Acetic Acid → HCID 59226969, Verbindung

HRID 1943110Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 1943110
[NH2:1][C:2]1[CH:3]=[C:4]([CH:26]=[CH:27][C:28]=1[C:29]#[N:30])[C:5]([NH:7][C:8]1[C:13]([CH3:14])=[CH:12][C:11]([C:15]([F:24])([C:20]([F:23])([F:22])[F:21])[C:16]([F:19])([F:18])[F:17])=[CH:10][C:9]=1[CH3:25])=[O:6].C=O.[C:33](O)(=O)C.[BH4-].[Na+]>C(#N)C>[C:29]([C:28]1[CH:27]=[CH:26][C:4]([C:5]([NH:7][C:8]2[C:13]([CH3:14])=[CH:12][C:11]([C:15]([F:24])([C:20]([F:21])([F:22])[F:23])[C:16]([F:17])([F:18])[F:19])=[CH:10][C:9]=2[CH3:25])=[O:6])=[CH:3][C:2]=1[NH:1][CH3:33])#[N:30]

Komponenten

6

Edukt 4

HCID 176Acetic Acid2×HCID 712FormaldehydeHCID 4311764Sodium borohydrideHCID 59226943HCID 59226943, Verbindung

Produkt 1

HCID 59226969HCID 59226969, VerbindungAusbeute 58 %

Reagenzien, Katalysatoren, Lösungsmittel 1

HCID 6342AcetonitrileLösungsmittel

Versuchsvorschrift

3-Amino-4-cyano-N-[2,6-dimethyl-4-(1,2,2,2-tetrafluoro-1-trifluoromethyl-ethyl)-phenyl]-benzamide (3.01 g, 6.95 mmol) (Example I2) was dissolved in acetonitrile (50 ml) and aqueous formaldehyde (36.5% w/v) (0.64 ml, 6.95 mmol) and acetic acid (30 ml) were added successively. The reaction mixture was stirred at ambient temperature for 45 minutes. Then sodium borohydride (0.44 g, 6.95 mmol) and more acetic acid (5 ml) were added. The reaction mixture was stirred at ambient temperature for 2 hours. The reaction mixture was concentrated. The residue was dissolved in ethyl acetate and the solution washed with aqueous sodium hydroxide (1N). 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 1:5) to give 4-cyano-N-[2,6-dimethyl-4-(1,2,2,2-tetrafluoro-1-trifluoromethyl-ethyl)-phenyl]-3-methylamino-benzamide (1.80 g, 58% yield). M.p. 204-206° C. 1H-NMR (400 MHz, CDCl3): 7.53 (d, 1H), 7.37 (s, 3H), 7.23 (s, 1H), 7.10 (q, 1H), 5.88 (d, 1H), 3.02 (d, 3H), 2.35 (s, 6H) ppm.

Aufarbeitung

  1. stirringThe reaction mixture was stirred at ambient temperature for 2 hours
  2. concentrationThe reaction mixture was concentrated
  3. dissolutionThe residue was dissolved in ethyl acetate
  4. washthe solution washed with aqueous sodium hydroxide (1N)
  5. extractionThe aqueous phase was extracted three times with ethyl acetate (200 ml)
  6. dry with materialThe combined organic extracts were dried over sodium sulfate
  7. concentrationconcentrated
  8. customThe residue was purified by column chromatography on silica gel (eluent: cyclohexane/ethyl acetate 1:5)

Quellen und Nachweise

ORD-Eintrag
ord-63de57dfb51c4c1286f51e0ce4187981
Quelldatensatz
uspto-grants-2013_03
Patentnummer
US08389766B2

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