Stannous chloride dihydrate → HCID 67271472, compound

HRID 1696520Notes

Reaction equation

HRID 1696520 reaction equation
[NH2:1][C:2]1[CH:3]=[C:4]2[C:9](=[CH:10][CH:11]=1)[CH2:8][NH:7][C:6](=[O:12])[CH2:5]2.[N:13]([O-])=O.[Na+].O.O.Cl[Sn]Cl.[C:22]([CH2:28][C:29]#[N:30])(=O)[C:23]([CH3:26])([CH3:25])[CH3:24]>Cl.C(O)C>[C:23]([C:22]1[CH:28]=[C:29]([NH2:30])[N:1]([C:2]2[CH:3]=[C:4]3[C:9](=[CH:10][CH:11]=2)[CH2:8][NH:7][C:6](=[O:12])[CH2:5]3)[N:13]=1)([CH3:26])([CH3:25])[CH3:24]

Participants

7

Reactant 4

HCID 61436Stannous chloride dihydrateHCID 108871Pentanenitrile, 4,4-dimethyl-3-oxo-HCID 23668193Sodium NitriteHCID 67271462HCID 67271462, compound

Product 1

HCID 67271472HCID 67271472, compoundYield 35%

Reagents, catalysts & solvents 2

HCID 313Hydrochloric AcidSolventHCID 702EthanolSolvent

Conditions

Temperature
-10 °C

Procedure

To a suspension of 6-amino-1,2-dihydroisoquinolin-3(4H)-one (4.00 g, 20.1 mmol) in 2M HCl (40 mL) at −10° C. was added solid NaNO2 (1.39 g, 20.1 mmol) causing all solids to dissolve. The mixture was stirred at −10° C. for 30 min and then solid SnCl2.2H2O (9.09 g, 40.3 mmol) was added at −10° C. The mixture was allowed to warm to RT over a period of 30 min and then stirred for 2 h. Ethanol (160 mL) and pivaloylacetonitrile (2.52 g, 20.1 mmol) were added and the solution was heated at reflux overnight under Ar atm. The EtOH was removed under reduced pressure, H2O (200 mL) was added, and the mixture was extracted with CH2Cl2 (3×200 mL), dried (MgSO4), concentrated and purified via column chromatography to yield 6-(3-t-butyl-5-amino-1H-pyrazol-1-yl)-1,2-dihydroisoquinolin-3(4H)-one (1.98 g, 35% yield). 1H NMR (400 MHz, CDCl3): δ 7.82 (brs, 1H), 7.40 (brs, 1H), 7.35 (dd, J=8.4, and 2.4 Hz, 1H), 6.80 (d, J=8.8 Hz, 1H), 5.52 (s, 1H), 3.67 (brs, 2H), 3.01 (t, J=7.8 Hz, 2H), 2.65 (t, J=7.4 Hz, 2H), 1.30 (s, 9H); MS (ESI) m/z: 285.2 (M+H+).

Workup

  1. dissolutionto dissolve
  2. temperatureto warm to RT over a period of 30 min
  3. stirringstirred for 2 h
  4. temperaturethe solution was heated
  5. temperatureat reflux overnight under Ar atm
  6. customThe EtOH was removed under reduced pressure, H2O (200 mL)
  7. additionwas added
  8. extractionthe mixture was extracted with CH2Cl2 (3×200 mL)
  9. dry with materialdried (MgSO4)
  10. concentrationconcentrated
  11. custompurified via column chromatography

Sources & evidence

ORD record
ord-3f4c90a45a454ca38b00e85439e2c90b
Source dataset
uspto-grants-2012_04
Patent number
US08163756B2

Reaction notes

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