L. Kro¨ger, J. Thiem / Carbohydrate Research 342 (2007) 467–481
479
3.12. (3-Fluoro-4-nitrophenyl) b-D-galactopyranoside (16)
3.16.1. (3-Acetoxymethyl-4-nitrophenyl) 2,3,4,6-tetra-O-
acetyl-b-D-galactopyranoside (22). White crystals: mp
20
According to GP2. Crystallization from MeOH gave the
137 ꢁC; ½aꢀD +7.4 (c 0.2, CHCl3); MALDI-TOFMS:
20
product as yellowish crystals: mp 174 ꢁC; ½aꢀD ꢁ81 (c 0.6,
m/z 564.3 [M+Na]+, 580.2 [M+K]+.
MeOH); MALDI-TOFMS: m/z 342.1 [M+Na]+, 358.0
[M+K]+. Anal. Calcd for C12H14FNO8: C, 45.15; H,
4.42; N, 4.39. Found: C, 45.36; H, 4.63; N, 4.40.
3.16.2. (3-Hydroxymethyl-4-nitrophenyl) 2,3,4,6-tetra-O-
acetyl-b-D-galactopyranoside (23). White crystals: mp
20
156 ꢁC; ½aꢀD ꢁ3.5 (c 0.25, CHCl3); MALDI-TOFMS:
3.13. (5-Fluoro-2-nitrophenyl) b-D-galactopyranoside (17)
m/z 522.1 [M+Na]+, 538.0 [M+K]+.
According to GP2. Crystallization from MeOH gave the
3.17. (3-Hydroxymethyl-4-nitrophenyl) b-D-galacto-
pyranoside (24)
20
product as yellowish crystals: mp 151 ꢁC; ½aꢀD ꢁ89 (c 0.7,
MeOH); MALDI-TOFMS: m/z 342.2 [M+Na]+, 358.1
[M+K]+. Anal. Calcd for C12H14FNO8: C, 45.15; H,
4.42; N, 4.39. Found: C, 45.32; H, 4.63; N, 4.36.
By deprotection of 22 according to GP2. FC (ethyl acet-
ate/MeOH 6:1).
By deprotection of 23 according to GP2. FC (6:1
20
3.14. (3,4-Methylenedioxyphenyl) b-D-galactopyranoside
EtOAc–MeOH). Glass; ½aꢀD ꢁ11 (c 0.13, MeOH);
(18)27
MALDI-TOFMS: m/z 354.1 [M+Na]+, 370.1 [M+K]+.
According to GP2 at 0 ꢁC. Crystallization from MeOH
3.18. Methyl 5-nitrosalicylate (27)28
20
gave the product as a glass: ½aꢀD +19 (c 0.3, DMSO).
5-Nitrosalicylic acid (9.16 g, 50.0 mmol) and Amberlite
IR-120 (4 g, H+-form) were stirred in MeOH (80 mL)
for 7 days. The ion-exchange resin was removed by fil-
tration and the filtrate concentrated to dryness. The res-
idue was dissolved in CHCl3 and washed with satd aq
NaHCO3 soln and water. After drying with magnesium
sulfate, the solvent was removed to give 27 as yellow
needles (8.39 g, 85%): mp 116 ꢁC, lit.28 117 ꢁC; 1H
NMR (400 MHz, DMSO): d 8.72 (d, 1H, J4,6 2.5 Hz,
H-6), 8.36 (dd, 1H, J3,4 9.2 Hz, H-4), 7.13 (d, 1H, H-
3), 4.03 (s, 3H, CH3); 13C NMR (100.6 MHz, Me2SO):
d 170.22 (CO2CH3), 167.15 (C-2), 141.39 (C-5), 131.42
(C-4), 127.44 (C-6), 119.64 (C-3), 113.84 (C-1), 53.63
(CO2CH3).
3.15. 1,2-Bis-(2,3,4,6-tetra-O-acetyl-b-D-galactopyrano-
syl)-4-nitrobenzene (20)
According to GP1. FC (2:1 light petroleum (50–70)–
EtOAc) gave the product as white crystals: mp 211 ꢁC
20
1
(decomp.); ½aꢀD ꢁ32 (c 1, CHCl3); H NMR (400 MHz,
CDCl3): d 7.99 (d, 1H, JAr-3,5 2.5 Hz, Ar-3), 7.90 (dd,
1H, JAr-5,6 9.2 Hz, Ar-5), 7.11 (d, 1H, Ar-6), 5.44–5.42
(m, 2H, H-4, H-40), 5.40 (dd, 1H, J1 ;2 7:6 Hz,
0
0
J2 ;3 10:2 Hz, H-20), 5.38 (dd, 1H, J1,2 7.6 Hz, J2,3
10.7 Hz, H-2), 5.16 (d, 1H, H-10), 5.10 (d, 1H, H-1),
5.08 (dd, 1H, J3,4 3.6 Hz, H-3), 5.07 (dd, 1H,
0
0
J3 ;4 3:6 Hz, H-30), 4.17–4.06 (m, 5 H, H-6a,b, H-50, H-
60a,b), 4.04 (vt, 1H, J5,6a = J5,6b 7.1 Hz, H-5), 2.13,
2.12, 2.05, 2.04, 2.02, 2.00, 1.95, 1.94 (8s, 24H, 8COCH3);
13C NMR (100.6 MHz, CDCl3): d 169.65, 169.21,
169.13, 169.05, 168.99, 168.37, 167.84, 167.76 (8C,
8COCH3), 150.76 (Ar-1), 145.75 (Ar-2), 142.20 (Ar-4),
118.45 (Ar-5), 115.77 (Ar-6), 112.11 (Ar-3), 98.96 (C-1),
98.37 (C-10), 70.97 (C-50), 70.61 (C-5), 69.68 (C-3),
69.66 (C-30), 67.48 (C-2), 67.40 (C-20), 66.14 (C-40),
65.86 (C-4), 60.91 (C-60), 60.27 (C-6), 19.64, 19.61,
19.60, 19.58, 19.56, 19.55, 19.53, 19.52 (8C, 8COCH3);
MALDI-TOFMS: m/z 838.6 [M+Na]+, 854.5 [M+K]+.
Anal. Calcd for C34H41NO22: C, 50.06; H, 5.07; N,
1.72. Found: C, 48.49; H, 5.01; N, 1.88.
0
0
3.19. Methyl 4-hydroxy-3-nitrobenzoate (30)29
4-Hydroxy-3-nitrobenzoic acid (11.0 g, 60.1 mmol) and
Amberlite IR-120 (5 g, H+-form) were stirred in MeOH
(100 mL) for 7 days. The reaction mixture was worked
up as described above to give 30 as yellow rhombic crys-
tals (11.0 g, 93%): mp 76 ꢁC, lit.29 117 ꢁC; 1H NMR
(400 MHz, MeOD): d 8.62 (d, 1H, J2,6 2.6 Hz, H-2),
8.15 (dd, 1H, J5,6 9.2 Hz, H-6), 7.20 (d, 1H, H-5), 3.91
(s, 3H, CH3); 13C NMR (100.6 MHz, MeOD): d
166.80 (CO2CH3), 158.87 (C-4), 138.09 (C-6), 136.46
(C-3), 128.56 (C-2), 123.65 (C-1), 121.53 (C-5), 53.32
(CO2CH3).
3.16. (3-Acetoxymethyl-4-nitrophenyl) 2,3,4,6-tetra-O-
acetyl-b-D-galactopyranoside (22) and (3-hydroxymethyl-
4-nitrophenyl) 2,3,4,6-tetra-O-acetyl-b-D-galactopyran-
oside (23)
3.20. (2-Formyl-4-nitrophenyl) 2,3,4,6-tetra-O-acetyl-b-
D-galactopyranoside (31)
According to GP1. FC (2:1 light petroleum (50–70)–
According to GP1. The products were separated by FC
(CH2Cl2/acetone 30:1).
EtOAc) gave the product as white crystals: mp 178 ꢁC;
20
½aꢀD ꢁ23 (c 0.5, CHCl3); MALDI-TOFMS: m/z 520.1