SPIRO COMPD EXAMPLE FOR NMR INTERPRETATION

(1S, 3'R, 4'S, 5'S, 6'R) -3 ', 4', 5 ', 6'-tetrahydro -6,6' - bis (hydroxymethyl) - spiro [ (3H), 2'-[2H] pyran] -3 ', 4', 5'-

Preparation of triol isobenzofuran-1

Crude 2 obtained in Step 4 - [2,5 - [bis (1 - methoxy-1 - methyl) ethoxy methyl] phenyl] -3,4,5 - tris (trimethylsilyloxy)-6 - trimethylsilyloxy methyl - tetrahydro pyran-2 - is cooled to -25 ℃ the methanol THF ol (theoretical 75.3mol) and (104.13kg) of (52.0kg) in a nitrogen stream, p-toluenesulfonic acid (2.9kg , I added a 15.6mol). For 3 hours 30 minutes of stirring at room temperature, it was confirmed the precipitation of a white solid. Was added methyl tert-butyl ether (108.7kg) the reaction mixture was stirred for 1 hour and cooled to 10 ℃. The solid was collected by filtration precipitated, washed with methanol with (104kg), to give (24.08kg) wet white powder. Was suspended in methanol (42.9kg) in the powder, and heated to 48 ℃ over 30 minutes, followed by stirring for 1 hour at 48 ℃. Was then stirred for 1 hour and cooled to 10 ℃. The solid was collected by filtering the suspension, washed with methanol (10.0kg), methyl tert-butyl ether by (10.0kg), to give (19.78kg) wet powder. And dried at reduced pressure below 40 ℃ This powder was obtained as white crystals (14.71kg, 63.4% 2 steps yield) of the title compound.

¹ H-NMR _(CD 3 OD) ^δ :3.47-3 .50 (1H, m) ,3.63-3 .69 (1H, m) ,3.75-3 .85 (4H, m), 4.63 (2H, s), 5.12 (1H, d, J = 12.6Hz), 5.18 (1H, d, J = 12.6Hz) ,7.23-7 .37 (3H, m ).
MS ^{(ESI +):} 299 [M ^+1] + 

http://www.google.com.au/patents/WO2011074675A1?cl=en

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(3R, 4S, 5R, 6R) -3,4,5 - tris (trimethylsilyloxy)-6 - trimethylsilyloxy methyl - tetrahydropyran-2: Step 3

Glucono -1,5 - - D-(+) in tetrahydrofuran (70kg) in the solution (35.8kg, 353.9mol) of N-methylmorpholine (7.88kg, 44.23mol) and lactone, chlorotrimethylsilane ( was added at 40 ℃ less 29.1kg, and 267.9mol), and the mixture was stirred for 2 hours at 30 ~ 40 ℃ resulting mixture. Was cooled to 0 ℃ the reaction mixture was added toluene (34kg) water (39kg), and the organic layer was separated. Twice sodium dihydrogen phosphate aqueous solution (5 wt%, 39.56kg) in, washed once with water (39kg) the organic layer the solvent was evaporated under reduced pressure. Was dissolved in toluene (34.6kg) and the residue obtained was obtained as a toluene solution of the title compound.

¹ H-NMR (CDCl ₃₎ ^δ: 0.13 (9H, s), 0.17 (9H, s), 0.18 (9H, s), 0.20 (9H, s), 3.74- 3.83 (3H, m), 3.90 (1H, t, J = 8.0Hz), 3.99 (1H, d, J = 8.0Hz), 4.17 (1H, dt, J = 2 .5,8.0 Hz).

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¹ H-NMR _{(DMSO-d 6)} ^δ: 4.49 (4H, t, J = 5.8Hz), 5.27 (1H, t, J = 5.8Hz), 5.38 (1H, t, J = 5.8Hz), 7.31 (1H, d, J = 7.5Hz), 7.47 (1H, d, J = 7.5Hz), 7.50 (1H, s).