s, 1H, NH), 2.61 (d, 1H, J = 4.23 Hz,
NHCH2 ), 2.63 (t, 1H, J = 6.96 Hz, NHCH2 ), 3.65 (s, 1H, OH),
4.63 (dd, 1H, J = 2.35 Hz, J = 2.33 Hz, ArCHOH), 7.31–7.33 (m, 5H,
HAr ).
IR (film) cm−1: 3401, 3034, 2604, 1969, 1719, 1624, 1490, 1375,
1269, 1006.
2.7.8. 2-(Butylamino)-1-phenylethyl acetate
(C12H19NO): Brown liquid, purity 97% (HPLC).
1H NMR ı (ppm): 0.87 (t, 3H, J = 6.90 Hz, CH2CH3), 1.26 (m, 2H,
13C NMR ı (ppm): 15.6 ( CH3), 43.6 ( NCH2 CH3), 58 ( CH2N),
70.6 ( HCOH), 127.2–142 (ArC).
CH2CH3), 1.39 (m, 2H, CH2CH2CH3), 2.19 (s, 3H,
O C CH3),
2.51 (t, 2H, J = 6.90 Hz, NHCH2CH2 ), 2.68 (s, 1H, NHCH2 ),
3.19 (d, 1H, J = 3.90 Hz, CHHNH CH2 ), 3.55 (t, 1H, J = 12.90 Hz,
CHHNH CH2 ), 5.90 (dd, 1H, J = 4.50 Hz, J = 4.60 Hz, ArCHO ),
7.37–7.39, (m, 5H, HAr ).
HPLC: Retention times of (S)-2a and (R)-2a are 5.3 and 9.14 min,
respectively.
IR (film) cm−1: 4046, 3224, 3086, 2881, 1955, 1885, 1758, 1659,
1555, 1416, 1268, 1201, 1065, 1026.
13C NMR
ı
(ppm): 13.8
( CH3), 21.0 (O C CH3), 21.4
(
(
CH2CH3), 39.5 ( CH2 CH2 CH2 ), 40.1 ( HNCH2 CH2), 50.4
2.7.4. 2-(Butylamino)-1-phenylethanol
CH2NH ), 73.6 ( COH), 126.8–149.9 (ArC), 172.5 (
HPLC: Retention time of (R)-4b is 6.80 min.
C O).
(C12H19NO): Yellow liquid, purity 99% (HPLC).
1H NMR ı (ppm): 0.86 (t, 3H, J = 12.50 Hz, CH2CH3), 1.31 (m,
2H, CH2CH3), 1.36 (m, 2H, CH2CH2CH3), 2.49 (t, 2H, J = 6.00 Hz,
CH2CH2 ), 2.60 (s, 1H, NH), 2.99 (d, 1H, J = 6.95 Hz, NHCH2 ),
3.31 (t, 1H, J = 9.57 Hz, CHHNH CH2 ), 3.65 (s, 1H, OH), 4.63 (dd,
1H, J = 4.18 Hz, J = 3.21 Hz, ArCHOH), 7.31–7.33 (m, 5H, HAr ).
IR (film) cm−1: 3033, 2961, 2939, 2875, 2593, 1959, 1723, 1623,
1439, 1372, 1237, 1065, 1027, 1005.
2.7.9. 2-(Hexylamino)-1-phenylethyl acetate
(C14H23NO): Brown liquid, purity 97% (HPLC).
13C NMR
39.9 CH2 CH2 CH2 ),
ı
(ppm): 14.4
(
CH3), 20.4
(
CH2CH3),
58.2
1H NMR ı (ppm): 0.82 (t, 3H, J = 11.90 Hz, CH2CH3), 1.19 (m,
4H, CH2CH2CH2CH3), 1.20 (m, 2H, CH2CH2CH3), 1.41 (m, 2H,
CH2CH2CH2 ), 1.90 (t, 2H, J = 12.50 Hz, NHCH2CH2 ), 2.0 (s,
1H, NHCH2 ), 2.05 (s, 3H,
CHHNH CH2 ), 3.54 (t, 1H, J = 12.30 Hz, CHHNH CH2 ), 5.90
(dd, 1H, J = 4.50 Hz, J = 4.50 Hz, ArCHO ), 7.37–7.39 (m, 5H, HAr).
(
49.2
(
NCH2 CH2),
(
CH2NH CH2 CH2 ), 70.6 ( HCOH), 127.2–142 (ArC).
HPLC: Retention times of (S)-4a and (R)-5a are 5.27 and
O C CH3), 3.17 (d, 1H, J = 3.60 Hz,
8.84 min, respectively.
IR (film) cm−1: 3422, 2975, 2958, 2738, 2491, 2365, 1621, 1475,
1433, 1397, 1171, 1036.
13C NMR
ı (ppm): 14.2 ( CH3), 21.3 (O C CH3), 22.4
(
(
CH2CH3), 31.5 ( CH2 CH2 CH3), 26.4 ( CH2 CH2 CH2 ), 31.3
NHCH2 CH2 ), 49.9 ( HNCH2 CH2 ), 53.1 ( CH2NHCH2 ),
2.7.5. 2-(Hexylamino)-1-phenylethanol
(C14H23NO): White solid, purity 99% (HPLC).
73.6 ( COH), 126.8–149.8 (ArC), 172.5 (
C O).
1H NMR ı (ppm): 0.86 (t, 3H, J = 11.90 Hz, CH2CH3), 1.24 (m,
4H, J = 12.50 Hz, CH2CH2CH2CH3), 1.28 (m, 2H, CH2CH2CH3),
1.38 (m, 2H, CH2CH2CH2 ), 2.52 (t, 2H, J = 9.24 Hz, NHCH2CH2 ),
2.62 (s, 1H, NHCH2 ), 2.64 (d, 1H, J = 4.50 Hz, CHHNH CH2 ),
3.41 (t, 1H, J = 9.60 Hz, CHHNH CH2 ), 3.65 (s, 1H, COH), 4.62
(dd, 1H, J = 3.73 Hz, J = 2.30 Hz, ArCHOH), 7.30–7.32 (m, 5H, HAr ).
HPLC: Retention time of (R)-5b is 7.17 min.
IR (film) cm−1: 3572, 2933, 2598, 1958, 1720, 1597, 1490, 1440,
1370, 1263, 1005.
2.8. Reusability of immobilized lipase
13C NMR
CH2CH2CH3), 26.9 ( CH2CH2CH2CH3), 30.0 ( CH2CH2CH2 ),
ı (ppm): 14.3 ( CH3), 22.6 ( CH2CH3), 25.4
The operational stability of immobilized lipase for asymmetric
acylation of 2-(hexylamino)-1-phenylethanol was investigated in a
screw capped glass tube. To 8 mL of TBME, 1 mL of 2-(hexylamino)-
1-phenylethanol solution (5.0 M) and 1 mL of vinyl acetate (9.60 M)
were added. The reaction was started by the addition 1 g of immobi-
lized lipase at 50 ◦C. After 4 h, the immobilized MML were separated
by filtration. After each experiment, the immobilized lipase prepa-
rations were washed with 5 mL of TBME and then dried under
vacuum. For the next operation, the fresh reaction medium was
loaded onto the reactor and these procedures were repeated 10
times.
(
49.5 ( NCH2 CH2 ), 58.2 ( CH2N), 71.8 ( COH), 126.4–142 (ArC).
HPLC: Retention times of (S)-5a and (R)-5a are 5.58 and
8.84 min, respectively.
IR (film) cm−1: 3418, 2977, 2940, 2739, 2491, 2359, 1475, 1397,
1172, 1036.
2.7.6. 2-(Methylamino)-1-phenylethyl acetate
(C11H15NO2): Brown liquid, purity 96% (HPLC).
1H NMR ı (ppm): 2.36 (s, 3H,
O C CH3), 2.72 (s, 1H,
NH CH3), 3.35 (t, 1H, J = 12.57 Hz, CHHNH CH3), 3.37 (s, 3H,
NH CH3), 3.93 (d, 1H, J = 4.90 Hz, CHHNH CH3), 5.90 (dd, 1H,
J = 4.90 Hz, J = 4.90 Hz, ArCHO ), 7.35–7.37 (m, 5H, HAr).
3. Results and discussion
13C NMR ı (ppm): 21.4 (O
C CH3), 39.9 ( HNCH3), 52.6
Since the surface of pure Florisil® support consists of the
inert hydroxyl groups, the surface of the support was modified
to immobilize lipase molecules. First, the inert hydroxyl groups
were silanized with 3-APTES to provide free NH2 groups then
these free NH2 groups were modified with PSI molecules. The
(
CH2HNCH3), 73.6 ( COH), 127.1–149.8 (ArC), 172.6 (
HPLC: Retention time of (R)-1b is 6.90 min.
C O).
IR (film) cm−1: 4068, 3400, 3033, 2601, 1970, 1715, 1597, 1490,
1371, 1264, 1025, 1005.