HCID 53253555, compound → HCID 53253754, compound

HRID 1464886Notes

Reaction equation

HRID 1464886 reaction equation
[F:1][C:2]([F:24])([F:23])[C:3]([C:9]1[CH:14]=[CH:13][CH:12]=[CH:11][C:10]=1[N:15]([CH3:22])[C:16]1[CH:21]=[CH:20][CH:19]=[CH:18][CH:17]=1)(O)[C:4]([F:7])([F:6])[F:5]>O=P(Cl)(Cl)Cl>[CH3:22][N:15]1[C:16]2[C:21](=[CH:20][CH:19]=[CH:18][CH:17]=2)[C:3]([C:4]([F:7])([F:6])[F:5])([C:2]([F:24])([F:23])[F:1])[C:9]2[CH:14]=[CH:13][CH:12]=[CH:11][C:10]1=2

Participants

3

Reactant 1

HCID 53253555HCID 53253555, compound

Product 1

HCID 53253754HCID 53253754, compoundYield 80%

Reagents, catalysts & solvents 1

HCID 24813Phosphorus oxychlorideSolvent

Procedure

1,1,1,3,3,3-hexafluoro-2-(2-(methyl(phenyl)amino)phenyl)propan-2-ol (0.2 g, 0.57 mmol) was dissolved in 15 mL POCl3 and the solution refluxed under argon for 3 d. Excess POCl3 was distilled off using a short path distillation head, the residue was dissolved in CHCl3, poured into a 10% (v/v) aqueous ammoniacal solution and the biphasic system stirred at room temperature for one hour. The organic layer was separated and the aqueous layer extracted with Et2O (3×50 mL). The organic layers were combined, washed with brine and water and dried over MgSO4, and the solvent evaporated under reduced pressure. The residue was purified by flash column chromatography using 10% dichloromethane in hexanes as the eluent to yield 0.15 g (80%) of the desired compound as a light-blue oil. 1H NMR (400 MHz, CHCl3) δ 3.46 (s, 3H), 7.00 (m, 4H), 7.42 (m, 2H), 7.89 (m, 2H). 13C NMR (100 MHz, CHCl3) δ 29.8, 35.1, 111.8, 114.7, 120.3, 130.3 (quintet), 130.7, 141.8. 19F NMR (380 MHz, CHCl3) δ −65.9. HRMS (EI) calc for C16H11F6N [M]+ 332.0868, found 332.0874. IR (KBr plate) 479 (m), 693 (s), 709 (s), 758 (s), 848 (m), 954 (s), 1116 (s), 1163 (m), 1192 (s), 1260 (s), 1489 (s), 1573 (m), 1594 (m), 2840 (m), 2972 (m), 3054 (m) cm−1.

Workup

  1. temperaturethe solution refluxed under argon for 3 d
  2. distillationExcess POCl3 was distilled off
  3. distillationa short path distillation head
  4. dissolutionthe residue was dissolved in CHCl3
  5. additionpoured into a 10% (v/v) aqueous ammoniacal solution
  6. customThe organic layer was separated
  7. extractionthe aqueous layer extracted with Et2O (3×50 mL)
  8. washwashed with brine and water
  9. dry with materialdried over MgSO4
  10. customthe solvent evaporated under reduced pressure
  11. customThe residue was purified by flash column chromatography

Sources & evidence

ORD record
ord-3d5469e678414052a398dc5e8067e844
Source dataset
uspto-grants-2015_04
Patent number
US08999722B2

Reaction notes

Loading…