Ethyl Acetate → HCID 85256537, compound

HRID 70761Notes

Reaction equation

HRID 70761 reaction equation
O[CH2:2][CH:3]([NH:7][C:8](=[O:17])[O:9][CH2:10][C:11]1[CH:16]=[CH:15][CH:14]=[CH:13][CH:12]=1)[CH:4]([CH3:6])[CH3:5].C1(P([N:32]=[N+:33]=[N-:34])(C2C=CC=CC=2)=O)C=CC=CC=1.C1CCN2C(=NCCC2)CC1.C(OCC)(=O)C>O1CCOCC1.CCCCCC.C(OCC)(=O)C.O>[N:32]([CH2:2][CH:3]([NH:7][C:8](=[O:17])[O:9][CH2:10][C:11]1[CH:16]=[CH:15][CH:14]=[CH:13][CH:12]=1)[CH:4]([CH3:6])[CH3:5])=[N+:33]=[N-:34]

Participants

8

Reactant 4

HCID 8857Ethyl AcetateHCID 811841,8-Diazabicyclo(5.4.0)undec-7-eneHCID 199401P,P-Diphenylphosphinic azideHCID 14036742Cbz-DL-Valinol

Product 1

HCID 85256537HCID 85256537, compound

Reagents, catalysts & solvents 3

HCID 962WaterSolventHCID 312751,4-DioxaneSolventHCID 21226206Ethyl acetate hexaneSolvent

Procedure

To 11.0 g (0.0464 mole) of benzyl N-[1-(hydroxymethyl)-2-methyl-propyl]carbamate in dioxane (100 mL) cooled to 0° C. was added diphenylphosphoryl azide 10.99 mL (1.1 eq) followed by the addition of DBU 8.32 mL (1.2 eq). The contents were allowed to warm to room temperature and stirred for 16 hrs. After the addition of ethyl acetate (300 mL) and water (100 mL), the organic layer was separated and then washed with satd. NaHCO3 (100 mL). The organic layer was then dried (magnesium sulfate) and then concentrated under vacuum. To this intermediate in DMSO (100 mL) was added sodium azide 7.54 g and the contents then heated to 90 degrees for 2 hrs. After addition of ethyl acetate and water the layers were separated. The organic layer was dried with magnesium sulfate followed by concentration under vacuum to afford an oil that was columned using hexane/ethyl acetate (0-70%) to afford benzyl N-[1-(azidomethyl)-2-methyl-propyl]carbamate 6.9 g as a colorless oil.

Workup

  1. customthe organic layer was separated
  2. washwashed with satd
  3. dry with materialThe organic layer was then dried (magnesium sulfate)
  4. concentrationconcentrated under vacuum
  5. additionTo this intermediate in DMSO (100 mL) was added sodium azide 7.54 g
  6. temperaturethe contents then heated to 90 degrees for 2 hrs
  7. additionAfter addition of ethyl acetate and water the layers
  8. customwere separated
  9. dry with materialThe organic layer was dried with magnesium sulfate
  10. concentrationfollowed by concentration under vacuum
  11. customto afford an oil that

Sources & evidence

ORD record
ord-c0c64c56c88c49c8b0ff827b866ca7db
Source dataset
uspto-grants-2014_09
Patent number
US08822683B2

Reaction notes

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