Triphenylphosphine → 1-Amino-11-azido-3,6,9-trioxaundecane
Reaction equation
[N:1]([CH2:4][CH2:5][O:6][CH2:7][CH2:8][O:9][CH2:10][CH2:11][O:12][CH2:13][CH2:14][N:15]=[N+]=[N-])=[N+:2]=[N-:3].C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1>Cl.CCOCC>[N:1]([CH2:4][CH2:5][O:6][CH2:7][CH2:8][O:9][CH2:10][CH2:11][O:12][CH2:13][CH2:14][NH2:15])=[N+:2]=[N-:3]Participants
Reactant 2
Product 1
Reagents, catalysts & solvents 2
Procedure
To a mechanically, vigorously stirred suspension of 1,11-diazido-3,6,9-trioxaundecane (20.8 g, 0.085 mol) in 5% hydrochloric acid (200 ml) was added a solution of triphenylphosphine (19.9 g, 0.073 mol) in ether (150 ml) over 3 hrs at room temperature. The reaction mixture was stirred for additional 24 hrs. The phases were separated and the aqueous phase was extracted with dichloromethane (3×40 ml). The aqueous phase was cooled in an ice/water bath and pH was adjusted to ca 12 by addition of KOH. The product was extracted into dichloromethane (5×50 ml). Combined organic phases were dried (MgSO4). Filtration and evaporation gave 14.0 g (88%) of yellow oil. Analysis by MALDI-TOF mass spectroscopy (matrix: α-cyano-4-hydroxycinnamic acid) gave a M+H peak at 219 as expected. Further characterisation using 1H (500 MHz) and 13C (125 MHz) NMR spectroscopy verified the structure.
Workup
- customThe phases were separated
- extractionthe aqueous phase was extracted with dichloromethane (3×40 ml)
- temperatureThe aqueous phase was cooled in an ice/water bath
- additionby addition of KOH
- extractionThe product was extracted into dichloromethane (5×50 ml)
- dry with materialCombined organic phases were dried (MgSO4)
- filtrationFiltration and evaporation
Sources & evidence
- ORD record
- ord-de22a679d57e44f285623098b78a98eb
- Source dataset
- uspto-grants-2012_10
- Patent number
- US08299030B2
Reaction notes
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