M. A. E. Sallam / Carbohydrate Research 345 (2010) 2233–2238
2237
4.5. 2-Phenyl-4-(1,2,3,4-tetra-O-acetyl-5-chloro-5-deoxy-
manno-pentitol-1-yl)-2H-1,2,3-triazole (10)
D
-
68 (11, furan), 59 (57, CH3COO), 58 (28, CH3COCH3), and 43 (72,
CH3CO), HRMS [M]+ calcd for C16H19NaN3: m/z 340.1273; found,
m/z 340.1273.
Compound 9 (10 mg) was treated with a 1:1 mixture of pyri-
dine–Ac2O (2 mL) and kept overnight at room temperature. The
mixture was processed as described for compound 8. It gave a
colorless syrup. Rf 0.29 (solvent C). For 1H NMR spectral data see
Table 1; EIMS (selected ions): m/z 484 (0.1, 37MH), 483 (0.3,
37M), 482 (0.2, 35MH), 481 (0.7, 35M), 422 (0.2, MꢀOAc), 319 (7,
MꢀAcOꢀAcOHꢀAc), 277 (6, MꢀAcOꢀAcOHꢀ2 Ac), 258 (8), 217
(6, BCHOHCH2CHO), 216 (12, BCHOHCH2CO), 187 (3, BCH2CHO),
174 (21, BCHOH), 173 (3, BCHO), 145 (1, BH), 144 (0.2, B), 103 (3,
BꢀHCN), 91 (6, PhN), 77 (5, Ph), and 43 (100, CH3CO); HREIMS
[M]+ calcd for C21H2435ClN3O8: m/z 481.1252; found, m/z 481.1239.
4.9. 4-(1-O-Acetyl-2,5-anhydro-3,4-O-isopropylidene-
manno-pentitol-1-yl)-2-phenyl-2H-1,2,3-triazole (6)
D-
Compound 5 (10 mg) was acetylated with a 1:1 mixture of pyr-
idine–Ac2O (2 mL) for 24 h. The mixture was worked up as de-
scribed for 8 to give a syrup that was purified on a short column
(1 ꢁ 10 cm) of silica gel using solvent A as an eluent, giving 6 as
a colorless syrup, (yield 15 mg). For 1H and 13C NMR data see
Tables 1 and 2; EIMS (selected ions): m/z 360 (27, MH), 359
(45, M), 344 (36, MꢀCH3), 300 (46, MꢀOAc), 299 (37, MꢀAcOH),
284 (7, MꢀCH3ꢀAcOH), 256 (23, MꢀAcOHꢀAc), 242 (39,
MꢀCH3COCH3ꢀOAc), 240 (20, MꢀAcOHꢀOAc), 224 (20,
MꢀCH3COCH3ꢀOAcꢀH2O), 187 (10, BCHCHOH), 175 (23, BCH2OH),
174 (100, BCHOH), 173 (21, BCHO), 172 (19, BCO), 158 (14, BCH2),
14 (8, B), 143 (65, BꢀH), 91 (29, PhN), 85 (24), 77 (29, ph), 69 (28,
protonated furan), and 68 (4, Furan); HRMS [M]+ calcd for
4.6. 4-(2,5-Anhydro-D-manno-pentitol)-2-phenyl-2H-1,2,3-
triazole (3)
Compound 3 was eluted from the column after compound 9
(solvent A). Fractions 10–30, which were identical, were collected
and evaporated to dryness to give a colorless syrup, (yield
C18H21N3NaO5: m/z 382.1379; found, m/z 382.1373.
270 mg, 54%); Rf 0.23 (B). ½a D20
ꢂ
+3.5 (c 1.12, MeOH). For 1H and
13C NMR data see Tables 1 and 2; EIMS: m/z 278 (13, MH), 277
(4, M), 260 (12, MꢀOH), 200 (10, MꢀPh), 188 (14, BHCH2CHO),
176 (17, BHCH2OH), 175 (100, BCH2OH), 174 (90, BCHOH), 173
(97, BCHO), 172 (10, BCO), 158 (11, BCH2), 146 (5, BH2), 145 (2,
BH), 117 (6, BꢀHCN), 103 (9, MꢀCHOH), 92 (1, PhNH), 91 (48,
PhN), 86 (74, MꢀBCHOHꢀOH), and 77 (41, Ph); HRMS [M]+ calcd
for C13H15N3NaO4: m/z 300.0967; found, m/z 300.0967.
4.10. 4-( -Arabinopyranosyl)-2-phenyl-2H-1,2,3-triazole (11)
a-D
Compound 11 was eluted in the last fractions of the silica gel
column after elution of compound 3. Identical fractions 32–55
were collected and evaporated to dryness giving a colorless syrup
(yield 16 mg; 3%): Rf 0.09 (solvent B). Recrystallization from
MeOH–toluene gave colorless needles: mp 130–132 °C (lit2,21 mp
134–135 °C).
4.7. 4-(1,3,4-Tri-O-acetyl-2,5-anhydro-D-manno-pentitol-1-yl)-
2-phenyl-2H-1,2,3-triazole (4)
4.11. 4-(1,2,3,4,5-Penta-O-acetyl-D-manno-pentitol-1-yl)-2-
phenyl-2H-1,2,3-triazole (2)
Compound 3 (10 mg) was acetylated with a 1:1 mixture of pyr-
idine–Ac2O (2 mL) for 24 h at room temperature. The reaction mix-
ture was worked up as described for 8 and purified on a short
column (1 ꢁ 10 cm) by eluting with solvent C to give a colorless
syrup (yield 15 mg); Rf 0.44 (C). For 1H and 13C NMR data see
Tables 1 and 2); EIMS (selected ions): m/z 404 (3, MH), 403 (1,
M), 241 (14, MꢀOAcꢀAcOHꢀAc), 216 (5, BCHOAc), 188 (11,
BHCH2CHO), 187 (100, BCH2CHO), 174 (10, BCHOH), 173 (11,
BCHO), 127 (28, MꢀBCHOAcꢀAcOH), 91 (12, PhN), 85 (48,
MꢀBCHOAcꢀAcOHꢀCH2CO), 77 (9, Ph), 68 (12), and 43
(85,CH3CO); HRCIMS [M]+ calcd for C19H21N3O7: m/z 403. 1379;
found, m/z 403. 1373.
Compound 2 was prepared by acetylation of 1 (50 mg) with a
1:1 mixture of Ac2O–pyridine (4 mL) for 48 h at room temperature.
The solution was processed as described for 10 to give a colorless
syrup (yield 70 mg) that was recrystallized from EtOAc–hexane
as colorless elongated plates mp 114–116 °C, [
a
]
ꢀ4.5 (c 1.02,
D
CHCl3), (Lit22 mp 115–116 °C, [
a
]
D
ꢀ5 (c 0.96 CHCl3).
Acknowledgment
The author thanks Professor J.R. Parquette, Department of
Chemistry, The Ohio State University, USA for the high-resolution
mass spectra.
4.8. 4-(2,5-Anhydro-3,4-O-isopropylidene-D-manno-pentitol-
1-yl)-2-phenyl-2H-1,2,3-triazole (5)
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Compound 3 (25 mg) was dissolved in dry acetone (30 mL) and
treated with p-toluenesulfonic acid (12 mg). The mixture was kept
at room temperature for 48 h with monitoring of the reaction by
TLC. The mixture was then poured onto an ice-cold, saturated solu-
tion of sodium hydrogen carbonate and extracted with CHCl3, and
the organic layer was washed with water, dried over anhyd MgSO4,
and evaporated to dryness to give a colorless syrup that was puri-
fied by chromatography on PLC silica gel plates, eluting with sol-
vent A. The more mobile spot was scraped off the plate and
extracted with EtOAc. The solvent was evaporated, giving a chro-
matographically pure syrup; (yield 19 mg); Rf 0.64 (B). For 1H
and 13C NMR data see Tables 1 and 2; EIMS (selected ions); m/z
318 (50, MH), 317 (21, M), 302 (18, MꢀCH3) 300 (25), 242 (20,
MꢀCH3ꢀAcOH), 224 (11), 187 (4, BCHCHOH), 175 (70, BCHOH),
174 (100, BCHOH), 173 (26, HCHO), 145 (9, BH), 144 (68, B), 143
(27), 126 (62), 92 (22, PhNH), 91 (35, phN), 86 (90,
MHꢀBCHOHꢀCH3COCH3), 77 (35, Ph), 69 (60, protonated furan),