Nitromethane → 2,2,5-Trimethyl-4-oxocyclopentane-1-carbaldehyde

HRID 1283572Notes

Reaction equation

HRID 1283572 reaction equation
[CH3:1][C:2]1[C:3](=[O:9])[CH2:4][C:5]([CH3:8])([CH3:7])[CH:6]=1.[N+]([CH3:13])([O-])=O.[OH-:14].C([N+](C)(C)C)C1C=CC=CC=1>CO.CCOCC>[CH:13]([CH:6]1[C:5]([CH3:8])([CH3:7])[CH2:4][C:3](=[O:9])[CH:2]1[CH3:1])=[O:14]

Participants

6

Reactant 3

HCID 6375NitromethaneHCID 66854Benzyltrimethylammonium hydroxideHCID 6424962,4,4-trimethylcyclopent-2-en-1-one

Product 1

HCID 215183822,2,5-Trimethyl-4-oxocyclopentane-1-carbaldehyde

Reagents, catalysts & solvents 2

HCID 887MethanolSolventHCID 3283Diethyl EtherSolvent2×

Procedure

124 g. of 2,4,4-trimethyl-cyclopent-2-en1-one are introduced into 67 g. of nitromethane and, after the addition of 10 ml. of a 40% solution of benzyltrimethylammonium hydroxide in methanol, stirred at 70°C. for 3 days. The mixture is then taken up in ether The ether solution is washed with 10% sulfuric acid, dried over sodium sulfate and evaporated under reduced presssure. The remaining 2,4,4-trimethyl-3-nitromethyl-cyclopentanone boils after rectification in a high vacuum at 97°-100°C/0.2 mmHg. 83 g. of the 2,4,4-trimethyl-3-nitromethyl-cyclopentanone are treated with 36 g. of sodium hydroxide in 600 ml. of water. After the addition of 300 ml. of a saturated aqueous magnesium sulfate solution, the mixture is stirred for 30 minutes, then treated dropwise at 0°C. within 1 hour with a solution of 49.7 g. of potassium permanganate in 800 ml. of water and subsequently filtered. The filtrate is extracted with methylene chloride. The extract is dried over sodium sulfate and evaporated under reduced pressure. There is obtained 1-formyl-3-oxo-2,5,5-trimethyl-cyclopentane, whose 2,4-dinitrophenylhydrazone has a melting point of 174°-177°C.

Workup

  1. washis washed with 10% sulfuric acid
  2. dry with materialdried over sodium sulfate
  3. customevaporated under reduced presssure
  4. customat 97°-100°C
  5. additionof the 2,4,4-trimethyl-3-nitromethyl-cyclopentanone are treated with 36 g
  6. additionAfter the addition of 300 ml
  7. additiontreated dropwise at 0°C. within 1 hour with a solution of 49.7 g
  8. filtrationof water and subsequently filtered
  9. extractionThe filtrate is extracted with methylene chloride
  10. dry with materialThe extract is dried over sodium sulfate
  11. customevaporated under reduced pressure

Sources & evidence

ORD record
ord-af6da8fef2ee4423ae52f48bfc16e26b
Source dataset
uspto-grants-1976_08
Patent number
US03975445

Reaction notes

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