Acetic Acid → HCID 18438119, compound

HRID 1643204Notes

Reaction equation

HRID 1643204 reaction equation
[Li]C.[CH2:3]([C:7]1[C:8]([C:13]2[CH:18]=[CH:17][CH:16]=[CH:15][CH:14]=2)=[N:9][CH:10]=[N:11][CH:12]=1)[CH2:4][CH2:5][CH3:6].[CH3:19]C(O)=O.[OH-].[Na+]>CCOCC.C1COCC1.O>[CH2:3]([C:7]1[C:12]([CH3:19])=[N:11][CH:10]=[N:9][C:8]=1[C:13]1[CH:18]=[CH:17][CH:16]=[CH:15][CH:14]=1)[CH2:4][CH2:5][CH3:6]

Participants

8

Reactant 4

HCID 176Acetic AcidHCID 14798Sodium HydroxideHCID 18438120HCID 18438120, compoundHCID 178418348HCID 178418348, compound

Product 1

HCID 18438119HCID 18438119, compound

Reagents, catalysts & solvents 3

HCID 962WaterSolvent2×HCID 3283Diethyl EtherSolvent2×HCID 8028TetrahydrofuranSolvent2×

Conditions

Temperature
-30 °C

Procedure

1.4 M MeLi in Et2O (1.54 ml, 2.16 mmol) is slowly added to a solution of 5-butyl-4-phenyl-pyrimidine (436 mg, 2.05 mmol) in Et2O (6 mL) at −30° C. under N2. The reaction mixture is stirred at −30° C. for 30 minutes and then at 0° C. for 45 minutes. Next, a solution of AcOH (0.12 mL) and H2O (0.02 mL) in THF (2 mL) is added, followed by a solution of 2,3-dichloro-5,6-dicyano-1,4-benzophenone (DDQ) (466 mg, 2.05 mmol) in THF (5 mL). The resulting mixture is stirred at room temperature for 5 minutes, recooled to 0° C., and then treated with 3.0 M aqueous NaOH. The mixture is stirred at 0° C. for 5 minutes, diluted with H2O, and extracted twice with Et2O. The combined extracts are dried over Na2SO4 and concentrated. The dark residue is purified by flash chromatography on silica gel. Elution with 2:1 Hex-EtOAc followed by 1:1 hexanes-EtOAc affords 5-butyl-4-methyl-6-phenyl-pyrimidine as a light yellow oil. 1H NMR (CDCl3, 300 MHz) δ 8.95 (s, 1H), 7.45 (m, 5H), 2.67-2.62 (m, 2H), 2.61 (s, 3H), 1.48-1.40 (m, 2H), 1.25 (sext, J=7.2 Hz), 0.82 (t, J=7.2 Hz, 3H) ppm. MS: m/z 227 [M+1].

Workup

  1. waitat 0° C. for 45 minutes
  2. stirringThe resulting mixture is stirred at room temperature for 5 minutes
  3. customrecooled to 0° C.
  4. stirringThe mixture is stirred at 0° C. for 5 minutes
  5. extractionextracted twice with Et2O
  6. dry with materialThe combined extracts are dried over Na2SO4
  7. concentrationconcentrated
  8. customThe dark residue is purified by flash chromatography on silica gel
  9. washElution with 2:1 Hex-EtOAc

Sources & evidence

ORD record
ord-180cda5c17fa4d458032028dabf75a34
Source dataset
uspto-grants-2012_02
Patent number
US08119665B2

Reaction notes

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