Propanal → 2-Methyl-4-(2,2,3-trimethylcyclopent-3-en-1-yl)but-2-enal

HRID 972169Notes

Reaction equation

HRID 972169 reaction equation
[CH3:1][C:2]1[C:6]([CH3:8])([CH3:7])[CH:5]([CH2:9][CH:10]=O)[CH2:4][CH:3]=1.[CH:12](=[O:15])[CH2:13][CH3:14].[OH-].[Na+].CO>O>[CH3:14][C:13](=[CH:10][CH2:9][CH:5]1[CH2:4][CH:3]=[C:2]([CH3:1])[C:6]1([CH3:7])[CH3:8])[CH:12]=[O:15]

Participants

6

Reactant 4

HCID 527PropanalHCID 887MethanolHCID 14798Sodium HydroxideHCID 984973-Cyclopentene-1-acetaldehyde, 2,2,3-trimethyl-

Product 1

HCID 30175572-Methyl-4-(2,2,3-trimethylcyclopent-3-en-1-yl)but-2-enal

Reagents, catalysts & solvents 1

HCID 962WaterSolvent

Procedure

A mixture of campholenic aldehyde (456 g, 3.0 mol) and freshly distilled propionaldehyde (348 g, 6.0 mol) was slowly added, over a 1.0 hour period, to a stirred refluxing solution of 18 ml of 40% aqueous sodium hydroxide and 800 ml methanol. The mixture was refluxed an additional two hours, cooled to room temperature and poured into 1,000 ml of water. The resultant solution was extracted three times with 300 ml of hexane. The hexane extracts were combined, washed first with 600 ml of water and then with 600 ml of brine. The solvent was removed by distillation and the oil fractionally distilled to yield the 2-methyl-4-(2,2,3-trimethylcyclopent-3-en-1-yl)but-2-enal. Yield 323 g (56.1% theory); bp 64°-65° C (0.9 mm); mol wt. 192 (ms); ir, 3035, 2710, 1690 (s), 1640 (s), 800 cm-1 ; nmr, 0.8δ and 1.0 (6 H, 2s, geminal dimethyl groups), 1.7 (3H, broad s, olefinic methyl attached to the cyclopentenyl group), 1.9-2.2 (3H, broad multiplet), 2.3-2.6 (3H, broad multiplet), 5.3 (1H, broad multiplet, olefinic H), 6.6 (1H, t, J~7.5 Hz), 9.4 (1H, sharp s, aldehyde H).

Workup

  1. additionwas slowly added, over a 1.0 hour period, to a stirred
  2. temperatureThe mixture was refluxed an additional two hours
  3. extractionThe resultant solution was extracted three times with 300 ml of hexane
  4. washwashed first with 600 ml of water
  5. customThe solvent was removed by distillation
  6. distillationthe oil fractionally distilled

Sources & evidence

ORD record
ord-6ec228b658704d33b8d96119708f6a21
Source dataset
uspto-grants-1977_10
Patent number
US04052341

Reaction notes

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