Triethylamine → 7-[5-Formyl-2-trifluoromethoxy-phenyl]-3,3-dimethyl-2,3-dihydro-benzofuran-5-carboxylic acid dimethylamide

HRID 460292

反応式

HRID 460292 の反応式
[CH3:1][N:2]([CH3:17])[C:3]([C:5]1[CH:6]=[C:7](Br)[C:8]2[O:12][CH2:11][C:10]([CH3:14])([CH3:13])[C:9]=2[CH:15]=1)=[O:4].C(N(CC)CC)C.C1(P(C2CCCCC2)C2C=CC=CC=2C2C=CC=CC=2)CCCCC1.[B]1OC(C)(C)C(C)(C)O1.Br[C:60]1[CH:61]=[C:62]([CH:65]=[CH:66][C:67]=1[O:68][C:69]([F:72])([F:71])[F:70])[CH:63]=[O:64]>O1CCOCC1.C(OCC)(=O)C.CC([O-])=O.CC([O-])=O.[Pd+2].O>[CH3:1][N:2]([CH3:17])[C:3]([C:5]1[CH:6]=[C:7]([C:60]2[CH:61]=[C:62]([CH:63]=[O:64])[CH:65]=[CH:66][C:67]=2[O:68][C:69]([F:70])([F:72])[F:71])[C:8]2[O:12][CH2:11][C:10]([CH3:14])([CH3:13])[C:9]=2[CH:15]=1)=[O:4]

参加物

10

反応物 5

HCID 8471TriethylamineHCID 27342162-(Dicyclohexylphosphino)biphenylHCID 6364989PinacolboraneHCID 131504163-Bromo-4-(trifluoromethoxy)benzaldehydeHCID 695216765-Benzofurancarboxamide, 7-bromo-2,3-dihydro-N,N,3,3-tetramethyl-

生成物 1

HCID 865888657-[5-Formyl-2-trifluoromethoxy-phenyl]-3,3-dimethyl-2,3-dihydro-benzofuran-5-carboxylic acid dimethylamide収率 50%

試薬・触媒・溶媒 4

HCID 167845palladium(II) acetate触媒HCID 962Water溶媒HCID 8857Ethyl Acetate溶媒HCID 312751,4-Dioxane溶媒2 回

反応条件

温度
80 °C

実験手順

To a solution of 7-bromo-3,3-dimethyl-2,3-dihydro-benzofuran-5-carboxylic acid dimethylamide (437 mg, 1.46 mmol) in dioxane (4 mL), were added under argon, triethylamine (0.82 mL, 5.86 mmol), Pd(OAc)2 (16 mg, 0.07 mmol), 2-(dicyclohexylphosphino)biphenyl (103 mg, 0.29 mmol) and pinacolborane (0.64 mL, 4.40 mmol) dropwise. The mixture was heated at 80° C. under argon for 2 hrs then cooled to room temperature. Water (0.5 mL) was added dropwise, then Ba(OH)2.8H2O (1.38 g, 4.40 mmol) followed by 3-bromo-4-trifluoromethoxy benzaldehyde (example 1h) (473 mg, 1.76 mmol) dissolved in dioxane (1.2 mL). The mixture was refluxed for 4 hours then cooled to room temperature, diluted with ethyl acetate and filtered over celite. The solution was further washed with water and brine, dried over anhydrous magnesium sulfate, filtered and evaporated. The residue was purified on silica gel (5% methanol in dichloromethane) to give 264 mg of 7-[5-formyl-2-trifluoromethoxy-phenyl]-3,3-dimethyl-2,3-dihydro-benzofuran-5-carboxylic acid dimethylamide (containing 50% of 3,3-dimethyl-2,3-dihydro-benzofuran-5-carboxylic acid dimethylamide as determined by 1H NMR) use as this in the next step.

後処理

  1. temperaturethen cooled to room temperature
  2. temperatureThe mixture was refluxed for 4 hours
  3. temperaturethen cooled to room temperature
  4. filtrationfiltered over celite
  5. washThe solution was further washed with water and brine
  6. dry with materialdried over anhydrous magnesium sulfate
  7. filtrationfiltered
  8. customevaporated
  9. customThe residue was purified on silica gel (5% methanol in dichloromethane)

出典と根拠

ORDレコード
ord-6908386d08bc40eab6b69f5163dec099
出典データセット
uspto-grants-2007_03
特許番号
US07196108B2

関連ノート

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