Hydrochloric Acid → HCID 59226943, compound

HRID 1943108Notes

Reaction equation

HRID 1943108 reaction equation
[C:1]([C:3]1[CH:29]=[CH:28][C:6]([C:7]([NH:9][C:10]2[C:15]([CH3:16])=[CH:14][C:13]([C:17]([F:26])([C:22]([F:25])([F:24])[F:23])[C:18]([F:21])([F:20])[F:19])=[CH:12][C:11]=2[CH3:27])=[O:8])=[CH:5][C:4]=1[N+:30]([O-])=O)#[N:2].[Sn](Cl)(Cl)(Cl)Cl.Cl.[OH-].[Na+]>COCCOCCOC>[NH2:30][C:4]1[CH:5]=[C:6]([CH:28]=[CH:29][C:3]=1[C:1]#[N:2])[C:7]([NH:9][C:10]1[C:15]([CH3:16])=[CH:14][C:13]([C:17]([F:26])([C:22]([F:23])([F:24])[F:25])[C:18]([F:19])([F:20])[F:21])=[CH:12][C:11]=1[CH3:27])=[O:8]

Participants

6

Reactant 4

HCID 313Hydrochloric AcidHCID 14798Sodium HydroxideHCID 24287Tin tetrachlorideHCID 59226970HCID 59226970, compound

Product 1

HCID 59226943HCID 59226943, compoundYield 51.3%

Reagents, catalysts & solvents 1

HCID 8150DiglymeSolvent

Conditions

Temperature
0 °C

Procedure

4-Cyano-N-[2,6-dimethyl-4-(1,2,2,2-tetrafluoro-1-trifluoromethyl-ethyl)-phenyl]-3-nitro-benzamide (1.0 g, 2.16 mmol) (Example I1) was dissolved in diethylene glycol dimethyl ether (“diglyme”) (25 ml) and tin chloride (1.229 g, 6.48 mmol) was added. The mixture was cooled to 0° C. and aqueous hydrochloric acid (concentrated) (4 ml) was added slowly. The reaction mixture was stirred at 80° C. for 0.5 hours. Aqueous sodium hydroxide (30% w/v) (80 ml) was added to adjust the pH to 7-8. The aqueous phase was extracted three times with ethyl acetate (200 ml). The combined organic extracts were dried over sodium sulfate and concentrated. The residue was purified by column chromatography on silica gel (eluent: cyclohexane/ethyl acetate 1:1 to 0:1) to give 3-amino-4-cyano-N-[2,6-dimethyl-4-(1,2,2,2-tetrafluoro-1-trifluoromethyl-ethyl)-phenyl]-benzamide (0.48 g, 51% yield). 1H-NMR (400 MHz, CDCl3): 7.54 (s, 1H), 7.49 (d, 2H), 7.36 (m, 3H), 7.15 (q, 1H), 2.3 (s, 6H) ppm.

Workup

  1. extractionThe aqueous phase was extracted three times with ethyl acetate (200 ml)
  2. dry with materialThe combined organic extracts were dried over sodium sulfate
  3. concentrationconcentrated
  4. customThe residue was purified by column chromatography on silica gel (eluent: cyclohexane/ethyl acetate 1:1 to 0:1)

Sources & evidence

ORD record
ord-cb367a0f211b4a89ab6a9004e7022c68
Source dataset
uspto-grants-2013_03
Patent number
US08389766B2

Reaction notes

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