Acetic Acid → 2-Methylenetetralin-1-one

HRID 1198009Notes

Reaction equation

HRID 1198009 reaction equation
[C:1]1(=[O:11])[C:10]2[C:5](=[CH:6][CH:7]=[CH:8][CH:9]=2)[CH2:4][CH2:3][CH2:2]1.[CH2:12](NCCCC)CCC.C(O)(=O)C.C=O>C1(C)C=CC=CC=1>[CH2:12]=[C:2]1[CH2:3][CH2:4][C:5]2[C:10](=[CH:9][CH:8]=[CH:7][CH:6]=2)[C:1]1=[O:11]

Participants

6

Reactant 4

HCID 176Acetic AcidHCID 712FormaldehydeHCID 8148DibutylamineHCID 107241-Tetralone

Product 1

HCID 3777512-Methylenetetralin-1-one

Reagents, catalysts & solvents 1

HCID 1140TolueneSolvent

Conditions

Temperature
90 °C

Procedure

A 100-ml pressure-proof glass reaction vessel was charged with 2.92 g (0.02 mole) of 1-tetralone, 2.59 g (0.02 mole) of di-n-butylamine, 1.20 g (0.02 mole) of acetic acid and 15 ml of toluene. To the mixture 0.974 g (0.012 mole) of an 37% aqueous formaldehyde solution was added and the vessel was sealed and heated up to 90° C. After maintaining the temperature at 90° C. for 30 minutes, the vessel was cooled to room temperature. The contents were separated by addition of 5 ml of water, and the water layer was washed off with a 50% aqueous acetic acid solution. The toluene layer was further washed with a 10% aqueous hydrochloric acid, saturated aqueous NaHCO3 solution and saturated aqueous sodium chloride solution, to give a solution of 2-methylene-1-tetralone in toluene. The reaction mixture was analyzed by GLC and its composition was found to be 1.45 g of 2-methylene-1-tetralone and 1.16 g of unreacted 1-tetralone (the conversion of 1-tetralone: 60.2%; selectivity: 82.1%).

Workup

  1. customA 100-ml pressure-proof glass reaction vessel
  2. customthe vessel was sealed
  3. temperatureAfter maintaining the temperature at 90° C. for 30 minutes
  4. temperaturethe vessel was cooled to room temperature
  5. customThe contents were separated by addition of 5 ml of water
  6. washthe water layer was washed off with a 50% aqueous acetic acid solution
  7. washThe toluene layer was further washed with a 10% aqueous hydrochloric acid, saturated aqueous NaHCO3 solution and saturated aqueous sodium chloride solution

Sources & evidence

ORD record
ord-a72cdc9df1474954aaac36fd441892bc
Source dataset
uspto-grants-1994_01
Patent number
US05278343

Reaction notes

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