6-Bromo-1-chloronaphthalen-2-ol → 1-Chloro-6-(1-pentynyl)-2-naphthol

HRID 645316Notes

Reaction equation

HRID 645316 reaction equation
[Cl:1][C:2]1[C:11]2[C:6](=[CH:7][C:8](Br)=[CH:9][CH:10]=2)[CH:5]=[CH:4][C:3]=1[OH:13]>Cl[Pd](Cl)([P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1)[P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1.[Cu](I)I.C(N(CC)CC)C>[Cl:1][C:2]1[C:11]2[C:6](=[CH:7][C:8]([C:11]#[C:2][CH2:3][CH2:4][CH3:5])=[CH:9][CH:10]=2)[CH:5]=[CH:4][C:3]=1[OH:13]

Participants

5

Reactant 1

HCID 220481596-Bromo-1-chloronaphthalen-2-ol

Product 1

HCID 673574061-Chloro-6-(1-pentynyl)-2-naphtholYield 177.5%

Reagents, catalysts & solvents 3

HCID 83717Copper iodideCatalystHCID 178418476HCID 178418476, compoundCatalystHCID 8471TriethylamineSolvent

Procedure

The compound (S7-3) was synthesized according to the method disclosed in Synthesis, No. 9, 1439 (2004). 38.3 g of 1-chloro-6-bromo-2-naphthol (S1-2), 5.2 g of PdCl2(PPh3)2, 0.71 g of copper iodide and 400 mL of triethylamine were added to a reactor under a nitrogen atmosphere and stirred at room temperature, to which 35.8 g of 1-heptine (S7-2) was added, followed by refluxing for 6 hours. The reaction mixture was cooled to room temperature, and the solvent was distilled off under reduced pressure. Ethyl acetate was added to the resulting residue, and the mixture was filtered with Celite. The resulting solution was washed with 1N hydrochloric acid and water, and dried over anhydrous magnesium sulfate. The solvent was distilled off under reduced pressure, and the resulting residue was purified by silica gel column chromatography with a mixed solvent of heptane and ethyl acetate (3/1) as a developing solvent and dried under reduced pressure to provide 32.3 g of 1-chloro-6-(1-pentynyl)-2-naphthol (S7-3).

Workup

  1. customThe compound (S7-3) was synthesized
  2. customdisclosed in Synthesis
  3. additionwas added
  4. temperatureby refluxing for 6 hours
  5. temperatureThe reaction mixture was cooled to room temperature
  6. distillationthe solvent was distilled off under reduced pressure
  7. additionEthyl acetate was added to the resulting residue
  8. filtrationthe mixture was filtered with Celite
  9. washThe resulting solution was washed with 1N hydrochloric acid and water
  10. dry with materialdried over anhydrous magnesium sulfate
  11. distillationThe solvent was distilled off under reduced pressure
  12. customthe resulting residue was purified by silica gel column chromatography with a mixed solvent of heptane and ethyl acetate (3/1) as a developing solvent
  13. customdried under reduced pressure

Sources & evidence

ORD record
ord-b8ba5a0fb7724ce59500e650d8aff193
Source dataset
uspto-grants-2010_04
Patent number
US07704409B2

Reaction notes

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