Propionic Acid → 4,6,6-Trimethyl-1,3-cyclohexadiene-1-carboxaldehyde

HRID 1867950Notes

Reaction equation

HRID 1867950 reaction equation
[CH3:1][C:2]([CH3:6])=[CH:3][CH:4]=[O:5].[C:7](O)([CH2:10][CH3:11])([CH3:9])[CH3:8].[C:13](O)(=[O:16])CC.S([O-])([O-])(=O)=O.[Na+].[Na+].[C:25](N)([CH2:28][C:29]([CH3:32])([CH3:31])[CH3:30])([CH3:27])[CH3:26].[C:34](=O)([O-])[O-].[K+].[K+]>CCCCCC.CCCCCCC>[CH3:1]/[C:2](/[CH:6]=[CH:11]/[CH:10]=[C:7]([CH3:9])[CH3:8])=[CH:3]\[CH:4]=[O:5].[CH3:26][C:25]1[CH2:28][C:29]([CH3:32])([CH3:31])[C:30]([CH:13]=[O:16])=[CH:34][CH:27]=1

Participants

10

Reactant 6

HCID 1032Propionic Acid2×HCID 64052-Methyl-2-butanolHCID 11430Potassium CarbonateHCID 24436Sodium SulfateHCID 61017tert-OctylamineHCID 610203-Methyl-2-butenal

Product 2

HCID 109206834,6,6-Trimethyl-1,3-cyclohexadiene-1-carboxaldehydeHCID 11126441HCID 11126441, compound

Reagents, catalysts & solvents 2

HCID 8058HexaneSolventHCID 8900HeptaneSolvent

Procedure

174 mg (2.07 mmol) of 3-methyl-2-butenal, 1.00 mL of heptane, 1.00 mL of tert-amyl alcohol, 0.20 mL (2.7 mmol) of propionic acid (99+%), 58 mg of anhydrous sodium sulfate (granular), and 17 mg of tert-octylamine were added to a stoppered 25 mL, 1-neck reaction flask containing a TEFLON®-coated spin bar. The reaction mixture was stirred at room temperature for 4 days, then diluted with 10 mL of hexane. 600 mg of anhydrous potassium carbonate was added, and the mixture subsequently was stirred at room temperature for 45 minutes to neutralize propionic acid. The product then was isolated in the manner described in Example 2 to afford 69 mg of dehydrolavandulal (1), dehydrocitral (2), and 4,6,6-trimethyl-1,3-cyclohexadiene-1-carboxaldehyde (3) in a ratio of 83:10:7, respectively. Approximately 30% of this product mixture was the N-tert-octyl imine derivative of 3-methyl-2-butenal, which can be removed from the polyenals according to the hydrolysis procedure described in Example 4.

Workup

  1. additioncontaining a TEFLON®-coated spin bar
  2. stirringthe mixture subsequently was stirred at room temperature for 45 minutes
  3. customThe product then was isolated in the manner

Sources & evidence

ORD record
ord-d811ba1aeb494810914927b3d80c73fd
Source dataset
uspto-grants-2009_12
Patent number
US07632973B2

Reaction notes

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