Stannous chloride dihydrate → HCID 67252512, compound

HRID 2042108Notes

Reaction equation

HRID 2042108 reaction equation
[N:1]([O-])=O.[Na+].[CH3:5][C:6]1[CH:15]=[CH:14][C:13]2[C:8](=[CH:9][CH:10]=[C:11]([NH2:16])[CH:12]=2)[N:7]=1.O.O.[Sn](Cl)Cl.[CH3:22][C:23]([CH3:30])([CH3:29])[C:24](=O)[CH2:25][C:26]#[N:27]>O.Cl.CCOCC.C(O)C>[C:23]([C:24]1[CH:25]=[C:26]([NH2:27])[N:16]([C:11]2[CH:12]=[C:13]3[C:8](=[CH:9][CH:10]=2)[N:7]=[C:6]([CH3:5])[CH:15]=[CH:14]3)[N:1]=1)([CH3:30])([CH3:29])[CH3:22]

Participants

9

Reactant 4

HCID 61436Stannous chloride dihydrateHCID 1031482-Methylquinolin-6-amineHCID 108871Pentanenitrile, 4,4-dimethyl-3-oxo-HCID 23668193Sodium Nitrite

Product 1

HCID 67252512HCID 67252512, compoundYield 24.2%

Reagents, catalysts & solvents 4

HCID 313Hydrochloric AcidSolvent2×HCID 702EthanolSolventHCID 962WaterSolventHCID 3283Diethyl EtherSolvent

Conditions

Temperature
0 °C

Procedure

A solution of sodium nitrite (502 mg, 7.27 mmol) in H2O (8 ml) was added dropwise to a well-stirred 0° C. mixture of 2-methylquinolin-6-amine (1.00 g, 6.32 mmol) in conc. HCl (10 ml). The resulting mixture was stirred at 0° C. for 1 h. Tin(II) chloride dihydrate (6.13 g, 27.2 mmol) in conc. HCl (8 ml) was added and stirring was continued at 0° C. for 1 h and then RT for 2 h. Ethanol (60 ml) and 4,4-dimethyl-3-oxopentanenitrile (1.03 g, 8.22 mmol) were added and the mixture was heated at reflux overnight. The completed reaction mixture was concentrated in vacuo and diluted with ethyl acetate (100 mL). The mixture was cooled in an ice/water bath and made basic (pH˜8) with solid sodium hydroxide. The solution was filtered through Celite, and the filter cake was washed with water (50 mL) and ethyl acetate (100 mL). The organic phase was separated, washed with brine, dried (Na2SO4), and concentrated to yield a foam. The foam was stirred in ether (50 mL) and allowed to stand for several hours. The resultant solid was collected by filtration and dried in vacuo to yield 3-tert-butyl-1-(2-methylquinolin-6-yl)-1H-pyrazol-5-amine (428 mg, 24% yield). MS (ESI) m/z: 281.2 (M+H+).

Workup

  1. stirringstirring
  2. waitwas continued at 0° C. for 1 h
  3. waitRT for 2 h
  4. temperaturethe mixture was heated
  5. temperatureat reflux overnight
  6. customThe completed reaction mixture
  7. concentrationwas concentrated in vacuo
  8. additiondiluted with ethyl acetate (100 mL)
  9. temperatureThe mixture was cooled in an ice/water bath
  10. filtrationThe solution was filtered through Celite
  11. washthe filter cake was washed with water (50 mL) and ethyl acetate (100 mL)
  12. customThe organic phase was separated
  13. washwashed with brine
  14. dry with materialdried (Na2SO4)
  15. concentrationconcentrated
  16. customto yield a foam
  17. waitto stand for several hours
  18. filtrationThe resultant solid was collected by filtration
  19. customdried in vacuo

Sources & evidence

ORD record
ord-1eb26509f4fe4a06bc09a4fc15cdfc46
Source dataset
uspto-grants-2013_11
Patent number
US08586565B2

Reaction notes

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