m-Chloroperbenzoic acid → 161229-62-5

HRID 375525Notes

Reaction equation

HRID 375525 reaction equation
[F:1][CH:2]([F:25])[C:3]1([CH:22]([F:24])[F:23])[CH2:8][N:7]([C:9]2[CH:14]=[CH:13][CH:12]=[CH:11][N:10]=2)[C:6]2[CH:15]=[C:16]([N+:19]([O-:21])=[O:20])[CH:17]=[CH:18][C:5]=2[O:4]1.C(=O)(O)[O-:27].[Na+].C(C1C(CO)=C(SC2C=CC=C(CCCC)C=2CO)C=CC=1)CCC.ClC1C=CC=C(C(OO)=O)C=1>ClCCl.O.ClCCCl>[F:25][CH:2]([F:1])[C:3]1([CH:22]([F:24])[F:23])[CH2:8][N:7]([C:9]2[CH:14]=[CH:13][CH:12]=[CH:11][N+:10]=2[O-:27])[C:6]2[CH:15]=[C:16]([N+:19]([O-:21])=[O:20])[CH:17]=[CH:18][C:5]=2[O:4]1

Participants

8

Reactant 4

HCID 70297m-Chloroperbenzoic acidHCID 516892Sodium Bicarbonate2×HCID 21462566HCID 21462566, compoundHCID 53990823HCID 53990823, compound

Product 1

HCID 9929430161229-62-5Yield 34.4%

Reagents, catalysts & solvents 3

HCID 111,2-DichloroethaneSolventHCID 962WaterSolventHCID 6344DichloromethaneSolvent

Procedure

2-(2,2-bis(difluoromethyl)-6-nitro-3,4-dihydro-2H-1,4-benzoxazine-4-yl)pyridine (1.32 g) 50% m-chloroperbenzoic acid (2.56 g), sodium bicarbonate (1.26 g), 1,2-dichloroethane (12 mL), water (12 mL), and butylhydroxymethylphenylsulfide (0.1 g) were stirred at reflux under nitrogen for 2 hours. Additional m-chloroperbenzoic acid (1.28 g), and sodium bicarbonate (0.063 g) were added and reflux was continued overnight. The reaction mixture was cooled, diluted with dichloromethane and washed with sodium bicarbonate solution. The organic layer was separated, washed (water), dried and concentrated. Chromatography, eluting with dichloromethane followed by ethyl acetate, gave the title compound as a yellow amorphous solid (0.475 g); mp 138°-140° C.; NMR: 4.12 (s,2), 6.61 (t,2), 7.12 (s,1), 7.33 (d,1), 7.49 (m,2) 7.62 (d,1), 7.79 (d,1), 8.42 (d,1); MS: m/z=374(M+1). Analysis for C15H11F4N3O4 : Calculated: C, 48.27; H, 2.97; N, 11.26; Found: C, 48.30; H, 2.97; N, 11.25.

Workup

  1. temperatureat reflux under nitrogen for 2 hours
  2. temperaturereflux
  3. temperatureThe reaction mixture was cooled
  4. washwashed with sodium bicarbonate solution
  5. customThe organic layer was separated
  6. washwashed (water)
  7. customdried
  8. concentrationconcentrated
  9. washChromatography, eluting with dichloromethane

Sources & evidence

ORD record
ord-4d61be061fc0449eba0400cee7b53998
Source dataset
uspto-grants-1996_01
Patent number
US05486515

Reaction notes

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