Triethylamine → 4-(4'-Chloro-4-methylbiphenyl-3-yl)-2,2-dimethylpyran-3,5-dione

HRID 468211Notes

Reaction equation

HRID 468211 reaction equation
[Cl:1][C:2]1[CH:7]=[CH:6][C:5]([C:8]2[CH:13]=[CH:12][C:11]([CH3:14])=[C:10]([CH:15]=[C:16]3[O:21][C:20](=[O:22])[CH2:19][O:18][C:17]3([CH3:24])[CH3:23])[CH:9]=2)=[CH:4][CH:3]=1.C(N(CC)CC)C.[C-]#N.[K+]>C(#N)C.C(OCC)(=O)C.Cl>[Cl:1][C:2]1[CH:7]=[CH:6][C:5]([C:8]2[CH:13]=[CH:12][C:11]([CH3:14])=[C:10]([CH:15]3[C:20](=[O:22])[CH2:19][O:18][C:17]([CH3:23])([CH3:24])[C:16]3=[O:21])[CH:9]=2)=[CH:4][CH:3]=1

Participants

7

Reactant 3

HCID 8471TriethylamineHCID 9032Potassium CyanideHCID 670729426-[1-(4'-Chloro-4-methylbiphenyl-3-yl)methylidene]-5,5-dimethyl-[1,4]dioxan-2-one

Product 1

HCID 670726824-(4'-Chloro-4-methylbiphenyl-3-yl)-2,2-dimethylpyran-3,5-dioneYield 89.9%

Reagents, catalysts & solvents 3

HCID 313Hydrochloric AcidSolventHCID 6342AcetonitrileSolventHCID 8857Ethyl AcetateSolvent

Procedure

To a suspension of 6-[1-(4′-chloro-4-methylbiphenyl-3-yl)methylidene]-5,5-dimethyl-[1,4]dioxan-2-one (1.5 g, 4.38 mmol) in anhydrous acetonitrile (22 ml) is added triethylamine (0.67 ml, 4.81 mmol) and potassium cyanide (30 mg, 0.46 mmol). The reaction mixture is stirred under reflux for two hours. The cooled mixture is diluted with ethyl acetate, and 0.5N aqueous hydrochloric acid is added at 0° C. The organic layer is separated and the aqueous phase extracted twice with ethyl acetate. The combined organic extracts are dried over anhydrous sodium sulfate, filtered and the filtrate evaporated in vacuo. The residue is purified by flash chromatography (heptane/ethyl acetate 1:1 ratio) to afford 4-(4′-chloro-4-methylbiphenyl-3-yl)-2,2-dimethylpyran-3,5-dione (1.35 g) as a foam. A sample of the product is stirred in hexane/diisopropyl ether (4:1 ratio) and filtered to give a white solid with a melting point of 186-188° C.

Workup

  1. temperatureunder reflux for two hours
  2. additionis added at 0° C
  3. customThe organic layer is separated
  4. extractionthe aqueous phase extracted twice with ethyl acetate
  5. dry with materialThe combined organic extracts are dried over anhydrous sodium sulfate
  6. filtrationfiltered
  7. customthe filtrate evaporated in vacuo
  8. customThe residue is purified by flash chromatography (heptane/ethyl acetate 1:1 ratio)

Sources & evidence

ORD record
ord-64cc47b7d4694167bf8e26838a2dbf68
Source dataset
uspto-grants-2014_01
Patent number
US08623907B2

Reaction notes

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