Triphenylphosphine → N-Trifluoroacetyl-7-methoxy-1-methylene 2,3,4,5-tetrahydro-1H-3-benzazepine

HRID 221234ノート

反応式

HRID 221234 の反応式
[F:1][C:2]([F:18])([F:17])[C:3]([NH:5][CH2:6][CH2:7][C:8]1[CH:13]=[C:12]([O:14][CH3:15])[CH:11]=[CH:10][C:9]=1I)=[O:4].CC([O-])=O.[K+].[CH:24]1[CH:29]=CC(P(C2C=CC=CC=2)C2C=CC=CC=2)=C[CH:25]=1>CN(C)C=O.[N+](CCCC)(CCCC)(CCCC)CCCC.[Br-].CC([O-])=O.CC([O-])=O.[Pd+2]>[F:1][C:2]([F:18])([F:17])[C:3]([N:5]1[CH2:29][C:24](=[CH2:25])[C:9]2[CH:10]=[CH:11][C:12]([O:14][CH3:15])=[CH:13][C:8]=2[CH2:7][CH2:6]1)=[O:4]

参加物

7

反応物 3

HCID 11776TriphenylphosphineHCID 517044Potassium AcetateHCID 222927722,2,2-Trifluoro-N-[2-(2-iodo-5-methoxyphenyl)ethyl]acetamide

生成物 1

HCID 22292788N-Trifluoroacetyl-7-methoxy-1-methylene 2,3,4,5-tetrahydro-1H-3-benzazepine収率 462.7%

試薬・触媒・溶媒 3

HCID 74236Tetrabutylammonium Bromide触媒HCID 167845palladium(II) acetate触媒HCID 6228Dimethylformamide溶媒

実験手順

A solution of N-allyl, N-trifluoroacetyl-2-iodo-5-methoxyphenethylamine (20.5 g, 50 mmol) in dimethylformamide (250 mL) is treated with KOAc (14.6 g, 149 mmol), n-Bu4NBr (16.0 g, 50 mmol), PPh3 (1.3 g, 5.0 mmol), Pd(OAc)2 (0.56 g, 2.5 mmol) and stirred overnight at 90 C. The product mixture was cooled to 20 C, filtered, diluted with water (500 mL) and extracted with ether (3×500 mL). The combined organic phases were washed with water (100 mL), brine (100 mL), dried with Na2SO4 and concentrated. Flash chromatography (10% EtOAc in hexane, silica) resulted in 6.6 g of a yellow oil. 1H NMR (400 MHz, CDCl3) d 7.26 (d, J=8 Hz, 1 H), 6.77 (d, J=8 Hz, 1 H), 6.66 (s, 1H), 5.34-5.19 (m, 2 H), 4.40 (m, 2 H), 3.83 (m, 2 H), 3.80 (s, 3 H), 3.00 (m, 2 H). MS calculated for C14H14F3NO2+H: 285, observed: 285.

後処理

  1. temperatureThe product mixture was cooled to 20 C
  2. filtrationfiltered
  3. additiondiluted with water (500 mL)
  4. extractionextracted with ether (3×500 mL)
  5. washThe combined organic phases were washed with water (100 mL), brine (100 mL)
  6. dry with materialdried with Na2SO4
  7. concentrationconcentrated

出典と根拠

ORDレコード
ord-467b65b0fd9a4ff5a767421229242eed
出典データセット
uspto-grants-2012_06
特許番号
US08207158B2

反応ノート

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