Acetic Acid → HCID 59226969、化合物

HRID 1943110ノート

反応式

HRID 1943110 の反応式
[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]

参加物

6

反応物 4

HCID 176Acetic Acid2 回HCID 712FormaldehydeHCID 4311764Sodium borohydrideHCID 59226943HCID 59226943、化合物

生成物 1

HCID 59226969HCID 59226969、化合物収率 58%

試薬・触媒・溶媒 1

HCID 6342Acetonitrile溶媒

実験手順

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.

後処理

  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)

出典と根拠

ORDレコード
ord-63de57dfb51c4c1286f51e0ce4187981
出典データセット
uspto-grants-2013_03
特許番号
US08389766B2

反応ノート

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