Benzyl Alcohol → Benzyl oxolan-3-ylcarbamate

HRID 481346Notes

Reaction equation

HRID 481346 reaction equation
[O:1]1[CH2:5][CH2:4][CH:3](C(O)=O)[CH2:2]1.C1(P(N=[N+]=[N-])(C2C=CC=CC=2)=[O:16])C=CC=CC=1.C([N:28]([CH2:31]C)CC)C.[CH2:33]([OH:40])[C:34]1[CH:39]=[CH:38][CH:37]=[CH:36][CH:35]=1>O1CCOCC1>[CH2:33]([O:40][C:31]([NH:28][CH:3]1[CH2:4][CH2:5][O:1][CH2:2]1)=[O:16])[C:34]1[CH:39]=[CH:38][CH:37]=[CH:36][CH:35]=1

Participants

6

Reactant 4

HCID 244Benzyl AlcoholHCID 8471TriethylamineHCID 199401P,P-Diphenylphosphinic azideHCID 4661317(R)-Tetrahydro-3-furoic acid

Product 1

HCID 21864525Benzyl oxolan-3-ylcarbamateYield 51.2%

Reagents, catalysts & solvents 1

HCID 312751,4-DioxaneSolvent

Procedure

A mixture of 3-tetrahydrofuroic acid (3.5 gm, 30 mmol), diphenylphosphorylazide (6.82 ml, 32 mmol), triethylamine (5 ml, 36 mmol) in dioxane (35 ml) was stirred at RT for 20 min then heated in a 100° C. oil bath under dry nitrogen for 2 hours. Benzyl alcohol (4.7 ml, 45 mmol) was added, and continued heating at 100° C. for 22 hours. The mixture was cooled, filtered from a white precipitate and concentrated. The residue was dissolved in 2N HCI and extracted twice using EtOAc. The extracts were washed with water, sodium bicarbonate, brine dried over MgSO4, and then concentrated to an oil which solidifies upon standing. The oil was chromatographed (30% to 60% EtOAc/Hex) to give 3.4 g of an oil (51%).

Workup

  1. temperaturethen heated in a 100° C. oil bath under dry nitrogen for 2 hours
  2. temperaturecontinued heating at 100° C. for 22 hours
  3. temperatureThe mixture was cooled
  4. filtrationfiltered from a white precipitate
  5. concentrationconcentrated
  6. dissolutionThe residue was dissolved in 2N HCI
  7. extractionextracted twice using EtOAc
  8. washThe extracts were washed with water, sodium bicarbonate, brine
  9. dry with materialdried over MgSO4
  10. concentrationconcentrated to an oil which
  11. customThe oil was chromatographed (30% to 60% EtOAc/Hex)

Sources & evidence

ORD record
ord-c15d9c2a8d7d4793951ee2e3b6757706
Source dataset
uspto-grants-1998_08
Patent number
US05789416

Reaction notes

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