Triphenylphosphine → (3-(Ethoxycarbonyl)propyl)triphenylphosphonium Bromide

HRID 1883561Notes

Reaction equation

HRID 1883561 reaction equation
[C:1]1([P:7]([C:14]2[CH:19]=[CH:18][CH:17]=[CH:16][CH:15]=2)[C:8]2[CH:13]=[CH:12][CH:11]=[CH:10][CH:9]=2)[CH:6]=[CH:5][CH:4]=[CH:3][CH:2]=1.[Br:20][CH2:21][CH2:22][CH2:23][C:24]([O:26][CH2:27][CH3:28])=[O:25]>C(OCC)C>[Br-:20].[CH2:27]([O:26][C:24]([CH2:23][CH2:22][CH2:21][P+:7]([C:1]1[CH:2]=[CH:3][CH:4]=[CH:5][CH:6]=1)([C:8]1[CH:13]=[CH:12][CH:11]=[CH:10][CH:9]=1)[C:14]1[CH:15]=[CH:16][CH:17]=[CH:18][CH:19]=1)=[O:25])[CH3:28]

Participants

4

Reactant 2

HCID 11776TriphenylphosphineHCID 76300Ethyl 4-bromobutyrate

Product 1

HCID 2773643(3-(Ethoxycarbonyl)propyl)triphenylphosphonium Bromide

Reagents, catalysts & solvents 1

HCID 3283Diethyl EtherSolvent2×

Conditions

Temperature
100 °C

Procedure

A mixture of triphenylphosphine (24.6 g; 0.0936 mol) and ethyl 4-bromobutyrate (from Aldrich) (14.4 mL; 0.101 mol) was heated from room temperature to 105° C. over a period of 15-20 minutes; then heating was continued at 105° C. for 10 minutes. The solution was allowed to cool, but while still warm, diethyl ether (50 mL) was cautiously added via a condenser. The resultant gum was triturated to obtain a white powder. Ether was decanted, fresh diethyl ether (50 mL) was added, and trituration continued for 10 min. The reaction mixture was filtered, the filter cake washed with diethyl ether, and then solvent was removed under vacuum from the combined filtrate and washings to obtain a mixture of oil and solids. This mixture was heated to 100° C.; was cautiously treated with diethyl ether (2×55 mL); and the trituration, filtration, and concentration sequence described above was repeated. The two batches of white solids obtained from this process were combined, triturated with toluene (150 mL), filtered, and the collected solids were washed with toluene and dried under high vacuum to obtain the title salt (53). FABMS 377 (M+) mp 177-179° C.

Workup

  1. temperaturewas heated from room temperature to 105° C. over a period of 15-20 minutes
  2. temperaturethen heating
  3. temperatureto cool
  4. temperaturewhile still warm
  5. customThe resultant gum was triturated
  6. customto obtain a white powder
  7. customEther was decanted
  8. additionfresh diethyl ether (50 mL) was added
  9. waittrituration continued for 10 min
  10. filtrationThe reaction mixture was filtered
  11. washthe filter cake washed with diethyl ether
  12. customsolvent was removed under vacuum from the combined filtrate and washings
  13. customto obtain
  14. additiona mixture of oil and solids
  15. filtrationand the trituration, filtration, and concentration sequence
  16. customThe two batches of white solids obtained from this process
  17. customtriturated with toluene (150 mL)
  18. filtrationfiltered
  19. washthe collected solids were washed with toluene
  20. customdried under high vacuum

Sources & evidence

ORD record
ord-b913cd0edcc34ca3a36529b4be43cd02
Source dataset
uspto-grants-2004_07
Patent number
US06762186B2

Reaction notes

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