Pyruvic Acid → 2-Ethyl-3-methyl-3-phenylbutanoic acid

HRID 1865750

Reaktionsgleichung

Reaktionsgleichung von HRID 1865750
[CH3:1][C:2]([CH3:13])([C:7]1[CH:12]=[CH:11][CH:10]=[CH:9][CH:8]=1)[CH2:3][C:4]([OH:6])=[O:5].C(=O)=O.[CH3:17][C:18](C)=O.C([N-]C(C)C)(C)C.[Li+].C(O)(=O)C(C)=O.N1C=CC=NC1=O.C(I)C>O1CCCC1>[CH2:17]([CH:3]([C:2]([CH3:13])([C:7]1[CH:12]=[CH:11][CH:10]=[CH:9][CH:8]=1)[CH3:1])[C:4]([OH:6])=[O:5])[CH3:18]

Komponenten

8

Edukt 6

HCID 1060Pyruvic AcidHCID 6340IodoethaneHCID 13890beta-Phenylisovaleric acidHCID 684012(1H)-PyrimidinoneHCID 2724682Lithium diisopropylamideHCID 18522661Acetone cardice

Produkt 1

HCID 112757642-Ethyl-3-methyl-3-phenylbutanoic acidAusbeute 30 %

Reagenzien, Katalysatoren, Lösungsmittel 1

HCID 8028TetrahydrofuranLösungsmittel

Versuchsvorschrift

In accordance with a modified literature procedure (Pfeffer, P. E.; Silbert, L. S.; Chirinko, J. M. J. Org. Chem. 37(3), 1972, 451-458), a solution of 3,3-dimethyl-3-phenyl propionic acid (0.47 g, 2.6 mmol, from Reference Example 22) in tetrahydrofuran (4.5 mL) is cooled to −40° C. (dry ice/acetone) while stirring under a nitrogen atmosphere. Lithium diisopropylamide (Aldrich, 2.0 M solution in tetrahydrofuran/ethylbenzene/heptane, 2.9 mL, 5.8 mmol) is added dropwise via syringe, followed by 1,3-dimethyl-3,4,5,6-tetrahydro-2(1H-pyrimidinone (DMPU, 0.35 mL, 2.9 mmol). The reaction mixture is then allowed to warm to room temperature and to stir for 30 minutes before being re-cooled to 0° C. (ice water bath). Ethyl iodide (0.31 mL, 3.9 mmol) is then added neat via syringe and the reaction mixture is allowed to stir overnight while warming to room temperature. The reaction is quenched by the addition of 10% aqueous hydrochloric acid solution and extracted thrice with ethyl acetate. The combined extracts are washed twice with 10% aqueous hydrochloric acid solution and once with saturated sodium chloride solution, dried over anhydrous sodium sulfite, and concentrated under reduced pressure. The crude solid is recrystallized from hexanes to afford pure material as a white solid (0.16 g, 30%). MS (ES−): (M−H)=205.0

Aufarbeitung

  1. stirringto stir for 30 minutes
  2. stirringto stir overnight
  3. temperaturewhile warming to room temperature
  4. customThe reaction is quenched by the addition of 10% aqueous hydrochloric acid solution
  5. extractionextracted thrice with ethyl acetate
  6. washThe combined extracts are washed twice with 10% aqueous hydrochloric acid solution and once with saturated sodium chloride solution
  7. dry with materialdried over anhydrous sodium sulfite
  8. concentrationconcentrated under reduced pressure
  9. customThe crude solid is recrystallized from hexanes

Quellen und Nachweise

ORD-Eintrag
ord-dbfdfd66fe23490e92ba4e7b8046afb0
Quelldatensatz
uspto-grants-2009_12
Patentnummer
US07626023B2

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