Ethyl Acetate → HCID 178438677, compound

HRID 2048569Notes

Reaction equation

HRID 2048569 reaction equation
[Si]([O:8][C@H:9]1[CH2:14][CH2:13][C@H:12]([N:15]2[C:20](=[O:21])[C:19]([CH2:22][C:23]3[CH:28]=[CH:27][C:26]([C:29]4[C:30]([C:35]#[N:36])=[CH:31][CH:32]=[CH:33][CH:34]=4)=[CH:25][CH:24]=3)=[C:18]([CH2:37][CH2:38][CH3:39])[N:17]3[N:40]=[CH:41][C:42]([F:43])=[C:16]23)[CH2:11][CH2:10]1)(C(C)(C)C)(C)C.[F-].C([N+](CCCC)(CCCC)CCCC)CCC.[C:62]([O:65][CH2:66][CH3:67])(=[O:64])[CH3:63].[Cl-].[NH4+]>O1CCCC1>[C:35]([C:30]1[CH:31]=[CH:32][CH:33]=[CH:34][C:29]=1[C:26]1[CH:27]=[CH:28][C:23]([CH2:22][C:19]2[C:20](=[O:21])[N:15]([C@H:12]3[CH2:11][CH2:10][C@H:9]([O:8][CH2:63][C:62]([O:65][CH2:66][CH3:67])=[O:64])[CH2:14][CH2:13]3)[C:16]3[N:17]([N:40]=[CH:41][C:42]=3[F:43])[C:18]=2[CH2:37][CH2:38][CH3:39])=[CH:24][CH:25]=1)#[N:36]

Participants

6

Reactant 4

HCID 8857Ethyl AcetateHCID 25517Ammonium ChlorideHCID 2724141Tetrabutylammonium FluorideHCID 178438691HCID 178438691, compound

Product 1

HCID 178438677HCID 178438677, compoundYield 42%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Conditions

Temperature
70 °C

Procedure

To a solution of 4′-{[4-(trans-4-{[tert-butyl(dimethyl)silyl]oxy}cyclohexyl)-3-fluoro-5-oxo-7-propyl-4,5-dihydropyrazolo[1,5-a]pyrimidin-6-yl]methyl}biphenyl-2-carbonitrile (0.24 g) in tetrahydrofuran (2 mL) was added tetrabutylammonium fluoride (1 mL), and the mixture was stirred at 70° C. for 2 hr. Ethyl acetate and saturated aqueous ammonium chloride solution were added to the reaction mixture, and the mixture was extracted with ethyl acetate. The organic layer was washed with water and then with saturated brine, dried over anhydrous magnesium sulfate, and concentrated. The residue was dissolved in toluene (2 mL), rhodium acetate (dimer, 0.016 g) was added, ethyl diazoacetate (0.19 mL) was added dropwise at 100° C., and the mixture was stirred for 3 hr. Ethyl acetate and water were added to the reaction mixture, and the mixture was extracted with ethyl acetate. The organic layer was washed with water and then with saturated brine, dried over anhydrous magnesium sulfate, and concentrated. The residue was purified by silica gel column chromatography to give the title compound as a pale-yellow amorphous solid (0.087 g, 42%).

Workup

  1. extractionthe mixture was extracted with ethyl acetate
  2. washThe organic layer was washed with water
  3. dry with materialwith saturated brine, dried over anhydrous magnesium sulfate
  4. concentrationconcentrated
  5. dissolutionThe residue was dissolved in toluene (2 mL)
  6. additionrhodium acetate (dimer, 0.016 g) was added
  7. additionethyl diazoacetate (0.19 mL) was added dropwise at 100° C.
  8. stirringthe mixture was stirred for 3 hr
  9. additionEthyl acetate and water were added to the reaction mixture
  10. extractionthe mixture was extracted with ethyl acetate
  11. washThe organic layer was washed with water
  12. dry with materialwith saturated brine, dried over anhydrous magnesium sulfate
  13. concentrationconcentrated
  14. customThe residue was purified by silica gel column chromatography

Sources & evidence

ORD record
ord-69a682f32ee548849c73450c9c912569
Source dataset
uspto-grants-2013_11
Patent number
US08592431B2

Reaction notes

Loading…