Benzaldehyde → 1,3:4,6-Di-O-benzylidene-D-mannitol

HRID 2289171Notes

Reaction equation

HRID 2289171 reaction equation
[CH2:1](O)[C@H:2]([C@H:4]([C@@H:6]([C@@H:8]([CH2:10][OH:11])[OH:9])O)O)[OH:3].[CH:13](=[O:20])[C:14]1[CH:19]=[CH:18][CH:17]=[CH:16][CH:15]=1.S(=O)(=O)(O)O.[C:26](=[O:29])([O-])[O-:27].[K+].[K+]>CN(C)C=O.CCCCCC>[CH2:10]1[O:11][CH:13]([C:14]2[CH:19]=[CH:18][CH:17]=[CH:16][CH:15]=2)[O:20][C@@H:6]([C@@H:4]2[O:29][CH:26]([C:14]3[CH:19]=[CH:18][CH:17]=[CH:16][CH:15]=3)[O:27][CH2:1][C@H:2]2[OH:3])[C@@H:8]1[OH:9]

Participants

7

Reactant 4

HCID 240Benzaldehyde2×HCID 1118Sulfuric AcidHCID 6251MannitolHCID 11430Potassium Carbonate

Product 1

HCID 99468561,3:4,6-Di-O-benzylidene-D-mannitolYield 102.6%

Reagents, catalysts & solvents 2

HCID 6228DimethylformamideSolventHCID 8058HexaneSolvent2×

Procedure

DBM was obtained according to the method described in J. Chem. Soc., I, 1977, 1123 or by the following procedure. A mixture of 12.5 g of D-mannitol, 12.5 g of benzaldehyde in 40 mL of dimethylformamide was treated with 5 mL of sulfuric acid added in one portion. The resulting mixture was allowed to stand at room temperature for 72 h and then poured into a mixture of 5 g of potassium carbonate, 0.5 L of ice water covered with a layer of hexane. The hexane layer containing unreacted benzaldehyde was removed and the aqueous layer was allowed to stand at 5-10° C. whereupon a white, cheese-like solid deposited thereon. The aqueous layer was filtered, and the solid air-dried and recrystallized from CHCl3 to afford 13.3 g (53%) of the above-titled compound as white crystals. The resulting white crystals were washed with dry hexane (2×10 mL) and benzene (10 mL), and then dissolved in hot benzene. The benzene solution was evaporated and the resulting solid residue dried over P2O5 in an Abderhalden apparatus for 18 h at 40° C./0.3 torr to provide an analytical specimen melting at 152-53° C. (189-91° C. (MeOH)): 1H NMR (90 MHz, CDCl3) δ3.54-3.65 (m, 2H, H-2 and H-5), 4.0 (d, 4H, H-1 and H-6), 4.22 (d, 2H, H-3 and H-4), 4.38 (br. s., 2H, OH), 5.52 (c, 2H, H-7 and H-8), 7.24-7.48 (m, Ph, Ph); 13C δ58.8 (C-3 and C-4), 70.55 (C-2, C-5), 78.1 (C-1, C-6), 100.34 (C-7, C-8), 125.49, 127.05, 127.17, 137.77 (Ph groups).

Workup

  1. customDBM was obtained
  2. additionadded in one portion
  3. customwas removed
  4. customto stand at 5-10° C.
  5. filtrationThe aqueous layer was filtered
  6. customthe solid air-dried
  7. customrecrystallized from CHCl3

Sources & evidence

ORD record
ord-2f3ec52638ae404e85c9da789aaa6edc
Source dataset
uspto-grants-2000_07
Patent number
US06090950

Reaction notes

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