Methane, dichloromethoxy- → HCID 178450318, compound

HRID 35773Notes

Reaction equation

HRID 35773 reaction equation
[C:1]([C:6]1[C:7](=[O:22])[CH2:8][CH:9]([C:13]2[C:18]([CH3:19])=[CH:17][C:16]([CH3:20])=[CH:15][C:14]=2[CH3:21])[CH2:10][C:11]=1[OH:12])(=[O:5])[CH2:2][CH2:3][CH3:4].[CH3:23][O:24]C(Cl)Cl>ClC(Cl)C.[Ti](Cl)(Cl)(Cl)Cl>[C:1]([C:6]1[C:11](=[O:12])[CH2:10][CH:9]([C:13]2[C:14]([CH3:21])=[CH:15][C:16]([CH3:20])=[C:17]([CH:23]=[O:24])[C:18]=2[CH3:19])[CH2:8][C:7]=1[OH:22])(=[O:5])[CH2:2][CH2:3][CH3:4]

Participants

5

Reactant 2

HCID 21004Methane, dichloromethoxy-HCID 178450313HCID 178450313, compound

Product 1

HCID 178450318HCID 178450318, compoundYield 26.7%

Reagents, catalysts & solvents 2

HCID 24193Titanium TetrachlorideCatalystHCID 63651,1-DichloroethaneSolvent2×

Procedure

To a solution of 2-butyryl-3-hydroxy-5-mesitylcyclohex-2-en-1-one (1.20 g) in dichloroethane (20 ml) at 0° C. was added titanium tetrachloride (300 g) over a period of 3 minutes. While the solution was stirred and cooled dichloromethyl methyl ether (0.46 g) in dichloroethane(20 ml) was added dropwise over a 25 minute period. After the addition was complete, the mixture was stirred for 5 minutes at 0° C., for 30 minutes at room temperature and for 2 hours under reflux. The cooled reaction mixture was poured into a separatory funnel containing crushed ice and was shaken thoroughly. The organic layer was separated, and the aqueous solution was extracted with methylene chloride. The combined organic solution was washed with water, dried over anhydrous sodium sulfate and evaporated to dryness to give a crude brown oil (0.70 g). Purification by column chromatography over silica gel (eluant dichloromethane) gave 2-butyryl-3-hydroxy-5-(3-formyl-2,4,6-trimethylphenyl)cyclohex-2-en-1-one (0.35 g) as a pale yellow oil. Proton nuclear magnetic resonance spectrum (CDCl3 ; δ in ppm): 1.0 (3H, t); 1.68 (2H, m); 2.43 (3H, s); 2.48 (3H, s); 2.61 (3H, s); 2.65-4.20 (7H, m); 6.94 (1H, s); 10.54 (1H, s); 18.33 (1H, s).

Workup

  1. additionwas added dropwise over a 25 minute period
  2. additionAfter the addition
  3. stirringthe mixture was stirred for 5 minutes at 0° C., for 30 minutes at room temperature and for 2 hours
  4. temperatureunder reflux
  5. customThe cooled reaction mixture
  6. additionwas poured into a separatory funnel
  7. additioncontaining
  8. customcrushed ice
  9. stirringwas shaken thoroughly
  10. customThe organic layer was separated
  11. extractionthe aqueous solution was extracted with methylene chloride
  12. washThe combined organic solution was washed with water
  13. dry with materialdried over anhydrous sodium sulfate
  14. customevaporated to dryness
  15. customto give a crude brown oil (0.70 g)
  16. customPurification by column chromatography over silica gel (eluant dichloromethane)

Sources & evidence

ORD record
ord-6b7f57e2f2ed4efbaf73f7951fb4294f
Source dataset
uspto-grants-1988_08
Patent number
US04767879

Reaction notes

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