Ethyl Acetate → HCID 85256537, compound

HRID 2362275Notes

Reaction equation

HRID 2362275 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-be427f50757a4a0eaa312ee0ab0070e2
Source dataset
uspto-grants-2014_04
Patent number
US08691830B2

Reaction notes

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