Acetaldehyde → HCID 117899618, compound

HRID 522296Notes

Reaction equation

HRID 522296 reaction equation
[ClH:1].[CH3:2][N:3]1[C:7]2[N:8]=[C:9]([C:31]#[N:32])[N:10]=[C:11]([C:12]3[CH:13]=[N:14][C:15]([O:22][CH2:23][CH2:24][CH:25]4[CH2:30][CH2:29][CH2:28][NH:27][CH2:26]4)=[C:16]([C:18]([F:21])([F:20])[F:19])[CH:17]=3)[C:6]=2[CH:5]=[CH:4]1.[C:33](O[BH-](OC(=O)C)OC(=O)C)(=O)[CH3:34].[Na+].C(=O)C.C([O-])(O)=O.[Na+]>ClC(Cl)C.CCOC(C)=O.C(O)(=O)C.C(N(CC)CC)C>[ClH:1].[CH2:33]([N:27]1[CH2:28][CH2:29][CH2:30][CH:25]([CH2:24][CH2:23][O:22][C:15]2[N:14]=[CH:13][C:12]([C:11]3[C:6]4[CH:5]=[CH:4][N:3]([CH3:2])[C:7]=4[N:8]=[C:9]([C:31]#[N:32])[N:10]=3)=[CH:17][C:16]=2[C:18]([F:20])([F:21])[F:19])[CH2:26]1)[CH3:34]

Participants

9

Reactant 4

HCID 177AcetaldehydeHCID 516892Sodium BicarbonateHCID 5049666Sodium triacetoxyborohydrideHCID 117899604HCID 117899604, compound

Product 1

HCID 117899618HCID 117899618, compoundYield 86.8%

Reagents, catalysts & solvents 4

HCID 176Acetic AcidSolventHCID 63651,1-DichloroethaneSolventHCID 8471TriethylamineSolventHCID 8857Ethyl AcetateSolvent

Procedure

Triethylamine (90 μL) was added to a solution of 7-methyl-4-{6-[2-(piperidin-3-yl)ethoxy]-5-(trifluoromethyl)pyridin-3-yl}-7H-pyrrolo[2,3-d]pyrimidine-2-carbonitrile monohydrochloride (100 mg) in dichloroethane (2 mL) at room temperature, and the mixture was stirred at the same temperature for 20 minutes. After mixture was ice-cooled, acetic acid (61 μL), sodium triacetoxyborohydride (91 mg), and acetaldehyde (36 μL) were added thereto, and the mixture was stirred for 1 hour under ice-cooling. After a saturated aqueous NaHCO3 solution was added to the reaction mixture, extraction thereof was performed using EtOAc, and the extract was washed with water and saturated brine. The organic layer was dried over MgSO4 and filtered, and the filtrate was concentrated under reduced pressure. The residue was purified by basic silica gel column chromatography (Hex:EtOAc=80:20 to 40:60). The obtained product was dissolved in EtOAc (1 mL), then a 4 M solution of hydrogen chloride in EtOAc (0.3 mL) was added thereto at room temperature, and the mixture was stirred at the same temperature for 10 minutes. The precipitate was collected by filtration, whereby 4-{6-[2-(1-ethylpiperidin-3-yl)ethoxy]-5-(trifluoromethyl)pyridin-3-yl}-7-methyl-7H-pyrrolo[2,3-d]pyrimidine-2-carbonitrile monohydrochloride (92 mg) was obtained as a pale yellow solid.

Workup

  1. temperaturecooled
  2. stirringthe mixture was stirred for 1 hour under ice-
  3. temperaturecooling
  4. washthe extract was washed with water and saturated brine
  5. dry with materialThe organic layer was dried over MgSO4
  6. filtrationfiltered
  7. concentrationthe filtrate was concentrated under reduced pressure
  8. customThe residue was purified by basic silica gel column chromatography (Hex:EtOAc=80:20 to 40:60)
  9. dissolutionThe obtained product was dissolved in EtOAc (1 mL)
  10. additiona 4 M solution of hydrogen chloride in EtOAc (0.3 mL) was added
  11. stirringat room temperature, and the mixture was stirred at the same temperature for 10 minutes
  12. filtrationThe precipitate was collected by filtration

Sources & evidence

ORD record
ord-54e262818d1b4315976b566ba779bb1d
Source dataset
uspto-grants-2016_05
Patent number
US09328118B2

Reaction notes

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