Hydrochloric Acid → HCID 22461963, compound

HRID 1936521Notes

Reaction equation

HRID 1936521 reaction equation
[F:1][C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][C:3]=1[F:8].C([Li])CCC.[O:14]1[CH:16]([CH2:17][CH2:18][CH2:19][CH2:20][CH2:21][CH3:22])[CH2:15]1.B(F)(F)F.CCOCC.Cl>C1COCC1>[F:1][C:2]1[C:3]([F:8])=[CH:4][CH:5]=[CH:6][C:7]=1[CH2:15][CH:16]([OH:14])[CH2:17][CH2:18][CH2:19][CH2:20][CH2:21][CH3:22]

Participants

7

Reactant 5

HCID 313Hydrochloric AcidHCID 8000Boron trifluoride etherateHCID 97061,2-DifluorobenzeneHCID 181262-HexyloxiraneHCID 178418339Butyllithium

Product 1

HCID 22461963HCID 22461963, compoundYield 75.2%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Conditions

Temperature
-70 °C

Procedure

To a stirred solution of 1,2-difluorobenzene 1 (20.0 g, 0.175 mol) in dry THF (300 ml) was added dropwise a solution of 2.5 M n-butyllithium (68 ml, 0.17 mol) at −70° C. under dry nitrogen. The addition rate was such that the temperature did not rise above −60° C. After the addition was completed the reaction was stirred at −70° C. for 2 h. 1,2-Epoxyoctane (21.6 g, 0.169 mol) was added slowly followed by the dropwise addition of boron trifluoride etherate (21 ml, 0.17 mol). The mixture was allowed to warm to room temperature overnight, acidified with 10% hydrochloric acid and extracted into ether. The combined extracts were washed with sat. aqueous sodium chloride and evaporated to give a viscous liquid. Kugelrohr distillation (130° C., 0.15 mm Hg) yielded 1-(2,3-difluorophenyl)-octan-2-ol (30.8 g, 74%) which crystallised on standing; Vmax 3370 br (OH), 2950, 2920, 2850, 1620, 1590, 1480 s, 1280, 1205, 1070 br, 825, 775, and 730 cm−1, δH 0.88 (3 H, t, Me), 1.23-1.40 (10H, m, CH2), 1.40-1.58 (4 H, m overlapping br s, CH2CHOH and OH), 2.72 (1 H, ddd, J16, 8 and 2 Hz, ArCH2), 2.91 (1 H, ddd, J16, 6, and 2 Hz, ArCH2), 3.86 (1 H, m, CHOH), and 6.94-7.09 (3 H, m, ArH); m/z 242 (M+), 225, 198, 157, 139, 128, and 97.

Workup

  1. customdid not rise above −60° C
  2. additionAfter the addition
  3. temperatureto warm to room temperature overnight
  4. extractionextracted into ether
  5. washThe combined extracts were washed with sat. aqueous sodium chloride
  6. customevaporated
  7. customto give a viscous liquid
  8. distillationKugelrohr distillation (130° C., 0.15 mm Hg)

Sources & evidence

ORD record
ord-2f58e652e3ca4aad945ad5a9603c11c4
Source dataset
uspto-grants-2002_05
Patent number
US06391397B1

Reaction notes

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