1-Bromopropane → HCID 12137884, compound

HRID 2179871Notes

Reaction equation

HRID 2179871 reaction equation
[F:1][C:2]1[CH:3]=[CH:4][CH:5]=[C:6]2[C:15]=1[C:14]([F:16])=[C:13]1[C:8]([CH2:9][CH:10]([CH3:17])[CH2:11][O:12]1)=[CH:7]2.[CH2:18]([Li])[CH2:19][CH2:20]C.CC(C)([O-])C.[K+].C(Br)CC>O1CCCC1>[F:1][C:2]1[C:3]([CH2:18][CH2:19][CH3:20])=[CH:4][CH:5]=[C:6]2[C:15]=1[C:14]([F:16])=[C:13]1[C:8]([CH2:9][CH:10]([CH3:17])[CH2:11][O:12]1)=[CH:7]2

Participants

6

Reactant 4

HCID 78401-BromopropaneHCID 22486549HCID 22486549, compoundHCID 23665647Potassium tert-butoxideHCID 178418339Butyllithium

Product 1

HCID 12137884HCID 12137884, compoundYield 23.7%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent2×

Conditions

Temperature
-95 °C

Procedure

The 8,9-difluoro-3-methyl-1,2,3,4-tetrahydro-1-oxaanthracene (1.5 g) obtained in this way was dissolved in 40 ml of tetrahydrofuran and admixed at −75° C. with 7 mmol of n-butyllithium. After stirring for a further 30 minutes, a solution of 7 mmol of potassium tert-butoxide in 20 ml of tetrahydrofuran was added dropwise. After cooling to −95° C., 15 mmol of propyl bromide were added dropwise. After 2 h, the temperature was cooled to −70° C., the mixture was stirred at this temperature for a further 1 h and was then allowed to come to 0° C. overnight. The mixture was added to 200 ml of ice-water and extracted twice with 100 ml each time of tert-butyl methyl ether, and the organic phases were combined, washed with water and saturated sodium chloride solution and dried. The solvent was distilled off under reduced pressure and the brown residue was chromatographed through 500 g of silica gel using heptane/toluene (9:1, v/v). 0.42 g of 8,9-difluoro-3-methyl-7-propyl-1,2,3,4-tetrahydro-1-oxaanthracene was obtained as a colorless syrup.

Workup

  1. waitAfter 2 h
  2. temperaturethe temperature was cooled to −70° C.
  3. stirringthe mixture was stirred at this temperature for a further 1 h
  4. waitto come to 0° C. overnight
  5. extractionextracted twice with 100 ml each time of tert-butyl methyl ether
  6. washwashed with water and saturated sodium chloride solution
  7. customdried
  8. distillationThe solvent was distilled off under reduced pressure
  9. customthe brown residue was chromatographed through 500 g of silica gel

Sources & evidence

ORD record
ord-663bdf749fb14a74a6dad668e7cc9c73
Source dataset
uspto-grants-2005_05
Patent number
US06887533B2

Reaction notes

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