5
24
H.-S. Gao et al.
(
ES+) m/z Calc. for [C11H22NO2]+ 200.3. Found 200.2. Calc.
Calc. for C11H22F6NO2 P C 38.3, H 6.4, N 4.1. Found C 38.0,
H 6.4, N 3.9%.
for C11H22NO2I C 40.4, H 6.8, N 4.3. Found C 40.4, H 6.8,
N 4.3%.
N,N-Dimethyl-L-proline Ethyl Ester Iodide,
L-Pro-C2-C1I 3a
N,N-Diethyl-L-proline Ethyl Ester Bromide,
L-Pro-C2-C2Br 2b
This compound was synthesized in the same manner as that
This compound was synthesized in the same manner as that
described for l-Pro-C1-C1I using anhydrous ethanol (300 mL).
◦
20
described for l-Pro-C1-C1I using anhydrous ethanol (300 mL),
Lightyellowsolid, 86%, mp109 C. [α] −20.5(c2.0, CH3OH).
D
◦
−1
and CH3CH2Br (22.8 mL). Light yellow solid, 78%, mp 71 C.
ν
max
(KBr)/cm 3478, 3005, 1746, 1468, 1240, 1184, 1022,
2
0
−1
[
α] −35.2 (c 2.0, CH3OH). νmax (KBr)/cm 3427, 2986,
H 3
863. δ (400 MHz, CDCl ) 5.27 (t, J 9.6, 1H, CH), 4.77–4.79 (m,
1H, CH ), 4.28 (q, J 4, 2H, CH ), 4.10–4.17 (m, 1H, CH ), 3.73
2 2 2
D
1
737, 1471, 1237, 1020. δH (400 MHz, CD3COCD3) 4.99 (t,
J 8.2, 1H, CH), 4.33 (q, J 7.4, 2H, CH2), 3.77–4.08 (m, 4H,
CH2, CH2), 3.64 (q, J 7.2, 2H, CH2), 2.68–2.77 (m, 1H, CH2),
3 3 2
(s, 3H, CH ), 3.29 (s, 3H, CH ), 2.71–2.79 (m, 1H, CH ), 2.35–
2.45 (m, 3H, CH CH ), 1.34 (t, J 9.2, 3H, CH ). δ (100 MHz,
2
2
3
C
2
1
7
.38–2.52 (m, 3H, CH2CH2), 1.42–1.52 (m, 6H, CH3, CH3),
.35 (t, J 7.2, 3H, CH3). δC (100 MHz, CD3COCD3) 167.5,
CDCl ) 166.5, 74.4, 68.8, 64.0, 53.1, 48.5, 25.6, 20.0, 14.9.TOF-
3
+
MS (ES+) m/z Calc. for [C H NO ] 172.2. Found 172.2.
9
18
2
2.3, 63.5, 61.5, 56.5, 53.3, 26.5, 20.5, 14.1, 9.5, 9.3. TOF-MS
9 18 2
Calc. for C H NO I C 36.1, H 6.0, N 4.7. Found C 36.0, H 6.1,
+
(
ES+) m/z Calc. for [C11H22NO2] 200.3. Found 200.2. Calc.
N 4.67%.
for C11H22NO2Br C 47.2, H 7.9, N 5.0. Found C 46.8, H 7.8,
N 4.8%.
N,N-Dimethyl-L-proline Ethyl Ester Nitrate,
L-Pro-C2-C1NO3 3b
N,N-Diethyl-L-proline Ethyl Ester Nitrate,
L-Pro-C2-C2NO3 2c
This compound was synthesized in the same manner as that
described for l-Pro-C1-C1NO3 using l-Pro-C2-C1I (3.58 g,
◦
20
This compound was synthesized in the same manner as that
described for l-Pro-C1-C1NO3 using l-Pro-C2-C2I (3.75 g,
0.012 mol). Light yellow liquid, 85%, mp 18 C. [α] −25.3 (c
D
−
1
2.0, CH OH). ν
3
max
(KBr)/cm 3478, 2989, 1740, 1646, 1378,
◦
20
D
0
2
1
2
1
.012 mol). Light yellow solid, 81%, mp 62 C. [α] −36.5 (c
H 3 3
1099, 1040, 831. δ (400 MHz, CD COCD ) 4.91 (t, J 9.6, 1H,
−
1
.0, CH3OH). νmax (KBr)/cm 3464, 2988, 1739, 1378, 1199,
019. δH (400 MHz, CDCl3) 4.75 (t, J 8, 1H, CH), 4.31 (q, J 7,
H, CH2), 3.44–3.92 (m, 6H, CH2, CH2, CH2), 2.66–2.75 (m,
H, CH2), 2.19–2.41 (m, 3H, CH2CH2), 1.39–1.49 (m, 6H, CH3,
CH), 4.37 (q, J 7, 2H, CH2), 3.91–4.06 (m, 2H, CH2), 3.59 (s, 3H,
CH3), 3.34 (s, 3H, CH3), 2.52–2.73 (m, 2H, CH2), 2.29–2.39 (m,
2H, CH2), 1.36 (t, J 5.6, 3H, CH3). δC (100 MHz, CD3COCD3)
166.9, 74.2, 68.7, 63.5, 52.9, 47.1, 25.5, 19.7, 14.2. TOF-MS
+
CH3), 1.34 (t, J 7.2, 3H, CH3). δC (100 MHz, CDCl3) 167.3,
(ES+) m/z Calc. for [C9H18NO2] 172.2. Found 172.2. Calc.
7
2.1, 63.9, 61.4, 56.5, 52.9, 26.7, 20.7, 14.7, 9.8, 9.4. TOF-MS
for C9H18N2O5 C 46.2, H 7.8, N 12.0. Found C 46.3, H 7.5, N
11.7%.
+
(
ES+) m/z Calc. for [C11H22NO2] 200.3. Found 200.2. Calc.
for C11H22N2O5 C 50.4, H 8.5, N 10.7. Found C 50.3, H 8.3,
N 10.6%.
N,N-Dimethyl-L-proline Ethyl Ester Tetrafluoroborate,
L-Pro-C2-C1BF4 3c
N,N-Diethyl-L-proline Ethyl Ester Tetrafluoroborate,
L-Pro-C2-C2BF4 2d
This compound was synthesized in the same manner as that
described for l-Pro-C1-C1NO3 using l-Pro-C2-C1I (3.58 g,
0.012 mol), and AgBF4 (2.34 g, 0.012 mol). Light yellow waxy
This compound was synthesized in the same manner as that
described for l-Pro-C1-C1NO3 using l-Pro-C2-C2I (3.75 g,
◦
20
solid, 80% yield, mp 35 C. [α] −24 (c 2.0, CH3OH). νmax
D
−
1
0
7
3
.012 mol), and AgBF4 (2.34 g, 0.012 mol). Light yellow solid,
(KBr)/cm
3634, 2987, 1743, 1474, 1253, 1058, 849. δH
◦
20
−1
6%, mp 79 C. [α]D −31.5 (c 2.0, CH3OH). νmax (KBr)/cm
3 3
(400 MHz, CD COCD ) 4.74 (t, J 9.6, 1H, CH), 4.37 (q, J 7, 2H,
564, 2993, 1739, 1379, 1062. δH (400 MHz, CD3COCD3) 4.68
CH ), 3.82–4.02 (m, 2H, CH ), 3.56 (s, 3H, CH ), 3.33 (s, 3H,
2
2
3
(
t, J 8, 1H, CH), 4.33 (q, J 7, 2H, CH2), 3.55–3.84 (m, 6H,
3 2 2
CH ), 2.54–2.75 (m, 2H, CH ), 2.33–2.41 (m, 2H, CH ), 1.36 (t,
CH2, CH2, CH2), 2.60–2.69 (m, 1H, CH2), 2.34–2.53 (m, 3H,
CH2CH2), 1.39–1.48 (m, 6H, CH3, CH3), 1.33 (t, J 7, 3H,
CH3). δC (100 MHz, CD3COCD3) 167.2, 72.0, 63.7, 61.0, 56.0,
3 C 3 3
J 7.2, 3H, CH ). δ (100 MHz, CD COCD ) 166.8, 74.2, 68.7,
63.5, 52.9, 47.1, 25.4, 19.63, 14.1. TOF-MS (ES+) m/z Calc. for
+
[C H NO ] 172.2. Found 172.2. Calc. for C H BF NO C
9
18
2
9
18
4
2
5
3.2, 26.3, 20.4, 14.03, 9.0, 8.6. TOF-MS (ES+) m/z Calc. for
41.7, H 7.0, N 5.4. Found C 41.6, H 7.0, N 5.3%.
+
[
C11H22NO2] 200.3. Found 200.2. Calc. for C11H22BF4NO2
C 46.0, H 7.7, N 4.9. Found C 45.9, H 7.6, N 4.7%.
N,N-Dimethyl-L-proline Ethyl Ester
Hexafluorophosphorate, L-Pro-C2-C1PF6 3d
N,N-Diethyl-L-proline Ethyl Ester Hexafluorophosphorate,
L-Pro-C2-C2PF6 2e
This compound was synthesized in the same manner as that
described for l-Pro-C1-C1PF6 using l-Pro-C2-C1I (3.58 g,
◦
20
D
This compound was synthesized in the same manner as that
0.012 mol). Light yellow waxy solid, 75%, mp 32 C. [α] −15
−
1
described for l-Pro-C1-C1PF6 using l-Pro-C2-C2I (6.78 g,
(c 2.0, CH OH). ν
max
(KBr)/cm 3675, 2989, 1737, 1463,
3
◦
20
0
2
8
.0217 mol). Light yellow solid, 73%, mp 94 C. [α] −17 (c
H 3 3
1232, 1040, 838. δ (400 MHz, CD COCD ) 4.67 (t, J 9.6, 1H,
D
−
1
.0, CH3OH). νmax (KBr)/cm 3462, 2994, 1735, 1261, 1039,
42. δH (400 MHz, CD3COCD3) 4.66 (t, J 8, 1H, CH), 4.33 (q,
CH), 4.37 (q, J 5.4, 2H, CH2), 3.89–4.02 (m, 2H, CH2), 3.56 (s,
3H, CH3), 3.32 (s, 3H, CH3), 2.52–2.74 (m, 2H, CH2), 2.31–2.39
(m, 2H, CH2), 1.36 (t, J 7, 3H, CH3). δC (100 MHz, CD3COCD3)
166.6, 74.4, 68.8, 63.6, 53.1, 47.2, 25.4, 19.7, 14.1. TOF-MS
J 7.2, 2H, CH2), 3.53–3.85 (m, 6H, CH2, CH2, CH2), 2.57–2.67
m, 1H, CH2), 2.25–2.52 (m, 3H, CH2CH2), 1.39–1.46 (m, 6H,
CH3, CH3), 1.29 (t, J 7.2, 3H, CH3). δC (100 MHz, CD3COCD3)
(
+
(ES+) m/z Calc. for [C9H18NO2] 172.2. Found 172.2. Calc.
1
67.2, 72.0, 63.7, 61.0, 55.9, 53.3, 26.3, 20.4, 14.0, 9.0, 8.6.TOF-
for C9H18F6NO2P C 34.1, H 5.7, N 4.4. Found C 33.7, H 5.6,
N 4.4%.
+
MS (ES+) m/z Calc. for [C11H22NO2] 200.3. Found 200.2.