References
- Bernabé , M. , Martih-Lomas , M. , Penadés , S. , Köster , R. and Dahlhoff , W. V. 1985 . J. Chem. Soc., Chem. Comm. , : 1001
- Alonso-López , M. , Bernabé , M. , Martin-Lomas , M. and Penadeas , S. 1985 . Carbohydr. Res. , 142 : 135
- Stoddart , J. F. 1979 . Chem. Soc. Rev. , 8 : 85
- 13C-n.m. r., CDCl3 δ(ppm): 143.6 (C-ipso), 128.6 - 127.1 (Ph), 87.1, (Ph3 C),3 72.0, 70.7, 64.9.
- Czernecki , S. , Georgoulis , C. and Provelenghiou , C. 1976 . Tetrahedron Lett. , 39 : 3535
- 1H-n.m.r., CDCl3 δ (ppm): 7.40-6.90 (m, 50H, Ph), 4.76-4.30 (m, 8H, Ph-CH2-O), 4.27 (d, 2H, J = 7.3 Hz, H-3, 4), 3.85 (m, 2H, H-2, 5), 3.66 (dd, 2H, J = 2Hz, J = 10.4 Hz, H-1, 6), 3. 28 (dd, 2H, J = 4. 3 Hz, H-1′, 6′). 13C-n.m.r., CDCl3 δ (ppm): 144.0, 138.8, 138.7 (C-ipso), 128.8-126.8 (Ph), 86.6 (Ph3C), 78.8, 78.0, 73.5, 71.6, 62.6 (C-1, C-6).
- Klemer , A. , Bieber , M. and Wilbers , H. 1983 . Liebigs Ann. Chem. , : 1416
- Compound 6 was obtained from 5 as follows: Compound 5, (16 g, 0.015 mol) in acetonitrile (500 mL) under argon atmosphere at 0[ddot]C was treated, after 10 min, with Nal (11.67 g, 0.078 mol) and TMSC1 (9 mL, 0.076 mol). After 30 min, Nal (1.16 g, 0.0078 mol) and TMSCl (1 mL) were added again, and the reaction mixture was stirred during 3 1/2 h. The reaction was worked as indicated in reference 7. 1H-n.m.r., CDCl3 δ (ppm): 7.40-7.20 (m, 20H, Ph), 4.78-4.37 (m, 8H, Ph-CH 2-O), 3.94-3.91 (m, 4H, H-1, 6, 3, 4), 3.86 (bd, 2H, H-1′, 6′), 3.66 (m, 2H, H-2, 5), 13C-n.m. r., CDCl3 δ(ppm): 138.8, 138.0 (C-ipso), 129.9 - 127.0 (Ph), 79.8, 78.9, 74.3, 71.5, 60.5 (C-1, C-6).
- Compound 1 was obtained from 6 as follows: Under argon atmosphere, 6 (310 mg, 0.572 mmol) was dissolved in THF (7 mL) and NaH (120 mg, 5 mmol) was added. The mixture was refluxed for 20 - 30 min, and tetraethylene glycol ditosylate (314 mg, 0.626 mmol) in THF (5 mL) was added dropwise during 4 h. Heating was continued for 72 h, and the mixture was then cooled. The excess of NaH was destroyed with methanol-water, and the mixture was extracted with chloroform. The organic layer was dried on Na2SO4. Column chromatography (hexane : ethyl acetate 1 :1) gave 1 (80 rng, 20) as a syrup. [α]D = +45.5[ddot] (c 0.2, CHCl3). 1H-n.m.r., CDC13 δ (ppm): 7.35-7.15 (m, 20H, Ph), 4.75-4.53 (m, 8H, Ph-CH 2-O), 3.99 (m, 2H, H-3, 4), 3.87 (m, 2H, H-2, 5), 3.78 (dd, 2H, J = 3. 9, J = 10. 8, H-1, 6), 3. 73 (dd, 2H, J = 5.4, H-1′, 6′), 65 -3. 55 (m, 16H, ethylenemoiety). 13C-n.m. r., CDCl3 δ (ppm): 139.2, 138.9 (C-ipso), 128.5-127.2 (Ph), 79.9, 74.3, 71.9, 70.9, 70.8, 70.7, 70.6, 70.5. Mass spectrum (f. a.b.): [M + Na]+m/z = 723. Analytical data for 2: [α]D = -4. 8[ddot] (c = 1.3, MeOH). 1H-n.m.r., (D2O, DSS int. ref.) δ (ppm): 3.93 (d, 2H, J = 5.68, H-3, 4), 3.71 (m, 2H, H-2, 5), 3.68 (m, 20H, H-l, 1′, 6, 6′, ethylene moiety). 13C-n. m. r., CD3OD δ (ppm): 73.1, 72.9, 71.8, 71.6, 71.3. Mass spectrum (f. a. b.): [M + Na]+m/z = 363. Analytical data for 3: [α]D = +29.59 (c = 0.6, CHCl3). 1H-n.m. r., CDCl3 δ (ppm): 5.52 (d, 2H, J = 4.35, H-3, 4), 5.21 (m, 2H, H-2, 5), 3.79-3.59 (m, 20H, H-1, 1′, 6, 6′, ethylene moiety), 2.07 (s, 3H, CH 3CO), 2.05 (s, 3H, CH 3CO). 13C-n.m.r., CDCl3 δ (ppm): 169.9, 169.5 (CH3 CO), 71.3, 71.1, 70.9, 70.7, 70.6, 68.5, 20.9, 20.7 (CH3CO). Mass spectrum (f.a.b.): [M +Na]+ m/z = 531.
- The f. a. b.-mass spectra were recorded by using a polyethylene glycol 200 matrix (1 3) or glycerol matrix (2) with a MS-50 Kratos instrument fitted with a 1,2 T magnet, having a mass range up to 1.300 u. m. a., and a f. a.b. 11 NF Ion Tech atomgun.