Ethyl Acetate → HCID 18475788, compound

HRID 1954834Notes

Reaction equation

HRID 1954834 reaction equation
Br[C:2]1[CH:3]=[CH:4][CH:5]=[C:6]2[C:11]=1[CH2:10][C:9]1([O:15][CH2:14][CH2:13][O:12]1)[CH2:8][CH2:7]2.[CH3:16][N:17]1[CH2:22][CH2:21][NH:20][CH2:19][CH2:18]1.CC(C)([O-])C.[Na+].C(OCC)(=O)C>C1(C)C=CC=CC=1.N>[CH3:16][N:17]1[CH2:22][CH2:21][N:20]([C:2]2[CH:3]=[CH:4][CH:5]=[C:6]3[C:11]=2[CH2:10][C:9]2([O:15][CH2:14][CH2:13][O:12]2)[CH2:8][CH2:7]3)[CH2:19][CH2:18]1

Participants

7

Reactant 4

HCID 8857Ethyl AcetateHCID 531671-MethylpiperazineHCID 10468278HCID 10468278, compoundHCID 23676156Sodium t-butoxide

Product 1

HCID 18475788HCID 18475788, compoundYield 86.7%

Reagents, catalysts & solvents 2

HCID 222AmmoniaSolvent2×HCID 1140TolueneSolvent

Conditions

Temperature
85 °C

Procedure

8'-Bromo-3',4'-dihydrospiro-[1,3-dioxolane-2,2'(1H)-naphthalene] (6.0 g, 22 mmol; described in Sunkyung L.; Stewart P. F.; David E. N. Synth. Commun. 1995, 25 (18), 2775-2780) was dissolved in toluene (180 mL) and flushed with argon. N-Methylpiperazine (3.0 mL, 27 mmol), R(+)-bis(diphenylphosphino)-1,1'-binaphthyl (830 mg, 1.3 mmol), tetrakis(dibenzylideneacetone)dipalladium (0) (510 mg, 0.45 mmol) and sodium t-butoxide (3.0 g, 31 mmol) were added and the reaction mixture was stirred at 85° C. for 2.5 h. After cooling to room temperature ethyl acetate (400 mL) and 2 M ammonia (60 mL) were added. The phases were separated and the organic layer was washed with 2 M ammonia (30 mL), brine (40 mL) and dried (MgSO4). Evaporation of the solvent gave 7.5 g of a crude product. Purification by column chromatography on silica using chloroform/methanol/conc. NH3 (180:5:0.5) as eluent afforded 5.5 g (84% yield) of the title compound as a yellowish solid: mp 127-128° C.; EIMS (70 eV) m/z (relative intensity) 288 (43, M+).

Workup

  1. customflushed with argon
  2. additionwere added
  3. customThe phases were separated
  4. washthe organic layer was washed with 2 M ammonia (30 mL), brine (40 mL)
  5. dry with materialdried (MgSO4)
  6. customEvaporation of the solvent
  7. customgave 7.5 g of a crude product
  8. customPurification by column chromatography on silica

Sources & evidence

ORD record
ord-2c50cf937cff4e4a88697bddba84476d
Source dataset
uspto-grants-2000_09
Patent number
US06124283

Reaction notes

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