Pyridine → 7-Bromo-3,3-dimethyl-2,3-dihydro-benzofuran-5-carboxylic acid methylamide

HRID 460288ノート

反応式

HRID 460288 の反応式
[Br:1][C:2]1[C:10]2[O:9][CH2:8][C:7]([CH3:12])([CH3:11])[C:6]=2[CH:5]=[C:4]([C:13]([OH:15])=O)[CH:3]=1.[CH3:16][N:17](C=O)C.Cl.CN.N1C=CC=CC=1>C1COCC1.C(OCC)(=O)C.O>[CH3:16][NH:17][C:13]([C:4]1[CH:3]=[C:2]([Br:1])[C:10]2[O:9][CH2:8][C:7]([CH3:12])([CH3:11])[C:6]=2[CH:5]=1)=[O:15]

参加物

8

反応物 4

HCID 1049PyridineHCID 6228DimethylformamideHCID 6364545Methylamine hydrochlorideHCID 220414067-Bromo-3,3-dimethyl-2,3-dihydrobenzofuran-5-carboxylic acid

生成物 1

HCID 695224787-Bromo-3,3-dimethyl-2,3-dihydro-benzofuran-5-carboxylic acid methylamide収率 223.8%

試薬・触媒・溶媒 3

HCID 962Water溶媒HCID 8028Tetrahydrofuran溶媒HCID 8857Ethyl Acetate溶媒

実験手順

To a solution of 7-bromo-3,3-dimethyl-2,3-dihydro-benzofuran-5-carboxylic acid (4.99 g, 18.41 mmol) in dry THF (40 mL) was added at room temperature thionychloride (2 mL, 27.61 mmol) and DMF (0.14 mL, 1.84 mmol). The reaction mixture was stirred 1 hr then methylamine hydrochloride (2.48 g, 36.82 mmol) was added followed by slow addition of pyridine (4.5 mL, 55.23 mmol). The reaction mixture was stirred overnight then water and ethyl acetate were added. The layers were separated. The aqueous layer was extracted twice with ethyl acetate. The combined extracts were washed successively with water and brine, dried over anhydrous magnesium sulfate, filtered and evaporated. The residue was chromatographed on silica gel (50% to 100% ethyl acetate in hexane, then 40% MeOH in Ethyl acetate) to give 1.17 g of 7-bromo-3,3-dimethyl-2,3-dihydro-benzofuran-5-carboxylic acid methylamide (22%). 1H NMR (300 MHz; CDCl3): 1.36 (s, 6H), 2.99 (d, J=4.5 Hz, 3H), 4.39 (s, 2H), 6.25 (br s, 1H), 7.54 (d, J=1.5 Hz, 1H), 7.70 (d, J=1.5 Hz, 1H).

後処理

  1. stirringThe reaction mixture was stirred overnight
  2. customThe layers were separated
  3. extractionThe aqueous layer was extracted twice with ethyl acetate
  4. washThe combined extracts were washed successively with water and brine
  5. dry with materialdried over anhydrous magnesium sulfate
  6. filtrationfiltered
  7. customevaporated
  8. customThe residue was chromatographed on silica gel (50% to 100% ethyl acetate in hexane

出典と根拠

ORDレコード
ord-996cdac4254441578be78053e653fca3
出典データセット
uspto-grants-2007_03
特許番号
US07196108B2

反応ノート

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