Bromide ion → HCID 178527054, compound

HRID 1934335Notes

Reaction equation

HRID 1934335 reaction equation
[Mg].II.[C:4]1([CH2:10][CH2:11][CH2:12]Br)[CH:9]=[CH:8][CH:7]=[CH:6][CH:5]=1.[Br-].C([O:17][P:18](Cl)[O:19]CC)C.C([Mg]Br)CC1C=CC=CC=1.Cl>O.C(OCC)C>[C:4]1([CH2:10][CH2:11][CH2:12][PH:18](=[O:17])[OH:19])[CH:9]=[CH:8][CH:7]=[CH:6][CH:5]=1

Participants

10

Reactant 7

HCID 259Bromide ionHCID 313Hydrochloric AcidHCID 807IodineHCID 12503(3-Bromopropyl)benzeneHCID 68530Ethyl phosphorochloriditeHCID 5462224Magnesium2×HCID 178419670HCID 178419670, compound

Product 1

HCID 178527054HCID 178527054, compoundYield 53.2%

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 3283Diethyl EtherSolvent3×

Conditions

Temperature
35 °C

Procedure

To magnesium turnings (2.44 g, 0.10 mol) in 20 Ml of dry diethyl ether under an atmosphere of nitrogen was added several iodine crystals. Phenylpropyl bromide (20.0 g, 0.10 mol) in 80 Ml of diethyl ether was placed in a dropping funnel. Approximately 10 Ml of the bromide solution was added to the magnesium turnings and stirring was initiated. After several minutes the iodine was consumed and additional phenylpropyl bromide was added while maintaining a temperature of 35° C. Once addition was complete (1.5 hours) the mixture was sealed and stored at 5° C. Diethylchlorophosphite (15.7 g, 0.1 mol) in 50 Ml of dry diethyl ether was cooled to 5° C. under an atmosphere of nitrogen. Phenethylmagnesium bromide (100 Ml, 0.1 mol, 1.0 M solution of in Et2O) was added dropwise over 2 hours while maintaining a temperature between 0-10° C. A thick white slurry formed and was stirred for an additional 30 minutes. The mixture was filtered under a nitrogen atmosphere and the filtrate evaporated under reduced pressure to give a clear and colorless liquid. To the liquid was added 20 Ml of water followed by 0.5 ml of concentrated hydrochloric acid. An exothermic reaction was observed and stirring continued for 20 minutes followed by extraction with ethyl acetate. The organics were combined, washed with brine, dried (MgSO4) and evaporated. To the clear liquid was added sodium hydroxide (40 Ml, 2.0 M NaOH), the resulting solution stirred for 1 hour and then washed with diethyl ether. The aqueous layer was acidified to Ph 1.0 with concentrated hydrochloric acid and extracted twice with ethyl acetate. The organics were combined, dried (MgSO4) and evaporated to give 3-phenylpropylphosphinic acid (1, R=CH2CH2CH2Ph, R1=H) (9.8 g, 53%) as a clear and colorless oil.

Workup

  1. customAfter several minutes the iodine was consumed
  2. additionadditional phenylpropyl bromide was added
  3. additionOnce addition
  4. custom(1.5 hours)
  5. customwas sealed
  6. customstored at 5° C
  7. temperaturewhile maintaining a temperature between 0-10° C
  8. customA thick white slurry formed
  9. stirringwas stirred for an additional 30 minutes
  10. filtrationThe mixture was filtered under a nitrogen atmosphere
  11. customthe filtrate evaporated under reduced pressure
  12. customto give a clear and colorless liquid
  13. customAn exothermic reaction
  14. stirringstirring
  15. extractionfollowed by extraction with ethyl acetate
  16. washwashed with brine
  17. dry with materialdried (MgSO4)
  18. customevaporated
  19. additionTo the clear liquid was added sodium hydroxide (40 Ml, 2.0 M NaOH)
  20. stirringthe resulting solution stirred for 1 hour
  21. washwashed with diethyl ether
  22. extractionextracted twice with ethyl acetate
  23. dry with materialdried (MgSO4)
  24. customevaporated

Sources & evidence

ORD record
ord-9894ef0336eb4b959734953502fc5164
Source dataset
uspto-grants-2002_05
Patent number
US06384022B1

Reaction notes

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