Diethyl Malonate → HCID 13280837, compound

HRID 1448979Notes

Reaction equation

HRID 1448979 reaction equation
[CH2:1]([C:3]1[CH:10]=[CH:9][C:6]([CH:7]=O)=[CH:5][CH:4]=1)[CH3:2].C(OP([CH2:19][C:20]#[N:21])(OCC)=O)C.[Na].[CH2:23]([O:25][C:26](=[O:33])[CH2:27][C:28]([O:30][CH2:31][CH3:32])=[O:29])[CH3:24]>C(Cl)Cl.[Br-].C([N+](CCCC)(CCCC)CCCC)CCC.[OH-].[Na+].C(O)C>[CH2:23]([O:25][C:26](=[O:33])[CH:27]([C:28]([O:30][CH2:31][CH3:32])=[O:29])[CH:7]([C:6]1[CH:9]=[CH:10][C:3]([CH2:1][CH3:2])=[CH:4][CH:5]=1)[CH2:19][C:20]#[N:21])[CH3:24]

Participants

9

Reactant 4

HCID 7761Diethyl MalonateHCID 208614-EthylbenzaldehydeHCID 75676Diethyl (cyanomethyl)phosphonateHCID 5360545Sodium

Product 1

HCID 13280837HCID 13280837, compound

Reagents, catalysts & solvents 4

HCID 74236Tetrabutylammonium BromideCatalystHCID 702EthanolSolventHCID 6344DichloromethaneSolvent2×HCID 14798Sodium HydroxideSolvent

Procedure

A solution of 43 g of 4-ethylbenzaldehyde and 52 g of diethylphosphonoacetonitrile in 300 ml of methylene chloride is added dropwise within 15 minutes, with ice cooling, to a well-stirred emulsion of 6.5 g of tetrabutylammonium bromide in 180 ml of 50% sodium hydroxide solution and 150 ml of methylene chloride. Stirring is maintained at room temperature for 30 minutes, the organic phase is separated, washed neutral with water, dried over sodium sulphate and concentrated in vacuo. The crude p-ethyl-cinnamic acid nitrile thus obtained is added to a solution of 8 g of sodium in 53 g of malonic acid diethyl ester and 400 ml of absolute ethanol, and the mixture is refluxed for 2 hours. It is then concentrated in vacuo to a third of the volume; 500 ml of 0.5 N acetic acid is added, and extraction is performed three times with 500 ml of ether each time. The organic phases are washed until neutral, dried over sodium sulphate and concentrated in vacuo to dryness. Chromatography of the residue on 1 kg of silica gel with methylene chloride as the eluant yields 2-carboethoxy-3-(4-ethylphenyl)-4-cyano-butyric acid ethyl ester as colourless oil.

Workup

  1. customthe organic phase is separated
  2. washwashed neutral with water
  3. dry with materialdried over sodium sulphate
  4. concentrationconcentrated in vacuo
  5. customThe crude p-ethyl-cinnamic acid nitrile thus obtained
  6. temperaturethe mixture is refluxed for 2 hours
  7. concentrationIt is then concentrated in vacuo to a third of the volume
  8. addition500 ml of 0.5 N acetic acid is added
  9. extractionextraction
  10. washThe organic phases are washed until neutral,
  11. dry with materialdried over sodium sulphate
  12. concentrationconcentrated in vacuo to dryness

Sources & evidence

ORD record
ord-ff3e601a66a246db8041ee23bdc50ef0
Source dataset
uspto-grants-1980_02
Patent number
US04188396

Reaction notes

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