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off. Next, the solvent was removed under reduced pressure
and the product was precipitated with distilled water. The
crude product was either extracted in a Soxhlet apparatus
using diethyl ether (A1, A2) or purified with ethanol (A3).
extracted in a Soxhlet apparatus using diethyl ether, whereas
ethanol was used for the diacetals (A5, A6).
20-(Hydroxymethyl)phenyl 4,6-O-salicylidene-b-D-
glucopyranoside (A4)
Methyl 4,6-O-benzylidene-a-D-glucopyranoside (A1) was pre-
1H NMR (300 MHz, DMSO-d6, d): 3.35–3.80 (m, 5H, H-2,
ACH2-OH, H-4, H-5, H-6), 4.19 (dd, 1H, J 5 8.5 Hz, J 5 3.2 Hz,
H-6), 4.48 (dd, 1H, J 5 14.5 Hz, J 5 6.3 Hz, ACH2AOH), 4.65
(dd, 1H, J 5 14.5 Hz, J 5 5.5 Hz, ACH2AOH), 4.96–5.06 (m,
2H, Han, H-3), 5.39 (d, 1H, J 5 5.3 Hz, AOH), 5.61 (d, 1H,
J 5 5.1 Hz, AOH), 5.81 (s, 1H, AOCHOA), 6.81 (dd, 2H,
J 5 13.1 Hz, J 5 7.3 Hz, HC, HE); 7.02 (t, 1H, J 5 7.3 Hz, HD),
7.08–7.25 (m, 3H, HL, HJ, HK), 7.38 (d, 2H, J 5 7.6 Hz, HF, HI),
9.56 (s, 1H, ArAOH); 13C NMR (75 Hz, DMSO-d6, d): 58.0
(ACH2OH), 65.8 (C-6), 67.9 (C-5), 72.6 (C-4), 74.1 (C-2), 80.5
(C-3), 96.5 (C-1), 101.3 (AOCHOA), 114.5 (CL), 115.3 (CC),
118.5 (CE), 121.8 (CJ), 123.8 (CA), 127.1 (CI), 127.2 (CK),
127.5 (CF), 129.7 (CD), 131.5 (CH), 154.1 (CB), 154.3 (CG).
Anal. calcd: C 61.53, H 5.68, O 32.78; found: C 61.17, H 5.84.
pared according to a procedure described in the literature.26
1H NMR (300 MHz, DMSO-d6, d): 3.33–3.40 (m, 4H, AOCH3,
H-2), 3.50–3.75 (m, 4H, H-3, H-4, H-5, H-6), 4.17 (dd, 1H,
J 5 4.5 Hz, J 5 9.6 Hz, H-6), 4.63 (d, 1H, J 5 3.6 Hz, Han), 5.04
(d, 1H, J 5 6.9 Hz, AOH), 5.21 (d, 1H, J 5 5.1 Hz, AOH), 5.57
(s, 1H, AOCHOA), 7.36–7.38 (m, 3H, HC,D), 7.43–7.46 (m, 2H,
HB); 13C NMR (75MHz, DMSO-d6, d): 54.7 (AOCH3), 62.3
(C-6), 68.1 (C-5), 69.8 (C-4), 72.3 (C-2), 81.3 (C-3), 100.5 (C-
1), 100.8 (AOCHOA), 126.3 (CB), 127.9 (CC), 128.7 (CA),
137.7 (CD). Anal. calcd: C 59.57, H 6.43, O 34.01; found:
C 59.57, H 6.04.
Methyl 4,6-O-salicylidene-a-D-glucopyranoside (A2)
1H NMR (300 MHz, DMSO-d6, d): 3.33–3.41 (m, 5H, H-2, H-6,
AOCH3), 3.50-3.69 (m, 3H, H-3, H-4, H-5), 4.12 (dd, 1H,
J 5 3.6 Hz, J 5 8.6 Hz, H-6), 4.63 (d, 1H, J 5 3.6 Hz, Han), 4.99
(d, 1H, J 5 5.7 Hz, AOH), 5.13 (d, 1H, J 5 4.8 Hz, AOH), 5.78
(s, 1H, AOCHOA), 6.79 (dd, 2H, J 5 7.7 Hz, J 5 6.4 Hz, HC,
HE), 7.16 (t, 1H, J 5 7.7 Hz, HD), 7.36 (d, 1H, J 5 6.4 Hz, HF),
9.56 (s, 1H, ArAOH); 13C NMR (75MHz, DMSO-d6, d): 54.7
(AOCH3), 62.5 (C-6), 68.4 (C-5), 69.9 (C-4), 72.4 (C-2), 81.6
(C-3), 99.6 (C-1), 100.5 (AOCHOA), 115.3 (CC), 118.6 (CE),
124.0 (CA), 127.4 (CF), 129.7 (CD), 154.3 (CB). Anal. calcd: C
56.37, H 6.08, O 37.54; found: C 56.73, H 6.32.
4,6:40,60-O-Terephtalidene-bis-[200-(hydroxymethyl)phenyl
b-D-glucopyranoside] (A5)
1H NMR (300 MHz, DMSO-d6, d): 3.40–3.80 (m, 10H, H-2, H-4,
H-5, H-6; ACH2OH), 4.24 (dd, 2H, J 5 9.4 Hz, J 5 4.3 Hz, H-6),
4.48 (dd, 2H, J 5 14.5 Hz, J 5 6.1 Hz, ACH2AOH), 4.65 (dd,
2H, J 5 14.4 Hz, J 5 5.4 Hz, ACH2AOH), 5.04 (m, 4H, Han, H-
3), 5.48 (d, 2H, J 5 5.0 Hz, AOH), 5.63 (s, 2H, AOCHOA), 5.68
(d, 2H, J 5 5.3 Hz, AOH), 7.03 (t, 2H, J 5 7.3 Hz, HJ), 7.11 (d,
2H, J 5 8.0 Hz, HL), 7.22 (t, 2H, J 5 7.6 Hz, HK), 7.39 (d, 2H,
J 5 7.3 Hz, HI), 7.48 (s, 4H, HB); 13C NMR (75 Hz, DMSO-d6,
d): 58.1 (ACH2OH), 65.8 (C-6), 67.9 (C-5), 72.7 (C-4), 74.3 (C-
2), 80.4 (C-3), 100.4 (C-1), 101.5 (AOCHOA), 114.8 (CH),
122.0 (CL), 126.1 (CB), 127.2 (CA), 127.7 (CJ), 131.7 (CI), 138.3
(CK), 154.2 (CG); ESI-MS (m/z): calcd for C34H38O14 608.6;
found for [M1H]1 609.3, [M1Na]1 631.6. Anal. calcd: C
60.89, H 5.96, O 33.40; found: C 61.27, H 5.96.
4,6:40,60-O-Terephtalidene-bis-(methyl
a-D-glucopyranoside)
(A3) was prepared according to a procedure described in
the literature.26
1H NMR (300 MHz, DMSO-d6, d): 3.35–3.46 (m, 10H, H-2,
H-3, AOCH3), 3.51–3.63 (m, 4H, H-5, H-6), 3.65 (t, 2H,
J 5 9.9 Hz, J 5 13.2 Hz, H-4), 4.16 (dd, 2H, J 5 4.5 Hz, J 5 9.6
Hz, H-6), 4.63 (d, 2H, J 5 3.6 Hz, Han), 5.03 (d, 2H, J 5 6.6 Hz,
AOH), 5.19 (d, 2H, J 5 5.1 Hz, AOH), 5.58 (s, 2H, AOCHOA),
7.45 (s, 4H, HAr); 13C NMR (75 MHz, DMSO-d6, d): 54.7
(AOCH3), 62.3 (C-6), 68.2 (C-5), 69.9 (C-4), 72.4 (C-2), 81.3
(C-3), 100.5 (C-1, AOCHOA), 126.06 (CB), 138.32 (CA);
5,50-Methylene-bis-[200-(hydroxymethyl)phenyl
4,6-O-salicylidene-b-D-glucopyranoside] (A6)
1H NMR (300 MHz, DMSO-d6, d): 3.35–3.88 (m, 12H, H-2,
H-3, H-4, H-6, ACH2OH), 4.17 (d, 2H, J 5 4.9 Hz, H-5), 4.47
(dd, 2H, J 5 14.6 Hz, J 5 4.2 Hz, ACH2OH), 4.64 (dd, 2H,
J 5 14.2 Hz, J 5 2.9 Hz, CH2OH), 4.95–5.15 (m, 4H, J 5 7.7 Hz,
Han, ACH2A), 5.39 (d, 2H, J 5 4.8 Hz, AOH), 5.61 (d, 2H,
J 5 4.7 Hz, AOH), 5.78 (s, 2H, AOCHOA), 6.75 (d, 4H, J 5 8.3
Hz, HC, HE), 6.92–7.30 (m, 8H, HD, HL, HJ, HK), 7.38 (d, 4H,
J 5 7.5 Hz, HF, HI), 9.56 (s, 2H, ArAOH); 13C NMR (75MHz,
DMSO-d6, d): 58.0 (CH2OH), 65.7 (C-6), 67.9 (C-5), 72.5
(C-4), 74.1 (C-2), 80.6 (C-3), 96.6 (C-1), 101.3 (–OCHO–),
114.5 (CL), 115.2 (CC), 121.8 (CJ), 123.6 (CA), 127.1 (CI),
127.5 (CK), 130.0 (CE), 131.5 (CH), 131.6 (CF, CD), 152.5 (CB),
154.1 (CG); ESI-MS (m/z): calcd for C41H44O16 792.8; found
for [M1Na]1 815.4. Anal. calcd: C 62.12, H 5.59, O 32.29;
found: C 61.86, H 5.96.
ESI-MS (m/z): calcd for
C22H30O12, 486.5; found for
[M12DMF1H]1 650.5. Anal. calcd: C 54.32, H 6.22, O 39.46;
found: C 53.92, H, 6.31.
Synthesis of Acetal Derivatives of Salicin (A4, A5, A6)
A mixture of monosaccharide salicin and monoaldehyde SLA
(20.0:20.0 mmol; 1:1) or dialdehydes TPhA (17.5:8.7 mmol;
2:1) and MBSA (9.0:4.0 mmol; 2:1) in benzene/DMSO contain-
ing catalyst Amb15 (7/7 mL/mL and 0.6 g for A4, 35/16 mL/
mL and 0.2 g for A5, and 15/13 mL/mL and 0.2 g for A6) was
placed in a round-bottom flask equipped with a magnetic
stirrer. Further procedures were similar to those described
above for monoacetals, with the exception of the deactivation
of the catalyst, which was omitted. The monoacetal (A4) was
Synthesis of Bromoester Functionalized Acetal
Derivatives of MeaDGlu (I1, I2, I3) and Salicin (I4, I5, I6)
The acetals A1 and A3 (1.0 g of each) were dissolved in PYR,
A2 and A4 in CH2Cl2, and diacetals A5 and A6 in
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