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P. Potier et al. / Tetrahedron: Asymmetry 12 (2001) 2409–2419
1
Pure sucrose 1%-O-monodecanoate 8a: H NMR (D2O,
500 MHz): l 5.42 (d, 1H, J1-2=2.94 Hz, H1); 4.34 (d,
1H, J1%a-b=12.07 Hz, H1%a); 4.15–4.12 (3H, H1%b, H3%,
H4%); 3.85–3.72 (7H, H5, H6%a,b, H6a,b, H5%, H3); 3.54
(dd, 1H, J1-2=3.17, J2-3=9.97 Hz, H2); 3.47 (t, 1H,
CO); 13.5 (1CH3); Anal. calcd for C24H44O12·H2O: C,
53.1; H, 8.6. Found: C, 53.2; H, 8.7%; [h]2D0=+51 (c 1,
MeOH); SMHR (FAB+) m/z calcd (M+Na) 547.2730,
1
found 547.2718. Sucrose 6%-O-monolaurate 5: H NMR
(D2O, 500 MHz): l 5.37 (d, 1H, J1-2=3.81 Hz, H1);
4.40 (dd, 1H, J6%a-b=11.69 Hz, J6%a-5=7.79 Hz, H6%a);
4.34 (d, 1H, J6%a-b=11.71 Hz, J6%b-5=7.79 Hz, H6%b);
J
3-4=J4-5=9.49 Hz, H4); 2.39 (t, 2H, J=7.04 Hz, CO-
CH2); 1.61 (m, 2H, CO-CH2CH2); 1.28 (m, 12H, 6
CH2); 0.86 (t, 3H, J=6.34 Hz, CH3); 13C NMR (D2O,
125 MHz): l 174.73 (1C, CO); 102.79 (1C, C2%); 93.04
(1CH, C1); 82.11 (1CH, C5%); 77.0 (1CH, C3%); 73.17
(1CH, C4%); 72.95 (1CH, C5); 72.91 (1CH, C3); 71.3
(1CH, C2); 69.50 (1CH, C4); 62.60 (1CH2, C1%); 61.80
(1CH2, C6%); 60.50 (1CH2, C6); 34.26 (1CH2, CH2-CO);
32.36, 30.07, 29.85, 29.61, 23.04 (6CH2); 25.10 (1CH2,
CH2CH2-CO); 14.24 (1CH3); Anal. calcd for
C22H40O12·1.4H2O: C, 50.6; H, 8.3. Found: C, 50.9; H,
8.1%; [h]2D0=+52 (c 1, MeOH); SMHR (FAB+) m/z
calcd (M+Na) 519.2417, found 519.2419.
4.12 (d, 1H, J3%-4%=8.20 Hz, H3%); 4.03 (t, 1H, J4%-3%
=
8.08 Hz, H4%); 3.95 (m, 1H, H5%); 3.84 (m, 2H, H6a,
H5); 3.72 (m, 2H, H6b, H3); 3.66 (d, 1H, J1%a-b=12.30
Hz, H1%a); 3.63 (d, 1H, J1%a-b=12.26 Hz, H1%b); 3.44
(dd, 1H, J1-2=3.82, J2-3=9.77 Hz, H2); 3.35 (t, 1H,
J
3-4=J4-5=9.61 Hz, H4); 2.36 (t, 2H, J=7.37, CO-
CH2); 1.63 (m, 2H, CO-CH2CH2); 1.39 (m, 16H, 8
CH2); 0.92 (t, 3H, J=7.04 Hz, CH3); 13C NMR (D2O,
75 MHz): l 174.5 (1C, CO on 6%); 104.6 (1C, C2%); 92.5
(1CH, C1); 79.7 (1CH, C5%); 78.1 (1CH, C3%); 76.0
(1CH, C4%); 73.8 (1CH, C3); 73.2 (1CH, C5); 72.3
(1CH, C2); 70.6 (1CH, C4); 65.9 (1CH2, C6%); 62.9
(1CH2, C1%); 61.6 (1CH2, C6); 34.0 (1CH2, CH2-CO);
32.0, 29.7–29.2, 27.7 (8CH2); 25.0 (1CH2, CH2CH2-
CO); 13.4 (1CH3); Anal. calcd for C24H44O12·H2O: C,
53.1; H, 8.6. Found: C, 52.9; H, 8.6%; [h]2D0=+52 (c 1,
MeOH); SMHR (FAB+) m/z calcd (M+Na) 547.2730,
found 547.2718.
4.12. Sucrose monolaurates 4, 5 and 9a
Sucrose (1.1 g, 3 mmol), vinyl laurate (4.2 mL, 5
equiv.), PN/C (1/3 m/m) (7.2 U/mg, 2.5 g), DMF–H2O
(vH O/vtot=4%, 8 mL), 3 days. FC eluent: CH2Cl2/
Me22CO/MeOH/H2O 56/20/20/4 (Rf=0.45). Yield:
lyophilised white foam (360 mg, 21%); regioisomers
proportion 6/1%/6%=9/75/13+3% on secondary hydroxyl
groups, separated by semi-preparative HPLC. Sucrose
1%-O-monolaurate 9a. 1H NMR (D2O, 300 MHz): l
References
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Organic Chemistry; Elsevier: Oxford, 1994.
5.37 (1H, d, J1-2=2.81 Hz, H1); 4.33 (1H, d, J1%a-b
=
12.18 Hz, H1%a); 4.13–4.12 (3H, H1%b, H3%, H4%); 3.85–
3.72 (7H, H5, H6%a,b, H6a,b, H5%, H3); 3.56 (1H, dd,
2. Wang, Y.-F.; Lalonde, J. J.; Momongan, M.; Bergbreiter,
D. E.; Wong, C.-H. J. Am. Chem. Soc. 1988, 110, 7200–
7205.
J1-2=3.04, J2-3=9.74 Hz, H2); 3.47 (1H, t, J3-4=J4-5=
9.34 Hz, H4); 2.39 (2H, m, CO-CH2); 1.61 (2H, m,
CO-CH2CH2); 1.28 (16H, m, 8 CH2); 0.86 (3H, t,
J=6.41 Hz, CH3); 13C NMR (D2O, 75 MHz): l 174.61
(1C, CO); 102.85 (1C, C2%); 93.1 (1CH, C1); 82.16
(1CH, C5%); 77.10 (1CH, C3%); 73.44 (1CH, C4%); 72.99
(2CH, C5, C3); 71.39 (1CH, C2); 69.51 (1CH, C4);
62.70 (1CH2, C1%); 61.74 (1CH2, C6%); 60.63 (1CH2, C6);
34.32 (1CH2, CH2-CO); 32.49, 30.37, 30.03, 29.78, 23.12
(8CH2); 25.19 (1CH2, CH2CH2-CO); 14.28 (1CH3);
Anal. calcd for C24H44O12·0.9H2O: C, 53.2; H, 8.6.
Found: C, 52.9; H, 8.5%; [h]2D0=+50 (c 1, MeOH);
SMHR (FAB+) m/z calcd (M+Na) 547.2730, found
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1
547.2718. Sucrose 6-O-monolaurate 4: H NMR (D2O,
9. Coulon, D.; Ghoul, M. Agro-Food-Ind. Hi-Tech 1998, 9,
22–26; Chem. Abstr. 1999, 130, 97178c.
500 MHz): l 5.39 (d, 1H, J1-2=3.81 Hz, H1); 4.42 (dd,
1H, J6a-b=11.92 Hz, J6a-5=2.12 Hz, H6a); 4.19 (dd,
1H, J6a-b=11.97 Hz, J6b-5=5.37 Hz, H6b); 4.12 (d, 1H,
J3%-4%=8.07 Hz, H3%); 4.05 (m, 1H, H5); 4.00 (1H, t,
J4%-3%=J4%-5%=8.02 Hz, H4%); 3.85–3.73 (m, 4H, H5%,
H6%a,b, H3); 3.65 d, (1H, J1%a-b=12.36 Hz, H1%a); 3.61
10. de Goede, A. T. J. W.; Woudenberg-van Oosterom, M.;
van Rantwijk, F. Carbohydr. Eur. 1994, 10, 18–20.
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(d, 1H, J1%a-b=12.27 Hz, H1%b); 3.45 (dd, 1H, J1-2
=
3.80, J2-3=9.76 Hz, H2); 3.31 (t, 1H, J3-4=J4-5=9.12
Hz, H4); 2.35 (t, 2H, CO-CH2); 1.60 (m, 2H, CO-
CH2CH2); 1.41 (m, 16H, 8 CH2); 0.96 (t, 3H, CH3); 13C
NMR (D2O, 75 MHz): l 174.5 (1C, CO on 6); 104.2
(1C, C2%); 92.4 (1CH, C1); 82.9 (1CH, C5%); 78.3 (1CH,
C3%); 74.4 (1CH, C4%); 73.5 (1CH, C3); 72.2 (1CH, C2);
71.0 (1CH, C5); 70.6 (1CH, C4); 63.7 (1CH2, C6); 63.1
(1CH2, C1%); 63.0 (1CH2, C6%); 34.0 (1CH2, CH2-CO);
32.1, 29.7–29.2, 27.7 (8CH2); 25.0 (1CH2, CH2CH2-
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