Potassium Acetate → 2-Bromo-6-(6-tert-butyl-8-fluoro-1-oxophthalazin-2(1H)-yl)-4-fluorobenzaldehyde

HRID 407611

反応式

HRID 407611 の反応式
Br[C:2]1[CH:9]=[C:8]([F:10])[CH:7]=[C:6]([Br:11])[C:3]=1[CH:4]=[O:5].[C:12]([C:16]1[CH:17]=[C:18]2[C:23](=[C:24]([F:26])[CH:25]=1)[C:22](=[O:27])[NH:21][N:20]=[CH:19]2)([CH3:15])([CH3:14])[CH3:13].CC([O-])=O.[K+].COC1C2C(=C3C(=CC=2)C(OC)=CC=N3)N=CC=1>O1CCOCC1.[Cu]I>[Br:11][C:6]1[CH:7]=[C:8]([F:10])[CH:9]=[C:2]([N:21]2[N:20]=[CH:19][C:18]3[C:23](=[C:24]([F:26])[CH:25]=[C:16]([C:12]([CH3:13])([CH3:15])[CH3:14])[CH:17]=3)[C:22]2=[O:27])[C:3]=1[CH:4]=[O:5]

参加物

7

反応物 4

HCID 517044Potassium AcetateHCID 104622984,7-Dimethoxy-1,10-phenanthrolineHCID 444746662,6-Dibromo-4-fluorobenzaldehydeHCID 594737656-(tert-Butyl)-8-fluorophthalazin-1(2H)-one

生成物 1

HCID 866839112-Bromo-6-(6-tert-butyl-8-fluoro-1-oxophthalazin-2(1H)-yl)-4-fluorobenzaldehyde収率 30%

試薬・触媒・溶媒 2

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)触媒HCID 312751,4-Dioxane溶媒

実験手順

To a solution of 102a (767 mg, 2.72 mmol), 6-tert-butyl-8-fluorophthalazin-1(2H)-one 101h (300 mg, 1.36 mmol) in dioxane (50 mL) was added KOAc (267 mg, 2.72 mmol), CuI (259 mg, 1.36 mmol), and 4,7-dimethoxy-1,10-phenanthroline (327 mg, 1.36 mmol). After bubbling nitrogen through the resulting solution for 30 min, the mixture was stirred at 90 degree for 10 h. It was allowed to cool down to room temperature and H2O (100 mL) was added. The aqueous layer was separated and extracted with ethyl acetate (2×200 mL). The combined organic layers was washed with brine (100 mL) and dried over sodium sulfate. The drying agent was removed by filtration and the filtrate was concentrated under reduced pressure. The residue was purified on flash column eluting with PE/EA (15:1) to afford 102b (172 mg, 30%). LCMS: [M+H]+ 421. 1H NMR (500 MHz, CDCl3) δ 10.20 (s, 1H), 8.20 (s, 1H), 7.49-7.51 (m, 3H), 7.25 (m, 1H), 1.36 (s, 9H).

後処理

  1. customAfter bubbling nitrogen through the resulting solution for 30 min
  2. additionH2O (100 mL) was added
  3. customThe aqueous layer was separated
  4. extractionextracted with ethyl acetate (2×200 mL)
  5. washThe combined organic layers was washed with brine (100 mL)
  6. dry with materialdried over sodium sulfate
  7. customThe drying agent was removed by filtration
  8. concentrationthe filtrate was concentrated under reduced pressure
  9. customThe residue was purified on flash column
  10. washeluting with PE/EA (15:1)

出典と根拠

ORDレコード
ord-a96a7249d9484a8d9fa873d6a3533910
出典データセット
uspto-grants-2014_06
特許番号
US08754077B2

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