380
TOLMACHEVA et al.
with triethylamine (1.2 mmol, 0.17 ml) in a solution of 28.74, 29.37, 30.70, 32.63, 32.72, 34.27, 36.22, 36.60,
anhydrous dichloromethane (20 ml) in an argon 40.41, 41.08, 41.42, 42.16, 45.59, 46.55, 46.62, 50.63,
atmosphere for 1 h. The reaction mixture was stirred 52.06, 57.35, 71.23 (C28), 87.82 (C19), 118.86 (C2),
for 4–6 h at room temperature with TLC monitoring. 172.40 (СООСН ), 178.37 (C3).
3
The solvent was evaporated, and the residue was puriꢀ
fied by column chromatography.
Ethylꢀ
N
ꢀ[2,3
ꢀalaninate (IIId). Yield 0.33 g (53%); mp
ꢀoleꢀ 110–112 С (chloroform–ethyl acetate); Rf 0.3 (chloꢀ
ꢀ
secoꢀ1ꢀcyanoꢀ19
β
,28ꢀepoxyꢀ18
α
ꢀoleꢀ
aneꢀ3ꢀoyl]ꢀ
β
о
2
ꢀ
N
ꢀ[2,3ꢀsecoꢀ1ꢀcyanoꢀ19
β
,28ꢀepoxyꢀ18
α
aneꢀ3ꢀoyl]aminopropane (IIIa). Yield 0.22 g (39%);
Rf 0.4 (hexane–ethyl acetate, 7 : 3); mp 110–112°C
20
roform–ethyl acetate, 10 : 1); [
CHCl3); IR: 1668 (CONH), 1726 (COOC H ), 2238
α
]D + 12.89
°
(c 0.4,
2
0
2
5
(
hexane–ethyl acetate); [
IR: 1660 (CONH), 2240 (С
NMR: 0.79, 0.92, 0.96, 0.98, 1.00, 1.19, 1.23 (21 H,
s, 7CH ), 1.17 and 1.23 (6 H, 2 d, 6.6, 2CH ), 2.45
α
]
+ 29.20
°
(
c
0.4, CHCl3)
;
1
D
(C
≡
N), 3207 (NH); H NMR: 0.79, 0.92, 1.18, 1.23
1
≡
N), 3384, (NH); H (12 H, 4 s, 4CH ), 0.97 (9 H, s, 3CH ), 1.26 (3 H, t,
3
3
J
7.2, COOCH CH ), 2.43 and 2.53 (2 H, 2 d, JАВ
2 3
7
J
3
3
18.2, H1, AB system), 2.57 (2 H, t,
CH CH COOCH CH ) 3.37–3.47 (1 H, m,
СONHCH CH ), 3.45 and 3.76 (2 H, 2 d, JАВ 7.7
J 6.0,
and 2.60 (2 H, 2 d, JАВ 17.9, H1, AB system), 3.44 and
.75 (2 H, 2 d, JАВ 7.7, H28, AB system), 3.52 (1 H, s,
H19), 4.00 (1 H, g, 6.6, СН(СН ) ), 5.56 (1 H, d,
,
3
2
2
2
3
,
2
2
J
3
2
H28, AB system), 3.53 (1 H, s, H19), 3.60–3.70 (1 H,
6.9, NH); C NMR: 13.49, 15.53, 18.28, 20.47, m, СONHCH2), 4.15 (2 H, dd, 14.3, 7.2,
13
J
2
2
4
5
J
13
1.83, 21.94, 22.56, 22.63, 24.51, 26.13, 26.34, 26.41,
8.73, 28.76, 28.94, 32.66, 32.77, 34.30, 36.25, 36.63,
0.42, 41.12, 41.45, 42.10, 42.40, 45.44, 45.76, 46.58,
1.74, 71.25 (C28), 87.84 (C19), 119.45 (C2), 178.10
COOCH CH ), 6.50 (1 H, t,
J 6.0, NH); C NMR:
2
3
1
2
3
4
8
3.48, 14.16, 15.50, 18.44, 20.19, 21.71, 22.00, 24.48,
6.09, 26.28, 26.38, 28.31, 28.72, 29.09, 32.63, 32.80,
3.54, 34.21, 35.37, 36.22, 36.59, 40.44, 41.10, 41.42,
2.41, 45.43, 45.62, 46.55, 51.95, 60.72, 71.20 (C28),
(
C3).
7.84 (C19), 119.02 (C2), 172.58 (СООС Н ), 179.08
Ethylꢀ
N
ꢀ[2,3
ꢀ
secoꢀ1ꢀcyanoꢀ19
β
,28ꢀepoxyꢀ18
α
ꢀoleꢀ
2
5
aneꢀ3ꢀoyl]glycinate (IIIb). Yield 0.26 g (42%); mp 90– (C3).
92
°С
(chloroform–ethyl acetate); Rf 0.3 (chloroꢀ
5ꢀNꢀ[2,3
ꢀ
secoꢀ1ꢀcyanoꢀ19
β
,28ꢀepoxyꢀ18 ꢀoleaneꢀ
α
20
3ꢀoyl]amino valerate (IIIe). Yield 0.17 g (30%); mp
form–ethyl acetate, 10 : 1); [
α
]
+ 21.46
°
(c 0.4,
D
о
1
16–118 С (hexane–ethyl acetate); Rf 0.3 (hexane–
CHCl3); IR: 1652 (CONH), 1748 (COOC H ), 2237
2
5
2
D
0
1
ethyl acetate, 5 : 1); [
α
] + 13.70
°
(
c
0.4, CHCl3); IR:
N), 3371
J 6.9, COOCH CH ); 2.44and 2.53 (2 H, 2 d, JАВ (NH); H NMR: 0.79, 0.92, 0.96, 0.97, 0.98, 1.18,
(
1
C
≡
N), 3376 (NH); H NMR: 0.78, 0.92, 0.97, 1.22,
.30 (15 Н, 5 s, 5СН3), 0.97 (6 H, s, 2 CH ), 1.28 (3 H, 1634 (CONH), 1707 (COOH), 2242 (C
≡
3
1
t,
8.3, H1, AB system), 3.44 and 3.75 (2 H, 2 d, JАВ 7.8
H28, AB system), 3.52 (1 H, s, H19), 3.83, 3.84 and НООССН (СН ) NHСО), 2.43 and 2.53 (2 H, 2 d,
2
3
1
,
1.25 (21 H, 7 s, 7CH ), 2.38 (2 H, t, J 6.8,
3
2
2 3
4
.24, 4.26 (2 H, 4 d, JАВ 18.3, (
D
,
L
) СONHCH COO
,
JАВ 18.0, H1, AB system), 3.02–3.13 (2 H, m,
2
AB system), 4.21 (2 H, dd, 14.1, 6.9, COOCH CH )
J
,
НООССН (СН ) CH NHСО), 3.45 and 3.77 (2 H,
2
3
2
2 2
2
1
3
6
1
2
3
4
.31 (1 H, t,
J
6.2, NH); C NMR: 13.51, 14.10, 2 d, JАВ 7.8, H28, AB system), 3.54 (1 H, s, H19), 6.00
13
5.52, 18.68, 20.14, 21.68, 22.03, 24.48, 26.11, 26.28, (1 H, t,
J
5.4, NH); C NMR: 13.47, 15.53, 18.32,
6.40, 28.42, 28.74, 28.92, 32.64, 32.85, 34.22, 36.23, 20.18, 21.74, 21.77, 21.93, 24.49, 26.10, 26.31, 26.38,
6.61, 40.46, 41.11, 41.43, 41.57, 42.39, 45.50, 45.75, 28.21, 28.56, 28.73, 29.41, 32.63, 32.83, 33.34, 34.21,
6.57, 51.93, 61.46, 71.23 (C28), 87.83 (C19), 118.88 36.22, 36.60, 39.37, 40.46, 41.10, 41.43, 42.48, 45.41,
(
C2), 169.94 (СООС Н ), 179.07 (C3).
45.56, 46.55, 52.24, 71.19 (C28), 87.84 (C19), 119.27
C2), 177.73 (COOH), 179.25 (C3).
Methylꢀ ꢀ[2,3 secoꢀ1ꢀcyanoꢀ19
oleaneꢀ3ꢀoyl]ꢀ ꢀphenylalaninate (IIIe). Yield 0.34 g
(51%); mp 91–93 С (hexane–ethyl acetate);
2
5
(
Methylꢀ
oleaneꢀ3ꢀoyl]ꢀ
mp 85–87 (chloroform–ethyl acetate); Rf 0.4 (chloꢀ
N
ꢀ[2,3
ꢀ
secoꢀ1ꢀcyanoꢀ19
β
,28ꢀepoxyꢀ18
α
ꢀ
N
ꢀ
β
,28ꢀepoxyꢀ18 ꢀ
α
Lꢀvalinate (IIIb). Yield 0.18 g (28%);
L
°
С
о
2
D
0
R
f
0.4
roform–ethyl acetate, 10 : 1); [
α
]
+ 40.88
°
(c 0.4
2
D
0
(
chloroform–ethyl acetate, 10 : 1); [
α
]
+ 51.89
°
CHCl3); IR: 1665 (CONH), 1735 (СООСН ), 2237
3
1
(c 0.4, CHCl3); IR: 1659 (CONH), 1740 (COOCH3),
(
1
2
С
≡
N), 3393 (NH); H NMR: 0.79, 0.92, 0.94, 1.28,
.30 (15 H, 5 s, 5 CH ), 0.94 and 0.97 (6 H, 2 d,
6.9, 2238 (C
.93, 0.95, 1.12, 1.14 (21 H, 7 s, 7CH ), 2.46 (2 H, s,
1
J
≡
N), 3382 (NH); H NMR: 0.78, 0.88, 0.92,
3
0
CH ), 0.97 (6 H, s, 2CH ), 2.16–2.26 (1 H, m,
3
3
3
H1), 3.16 (2 H, t,
2 H, 2 d, JАВ 8.0, H28, AB system), 3.52 (1 H, s,
H19), 3.70 (3 H, с, COOCH ), 4.79 (1 H, dd, 13.5,
7.5, NH), 7.13–
); C NMR: 13.52, 15.52, 18.76,
0.74, 21.77, 23.89, 24.48, 26.10, 26.29, 26.39, 27.27, 20.42, 21.73, 23.02, 24.49, 26.11, 26.29, 26.40, 27.73,
J6.9, C H CH ), 3.44), 3.44 and 3.75
CH(CH ) ); 2.46 and 2.53 (2 H, 2 d, JАВ 18.6, H1, AB
system), 3.44 and 3.75 (2 H, 2 d, JАВ 7.9, H28, AB sysꢀ
6 5 2
3
2
(
J
tem), 3.52 (1 H, s, H19), 3.74 (3 Н, с, СООСН ); 4.49
3
3
6
.3, C H CH CH), 6.08 (1 H, d, J
(
1 H, dd,
J
7.9, 4.8, СONHCH), 6.18 (1 H, d,
J
8.1
,
6 5 2
13
13
NH); C NMR: 13.46, 15.54, 18.06, 18.79, 18.84, 7.33 (5 H, m,
C H
6 5
2
RUSSIAN JOURNAL OF BIOORGANIC CHEMISTRY Vol. 36
No. 3
2010