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Chloride → 3,4-Dihydro-6-(2-thienyl)-1(2H)-naphthalenone

HRID 264769
Notes
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Reaction equation

HRID 264769 reaction equation
FC(F)(F)S(O[C:7]1[CH:8]=[C:9]2[C:14](=[CH:15][CH:16]=1)[C:13](=[O:17])[CH2:12][CH2:11][CH2:10]2)(=O)=O.[S:20]1[CH:24]=[CH:23][CH:22]=[C:21]1[Sn](CCCC)(CCCC)CCCC.[Cl-].[Li+].[Cl-].[F-].[NH4+]>CN(C)C=O.C(OCC)(=O)C>[S:20]1[CH:24]=[CH:23][CH:22]=[C:21]1[C:7]1[CH:8]=[C:9]2[C:14](=[CH:15][CH:16]=1)[C:13](=[O:17])[CH2:12][CH2:11][CH2:10]2
ParticipantsConditionsProcedureWorkupSources & evidenceReaction notes

Participants

8

Reactant 5

HCID 312ChlorideHCID 25516Ammonium fluorideHCID 433294Lithium ChlorideHCID 27793732-(Tri-n-butylstannyl)thiopheneHCID 110983845-Oxo-5,6,7,8-tetrahydronaphthalen-2-yl trifluoromethanesulfonate

Product 1

HCID 190368773,4-Dihydro-6-(2-thienyl)-1(2H)-naphthalenone
Yield 79.2%

Reagents, catalysts & solvents 2

HCID 6228DimethylformamideSolventHCID 8857Ethyl AcetateSolvent

Conditions

Temperature
120 °C

Procedure

3,4-Dihydro-6-trifluoromethylsulfonyloxy-1(2H)-naphthalenone (3.96 g, 13.5 mmol) was dissolved in 40 ml of N,N-dimethylformamide in an argon atmosphere, and 6.03 g (16.1 mmol) of 2-thienyltributyltin, 1.71 g (40.4 mmol) of lithium chloride and 0.47 g (0.67 mmol) of bistriphenylphosphinepalladium chloride were added to the solution. The mixture was stirred at 120° C. for 4 hours. The reaction product was cooled to room temperature. Ethyl acetate and a 2M-ammonium fluoride aqueous solution were added thereto, followed by stirring the mixture at room temperature overnight. The precipitate was filtered through Celite, and the filtrate was extracted with ethyl acetate. The organic layer was washed with a saturated sodium chloride aqueous solution, and dried over anhydrous magnesium sulfate. After the solvent was distilled off under reduced pressure, the residue was purified by silica-gel column chromatography (eluent: a mixture of 20% ethyl acetate and hexane) to obtain 2.44 g of the above-mentioned compound (yield 79%). NMR (CDCl3) δ (ppm): 8.04(1H, d, J=8 Hz), 7.57-7.35(4H, m), 7.13-7.11(1H, m), 2.99(2H, t, J=6 Hz), 2.67(2H, t, J=6 Hz), 2.21-2.11 (2H, m) MS (m/e): 228 (M+), 200

Workup

  1. additionwere added to the solution
  2. temperatureThe reaction product was cooled to room temperature
  3. stirringby stirring the mixture at room temperature overnight
  4. filtrationThe precipitate was filtered through Celite
  5. extractionthe filtrate was extracted with ethyl acetate
  6. washThe organic layer was washed with a saturated sodium chloride aqueous solution
  7. dry with materialdried over anhydrous magnesium sulfate
  8. distillationAfter the solvent was distilled off under reduced pressure
  9. customthe residue was purified by silica-gel column chromatography (eluent
  10. additiona mixture of 20% ethyl acetate and hexane)

Sources & evidence

ORD record
ord-640a0a4cdeba4eb8a9b9c2ebf8b91f14
Source dataset
uspto-grants-1997_07
DOI
10.6084/m9.figshare.5104873.v1
Patent number
US05646283

Reaction notes

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On this pageParticipantsConditionsProcedureWorkupSources & evidenceReaction notes