Triphenylphosphine → (Carbethoxyhexyl)triphenylphosphonium bromide

HRID 1182499Notes

Reaction equation

HRID 1182499 reaction equation
[Br:1][CH2:2][CH2:3][CH2:4][CH2:5][CH2:6][CH2:7][C:8]([O:10][CH2:11][CH3:12])=[O:9].[C:13]1([P:19]([C:26]2[CH:31]=[CH:30][CH:29]=[CH:28][CH:27]=2)[C:20]2[CH:25]=[CH:24][CH:23]=[CH:22][CH:21]=2)[CH:18]=[CH:17][CH:16]=[CH:15][CH:14]=1>C1(C)C=CC=CC=1>[Br-:1].[C:8]([CH2:7][CH2:6][CH2:5][CH2:4][CH2:3][CH2:2][P+:19]([C:20]1[CH:21]=[CH:22][CH:23]=[CH:24][CH:25]=1)([C:26]1[CH:31]=[CH:30][CH:29]=[CH:28][CH:27]=1)[C:13]1[CH:14]=[CH:15][CH:16]=[CH:17][CH:18]=1)([O:10][CH2:11][CH3:12])=[O:9]

Participants

4

Reactant 2

HCID 11776Triphenylphosphine2×HCID 122490Ethyl 7-bromoheptanoate

Product 1

HCID 10994694(Carbethoxyhexyl)triphenylphosphonium bromideYield 87%

Reagents, catalysts & solvents 1

HCID 1140TolueneSolvent

Procedure

To a solution of ethyl 7-bromoheptanoate (10.0 g, 42.17 mmol) in toluene (280 mL) was added solid triphenylphosphine (11.06 g, 42.17 mmol). The solution was refluxed over 24 hours under nitrogen atmosphere and then cooled to room temperature. The supernatant was transferred into a different flask and an excess of triphenylphosphine (5.53 g, 21.09 mmol) was added. The solution was refluxed over 3 days and cooled to room temperature without stirring to favor sedimentation. The supernatant again removed by decantation and the resulting colorless oil was dried over high vacuum affording the title compound 176 (18.24 g) in 87% yield. 1H NMR: (300 MHz, CDCl3) δ: 7.96-7.62 (m, 9H), 7.37-7.08 (m, 6H), 4.11-4.00 (m, 2H), 3.86-3.70 (m, 2H), 2.37-2.32 (m, 4H), 2.28-2.19 (m, 2H), 1.72-1.46 (m, 6H), 1.31-1.25 (m, 2H), 1.22-1.15 (m, 3H). MS (ESI)=419 (Phosphonium Ion).

Workup

  1. temperatureThe solution was refluxed over 24 hours under nitrogen atmosphere
  2. customThe supernatant was transferred into a different flask
  3. temperatureThe solution was refluxed over 3 days
  4. temperaturecooled to room temperature
  5. customThe supernatant again removed by decantation
  6. customthe resulting colorless oil was dried over high vacuum

Sources & evidence

ORD record
ord-8db8d4fccdeb4f49b2ec54abf0d81cf6
Source dataset
uspto-grants-2007_10
Patent number
US07288567B2

Reaction notes

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