Sodium Nitrite → HCID 67781534, compound

HRID 1756256Notes

Reaction equation

HRID 1756256 reaction equation
[F:1][C:2]([F:16])([F:15])[C:3]1[CH:4]=[CH:5][C:6]2[O:13][C:10]3([CH2:12][CH2:11]3)[CH2:9][NH:8][C:7]=2[CH:14]=1.[N:17]([O-])=O.[Na+]>C(O)(=O)C.CO.O>[NH2:17][N:8]1[C:7]2[CH:14]=[C:3]([C:2]([F:1])([F:15])[F:16])[CH:4]=[CH:5][C:6]=2[O:13][C:10]2([CH2:11][CH2:12]2)[CH2:9]1

Participants

6

Reactant 2

HCID 23668193Sodium NitriteHCID 67781703HCID 67781703, compound

Product 1

HCID 67781534HCID 67781534, compoundYield 71.3%

Reagents, catalysts & solvents 3

HCID 176Acetic AcidSolventHCID 887MethanolSolventHCID 962WaterSolvent2×

Procedure

3,4-Dihydro-6-trifluoromethyl-2H-1,4-benzoxazine-2-spiro-cyclopropane (930 mg) was dissolved in 0.6 ml of acetic acid and 10 ml of methanol. Added dropwise to the resulting solution was a solution of 616 mg of sodium nitrite in 2 ml of water. The reaction mixture was stirred for 3 hours at room temperature, poured into water and then extracted with chloroform. The organic layer was washed with saturate saline and then dried over anhydrous magnesium sulfate. The chloroform was distilled off and the residue was dissolved in 1.1 ml of acetic acid and 12 ml of ethanol. Zinc powder (1.13 g) was added little by little, followed by stirring for 2 hours at room temperature. Insoluble substance was filtered off and the filtrate was concentrated. The residue was dissolved in chloroform. The solution so formed was successively washed with a 10% aqueous solution of sodium hydroxide, water and saturated brine and then dried over anhydrous magnesium sulfate. The solvent was distilled off and the residue was purified by silica gel chromatography, whereby 707 mg of the title compound were obtained (yield 71%).

Workup

  1. additionAdded dropwise to the resulting solution
  2. extractionextracted with chloroform
  3. washThe organic layer was washed
  4. concentrationwith saturate saline
  5. dry with materialdried over anhydrous magnesium sulfate
  6. distillationThe chloroform was distilled off
  7. dissolutionthe residue was dissolved in 1.1 ml of acetic acid
  8. additionZinc powder (1.13 g) was added little by little,
  9. stirringby stirring for 2 hours at room temperature
  10. filtrationInsoluble substance was filtered off
  11. concentrationthe filtrate was concentrated
  12. dissolutionThe residue was dissolved in chloroform
  13. customThe solution so formed
  14. washwas successively washed with a 10% aqueous solution of sodium hydroxide, water and saturated brine
  15. dry with materialdried over anhydrous magnesium sulfate
  16. distillationThe solvent was distilled off
  17. customthe residue was purified by silica gel chromatography

Sources & evidence

ORD record
ord-f97f5ab0e2934d499ae42af04b358e6a
Source dataset
uspto-grants-1995_08
Patent number
US05440036

Reaction notes

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