Sodium Carbonate → 3-Cyclopentene-1-acetaldehyde, 2,2,3-trimethyl-

HRID 972166Notes

Reaction equation

HRID 972166 reaction equation
[CH3:1][C:2]1([CH3:11])[CH:5]2[C:6]3([CH3:10])[O:9][CH:7]3[CH2:8][CH:3]1[CH2:4]2.C(=O)([O-])[O-].[Na+].[Na+]>C1C=CC=CC=1.[Cl-].[Zn+2].[Cl-]>[CH3:4][C:5]1[C:2]([CH3:1])([CH3:11])[CH:3]([CH2:8][CH:7]=[O:9])[CH2:10][CH:6]=1

Participants

5

Reactant 2

HCID 10340Sodium CarbonateHCID 91508alpha-Pinene oxide

Product 1

HCID 984973-Cyclopentene-1-acetaldehyde, 2,2,3-trimethyl-Yield 70.2%

Reagents, catalysts & solvents 2

HCID 3007855ZincchlorideCatalystHCID 241BenzeneSolvent

Conditions

Temperature
86 °C

Procedure

To a rapidly stirred refluxing suspension of 7.5 g (0.055 mole) of zinc chloride (anhydrous) in 1000 ml of benzene there was added 304 g (2.0 moles) of α-pinene epoxide over 1.0-1.25 hour period. The resultant mixture was heated at reflux (86° C) for 1.0-1.5 hours, cooled to 25° C and then poured into 400 ml of 5% sodium carbonate solution. The aqueous layer was drawn off and the benzene layer washed twice with 400 ml of brine. The solvent was removed and the oil fractionally distilled to give campholenic aldehyde: 193.2 g (70.2% yield), bp 51°-52° C (1.5 mm); nD20 1.4658; mol wt. 152 (ms); nmr, 0.8δ (3H, s), 1.0 (3H, s), 1.6 (3H, broad s, olefinic CH3), 2.1-2.6 (4H, broad complex), 5.2 (1H, broad multiplet, olefinic H), 9.7 (1H, doublet of doublets, J~3.5 + 1.5 Hz, aldehyde H); ir, 3020, 2700, 1714, 790 cm-1.

Workup

  1. temperaturerefluxing
  2. temperaturecooled to 25° C
  3. washthe benzene layer washed twice with 400 ml of brine
  4. customThe solvent was removed
  5. distillationthe oil fractionally distilled

Sources & evidence

ORD record
ord-b0af9a6c862743d8a91f2be3475c36da
Source dataset
uspto-grants-1977_10
Patent number
US04052341

Reaction notes

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