148
J. Hirsch et al./Carbohydrate Research 310 (1998) 145±149
H, J1 ,2 3.7 Hz, H-10), 4.90 (dt, 1 H, J4,5a 6.7 Hz,
J4,5b 9.7 Hz, H-4), 4.63 (dd, 1 H, H-20), 4.16 (d, 1
p-Nitrophenyl 2-O-(methyl 4-O-methyl-a-d-gluco-
pyranosyluronate)-b-d-xylopyranoside (9).ÐDe-O-
acetylation of 8 (0.5 g), as described for the pre-
paraꢁtion of 6, gave pure 9 (0.33 g, 89%); mp 139±
141 C (from ethanol); [ꢀ]d +32ꢁ (c 0.5, CHCl3).
0
0
H, J4 ,5 10.0 Hz, H-50), 3.91 (dd, 1 H, H-2), 3.86
(dd, 1 H, J5a,5b 9.7 Hz, H-5a), 3.77 (s, 3 H,
COOCH3), 3.50 (t, 1 H, H-5b), 3.34 (dd, 1 H, H-
40), 3.31 (s, 3 H, OCH3), 2.05, 2.02, 2.00, and 1.98
(4 s, each 3 H, 4 Ac); 13C NMR (CDCl3): 170.5,
169.9, 169.6, 169.2, 168.9 (5 CO ester), 93.8 (C-10),
90.6 (C-1), 78.8 (C-40), 73.8 (C-2), 70.6 (C-30), 70.4
(C-50), 69.9 (C-20), 69.5 (C-3), 68.3 (C-4), 60.8 (C-
5), 59.9 (OCH3), 52.6 (COOCH3), 20.7, 20.6, and
20.5 (2 C) (4 COCH3); EIMS m/z (Ir/%) 389 (12),
349 (51), 307 (22), 289 (41), 229 (38), 117 (36), 87
(26), 43 (100).
0
0
1
00
00
00 00
H NMR (CD3OD): ꢂ 8.27 (d, 2 H, J2 ,3 =J5 ,6
9.1 Hz, H-300 and H-500), 7.28 (d, 2 H, H-200 and H-
600), 5.42 (d, 1 H, J1 ,2 3.6 Hz, H-10), 5.31 (d, 1 H,
J1,2 7.3 Hz, H-1), 4.80 (d, 1 H, J4 ,5 10.0 Hz, H-50),
4.00 (dd, 1 H, J4,5a 5.0 Hz, J5a,5b 11.3 Hz, H-5a),
0
0
0
0
0
0
0
0
3.84 (s, 3 H, COOCH3), 3.83 (t, 1 H, J2 ,3 =J3 ,4
9.4 Hz, H-30), 3.70 (t, 1 H, J2,3=J3,4 9.3 Hz, H-3),
3.67 (dd, 1 H, H-2), 3.62 (dd, 1 H, H-20), 3.54 (s, 3
H, OCH3), 3.52 (dt, 1 H, J4,5b 9.3 Hz, H-4), 3.49
(dd, 1 H, H-5b), 3.32 (dd, 1 H, H-40); 13C NMR
(CD3OD): ꢂ 172.7 (CO ester), 163.4 (C-100), 144.1
(C-400), 126.5 (2 C) (C-300, C-500), 118.1 (2 C) (C-200,
C-600), 102.3 (C-1), 100.1 (C-10), 83.3 (C-40), 79.3
(C-3), 76.0 (C-20), 74.1 (C-30), 73.2 (C-4), 71.4 (C-2),
71.2 (C-50), 67.0 (C-5), 60.6 (OCH3), 52.8
(COOCH3). Anal. Calcd for C19H25NO13: C, 48.00;
H, 5.30; N, 2.95. Found: C, 47.78; H, 5.42; N, 2.82.
To a solution of the foregoing chloride 7
(0.95 g, 1.76 mmol), tetrabutylammonium hydro-
gen sulfate (0.6 g, 1.76 mmol), and p-nitrophenol
(0.5 g, 3.6 mmol) in dichloromethane (10 mL)
was added 1 M sodium hydroxide (10 mL), and
the mixture was vigorously stirred at room
temperature for 20 h. TLC (7:1 chloroform±ethyl
acetate) then showed that chloride 7 was con-
sumed and that a large amount of 8 (Rf 0.6) was
formed. Ethyl acetate (50 mL) was added, the
organic phase was separated, and washed succes-
sively with 1 M NaOH (three times), water (twice),
and brine. After drying (Na2SO4), the solvents
were evaporated at reduced pressure, and the
crude product was puri®ed by column chromato-
graphy (silica gel, 12:1 chloroform±ethyl acetate) to
give 8 (0.8 g, 71%); mp 183±185 ꢁC (from ethanol);
Acknowledgements
The authors are grateful to C. P. J. Glaudemans
(NIDDK) for his keen interest in this work and
helpful suggestions. We thank also K. Paule,
G. Kosicky, A. Karovicova, Dr. V. Patoprsty, and
E. Morhacova (Institute of Chemistry) for micro-
analyses, optical rotations, NMR and mass
spectral measurements, and technical assistance,
respectively. Financial support of this work by the
Scienti®c Grant Agency (VEGA, Slovak Academy
of Sciences and Ministry of Education, Bratislava,
Grant No. 2/4144/97) and National Science Foun-
dation (Grant No. NSF-INT 9507510) is gratefully
appreciated.
ꢁ
1
[ꢀ]d +38 (c 1.0, CHCl3). H NMR (CDCl3): ꢂ
0
7.06±8.33 (m, 4 H, aromatic), 5.54 (d, 1 H, J1 ,2
3.7 Hz, H-10), 5.35 (dd, 1 H, J2 ,3 10.4 Hz, J3 ,4
9.4 Hz, H-30), 5.34 (t, 1 H, J2,3=J3,4 9.2 Hz, H-3),
5.22 (d, 1 H, J1,2 6.9 Hz, H-1), 5.02 (dt, 1 H,
J3,4=J4,5b 9.2 Hz, J4,5a 5.3 Hz, H-4), 4.84 (dd, 1 H,
0
0
0
0
0
H-20), 4.25 (d, 1 H, J4 ,5 10.0 Hz, H-50), 4.15 (dd, 1
H, J5a,5b 11.8 Hz, H-5a), 4.00 (dd, 1 H, H-2), 3.85 (s,
3 H, COOCH3), 3.59 (dd, 1 H, H-40), 3.57 (dd, 1 H,
H-5b), 3.38 (s, 3 H, OCH3), 2.16, 2.08, 2.05, and
1.52 (4 s, each 3 H, 4 Ac); 13C NMR (CDCl3): ꢂ
169.9 (2 C), 169.7, 169.4, 169.0 (5 CO ester), 160.6
(C-100), 143.1 (C-400), 125.7 (2 C) (C-300, C-500),
116.5 (2 C) (C-200, C-600), 100.0 (C-1), 96.2 (C-10),
78.9 (C-40), 75.5 (C-2), 71.6 (C-3), 70.5 (C-30),
70.3 (2 C) (C-20, C-50), 69.1 (C-4), 62.7 (C-5),
59.9 (OCH3), 52.7 (COOCH3), 20.7, 20.6 (2 C),
and 20.0 (4 COCH3); CIMS m/z 723 (100%,
[M+C5H5NH]+). Anal. Calcd for C27H33NO17: C,
50.39; H, 5.17; N, 2.18. Found: C, 50.48; H, 5.29;
N, 2.16.
0
0
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