Boron trifluoride etherate → HCID 70360285, compound

HRID 1073459Notes

Reaction equation

HRID 1073459 reaction equation
[C:1]1([CH2:7][O:8][C@H:9]2[C@H:16]([O:17][CH2:18][C:19]3[CH:24]=[CH:23][CH:22]=[CH:21][CH:20]=3)[C@@H:15]([CH2:25][O:26]CC3C=CC=CC=3)[O:14][C@H:10]2[CH2:11][CH2:12][OH:13])[CH:6]=[CH:5][CH:4]=[CH:3][CH:2]=1.C1(C[O:41][CH2:42][C@H:43]2[O:63][C@H:62]([CH2:64][CH2:65][OH:66])[C@@H:53]([O:54][CH2:55][C:56]3[CH:61]=[CH:60][CH:59]=[CH:58][CH:57]=3)[C@@H:44]2[O:45][CH2:46][C:47]2[CH:52]=[CH:51][CH:50]=[CH:49][CH:48]=2)C=CC=CC=1.B(F)(F)F.CCOCC.C(=O)(O)[O-].[Na+]>C(OC(=O)C)(=O)C>[C:1]1([CH2:7][O:8][C@H:9]2[C@H:16]([O:17][CH2:18][C:19]3[CH:24]=[CH:23][CH:22]=[CH:21][CH:20]=3)[C@@H:15]([CH2:25][OH:26])[O:14][C@H:10]2[CH2:11][CH2:12][OH:13])[CH:2]=[CH:3][CH:4]=[CH:5][CH:6]=1.[C:56]1([CH2:55][O:54][C@H:53]2[C@H:44]([O:45][CH2:46][C:47]3[CH:52]=[CH:51][CH:50]=[CH:49][CH:48]=3)[C@@H:43]([CH2:42][OH:41])[O:63][C@@H:62]2[CH2:64][CH2:65][OH:66])[CH:57]=[CH:58][CH:59]=[CH:60][CH:61]=1

Participants

7

Reactant 4

HCID 8000Boron trifluoride etherateHCID 516892Sodium BicarbonateHCID 9981105HCID 9981105, compoundHCID 10411385HCID 10411385, compound

Product 2

HCID 70360285HCID 70360285, compoundHCID 70360297HCID 70360297, compound

Reagents, catalysts & solvents 1

HCID 7918Acetic AnhydrideSolvent

Conditions

Temperature
0 °C

Procedure

A cold (0°-5° C.) solution of 12.2 g of a mixture of 3,6-anhydro-2-deoxy-4,5,7-tris-O-(phenylmethyl)-D-gluco-heptitol and 2,5-anhydro-6-deoxy-1,3,4-tris-O-(phenylmethyl)-D-manno-heptitol in 64 ml of acetic anhydride was treated with 370 μl of borontrifluoride etherate under argon. After 13/4 hours, 53 ml of saturated aqueous sodium bicarbonate was added, the mixture was stirred at 0° C. for 15 minutes, then at ambient temperature for 15 minutes and the volatiles removed. The residue was taken up in ether/water. The organic layer was separated, dried and evaporated. The residue was taken up in 74 ml of methanol, a solution of 15.4 g of potassium carbonate in 90 ml of water added and this mixture stirred at reflux for 45 minutes. The volatiles were removed, the residue taken up in ether/water and the organic layer separated and evaporated. The 12 g of residue was purified by high pressure liquid chromatography on silica gel, eluting first with hexane:ethyl acetate (1:1), and then with hexane:ethyl acetate (1:3), giving 3,6-anhydro-2-deoxy-4,5-bis-O-(phenylmethyl)-D-gluco-heptitol in 20% yield and 3,6-anhydro-2-deoxy-4,5-bis-O-(phenylmethyl)-D-manno-heptitol in 65% yield.

Workup

  1. waitat ambient temperature for 15 minutes
  2. customthe volatiles removed
  3. customThe organic layer was separated
  4. customdried
  5. customevaporated
  6. additiona solution of 15.4 g of potassium carbonate in 90 ml of water added
  7. stirringthis mixture stirred
  8. temperatureat reflux for 45 minutes
  9. customThe volatiles were removed
  10. customthe organic layer separated
  11. customevaporated
  12. customThe 12 g of residue was purified by high pressure liquid chromatography on silica gel
  13. washeluting first with hexane:ethyl acetate (1:1)

Sources & evidence

ORD record
ord-914b89f279c84e7e949aede1c1bc8d9c
Source dataset
uspto-grants-1990_11
Patent number
US04968790

Reaction notes

Loading…