The Anilides of Glucuronic Acid
2.11, 2.08, 2.03 (each s, each 3H, each COCH3); selected 1H
NMR data for the â-anomer δ 8.02 (s, 1H, NH), 4.85 (d, 1H,
J1,2 ) 8.9, H-1), 4.13 (d, 1H, J4,5 ) 9.4, H-5); 13C NMR for the
R-anomer (125 MHz, CDCl3) δ 170.3, 169.9, 169.8 (each s, each
COCH3), 164.4 (s, CONH), 135.0, 134.1 (each s, each Ar C),
129.8, 120.8 (each d, each Ar C), 86.3 (d, C-1), 70.5, 70.3, 69.4,
69.0 (each d, C2-5), 21.1 (q, CH3) 20.9, 20.8, 20.7(each q, each
COCH3); selected 13C NMR for the â-anomer: 170.0, 169.8,
169.4 (each s, each COCH3), 163.8 (s, CONH), 135.2, 133.9
(each s, each Ar C), 121.0 (d, Ar C), 88.3 (d, C-1), 74.8, 72.0,
70.8, 69.4 (each d, C2-5), 20.8, 20.7, 20.7 (each q, each
COCH3); FTIR (CH2Cl2 solution) 3322, 2959, 2122, 1755, 1689,
1604, 1533, 1370, 1221, 1047, cm-1; ES-HRMS found 433.1364,
required 433.1359 [M - H]-.
2,3,4-Tri-O-acetyl-1-azido-1-deoxy-r/b-D-glucopyranu-
ronic Acid, p-Methoxyphenylamide 25e/24e. R-Anomer
25e and â-anomer 24e: 1H NMR data for the R-anomer (300
MHz, CDCl3) δ 7.94 (s, 1H, NH), 7.36 (d, 2H, J ) 8.9, Ar H),
6.80(d, 2H, J ) 9.1, Ar H), 5.75 (d, 1H, J1,2 ) 4.2, H-1), 5.48
(t, 1H, J2,3 ) 10.1, J3,4 ) 9.5, H-3), 5.20 (t, 1H, J3,4 ) 9.5, J4,5
) 10.1, H-4), 4.94 (dd, 1H, H-2), 4.49 (d, 1H, H-5), 3.78 (s, 3H,
OCH3), 2.11, 2.08, 2.03 (each s, each 3H, each COCH3); selected
1H NMR data for the â-anomer δ 7.98 (s, 1H, NH), 4.85 (d,
1H, J1,2 ) 8.9, H-1), 4.13 (d, 1H, J4,5 ) 9.5, H-5); 13C NMR for
the R-anomer (125 MHz, CDCl3) δ 170.3, 169.9, 169.88 (each
s, each COCH3), 164.4 (s, CONH), 157.2 (s, Ar C), 129.6 (s, Ar
C), 122.7, 114.5 (each d, each Ar C), 86.3 (d, C-1), 70.5, 70.3,
69.5, 68.9 (each d, C2-5), 55.7 (s, OCH3), 20.9, 20.8, 20.7 (each
s, each COCH3); selected 13C NMR for the â-anomer δ 170.0,
169.8, 169.4 (each s, each COCH3), 163.9 (s, CONH, â), 157.4
(s, Ar C), 129.5 (s, Ar C), 122.9 (d, Ar C), 88.3 (d, C-1), 74.8,
72.0, 70.8, 69.4 (each d, C2-5, â), 20.8, 20.7, 20.7 (each q, each
COCH3); FTIR (CH2Cl2 solution) 3332, 2959,2838, 2121, 1756,
1689, 1513, 1467, 1370, 1236, 1046, cm-1; ES-HRMS found
449.1295, required 449.1309 [M - H]-.
72.1 (each d, C2-5), 38.2 (N CH3); ES-HRMS found 325.0945,
required 325.0948 [M - H]-.
1-Azido-1-deoxy-r/b-D-glucopyranuronic Acid, N-Meth-
yl-p-chlorophenylamide 27b/26b. R-Anomer 27b and â-ano-
mer 26b: 1H NMR data for the R-anomer (300 MHz, D2O) δ
7.53 (d, 2H, J ) 8.8, Ar H), 7.30 (d, 2H, J ) 8.8, Ar H), 5.43
(d, 1H, J1,2 ) 4.4, H-1), 4.17 (d, 1H, J4,5 ) 9.7, H-5), 3.67 (t,
1H, J3,4 ) 9.5, J4,5 ) 9.7, H-4), 3.58 (dd, 1H, J2,3 ) 9.7, H-2),
1
3.29 (t, 1H, H-3), 3.25 (s, 3H, N CH3); selected H NMR data
for the â-anomer δ 4.41 (d, 1H, J1,2 ) 8.3, H-1), 3.88 (d,
1H, J4,5 ) 9.7, H-5); 13C NMR for the R-anomer (75 MHz,
MeOH-d4) δ 170.0 (s, CONCH3), 142.8 (s, Ar C), 135.4 (s, Ar
C), 131.1 (d, Ar C), 130.5 (d, Ar C), 92.6 (d, C-1), 74.2, 72.7,
72.6, 71.2 (each d, C2-5), 38.3 (N CH3); 13C NMR data for the
â-anomer δ 169.1 (s, CONCH3), 130.7 (s, Ar C), 130.5 (d, Ar
C), 92.5 (d, C-1), 77.4, 75.4, 74.4, 72.3 (each d, C2-5), 38.3 (N
CH3); ES-HRMS found 341.0666, required 341.0653 [M - H]-.
1-Azido-1-deoxy-â-D-glucopyranuronic Acid, N-Meth-
yl-p-bromophenylamide 26c. Compound 26c: 1H NMR data
(300 MHz, D2O) δ 7.66 (d, 2H, J ) 8.5, Ar H), 7.23 (d, 2H, J )
8.6, Ar H), 4.40 (d, 1H, J1,2 ) 8.5, H-1), 3.88 (d, 1H, J4,5 ) 9.6,
H-5), 3.70 (t, 1H, J3,4 ) 9.2, J4,5 ) 9.6, H-4), 3.25 (s, 3H, N
CH3), 3.23 (m, 2H, H-2 and H-3); 13C NMR (75 MHz, D2O) δ
169.2 (s, CONCH3), 141.1 (s, Ar C), 133.3 (d, Ar C), 129.2 (d,
Ar C), 122.4 (s, Ar C), 90.2 (d, C-1), 72.1, 71.1, 70.4, 69.5 (each
d, C2-5), 37.8 (NCH3); ES-HRMS found 385.0139, required
385.0148 [M - H]-.
1-Azido-1-deoxy-r-D-glucopyranuronic Acid, N-Meth-
yl-p-bromophenylamide 27c. Compound 27c: 1H NMR data
(300 MHz, D2O) δ 7.69 (d, 2H, J ) 8.8, Ar H), 7.24 (d, 2H, J )
8.8, Ar H), 5.43 (d, 1H, J1,2 ) 4.2, H-1), 4.17 (d, 1H, J4,5 ) 9.7,
H-5), 3.66 (t, 1H, J3,4 ) 9.4, J4,5 ) 9.7, H-4), 3.58 (dd, 1H, J2,3
) 9.67, H-2), 3.29 (t, 1H, H-3), 3.25 (s, 3H, N CH3); 13C NMR
(75 MHz, D2O) δ 168.4 (s, CONCH3), 133.3 (d, Ar C), 90.6 (d,
C-1), 75.0, 73.5, 72.5, 70.9 (each d, C2-5), 37.9 (N CH3); ES-
HRMS found 385.0139, required 385.0148 [M - H]-.
2,3,4-Tri-O-acetyl-1-azido-1-deoxy-r/b-D-glucopyranu-
ronic Acid, p-Methoxycarbonylphenylamide 25f/24f.
R-Anomer 25f and â-anomer 24f: 1H NMR data for the
R-anomer (300 MHz, CDCl3) δ 8.17 (s, 1H, NH), 8.01 (d, 2H, J
1-Azido-1-deoxy-r/b-D-glucopyranuronic Acid, N-Meth-
yl-p-methylphenylamide 27d/26d. R-Anomer 27d and â-a-
nomer 26d (E isomer): 1H NMR data for the R-anomer (300
MHz, D2O, E isomer) δ 7.34 (d, 2H, J ) 8.2. Ar H), 7.18 (d,
2H, J ) 8.4, Ar H), 5.42 (d, 1H, J1,2 ) 4.4, H-1), 4.20 (d, 1H,
J4,5 ) 9.8, H-5), 3.65 (t, 1H, J3,4 ) 9.5, J4,5 ) 9.8, H-4), 3.57 (dd,
1H, J2,3 ) 9.7, H-2), 3.26 (t, 1H, H-3), 3.25 (s, 3H, N CH3), 2.33
) 8.7, Ar H), 7.57 (d, 2H, J ) 8.7, Ar H), 5.78 (d, 1H, J1,2
)
4.1, H-1), 5.50 (t, 1H, J2,3 ) 10.0, J3,4 ) 9.8, H-3), 5.21 (t, 1H,
J3,4 ) 9.8, J4,5 ) 10.2, H-4), 4.96 (dd, 1H, H-2), 4.52 (d, 1H,
H-5), 3.90 (s, 3H, COOCH3), 2.12, 2.10, 2.04 (each s, each 3H,
1
1
each COCH3); selected H NMR data for the â-anomer δ 8.21
(s, 3H, CH3 ); selected H NMR data for the â-anomer δ 4.38
(s, 1H, NH), 4.88 (d, 1H, J1,2 ) 8.7, H-1), 4.17 (d, 1H, J4,5
)
(d, 1H, J1,2 ) 8.3, H-1), 3.88 (d, 1H, J4,5 ) 9.7, H-5); 13C NMR
for the R-anomer (75 MHz, MeOH-d4) δ 168.7 (s, CONCH3),
140.0 (s, Ar C), 138.2 (s, Ar C), 129.9 (d, Ar C), 126.9 (d, Ar
C), 91.0 (d, C-1), 72.6, 71.1, 71.0, 69.6 (each d, C2-5), 36.8
(NCH3), 19.7 (Ar CH3); ES-HRMS found 321.1184, required
321.1199 [M - H]-.
9.5, H-5); 13C NMR for the R-anomer (125 MHz, CDCl3) δ 170.2,
169.9, 169.8 (each s, each COCH3), 166.6 (s, COOCH3), 164.7
(s, CONH), 140.9 (s, Ar C), 131.0 (d, Ar C), 126.7 (s, Ar C),
119.7 (d, Ar C), 88.4 (d, C-1), 70.4, 70.2, 69.3, 68.8 (each d,
C2-5), 52.2 (s, COOCH3), 20.8, 20.8, 20.7 (each s, each
COCH3); selected 13C NMR for the â-anomer δ 170.0, 169.8,
169.4 (each s, each COCH3), 166.6 (s, COOCH3) 164.1 (s,
CONH), 140.7 (s, Ar C), 126.8 (s, Ar C), 119.9 (d, Ar C), 86.3
(d, C-1), 74.8, 71.9, 70.7, 69.2 (each d, C2-5), 20.8, 20.7, 20.7
(each q, each COCH3); FTIR (CH2Cl2 solution on NaCl plates)
3341, 2957, 2122, 1754, 1719, 1603, 1531, 1436, 1410, 1370,
1283, 1047, cm-1; ES-HRMS found 477.1264, required 477.1258
[M - H]-.
1-Azido-1-deoxy-r/b-D-glucopyranuronic Acid, N-Meth-
yl-p-methoxyphenylamide 27e/26e. R-Anomer 27e and
â-anomer 26e (E isomer): 1H NMR data for the R-anomer (300
MHz, D2O, E isomer) δ 7.24 (d, 2H, J ) 8.9, Ar H), 7.05 (d,
2H, J ) 9.0, Ar H), 5.40 (d, 1H, J1,2 ) 4.2, H-1), 4.16 (d, 1H,
J4,5 ) 9.7, H-5), 3.80 (s, 3H, OCH3), 3.67 (t, 1H, J3,4 ) 9.7, J4,5
) 9.7, H-4), 3.57 (dd, 1H, J2,3 ) 9.7, H-2), 3.28 (t, 1H, H-3),
1
3.23 (s, 3H, N CH3); selected H NMR data for the â-anomer
δ 4.37 (d, 1H, J1,2 ) 8.4, H-1), 3.88 (d, 1H, J4,5 ) 9.6, H-5); 13
C
1-Azido-1-deoxy-r/b-D-glucopyranuronic Acid, N-Me-
thyl-p-fluorophenylamide 27a/26a. R-Anomer 27a and
â-anomer 26a: 1H NMR data for the R-anomer (300 MHz, D2O)
δ 7.4-7.2 (m, 4H, Ar H), 5.43 (d, 1H, J1,2 ) 4.4, H-1), 4.16 (d,
1H, J4,5 ) 9.8, H-5), 3.67 (t, 1H, J3,4 ) 9.4, J4,5 ) 9.8, H-4),
3.58 (dd, 1H, J2,3 ) 9.7, H-2), 3.29 (t, 1H, H-3), 3.25 (s, 3H,
N-CH3); selected 1H NMR data for the â-anomer δ 4.41 (d,
1H, J1,2 ) 8.5, H-1), 3.89 (d, 1H, J4,5 ) 9.6, H-5); 13C NMR for
the R-anomer (75 MHz, D2O) δ 170.0 (s, CONCH3), 164.6 (s,
Ar C), 140.2, 140.2 (each d, each Ar C, J ) 7.0), 130.9, 130.8
(each d, each Ar C, J ) 8.7), 117.6, 117.4 (each d, each Ar C,
J ) 23.1), 92.5 (d, C-1), 74.1, 72.6, 72.5, 71.0 (each d, C2-5),
38.2 (N CH3); 13C NMR data for the â-anomer δ 169.0 (s,
CONCH3), 162.6 (s, Ar C), 130.8 (d, Ar C), 77.3, 75.2, 74.2,
NMR for the R-anomer (75 MHz, MeOH-d4) δ 171.6 (s,
CONCH3), 162.2 (s, Ar C), 137.9 (s, Ar C), 131.0 (d, Ar C), 117.2
(d, Ar C), 93.8 (d, C-1), 75.3, 73.8, 73.7, 72.2 (each d, C2-5),
57.3 (O CH3), 39.5 (N CH3); 13C NMR data for the â-anomer δ
173.0 (s, CONCH3), 170.5 (s, Ar C), 137.8 (s, Ar C), 132.1 (d,
Ar C), 118.7 (d, Ar C), 94.0 (d, C-1), 78.6, 76.5, 75.5, 73.3 (each
d, C2-5); ES-HRMS found 337.1162, required 337.1148 [M -
H]-.
1-Azido-1-deoxy-â-D-glucopyranuronic Acid, N-Meth-
yl-p-methoxycarbonylphenylamide 26f. Compound 26f:
1H NMR (300 MHz, D2O) δ 4.39 (d, 1H, J1,2 ) 8.5, H-1), 3.90
(s, 3H, COOCH3), 3.88 (d, 1H, J4,5 ) 9.5, H-5), 3.71 (t, 1H, J3,4
) 9.1, J4,5 ) 9.5, H-4), 3.29 (s, 3H, N CH3), 3.22 (m, 2H, H-2
J. Org. Chem, Vol. 70, No. 10, 2005 4105