Triethylamine → 2-(Benzoyloxy)-3-(octadecyloxy)propyl 3-pyridiniopropyl phosphate

HRID 986185Notes

Reaction equation

HRID 986185 reaction equation
[CH2:1]([O:19][CH2:20][CH:21]([CH2:31][OH:32])[O:22][C:23](=[O:30])[C:24]1[CH:29]=[CH:28][CH:27]=[CH:26][CH:25]=1)[CH2:2][CH2:3][CH2:4][CH2:5][CH2:6][CH2:7][CH2:8][CH2:9][CH2:10][CH2:11][CH2:12][CH2:13][CH2:14][CH2:15][CH2:16][CH2:17][CH3:18].[P:33](Cl)(Cl)(Cl)=[O:34].C(N(CC)CC)C.S(C1C=CC(C)=CC=1)([O-])(=O)=[O:46].[OH:56][CH2:57][CH2:58][CH2:59][N+:60]1[CH:65]=[CH:64][CH:63]=[CH:62][CH:61]=1.C(=O)([O-])O.[Na+]>C(Cl)(Cl)Cl.N1C=CC=CC=1>[P:33]([O-:34])([O:56][CH2:57][CH2:58][CH2:59][N+:60]1[CH:65]=[CH:64][CH:63]=[CH:62][CH:61]=1)([O:32][CH2:31][CH:21]([O:22][C:23](=[O:30])[C:24]1[CH:25]=[CH:26][CH:27]=[CH:28][CH:29]=1)[CH2:20][O:19][CH2:1][CH2:2][CH2:3][CH2:4][CH2:5][CH2:6][CH2:7][CH2:8][CH2:9][CH2:10][CH2:11][CH2:12][CH2:13][CH2:14][CH2:15][CH2:16][CH2:17][CH3:18])=[O:46]

Participants

8

Reactant 5

HCID 8471TriethylamineHCID 24813Phosphorus oxychlorideHCID 516892Sodium BicarbonateHCID 138719511-Octadecyl-2-benzoylglycerolHCID 201593883-Hydroxypropylpyridinium tosylate

Product 1

HCID 201594032-(Benzoyloxy)-3-(octadecyloxy)propyl 3-pyridiniopropyl phosphateYield 37.1%

Reagents, catalysts & solvents 2

HCID 1049PyridineSolventHCID 6212ChloroformSolvent2×

Procedure

Under ice-cooling, 4.6 g (10 mmole) of 1-octadecyl-2-benzoylglycerol (synthesized according to the procedure of Example 8) in 35 ml of chloroform was added dropwise to a mixture of 70 ml of chloroform, 1.62 g (10.5 mmole) of phosphorus oxychloride and 7.0 ml (52 mmole) of triethylamine over the period of time of 40 minutes. The resulting mixture was stirred at room temperature for 1 hour and then cooled on an ice-bath. 3.9 g (12.6 mmole) of 3-hydroxypropylpyridinium tosylate in 30 ml of pyridine was added dropwise to the mixture and the reaction mixture was stirred at room temperature overnight. An aqueous solution saturated with 7.0 g of sodium hydrogencarbonate was added to the mixture and the resulting mixture was concentrated to dryness under reduced pressure. To the residue were added 100 ml of toluene and 100 ml of dichloromethane and the insoluble material was removed by filtration. The filtrate was concentrated under reduced pressure, and then the residue was dissolved in water and subjected to chromatography on columns of 40 ml of Amberlite IRA-410 and 20 ml of Amberlite IR-120 and eluted with water and 95% hydrous tetrahydrofuran. The eluate was concentrated and the residue was subjected to column chromatography of silica gel (50 g) and eluted with chloroform-methanol-water (65:25:4). The desired fractions were concentrated to give 2-(benzoyloxy)-3-(octadecyloxy)propyl 3-pyridiniopropyl phosphate as a colorless solid material. Yield: 2.4 g (yield:37.1%).

Workup

  1. temperatureUnder ice-cooling
  2. temperaturecooled on an ice-bath
  3. stirringthe reaction mixture was stirred at room temperature overnight
  4. concentrationthe resulting mixture was concentrated to dryness under reduced pressure
  5. additionTo the residue were added 100 ml of toluene and 100 ml of dichloromethane
  6. customthe insoluble material was removed by filtration
  7. concentrationThe filtrate was concentrated under reduced pressure
  8. dissolutionthe residue was dissolved in water
  9. washeluted with water and 95% hydrous tetrahydrofuran
  10. concentrationThe eluate was concentrated
  11. washeluted with chloroform-methanol-water (65:25:4)
  12. concentrationThe desired fractions were concentrated

Sources & evidence

ORD record
ord-845419abdb734d96988a247400e0eaf6
Source dataset
uspto-grants-1987_12
Patent number
US04710579

Reaction notes

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