Sodium Nitrite → HCID 136352668, compound

HRID 241383Notes

Reaction equation

HRID 241383 reaction equation
N[C:2]1[C:28]([CH3:29])=[CH:27][C:5]2[C:6]([CH2:9][CH2:10][C:11]3[S:12][C:13]4[CH:22]=[C:21]([C:23]([F:26])([F:25])[F:24])[CH:20]=[CH:19][C:14]=4[C:15]=3[CH:16]([CH3:18])[CH3:17])=[N:7][O:8][C:4]=2[CH:3]=1.N([O-])=[O:31].[Na+]>OS(O)(=O)=O.O>[CH:16]([C:15]1[C:14]2[CH:19]=[CH:20][C:21]([C:23]([F:24])([F:25])[F:26])=[CH:22][C:13]=2[S:12][C:11]=1[CH2:10][CH2:9][C:6]1[C:5]2[CH:27]=[C:28]([CH3:29])[C:2]([OH:31])=[CH:3][C:4]=2[O:8][N:7]=1)([CH3:17])[CH3:18]

Participants

5

Reactant 2

HCID 23668193Sodium NitriteHCID 66883168HCID 66883168, compound

Product 1

HCID 136352668HCID 136352668, compoundYield 20%

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 1118Sulfuric AcidSolvent2×

Conditions

Temperature
120 °C

Procedure

The above-mentioned 6-amino-3-[2-[3-isopropyl-6-(trifluoromethyl)benzothiophen-2-yl]ethyl]-5-methylbenzisoxazole (100 mg, 0.239 mmol) was suspended in 25% H2SO4 (2.0 mL). A solution of sodium nitrite (25 mg, 0.36 mmol) in water (1.0 mL) was added to the suspension under cooling with ice. After the mixture was stirred for 30 min under the same conditions, and added dropwise to 75% H2SO4 (1.5 mL) that heated to 120° C. The mixture was heated for 1 h at 120° C., cooled to room temperature, diluted with ice-cold water, and extracted with ethyl acetate. The organic layer was washed with brine and dried over anhydrous sodium sulfate. After the solvent was removed, the residue was purified by silica gel column chromatography (hexane/ethyl acetate, 5:1) to give the titled compound (20 mg) as yellow crystal (20 mg, yield 20%).

Workup

  1. temperatureunder cooling with ice
  2. temperatureThe mixture was heated for 1 h at 120° C.
  3. temperaturecooled to room temperature
  4. additiondiluted with ice-cold water
  5. extractionextracted with ethyl acetate
  6. washThe organic layer was washed with brine
  7. dry with materialdried over anhydrous sodium sulfate
  8. customAfter the solvent was removed
  9. customthe residue was purified by silica gel column chromatography (hexane/ethyl acetate, 5:1)

Sources & evidence

ORD record
ord-aa1e975489db49ae9a11a6e043c1ba2a
Source dataset
uspto-grants-2014_02
Patent number
US08648208B2

Reaction notes

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