Triphenylphosphine → HCID 18617479, compound

HRID 1264206Notes

Reaction equation

HRID 1264206 reaction equation
[C:1]([C:3]1[C:11]2[C:6](=[CH:7][CH:8]=[C:9]([CH2:12][CH2:13][N:14]=[N+]=[N-])[CH:10]=2)[NH:5][CH:4]=1)#[N:2].C1(P([C:30]2[CH:35]=[CH:34]C=CC=2)C2C=CC=CC=2)C=CC=CC=1.[C:36](=O)([OH:38])[O-:37].[Na+].Cl[C:42]([O:44][CH2:45][CH:46]=[CH2:47])=[O:43]>C1COCC1.C(OCC)(=O)C.O>[CH2:45]([O:44][C:42]([N:5]1[C:6]2[C:11](=[CH:10][C:9]([CH2:12][CH2:13][NH:14][C:36]([O:38][CH2:34][CH:35]=[CH2:30])=[O:37])=[CH:8][CH:7]=2)[C:3]([C:1]#[N:2])=[CH:4]1)=[O:43])[CH:46]=[CH2:47]

Participants

8

Reactant 4

HCID 11776TriphenylphosphineHCID 18052Allyl chloroformate2×HCID 516892Sodium BicarbonateHCID 18617612HCID 18617612, compound

Product 1

HCID 18617479HCID 18617479, compoundYield 61.7%

Reagents, catalysts & solvents 3

HCID 962WaterSolvent2×HCID 8028TetrahydrofuranSolventHCID 8857Ethyl AcetateSolvent

Procedure

A solution of 1.89 g (8.95 mmol) 3-cyano-5-(2-azidoethyl)-indole (reference example 3) and 2.58 g (9.85 mmol) triphenylphosphine in 40 mL THF is stirred overnight to give a white precipitate. To this is added 0.32 mL H2O, and stirring is continued overnight. Then 4.75 g (44.8 mmol) sodium bicarbonate and 15 mL H2O, followed by 2.1 mL (20 mmol) allyl chloroformate, is added. After stirring overnight another 2 mL allyl chloroformate is added, followed by stirring overnight. The reaction mixture is diluted with ethyl acetate and washed with distilled water. The organic layer is concentrated, and the resulting residue chromatographed (3:1, then 1:1 hexane:ethyl acetate) to provide the product as a white solid in 61.7% yield. 1H NMR (CDCl3): δ 2.96 (2H, t, J=7.0 Hz), 3.50 (2H, m), 4.56 (2H, d, J=5.4 Hz), 4.97 (2H, d, J=5.9 Hz), 5.25 (2H, m), 5.46 (2H, m), 5.91 (1H, m), 6.06 (1H, m), 7.31 (1H, d, J=8.6 Hz), 7.54 (1H, s), 8.14 (1H, d, J=8.6 Hz), 8.15 (1H, s). MS (EI) m/z 353 M+, 268 (M−CO2Allyl)+.

Workup

  1. customto give a white precipitate
  2. additionis added
  3. additionis added
  4. stirringby stirring overnight
  5. washwashed with distilled water
  6. concentrationThe organic layer is concentrated
  7. customthe resulting residue chromatographed (3:1

Sources & evidence

ORD record
ord-f79624cbefde49668129108c160a328f
Source dataset
uspto-grants-2003_04
Patent number
US06541505B1

Reaction notes

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