Acetonitrile → (R)-1-dodecyl-3-trityl-glycerol

HRID 1501893Notes

Reaction equation

HRID 1501893 reaction equation
[CH2:1]([O:13][CH2:14][C@H:15]([CH2:17][OH:18])[OH:16])[CH2:2][CH2:3][CH2:4][CH2:5][CH2:6][CH2:7][CH2:8][CH2:9][CH2:10][CH2:11][CH3:12].[C:19]1([C:25]([C:33]2[CH:38]=[CH:37][CH:36]=[CH:35][CH:34]=2)([C:27]2[CH:32]=[CH:31][CH:30]=[CH:29][CH:28]=2)Cl)[CH:24]=[CH:23][CH:22]=[CH:21][CH:20]=1.O1CCCC1.C(#N)C>C(N(CC)CC)C>[CH2:1]([O:13][CH2:14][C@H:15]([CH2:17][O:18][C:25]([C:19]1[CH:24]=[CH:23][CH:22]=[CH:21][CH:20]=1)([C:33]1[CH:34]=[CH:35][CH:36]=[CH:37][CH:38]=1)[C:27]1[CH:28]=[CH:29][CH:30]=[CH:31][CH:32]=1)[OH:16])[CH2:2][CH2:3][CH2:4][CH2:5][CH2:6][CH2:7][CH2:8][CH2:9][CH2:10][CH2:11][CH3:12]

Participants

6

Reactant 4

HCID 6342AcetonitrileHCID 6456Trityl chlorideHCID 8028TetrahydrofuranHCID 10848948(S)-3-(dodecyloxy)propane-1,2-diol

Product 1

HCID 67229632(R)-1-dodecyl-3-trityl-glycerolYield 48.5%

Reagents, catalysts & solvents 1

HCID 8471TriethylamineSolvent2×

Procedure

19.83 grams of (S)-1-dodecyl-glycerol and 21.0 grams of triphenylchloromethane were added to a mixture of 250 ml dry tetrahydrofuran (THF) and 60 ml dry acetonitrile. 22 ml of dry triethylamine was added and the reaction mixture was refluxed for 17 hours under nitrogen. The reaction mixture was then cooled to room temperature, and 5 ml triethylamine and 10 grams of ice were added. The mixture was transferred to a separatory funnel and extracted with 100 ml MTBE. The organic phase was washed consecutively with 150 ml water, 150 ml of dilute (1.5%) H2SO4, 150 ml water, 150 ml of concentrated aqueous sodium bicarbonate, and again with 150 ml water. The solution was then dried over anhydrous Na2SO4 and the solvent was removed under reduced pressure. The residue, 40.63 grams of a brown oil, was dissolved in 200 ml ethyl acetate and cooled to −20° C. for a couple of days. The mixture was centrifuged at a temperature of −10° C. and the mother liquid was poured off. The solid melted at room temperature and was purified by chromatography on a silica gel column (195 grams). 18.57 grams of pure (R)-1-dodecyl-3-trityl-glycerol was eluted by mixtures of chloroform and hexane followed by a mixture of 9:1 (v/v) chloroform:ethyl acetate. The yield was 48.5%.

Workup

  1. temperaturethe reaction mixture was refluxed for 17 hours under nitrogen
  2. customThe mixture was transferred to a separatory funnel
  3. extractionextracted with 100 ml MTBE
  4. washThe organic phase was washed consecutively with 150 ml water, 150 ml
  5. additionof dilute (1.5%) H2SO4, 150 ml water, 150 ml of concentrated aqueous sodium bicarbonate
  6. dry with materialThe solution was then dried over anhydrous Na2SO4
  7. customthe solvent was removed under reduced pressure
  8. dissolutionThe residue, 40.63 grams of a brown oil, was dissolved in 200 ml ethyl acetate
  9. temperaturecooled to −20° C. for a couple of days
  10. customwas centrifuged at a temperature of −10° C.
  11. additionthe mother liquid was poured off
  12. customThe solid melted at room temperature and was purified by chromatography on a silica gel column (195 grams)
  13. wash18.57 grams of pure (R)-1-dodecyl-3-trityl-glycerol was eluted by mixtures of chloroform and hexane
  14. additionfollowed by a mixture of 9:1 (v/v) chloroform

Sources & evidence

ORD record
ord-19499495b7fa4d089443b052fab661ea
Source dataset
uspto-grants-2015_12
Patent number
US09206206B2

Reaction notes

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