Methane, dichloromethoxy- → HCID 11601212, compound

HRID 486397Notes

Reaction equation

HRID 486397 reaction equation
[CH3:1][C:2]1([CH3:16])[C:10]2[C:5](=[CH:6][C:7]([CH3:11])=[CH:8][CH:9]=2)[C:4]([CH3:15])([CH:12]([CH3:14])[CH3:13])[CH2:3]1.[CH3:17][O:18]C(Cl)Cl>[Ti](Cl)(Cl)(Cl)Cl.C(Cl)Cl>[CH:17]([C:8]1[CH:9]=[C:10]2[C:5]([C:4]([CH3:15])([CH:12]([CH3:13])[CH3:14])[CH2:3][C:2]2([CH3:16])[CH3:1])=[CH:6][C:7]=1[CH3:11])=[O:18]

Participants

5

Reactant 2

HCID 21004Methane, dichloromethoxy-HCID 19926097HCID 19926097, compound

Product 1

HCID 11601212HCID 11601212, compound

Reagents, catalysts & solvents 2

HCID 24193Titanium TetrachlorideCatalystHCID 6344DichloromethaneSolvent

Procedure

Next, 1,1,3,5-tetramethyl-3-isopropylindane (12.96 g) is placed in a 1 liter three-necked round bottom flask equipped with a reflux condenser, a stirrer and a dropping funnel. In accordance with the general procedures described in Organic Syntheses, Collective Vol. 5, pp. 49-50, by A. Rieche, H. Gross, and E. Hoft, edited by H.E. Baumgarten, John Wiley and Sons (New York, N.Y. 1973), methylene chloride (37.5 ml) is added to the flask. The solution is then cooled in an ice bath, and titanium tetrachloride (19.0 g) is added over a period of about 3 minutes. While the solution is stirred and cooled, α,α-dichloromethyl methyl ether (5.75 g) is added dropwise over a 25 minute period. After the addition is complete, the mixture is stirred for about 5 minutes in the ice bath, for about 30 minutes without cooling, and for about 15 minutes at about 35° C. The reaction mixture is then poured into a separatory funnel containing about 50 g of crushed ice and is shaken thoroughly. The organic layer is separated, and the aqueous solution is extracted with two 10 ml portions of methylene chloride. The combined organic solution is washed three times with 10 ml portions of water. A crystal of hydroquinone is added to the methylene chloride solution, which is then dried over anhydrous sodium sulfate. After evaporation of the solvent, the residue is distilled to yield as a crude product, 6-formyl-1,1,3,5-tetramethyl-3-isopropylindane. The 6 formyl-1,1,3,5 tetramethyl-3-isopropylindane is then further purified using standard fractional distillation techniques.

Workup

  1. customequipped with a reflux condenser, a stirrer and a dropping funnel
  2. temperatureThe solution is then cooled in an ice bath
  3. temperaturecooled
  4. additionAfter the addition
  5. temperaturewithout cooling
  6. additionThe reaction mixture is then poured into a separatory funnel
  7. stirringis shaken thoroughly
  8. customThe organic layer is separated
  9. extractionthe aqueous solution is extracted with two 10 ml portions of methylene chloride
  10. washThe combined organic solution is washed three times with 10 ml portions of water
  11. additionA crystal of hydroquinone is added to the methylene chloride solution, which
  12. dry with materialis then dried over anhydrous sodium sulfate
  13. customAfter evaporation of the solvent
  14. distillationthe residue is distilled

Sources & evidence

ORD record
ord-f491ca7d419743beae5c29a5ff23d163
Source dataset
uspto-grants-1994_03
Patent number
US05292720

Reaction notes

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