Triphenylphosphine → Methyl cis-3-azidomethylcyclopentancarboxylate

HRID 2187992Notes

Reaction equation

HRID 2187992 reaction equation
O[CH2:2][C@@H:3]1[CH2:7][CH2:6][C@H:5]([C:8]([O:10][CH3:11])=[O:9])[CH2:4]1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.N(C(OCC)=O)=NC(OCC)=O.[NH:43]=[N+:44]=[N-:45]>C1C=CC=CC=1>[N:43]([CH2:2][C@@H:3]1[CH2:7][CH2:6][C@H:5]([C:8]([O:10][CH3:11])=[O:9])[CH2:4]1)=[N+:44]=[N-:45]

Participants

6

Reactant 4

HCID 11776TriphenylphosphineHCID 24530Hydrazoic acidHCID 220568ethyl N-ethoxycarbonyliminocarbamateHCID 57351148HCID 57351148, compound

Product 1

HCID 86758274Methyl cis-3-azidomethylcyclopentancarboxylateYield 47.3%

Reagents, catalysts & solvents 1

HCID 241BenzeneSolvent

Procedure

To a mixture of methyl cis-3-hydroxymethylcyclopentancarboxylate (4.74 g, 30 mmol) in dry benzene (about 250 mL) was added triphenyl phosphine (7.86 g, 30 mmol), diethyl azodicarboxylate (5.22 g, 30 mmol) and hydrazoic acid (2.5 M in toluene, 14.0 mL, 35 mmol). The mixture was stirred at room temperature for about 16 h. The reaction mixture was concentrated and the residue was dissolved in ethyl acetate and hexane was added. A precipitate formed on standing in about 2 h and was removed by filtration. The filtrate was concentrated and the residue was passed through a column of silica gel using chloroform as eluent. The appropriate fractions were combined and concentrated to give 2.6 g (47%) of methyl cis-3-azidomethyl-cyclopentancarboxylate.

Workup

  1. concentrationThe reaction mixture was concentrated
  2. dissolutionthe residue was dissolved in ethyl acetate
  3. additionhexane was added
  4. customA precipitate formed
  5. waiton standing in about 2 h
  6. customwas removed by filtration
  7. concentrationThe filtrate was concentrated
  8. concentrationconcentrated

Sources & evidence

ORD record
ord-96935c9dd9924b879315532d017b6c4a
Source dataset
uspto-grants-2002_06
Patent number
US06410594B1

Reaction notes

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