Triphenylsilanol → (2,6,6-Trimethyl-4-oxocyclohex-2-en-1-ylidene)acetaldehyde

HRID 2051056

Reaction equation

HRID 2051056 reaction equation
C1([Si](C2C=CC=CC=2)(C2C=CC=CC=2)[OH:8])C=CC=CC=1.[CH3:21][C:22]1[C:27](O)([C:28]#[CH:29])[C:26]([CH3:32])([CH3:31])[CH2:25][C:24](=[O:33])[CH:23]=1>C1(C)C(C)=CC=CC=1.[V].C(O)(=O)CCCCCCCCCCCCCCCCC>[CH3:21][C:22]1[C:27](=[CH:28][CH:29]=[O:8])[C:26]([CH3:32])([CH3:31])[CH2:25][C:24](=[O:33])[CH:23]=1

Participants

6

Reactant 2

HCID 69925TriphenylsilanolHCID 578890HCID 578890, compound

Product 1

HCID 53790600(2,6,6-Trimethyl-4-oxocyclohex-2-en-1-ylidene)acetaldehydeYield 365.2%

Reagents, catalysts & solvents 3

HCID 5281Stearic AcidCatalystHCID 23990VanadiumCatalystHCID 7237O-XyleneSolvent

Procedure

Triphenylsilanol (22 g) and 80 g (0.45 mol) of 3,5,5-trimethyl-4-hydroxy-4-ethynylcyclohex-2-en-1-one and 1.6 g of stearic acid are dissolved in 800 ml of xylene, treated with 1.92 ml of vanadium isopropylate and heated to reflux temperature while stirring. After 31/2 hours the reaction mixture is cooled and washed with 5% sodium bicarbonate, whereby an emulsion results. The organic phase is then separated, the emulsion is also separated and extracted with ether. The organic phases are dried over magnesium sulphate and concentrated. The residue (117.9 g) is distilled (oil bath 130°-170°; 0.001 mm Hg). In this manner there are obtained 51.8 g (64.8%) of (2,6,6-trimethyl-4-oxo-2-cyclohexen-1-ylidene)acetaldehyde (Z:E=about 3:1).

Workup

  1. temperatureheated
  2. temperatureto reflux temperature
  3. temperatureAfter 31/2 hours the reaction mixture is cooled
  4. washwashed with 5% sodium bicarbonate, whereby an emulsion
  5. customresults
  6. customThe organic phase is then separated
  7. customthe emulsion is also separated
  8. extractionextracted with ether
  9. dry with materialThe organic phases are dried over magnesium sulphate
  10. concentrationconcentrated
  11. distillationThe residue (117.9 g) is distilled (oil bath 130°-170°; 0.001 mm Hg)

Sources & evidence

ORD record
ord-0359fddf0abb462580cf59fabb0bbe63
Source dataset
uspto-grants-1991_05
Patent number
US05015779

Linked notes

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