Urea → HCID 86654076, compound

HRID 521003Notes

Reaction equation

HRID 521003 reaction equation
N([O-])=O.[Na+].[CH2:5]1[C@H:14]2[C@H:9]([CH2:10][CH2:11][C:12]3[CH:18]=[CH:17][C:16](N)=[CH:15][C:13]=32)[NH:8][CH2:7][CH2:6]1.[NH2:20][C:21](N)=O.[C-]#N.[Na+].[Cu]C#N>O.S(=O)(=O)(O)O>[CH2:5]1[C@H:14]2[C@H:9]([CH2:10][CH2:11][C:12]3[CH:18]=[CH:17][C:16]([C:21]#[N:20])=[CH:15][C:13]=32)[NH:8][CH2:7][CH2:6]1

Participants

8

Reactant 5

HCID 1176UreaHCID 8929Sodium CyanideHCID 23668193Sodium NitriteHCID 86654077HCID 86654077, compoundHCID 178418546HCID 178418546, compound

Product 1

HCID 86654076HCID 86654076, compound

Reagents, catalysts & solvents 2

HCID 962WaterSolvent2×HCID 1118Sulfuric AcidSolvent

Conditions

Temperature
-5 °C

Procedure

Sodium nitrite (0.12 g) dissolved in water (0.7 mL) is added dropwise to a solution of cis-1,2,3,4,4a,5,6,10b-octahydro-benzo[f]quinolin-9-ylamine (0.36 g) in half-concentrated sulfuric acid (0.6 ml) cooled to ca. −5° C. The solution is stirred for 15 min in the cooling bath prior to the addition of urea (30 mg). The resulting solution is added to a vigorously stirred solution of sodium cyanide (0.32 g) and copper(I) cyanide (0.19 g) in water (1.4 mL) cooled to ca. −5° C. The mixture is stirred in the cooling bath for another 10 min and then the cooling bath is removed. After stirring at room temperature for 10 min, the mixture is heated to 70° C. and stirred at this temperature for 1 h. The mixture is cooled to room temperature, basified with 4 M NaOH solution (1.5 mL), and extracted with dichloromethane. The combined extracts are dried (Na2SO4) and the solvent is evaporated. The residue is chromatographed on silica gel [dichloromethane/(dichloromethane/methanol/NH4OH 50:48:2) 80:20→40:60] to give the title compound as a resin-like solid. Yield: 0.12 g (31% of theory); Mass spectrum (ESI+): m/z=213 [M+H]+.

Workup

  1. temperaturecooled to ca. −5° C
  2. stirringThe mixture is stirred in the cooling bath for another 10 min
  3. customthe cooling bath is removed
  4. stirringAfter stirring at room temperature for 10 min
  5. temperaturethe mixture is heated to 70° C.
  6. stirringstirred at this temperature for 1 h
  7. temperatureThe mixture is cooled to room temperature
  8. extractionextracted with dichloromethane
  9. dry with materialThe combined extracts are dried (Na2SO4)
  10. customthe solvent is evaporated
  11. customThe residue is chromatographed on silica gel [dichloromethane/(dichloromethane/methanol/NH4OH 50:48:2) 80:20→40:60]

Sources & evidence

ORD record
ord-7fca2d4e987847d98334952acc6fcd34
Source dataset
uspto-grants-2016_05
Patent number
US09328072B2

Reaction notes

Loading…