Di-tert-butyl dicarbonate → Naphthalene

HRID 895939Notes

Reaction equation

HRID 895939 reaction equation
BrN[C:3]1[C:12]2[C:7](=[CH:8][CH:9]=[CH:10][CH:11]=2)[CH:6]=[CH:5][CH:4]=1.C(OC(OC(OC(C)(C)C)=O)=O)(C)(C)C>C1(C)C=CC=CC=1>[CH:11]1[C:12]2[C:7](=[CH:6][CH:5]=[CH:4][CH:3]=2)[CH:8]=[CH:9][CH:10]=1

Participants

4

Reactant 2

HCID 90495Di-tert-butyl dicarbonateHCID 22066267HCID 22066267, compound

Product 1

HCID 931Naphthalene

Reagents, catalysts & solvents 1

HCID 1140TolueneSolvent

Conditions

Temperature
70 °C

Procedure

A mixture of 4-bromoaminonaphthalene (5.0 g) and di-tert-butyldicarbonate (5.9 g) in 100 mL toluene was heated at 70° C. for 15 hours, cooled to room temperature and the volatiles removed in vacuo. The residue was dissolved in ethyl acetate, washed with 0.1M HCl and brine, dried (MgSO4) and the volatiles removed in vacuo. Recrystallization of the residue from hot petroleum ether provided LXXXIV. 4-Vinylpyridine (0.86 mL) was added to a suspension of LXXXIV (2.0 g) in 5 mL of triethylamine, followed by palladium (II) acetate (0.014 g) and tri-ortho-tolylphosphine (0.038 g). The mixture was heated at 110° C. for four hours, cooled to room temperature, diluted with water and ethyl acetate. The organic layer was washed with brine, dried (MgSO4) and the volatiles removed in vacuo. Purification of the residue by flash chromatography using 50% ethyl acetate in hexanes as the eluent and concentration of the product-rich fractions in vacuo provided naphthalene LXXXV. A solution of LXXXV (0.34 g) in 10 mL TFA was stirred one hour and the volatiles removed in vacuo to provided LXXXVI. LXXXVI and LXVII (Example 1) were reacted according to Method B to provide 6, m.p. 203° C. (dec).

Workup

  1. temperaturecooled to room temperature
  2. customthe volatiles removed in vacuo
  3. dissolutionThe residue was dissolved in ethyl acetate
  4. washwashed with 0.1M HCl and brine
  5. dry with materialdried (MgSO4)
  6. customthe volatiles removed in vacuo
  7. customRecrystallization of the residue from hot petroleum ether provided LXXXIV
  8. addition4-Vinylpyridine (0.86 mL) was added to a suspension of LXXXIV (2.0 g) in 5 mL of triethylamine
  9. temperatureThe mixture was heated at 110° C. for four hours
  10. temperaturecooled to room temperature
  11. additiondiluted with water and ethyl acetate
  12. washThe organic layer was washed with brine
  13. dry with materialdried (MgSO4)
  14. customthe volatiles removed in vacuo
  15. customPurification of the residue by flash chromatography

Sources & evidence

ORD record
ord-1baabd0683c54138a0e8e4ae5cff1445
Source dataset
uspto-grants-2005_07
Patent number
US06916814B2

Reaction notes

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