Trimethyl Phosphate → L-ASCORBIC ACID 2-MONOPHOSPHATE TRI-CYCLOHEXYLAMMONIUM SALT

HRID 1195247Notes

Reaction equation

HRID 1195247 reaction equation
CC1(C)[O:6][C@H:5]([C@H:7]2[O:12][C:10](=[O:11])[C:9]([OH:13])=[C:8]2[OH:14])[CH2:4][O:3]1.O=C1O[C@H]([C@H](CO)O)C(O)=C1O.C[O:29][P:30](=O)([O:33]C)[O:31]C.[OH-].[Ca+2].[OH-].P(Cl)(Cl)(Cl)=O>O.N1C=CC=CC=1.CC(C)=O.CN(C)C=O>[P:30]([O:13][C:9]1[C:10]([O:12][C@H:7]([C@H:5]([CH2:4][OH:3])[OH:6])[C:8]=1[OH:14])=[O:11])([OH:33])([OH:31])=[O:29]

Participants

10

Reactant 5

HCID 10541Trimethyl PhosphateHCID 24813Phosphorus oxychlorideHCID 6093208Calcium HydroxideHCID 54670067L-Ascorbic Acid2×HCID 54691418(+)-5,6-O-Isopropylidene-L-ascorbic acid2×

Product 1

HCID 54679073L-ASCORBIC ACID 2-MONOPHOSPHATE TRI-CYCLOHEXYLAMMONIUM SALT

Reagents, catalysts & solvents 4

HCID 180AcetoneSolvent2×HCID 962WaterSolvent4×HCID 1049PyridineSolventHCID 6228DimethylformamideSolvent

Procedure

The above-described method is to react 5,6-isopropylidene-L-ascorbic acid or L-ascorbic acid with a phosphoric halide in a specific solvent (such as water, or a mixed solvent composed of water and acetone, dimethylformamide or trimethylphosphoric acid) in the presence of a base at temperature not higher than room temperature. More particularly, L-ascorbic derivative of which the hydroxyl groups at the 5- and 6-positions have been protected with acetone under acidic conditions (i.e., 5,6-isopropylidene-L-ascorbic acid) or L-ascorbic acid is dissolved in a mixed solvent composed of water and pyridine or a mixture of water and calcium hydroxide, and phosphorus oxychloride is added dropwise to the resulting solution or mixture at a temperature not higher than 0° C., and the reaction is continued at the same temperature for 90 minutes (reaction ratios: 94.5% and 70.6%, respectively). Then, the reaction mixture is treated with Amberlite Resin IR-120 (H+ -form) at room temperature to desalt the product, followed by neutralization with magnesium oxide, removal of the solvent by distillation, dropwise addition of ethanol to the residue to obtain white powder of magnesium salt of L-ascorbic acid 2-phosphate, which is recrylstallized from water-ethanol (yields: 75.1% and 55.3%, respectively).

Workup

  1. customhigher than room temperature
  2. dissolutionis dissolved in a mixed solvent
  3. additionis added dropwise to the resulting solution or mixture at a temperature not higher than 0° C.
  4. custom(reaction ratios
  5. additionThen, the reaction mixture is treated with Amberlite Resin IR-120 (H+ -form) at room temperature
  6. customfollowed by neutralization with magnesium oxide, removal of the solvent by distillation, dropwise addition of ethanol to the residue

Sources & evidence

ORD record
ord-959567bc198444f4b9035fa5607157b3
Source dataset
uspto-grants-1992_05
Patent number
US05110951

Reaction notes

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