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SEBYAKIN, BUDANOVA
ethanol); 1ç NMR (δ, ppm): 0.81 (6 H, t, 2 ëç3), 1.2
(52 H, s, 26 ëç2), 1.44 [18 H, s, 2 C(CH3)3], 1.6 (4 H,
m, 2 βëç2), 1.9–2.2 (4 H, m, 2 αëç2), 2.28 (4 H, m, 2
ëç2), 2.5 (2 H, t, ëç2ëéé), 3.9–4.3 (2 H, m, CH),
N-Succinimide ester of ÇÓÒ2-L-ornithine (VII),
yield 96%; Rf 0.34 (C); mp 116–118°ë, and N-succin-
imide ester of ÇÓÒ2-L-lysine (VIII), yield 86%; Rf 0.36
(C); mp 108–110°ë, were obtained similarly.
Dihexadecyl
N-(tris-Boc-arginyl)glutamate
4.34 (2 H, t, ëç2), 5.71 (1 H, d, CONH); IR (film, νmax
,
cm–): 3321 (NH), 2891 (CH), 2800 (CH), 1730 (C=O),
1660 (C=O, amide I), 1643 (NH, amide II), 1460 (CH),
1378 (CH), 1190 and 1110 (C–O), 800, 760.
(XVI). A 10% aqueous solution of KHCO3 (0.2 ml)
was added to a solution of (IX) (98 g, 0.17 mmol) in
THF (4 ml), and then di(hexadecyl) glutamate (X)
(110 mg, 0.18 mmol) was added in portions under stir-
ring. The mixture was kept for 5 h at room temperature
and evaporated in a vacuum. The product was isolated
by preparative TLC in system C; yield 52 mg (30%) of
Hexadecyl L-glutaminate (XII). A mixture of
L-glutamine (VI) (1 g, 13.6 mmol), hexadecanol
(2.49 g, 10.3 mmol), and p-toluenesulfonic acid
(2.86 g, 13.6 mmol) was refluxed in toluene using a
Dean–Stark trap for 5 h; the reaction was monitored by
TLC. After completion of the reaction, the reaction
mixture was cooled to room temperature, recrystallized
from acetone, and washed with diethyl ether. The
resulting residue was dissolved in chloroform (70 ml),
the solution was washed with 5% aqueous NaHCO3
(2 × 40 ml), then with water to pH 7, and dried with
sodium sulfate. The solvent was evaporated in a vac-
uum, and the residue was recrystallized from acetone to
yield 1.51 (61%) of the target product; Rf 0.67 (A); mp
33–35°ë; IR (mineral oil, νmax, cm–1): 3370 (NH), 2920
(CH), 2898 (CH), 1730 (C=O), 1610 (C=O, amide I,
NH, amide II), 1465 (CH), 1411 (CH), 1390 (CH),
1180 (C–O), 920, 860, 780, 713, 650 (CH). Found, %:
C 68.11, H 11.49, N 7.52. ë21ç42N2é3. Calc., %: C
68.06, H 11.42, N 7.56.
amorphous diester (XVI); Rf 0.71 (C); [α]2D0 +19° (Ò
0.1, ethanol); 1H NMR (δ, ppm): 0.83 (6 H, t, 2 ëç3),
1.0 (2 ç, s, ëç2); 1.27 (52 H, s, 26 ëç2), 1.45 [9 H, s,
ë(ëç3)3], 1.5 [18 H, s, 2 ë(ëç3)3], 1.6 (4 H, m, 2
βëç2); 1.8–2.1 (4 H, m, 2 αëç2), 2.28 (2 H, m, ëç2),
2.5 (2 H, t, ëç2ëéé), 3.8–4.2 (2 H, m, 2CH), 4.35 (2
H, t, ëç2), 5.6 (1 H, d, CONH); IR (mineral oil, νmax
,
cm–1): 3500 (NH), 2910 (CH), 2902 (CH),1740 (C=O),
1700 (C=O), 1630 (C=O, amide I), 1560 (NH, amide
II), 1450 (CH), 1400 (CH); 1364 (CH), 1210, 1100 (C–
O).
Dihexadecyl-N-(bis-Boc-ornithyl)glutamate (XIV)
was similarly obtained from ornithine derivative (VII)
(183 mg) and glutamate (X) (355 mg) in yield 171 mg
(44%); Rf 0.6 (C); mp 57–58°ë; [α]2D0 +16° (Ò 0.1, eth-
1-Hexadecyl 5-tert-butyl glutamate (XIII) was
obtained from (V) (100 mg); yield 136 mg (65%); Rf
0.71 (A); IR (film, νmax, cm–1): 3390 (NH), 2952 (CH),
2889 (CH), 1750 (C=O), 1620 (C=O, amide I, NH,
amide II), 1465 (CH), 1411 (CH), 1390 (CH), 1180 (C–
O), 713, 650. Found, %: C 70.19, H 11.56, N 3.21.
C25H49NO4. Calc., %: C 70.21, H 11.55, N 3.28.
anol); 1ç NMR (δ, ppm): 0.84 (6 H, t, 2 ëç3), 1.0 (2 H,
s, ëç2), 1.25 (52 H, s, 26 ëç2), 1.45 (18 H, s, 2
C(CH3)3), 1.6 (4 H, m, 2 βëç2), 1.8–2.2 (4 H, m, 2
αëç2); 2.28 (4 H, m, ëç2), 2.5 (2 H, t, ëç2ëéé),
3.8–4.2 (2 H, m, CH), 4.36 (2 H, t, ëç2), 5.7 (1H, d,
CONH); IR (mineral oil, νmax, cm–1): 3400 (NH), 2910
(CH), 2901 (CH), 1741 (C=O), 1680 (C=O, amide I),
1640 (NH, amide II), 1500 and 1460 (CH), 1374 (CH),
1200 and 1100 (C–O).
Hexadecyl
N-(bis-Boc-ornithyl)glutaminate
(XVIII) was obtained from (XII) (224 mg) and (VII)
(250 mg) similarly to (XVI); yield 168 mg (34%); Rf
0.61 (C); [α]2D0 +22° (Ò 0.1, ethanol); ç NMR (δ,
1
Dioctyl N-(bis-Boc-ornithyl)glutamate (XVII)
was similarly obtained from ornithine derivative (VII)
(250 mg) and glutamate (XI) (356 mg); yield 180 mg
ppm): 0.8 (3 H, t, ëç3), 1.0 (24 H, s, 12 ëç2), 1.41 [18
H, s, 2 ë(ëç3)3], 1.6 (2 H, m, βëç2), 1.70 (2 H, m,
αëç2), 2.15 (2 H, m, ëç2), 2.5 (2 H, m, ëç2), 4.4–4.7
(60%); Rf 0.5 (C); mp 36–37°ë; [α]2D0 +16.5° (Ò 0.1,
1
ethanol); ç NMR (δ ppm: 0.84 (6 H, t, 2 ëç3), 1.23
(2 H, m, CH), and 5.7 (1 H, s, NH); IR (film, νmax
,
cm−1): 3319 (NH), 2899 (CH), 2800 (CH), 1740 (C=O),
1691 (O, amide I), 1630 (NH, amide II), 1599, 1515,
and 1460 (CH), 1377 (CH), 1280, 1160, and 1115 (C–
O), 1037, 950, 735.
(20 H, s, 10 ëç2), 1.40 (18 H, s, 2 C(CH3)3), 1.5–1.7 (4
H, m, 2 βëç2), 1.8–2.2 (4 H, m, 2 αëç2); 2.24 (4 H,
m, 2 ëç2), 2.5 (2 H, t, ëç2ëéé), 3.8–4.2 (2 H, m,
CH), 4.36 (2 H, t, ëç2), 5.7 (1 H, d, CONH); IR (min-
eral oil, νmax, cm–1): 3996 (NH), 2914 (CH), 2900 (CH),
1741 (C=O), 1685 (C=O, amide I), 1644 (NH, amide
II), 1500 and 1460 (CH), 1374 (CH), 1200 and 1100
(C–O).
Hexadecyl N-(bis-Boc-lysyl)glutaminate (XIX)
was similarly obtained from lysine derivative (VIII)
(321 mg) and glutaminate (XII) (349 mg); yield
236 mg (47%); Rf 0.61 (C); [α]2D0 +16° (Ò 0.1, ethanol);
1ç NMR (δ, ppm): 0.8 (3 H, t, ëç3), 1.0 (24 H, s, 12
ëç2), 1.42 [18 H, s, 2 ë(ëç3)3], 1.6 (2 H, m, βëç2),
1.69 (2 H, m, αëç2), 2.14 (2 H, m, ëç2), 2.49 (4 H, m,
2 ëç2), 4.4–4.6 (2 H, m, CH), and 5.7 (1 H, NH); IR
Dihexadecyl N-(bis-Boc-lysyl)glutamate (XV)
was similarly obtained from lysine derivative (VIII)
(310 mg) and glutamate (X) (540 mg) in yield 468 mg
(74%); Rf 0.63 (B); mp 45–46°ë; [α]2D0 +12° (Ò 0.1,
RUSSIAN JOURNAL OF BIOORGANIC CHEMISTRY Vol. 32 No. 5 2006