Hydrochloric Acid → HCID 86081792, compound

HRID 747806Notes

Reaction equation

HRID 747806 reaction equation
[CH2:1]([Li])[CH2:2][CH2:3]C.CC(C)([O-])C.[K+].[F:12][C:13]1[CH:14]=[CH:15][C:16]2[CH:17]=[CH:18][C:19]3[C:24]([C:25]=2[C:26]=1[F:27])=[C:23]([F:28])[C:22]([O:29][CH3:30])=[CH:21][CH:20]=3.BrCCC.Cl>O1CCCC1.COC(C)(C)C.O>[F:12][C:13]1[C:14]([CH2:1][CH2:2][CH3:3])=[CH:15][C:16]2[CH:17]=[CH:18][C:19]3[C:24]([C:25]=2[C:26]=1[F:27])=[C:23]([F:28])[C:22]([O:29][CH3:30])=[CH:21][CH:20]=3

Participants

9

Reactant 5

HCID 313Hydrochloric AcidHCID 78401-BromopropaneHCID 23665647Potassium tert-butoxideHCID 59749866HCID 59749866, compoundHCID 178418339Butyllithium

Product 1

HCID 86081792HCID 86081792, compoundYield 33.9%

Reagents, catalysts & solvents 3

HCID 962WaterSolventHCID 8028TetrahydrofuranSolvent2×HCID 15413tert-Butyl methyl etherSolvent

Procedure

A solution of 11 mmol of n-butyllithium (1.6 M solution in hexane) in 20 ml of dry tetrahydrofuran was cooled to ≦−70° C. and admixed dropwise under a protective gas atmosphere with a solution of 11 mmol of potassium tert-butoxide in 12 ml of the same solvent. After stirring for 15-30 min, a solution of 2.8 g of 3,4,5-trifluoro-6-methoxyphenanthrene in 20 ml of tetrahydrofuran was added dropwise in such a way that the internal temperature was always below −70° C. Subsequently, stirring was continued at this temperature for 2 h. 2.5 g of 1-bromopropane were then added slowly and the mixture was subsequently brought slowly to −10° C. It was admixed at −10° C. with 6 ml of water and acidified to pH 1 with concentrated hydrochloric acid. 100 ml of tert-butyl methyl ether were added, the phases were separated, and the organic phase was washed with saturated sodium chloride solution and dried over sodium sulfate. The solvents were removed under reduced pressure, and the residue was chromatographed using silica gel with 9:1 (v/v) heptane/ethyl acetate. The product-containing fractions were combined, the solvent was distilled off under reduced pressure and the residue was recrystallized from acetonitrile. 1.1 g of 3,4,5-trifluoro-6-methoxy-2-propylphenanthrene were obtained.

Workup

  1. customwas always below −70° C
  2. stirringSubsequently, stirring
  3. waitwas continued at this temperature for 2 h
  4. customwas subsequently brought slowly to −10° C
  5. customthe phases were separated
  6. washthe organic phase was washed with saturated sodium chloride solution
  7. dry with materialdried over sodium sulfate
  8. customThe solvents were removed under reduced pressure
  9. customthe residue was chromatographed
  10. distillationthe solvent was distilled off under reduced pressure
  11. customthe residue was recrystallized from acetonitrile

Sources & evidence

ORD record
ord-9bbbbb27b06f40bf91173f16fb276863
Source dataset
uspto-grants-2008_07
Patent number
US07399505B2

Reaction notes

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