Ethyl cyanoacetate → 6-Ethyl-4-hydroxy-7-methyl-2-oxo-2H-1-benzopyran-3-carbonitrile

HRID 596902Notes

Reaction equation

HRID 596902 reaction equation
[C:1]([O:4][C:5]1[CH:13]=[C:12]([CH3:14])[C:11]([CH2:15][CH3:16])=[CH:10][C:6]=1[C:7](Cl)=[O:8])(=[O:3])[CH3:2].[Na].[C:18](CC(OCC)=O)#[N:19].[H-].[Na+].[OH-].[Na+]>CCOCC.O>[C:18]([C:2]1[C:1](=[O:3])[O:4][C:5]2[C:6]([C:7]=1[OH:8])=[CH:10][C:11]([CH2:15][CH3:16])=[C:12]([CH3:14])[CH:13]=2)#[N:19]

Participants

8

Reactant 5

HCID 7764Ethyl cyanoacetate2×HCID 14798Sodium HydroxideHCID 24758Sodium hydrideHCID 5360545SodiumHCID 12366432HCID 12366432, compound

Product 1

HCID 547236166-Ethyl-4-hydroxy-7-methyl-2-oxo-2H-1-benzopyran-3-carbonitrile

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 3283Diethyl EtherSolvent2×

Procedure

2-Acetoxy-5-ethyl-4-methylbenzoyl chloride (11.5 g) in dry ether (75 ml) was added slowly to a stirred, refluxing suspension of the sodium salt of ethyl cyanoacetate [prepared from ethyl cyanoacetate (14.97 g) and a 60% suspension of sodium hydride in mineral oil (5.00 g)] in dry ether (275 ml). Refluxing was continued for 18 hours, the mixture cooled and poured into water (500 ml) containing 2.5N sodium hydroxide (30 ml). The alkaline phase was separated, washed with ether (× 3), acidified with 12N hydrochloric acid and filtered. Recrystallisation from ethanol-dilute hydrochloric acid gave 3-cyano-6-ethyl-4-hydroxy-7-methyl coumarin, m.p. 224°-226° C. (Found; C, 68.22; H, 5.01; N, 5.64; C13H11NO3 requires; C, 68.11; H, 4.84; N, 6.11).

Workup

  1. temperaturerefluxing
  2. temperatureRefluxing
  3. temperaturethe mixture cooled
  4. customThe alkaline phase was separated
  5. washwashed with ether (× 3)
  6. filtrationfiltered
  7. customRecrystallisation from ethanol-dilute hydrochloric acid

Sources & evidence

ORD record
ord-e98819e95bf743ffa6e54418409d6bc0
Source dataset
uspto-grants-1977_03
Patent number
US04012407

Reaction notes

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