Triphenylphosphine → 1-Amino-11-azido-3,6,9-trioxaundecane

HRID 2111508Notes

Reaction equation

HRID 2111508 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

5

Reactant 2

HCID 11776TriphenylphosphineHCID 41574921,11-DIAZIDO-3,6,9-TRIOXAUNDECANE

Product 1

HCID 27352801-Amino-11-azido-3,6,9-trioxaundecaneYield 88%

Reagents, catalysts & solvents 2

HCID 313Hydrochloric AcidSolventHCID 3283Diethyl EtherSolvent

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

  1. customThe phases were separated
  2. extractionthe aqueous phase was extracted with dichloromethane (3×40 ml)
  3. temperatureThe aqueous phase was cooled in an ice/water bath
  4. additionby addition of KOH
  5. extractionThe product was extracted into dichloromethane (5×50 ml)
  6. dry with materialCombined organic phases were dried (MgSO4)
  7. filtrationFiltration and evaporation

Sources & evidence

ORD record
ord-1941df589bd14174b61e3444bc9eae6f
Source dataset
uspto-grants-2009_04
Patent number
US07521419B2

Reaction notes

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