Acetone → 5-fluoro-2-methyl-8-nitro-3,4-dihydro-2H-isoquinolin-1-one

HRID 604274ノート

反応式

HRID 604274 の反応式
[CH3:1][O:2][C:3](=[O:17])[C:4]1[C:9]([N+:10]([O-:12])=[O:11])=[CH:8][CH:7]=[C:6]([F:13])[C:5]=1[CH2:14][CH2:15]O.[Na].[Br-].[Na+].Cl[N:22]1C(=[O:28])N(Cl)C(=O)N(Cl)[C:23]1=O.C[C:34](C)=[O:35]>CC1(C)N([O])C(C)(C)CCC1.C(O)(C)C>[F:13][C:6]1[CH:7]=[CH:8][C:9]([N+:10]([O-:12])=[O:11])=[C:4]2[C:5]=1[CH2:14][CH2:15][N:22]([CH3:23])[C:3]2=[O:2].[CH3:1][O:2][C:3](=[O:17])[C:4]1[C:9]([N+:10]([O-:12])=[O:11])=[CH:8][CH:7]=[C:6]([F:13])[C:5]=1[CH2:14][CH2:15][C:34]([OH:35])=[O:28]

参加物

9

反応物 5

HCID 180AcetoneHCID 6909Trichloroisocyanuric AcidHCID 253881Sodium BromideHCID 5360545SodiumHCID 670377633-Fluoro-2-(2-hydroxyethyl)-6-nitro-benzoic acid methyl ester

生成物 2

HCID 598491765-fluoro-2-methyl-8-nitro-3,4-dihydro-2H-isoquinolin-1-oneHCID 598492232-(2-Carboxy-ethyl)-3-fluoro-6-nitro-benzoic acid methyl ester

試薬・触媒・溶媒 2

HCID 3776Isopropanol溶媒HCID 2724126Tempo溶媒

実験手順

To a solution of 3-fluoro-2-(2-hydroxyethyl)-6-nitro-benzoic acid methyl ester (51.4 g, 0.2 mol) in acetone (1000 mL), 2,2,6,6-tetramethylpiperidine 1-oxyl, Free radical, (460.6 mg, 2.95 mmol), an aqueous 15% solution of sodium hydrocarboxide (400 mL) and sodium bromide (3.02 g, 29.3 mmol) was added. Trichloroisocyanuric acid (68.4 g, 0.29 mol) was then slowly added within 30 min at rt. After completion of the addition and being stirred at rt for 2.5 hrs, 15 mL of isopropanol was added at 0° C. carefully. The mixture was concentrated under reduced pressure. The mixture was extracted three times with ethyl acetate. The organic layer was extracted three times with 1N sodium hydroxide. The combined water layer was washed once with ethyl acetate, then acidified with 5N hydrogen chloride at 0° C. After extraction four times with ethyl acetate, the organic layer was washed with water and brine, dried over magnesium sulfate, and evaporated in vacuo. The title compound 2-(2-carboxy-ethyl)-3-fluoro-6-nitro-benzoic acid methyl ester (28.7 g) was obtained as yellow solid in 72% yield (2 steps).

後処理

  1. additionAfter completion of the addition
  2. concentrationThe mixture was concentrated under reduced pressure
  3. extractionThe mixture was extracted three times with ethyl acetate
  4. extractionThe organic layer was extracted three times with 1N sodium hydroxide
  5. washThe combined water layer was washed once with ethyl acetate
  6. customacidified with 5N hydrogen chloride at 0° C
  7. extractionAfter extraction four times with ethyl acetate
  8. washthe organic layer was washed with water and brine
  9. dry with materialdried over magnesium sulfate
  10. customevaporated in vacuo

出典と根拠

ORDレコード
ord-8df17495f7fa48b19ae1f44bacf93d34
出典データセット
uspto-grants-2011_03
特許番号
US07910585B2

反応ノート

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