Hydrochloric Acid → 1-(2,3,4-Trifluorophenyl)hept-1-YN-3-OL

HRID 1765004Notes

Reaction equation

HRID 1765004 reaction equation
[C:1]([C:3]1[CH:8]=[CH:7][C:6]([F:9])=[C:5]([F:10])[C:4]=1[F:11])#[CH:2].C[Mg]Br.[CH:15](=[O:20])[CH2:16][CH2:17][CH2:18][CH3:19].Cl>C1COCC1>[OH:20][CH:15]([CH2:16][CH2:17][CH2:18][CH3:19])[C:2]#[C:1][C:3]1[CH:8]=[CH:7][C:6]([F:9])=[C:5]([F:10])[C:4]=1[F:11]

Participants

6

Reactant 4

HCID 313Hydrochloric AcidHCID 8063PentanalHCID 231157211-Ethynyl-2,3,4-trifluorobenzeneHCID 178418573HCID 178418573, compound

Product 1

HCID 231157251-(2,3,4-Trifluorophenyl)hept-1-YN-3-OLYield 107.2%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Procedure

Under nitrogen replacement, 110 g of 1-ethynyl-2,3,4-trifluorobenzene was dissolved in 440 mL of THF. To this, 846 mL of methylmagnesium bromide (1.0 M in Toluene/THF=4/1) was added dropwise for 1 hour while ice-cooling, and stirred for 30 minutes. To this, 72.8 g of pentanal was added dropwise for 1 hour, warmed to room temperature, and stirred for 1 hour. After the reaction solution was poured into 300 g of ice/300 mL of concentrated hydrochloric acid, and stirred for a while, an organic layer was separated and an aqueous layer was extracted with toluene. After the extract and the organic layer were mixed together, washed using water and a saturated saline solution in that order, and dried using anhydrous magnesium sulfate, the solvent was evaporated under a reduced pressure to obtain a brown oily material. This was purified by column chromatography (silica gel, toluene) to obtain 183 g of 1-(3-hydroxy-1-heptynyl)-2,3,4-trifluorobenzene as a reddish brown oily material.

Workup

  1. temperaturecooling
  2. stirringstirred for 1 hour
  3. stirringstirred for a while
  4. customan organic layer was separated
  5. extractionan aqueous layer was extracted with toluene
  6. extractionAfter the extract
  7. additionthe organic layer were mixed together
  8. washwashed
  9. customa saturated saline solution in that order, and dried
  10. customthe solvent was evaporated under a reduced pressure
  11. customto obtain a brown oily material
  12. customThis was purified by column chromatography (silica gel, toluene)

Sources & evidence

ORD record
ord-57572b5728a84560a1d8901e75540379
Source dataset
uspto-grants-2007_06
Patent number
US07226644B2

Reaction notes

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