(
)
K. Teranishi et al.rCarbohydrate Research 306 1998 177–187
185
.
Ž
.
g, 3.3 mmol , pyruvic aldehyde 0.76 mL, 5.0 mmol ,
Found: C, 59.92; H, 5.26; N, 13.90. SIMS mrz 302
Ž
.
Ž
.
w
x
5 N HCl 6.6 mL , 1,4-dioxane 20 mL , and water
10 mL was heated at 100 8C for 1 h. After cooling,
the mixture was evaporated to dryness. The residue
was chromatographed on an ODS column Fuji Silysia
Chromatorex-ODS DM1020T, acetonitrile–water to
give 13 0.37 g, 34% ; mp 205 8C dec ; UV MeOH
Mq1 .
X
I
I
Ž
.
[
(
)
6 - Deoxy - 6 - N - 5 - 4 - methoxyphenyl - 2 -
]
Ž
.
pyrazinyl succinamidocyclomaltohexaose 16 .—Pyr-
Ž
Ž
.
Ž
idine 4.0 mL was added to a mixture of 15 0.10 g,
0.33 mmol , WSC 0.51 g, 2.7 mmol , and 6 -amino-
I
.
.
Ž
.
I
Ž
.
Ž
.
Ž
.
Ž
.
6 -deoxycyclomlatohexaose 7 0.65 g, 0.67 mmol at
room temperature, and the mixture was stirred at
room temperature for 3.5 h. The pyridine was evapo-
rated to dryness under reduced pressure. The residue
was dissolved with water and filtered through a mem-
brane filter. The filtrate was chromatographed on an
Ž . Ž . Ž .
lmax nm
´
430 4640 , 355 3300 , and 263
y
1
Ž
.
Ž
.
12,100 ; IR KBr : n 3450, 1720, and 1570 cm
;
1 H NMR CD3OD :
d
Ž
2.10 m,
2
H,
Ž
.
Ž
.
.
Ž
HOOCH2CH2CH2O , 2.45 s, 3 H, CH3 , 2.51 t, 2
H, J 7.3 Hz, HOOCH2CH2CH2O , 4.10 t, 2 H, J
6.1 Hz, HOOCH2CH2CH2O , 7.08 d, 2 H, J 7.9
Hz, ArH , 7.62 d, 2 H, J 7.9 Hz, ArH , 7.63 brs, 1
H, CH pyrazine , 7.91 brs, 1 H, CH pyrazine ; Anal.
Calcd for C17H17N3O4: C, 62.38; H, 5.23; N, 12.84.
Found: C, 62.81; H, 5.66; N, 12.44. SIMS: mrz 328
.
Ž
.
Ž
Ž
ODS column Fuji Silysia Chromatorex-ODS
.
Ž
.
.
Ž
.
DM1020T column, 15 mm=150 mm using aceto-
nitrile–water mixtures as eluent to afford 16 0.25 g,
56% yield ; mp 293 8C dec, from acetonitrile–water ;
UV 0.03 M phosphate buffer, pH 8.3 l
Ž
.
Ž
.
Ž
.
Ž
.
Ž .
nm ´
max
w
x
Ž
.
Ž
.
Ž
.
Mq1 .
334 12,200 , 291 13,200 , and 279 14,300 ; IR
I
I
[[ [
[
]
Ž
.
6 -Deoxy-6 - 4- 2-methylimidazo 1,2-a pyrazin-
3 7 H -one-6-yl phenoxy butyryl amino-cyclomalto-
heptaose 14 .—This compound was prepared from
0.10 g 0.31 mmol of 13, WSC 0.50 g, 2.6 mmol ,
and 6 -amino-6 -deoxy-cyclomaltoheptaose 0.72 g,
0.63 mmol as described for the synthesis of 9, giving
0.15 g 33% yield ; mp 205 8C decomposition ; UV
0.03 M phosphate buffer, pH 8.3, with little oxygen
KBr : n 3400, 2950, 1640, 1545, 1500, 1470, 1415,
1
1355, 1250, and 1150 cmy ; H NMR CD3OD : d
1
(
)
]
]
]
Ž
.
Ž
.
Ž
.
Ž
2.5–2.9 m, 4 H, CH2CH2 , 3.0–4.0 m, H a-
cyclodextrin , 3.85 s, 3 H, OCH3 , 4.8–5.0 m, H-1
a-cyclodextrin , 7.04 d, 2 H, J 9.0 Hz, ArH , 7.94
d, 2 H, J 9.0 Hz, ArH , 8.75 s, 1 H, CH pyrazine ,
and 9.35 s, 1 H, CH pyrazine ; Anal. Calcd for
C51H74N4O32 P5H2O: C, 45.54; H, 6.29; N, 4.16.
Found: C, 45.46; H, 6.53; N, 4.01. FABMS mrz 1255
Ž
.
Ž
.
.
Ž
.
Ž
I
I
Ž
.
Ž
.
.
Ž
.
Ž
.
Ž
.
Ž
.
Ž
.
Ž
l
Ž
Ž
.
Ž .
Ž
.
Ž
.
nm ´ 273 16,400 , 345 6300 , and 396
max
1
4000 ; IR KBr : 3400, and 1640 cm 1; H NMR
y
.
Ž
.
w
x
Mq1 .
X
I
I
.
Ž
[
(
)
D2O :
d
2.0–5.3 m,
H
b-cyclodextrin,
6 - Deoxy - 6 - N - 5 - 4 - methoxyphenyl - 2 -
.
Ž
.
]
Ž
.
CH2CH2CH2O, and CH3 , 7.17 d, 2 H, J 8.5 Hz,
pyrazinyl succinamido - cyclomaltohepttaose 17 .—
.
Ž
Ž
Ž
ArH , 8.02 d, 2 H, J 8.5 Hz, ArH , 8.21 s, 1 H, CH
This compound was prepared from 0.10 g 0.33
mmol of 15, WSC 0.51 g, 2.7 mmol , and 6 -
amino-6 -deoxy-cyclomaltoheptaose 8 0.75 g, 0.66
mmol as described for the synthesis of 16, giving
0.22 g 0.43% yield ; mp 305 8C dec, from aceto-
nitrile–water ; UV 0.03 M phosphate buffer, pH 8.3
I
.
Ž
.
.
Ž
.
pyrazine , and 8.73 s, 1 H, CH pyrazine ; Anal.
Calcd for C59H86N37O4 P5H2O: C, 46.21; H, 6.31;
N, 3.65. Found: C, 46.00; H, 6.80; N, 3.21. FABMS:
I
Ž
.
w
x
Ž
.
Ž
mrz 1443 Mq1 .
[ (
)
]
.
Ž
.
5- 4-Methoxyphenyl -2-pyrazinyl succinamic acid
Ž
.
Ž
.
Ž . Ž . Ž .
nm ´ 333 13,000 , 294 15,300 , and 280
15 .—A mixture of 4 0.50 g, 2.5 mmol , succinic
anhydride 1.2 g, 12 mmol , and Me2 NCHO 10 mL
was heated at 120 8C for 3 h. The Me2 NCHO was
removed under reduced pressure and the resulting
solids were dissolved in ethyl acetate and the product
l
max
Ž
.
Ž
.
Ž
.
Ž
.
15,900 ; IR KBr :n 3400, 2950, 1650, 1540, 1350,
1
1160, and 1030 cmy ; H NMR CD3OD : d 2.5–2.9
1
Ž
.
Ž
.
Ž
m, 4 H, CH2CH2 , 3.1–4.0 m, b-cyclodextrin and
OCH3 , 4.8–5.0 m, H 1 b-cyclodextrin , 7.06 d, 2
H, J 8.5 Hz, ArH , 7.94 d, 2 H, J 8.5 Hz, ArH ,
8.76 s, 1 H, CH pyrazine , and 9.35 s, 1 H, CH
.
Ž
.
Ž
Ž
.
Ž
.
was crystallized to give compound 15 0.61 g, 81%
yield ; mp 238–239 8C; UV MeOH lmax nm ´
.
Ž
.
Ž .
Ž
.
Ž
Ž
.
Ž
.
Ž
.
.
334 15,200 , 291 18,850 , and 279 19,900 ; IR
pyrazine ; Anal. Calcd for C57H84N4O37 P7H2O: C,
Ž
.
KBr : n 3450, 3200, 3100, 1690, 1605, 1560, 1495,
44.36; H, 6.40; N, 3.63. Found: C, 44.10; H, 6.56; N,
1475, 1440, 1415, 1360, 1310, 1255, and 1170 cmy
;
1
w
x
3.36. FABMS: mrz 1417 Mq1 .
1
Ž
.
Ž
[
(
)
]
H NMR Me2SO-d6 : d 2.52 t, 2 H, J 6.7 Hz,
4 - 4 - 2 - acetamido- 5 - pyrazinyl phenoxy butyric
.
Ž
.
Ž
Ž
.
Ž
.
CH2 , 2.67 t, 2 H, J 6.7 Hz, CH2 , 3.82 s, 3 H,
acid 19 .—Acetyl chloride 0.16 mL, 2.3 mmol
.
Ž
.
Ž
Ž
.
OCH3 , 7.06 d, 2 H, J 9.0 Hz, ArH , 8.04 d, 2 H,
J 9.0 Hz , 8.92 s, 1 H, CH pyrazine , 9.31 s, 1 H,
CH pyrazine , and 10.88 s, 1 H, COOH ; Anal.
was added to a solution of 12 0.45 g, 1.5 mmol in a
mixture of dichloromethane 4.5 mL and pyridine
4.5 mL at 0 8C, and the mixture was stirred at 20 8C
.
Ž
.
Ž
.
Ž
.
.
Ž
Ž
.
Calcd for C15H15N3O4: C, 59.80; H, 5.02; N, 13.95.
for 1 h. The mixture was cooled to 0 8C and neutral-