Triphenylphosphine → (3-isopropoxycarbonylpropyl)triphenylphosphonium Bromide

HRID 1168000Notes

Reaction equation

HRID 1168000 reaction equation
[Br:1][CH2:2][CH2:3][CH2:4][C:5]([O:7][CH:8]([CH3:10])[CH3:9])=[O:6].[CH:11]1[CH:16]=[CH:15][C:14]([P:17]([C:24]2[CH:29]=[CH:28][CH:27]=[CH:26][CH:25]=2)[C:18]2[CH:23]=[CH:22][CH:21]=[CH:20][CH:19]=2)=[CH:13][CH:12]=1.O.CC#N>CC#N>[Br-:1].[CH:8]([O:7][C:5]([CH2:4][CH2:3][CH2:2][P+:17]([C:18]1[CH:19]=[CH:20][CH:21]=[CH:22][CH:23]=1)([C:24]1[CH:29]=[CH:28][CH:27]=[CH:26][CH:25]=1)[C:14]1[CH:13]=[CH:12][CH:11]=[CH:16][CH:15]=1)=[O:6])([CH3:10])[CH3:9]

Participants

5

Reactant 3

HCID 11776TriphenylphosphineHCID 12111255Isopropyl 4-bromobutanoateHCID 18373917Acetonitrile--water (1/1)

Product 1

HCID 11363419(3-isopropoxycarbonylpropyl)triphenylphosphonium Bromide

Reagents, catalysts & solvents 1

HCID 6342AcetonitrileSolvent

Procedure

A solution of 4-bromobutyric acid (50 g) in 2-propanol (200 mL) containing 1 mL of H2SO4 was refluxed for 3 h, then cooled to ambient temperature, diluted with ether (500 mL), washed with saturated NaHCO3 (3×300 mL), and brine (300 mL). The organic extract was dried (MgSO4), filtered and concentrated in vacuo to give isopropyl 4-bromo-butyrate (52 g) as an oil. This ester was dissolved in MeCN (380 mL). Ph3P (100 g) was added and the solution was heated at reflux for 72 h, after which TLC analysis (20% water/MeCN, C-18 RP TLC plates) showed complete reaction. The mixture was cooled and concentrated and the residue was slurried with toluene (400 mL) for 1 h. The solid was collected by filtration and was washed with toluene (100 mL) and then dried in vacuo at 50° C. to provide (3-(isopropoxycarbonyl)propyl)triphenylphosphonium bromide (100.6 g). 1H NMR (CDCl3): δ1.19-1.22 (d, 6H), 1.85-1.97 (mn, 2H), 2.85 (t, 2H), 3.95-4.10 (m, 2H), 4.89-5.03 (m, 1H), 7.65-7.94 (m, 15H).

Workup

  1. temperaturethe solution was heated
  2. temperatureat reflux for 72 h
  3. customreaction
  4. temperatureThe mixture was cooled
  5. concentrationconcentrated
  6. filtrationThe solid was collected by filtration
  7. washwas washed with toluene (100 mL)
  8. customdried in vacuo at 50° C.

Sources & evidence

ORD record
ord-15862cb0ffee4252974f61f1a651a168
Source dataset
uspto-grants-2003_09
Patent number
US06620947B2

Reaction notes

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