Sodium Hydroxide → HCID 59226974, compound

HRID 1943109Notes

Reaction equation

HRID 1943109 reaction equation
[Br:1][C:2]1[CH:7]=[C:6]([C:8]([F:20])([C:16]([F:19])([F:18])[F:17])[C:9]([F:15])([F:14])[C:10]([F:13])([F:12])[F:11])[CH:5]=[C:4]([CH2:21][CH3:22])[C:3]=1[NH:23][C:24](=[O:36])[C:25]1[CH:30]=[CH:29][C:28]([C:31]#[N:32])=[C:27]([N+:33]([O-])=O)[CH:26]=1.[OH-].[Na+].S([O-])(O)=O.[Na+]>O1CCCC1.[Br-].C([N+](CCCC)(CCCC)CCCC)CCC.C(OCC)(=O)C>[NH2:33][C:27]1[CH:26]=[C:25]([CH:30]=[CH:29][C:28]=1[C:31]#[N:32])[C:24]([NH:23][C:3]1[C:4]([CH2:21][CH3:22])=[CH:5][C:6]([C:8]([F:20])([C:16]([F:17])([F:18])[F:19])[C:9]([F:14])([F:15])[C:10]([F:12])([F:13])[F:11])=[CH:7][C:2]=1[Br:1])=[O:36]

Participants

7

Reactant 3

HCID 14798Sodium HydroxideHCID 23665763Sodium Bisulfite2×HCID 59226962HCID 59226962, compound

Product 1

HCID 59226974HCID 59226974, compoundYield 109.4%

Reagents, catalysts & solvents 3

HCID 74236Tetrabutylammonium BromideCatalystHCID 8028TetrahydrofuranSolventHCID 8857Ethyl AcetateSolvent

Conditions

Temperature
65 °C

Procedure

N-[2-Bromo-6-ethyl-4-(1,2,2,3,3,3-hexafluoro-1-trifluoromethyl-propyl)-phenyl]-4-cyano-3-nitro-benzamide (63.9 g, 102.6 mmol) was dissolved in tetrahydrofuran (1200 ml). Aqueous sodium hydroxide (0.1 M, 550 ml), sodium hydrogen sulfite (65.3 g, 307.7 mmol) and tetrabutylammonium bromide (“TBAB”) (3.4 g, 10.3 mmol) were added. The mixture was vigorously stirred at 65° C. Further portions of sodium hydrogen sulfite were added after 20 minutes (65.3 g, 307.7 mmol) and after 80 minutes (32.7 g, 153.8 mmol). The reaction mixture was stirred at 65° C. for 30 minutes. Then the reaction mixture was cooled to 25° C. and diluted with ethyl acetate (1300 ml). The phases were separated and the organic phase was extracted with ethyl acetate (300 ml). The combined organic phases were washed with water, aqueous sodium hydrogen carbonate (10% w/v) (400 ml) and brine, dried over sodium sulfate and concentrated to yield 3-amino-N-[2-bromo-6-ethyl-4-(1,2,2,3,3,3-hexafluoro-1-trifluoromethyl-propyl)-phenyl]-4-cyano-benzamide as a yellow solid (63.1 g) which was used in the next step without further purification.

Workup

  1. stirringThe reaction mixture was stirred at 65° C. for 30 minutes
  2. temperatureThen the reaction mixture was cooled to 25° C.
  3. customThe phases were separated
  4. extractionthe organic phase was extracted with ethyl acetate (300 ml)
  5. washThe combined organic phases were washed with water, aqueous sodium hydrogen carbonate (10% w/v) (400 ml) and brine
  6. dry with materialdried over sodium sulfate
  7. concentrationconcentrated

Sources & evidence

ORD record
ord-3152399ad05a4cf29ada82df9014ef52
Source dataset
uspto-grants-2013_03
Patent number
US08389766B2

Reaction notes

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