Triphenylphosphine → N-Trifluoroacetyl-8-chloro-1-methylene-2,3,4,5-tetrahydro-1H-3-benzazepine

HRID 2108559ノート

反応式

HRID 2108559 の反応式
[CH2:1]([N:4]([CH2:11][CH2:12][C:13]1[CH:18]=[CH:17][C:16]([Cl:19])=[CH:15][C:14]=1I)[C:5](=[O:10])[C:6]([F:9])([F:8])[F:7])[CH:2]=[CH2:3].CC([O-])=O.[K+].C1C=CC(P(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1>CN(C)C=O.[N+](CCCC)(CCCC)(CCCC)CCCC.[Br-].CC([O-])=O.CC([O-])=O.[Pd+2]>[F:7][C:6]([F:9])([F:8])[C:5]([N:4]1[CH2:1][C:2](=[CH2:3])[C:14]2[CH:15]=[C:16]([Cl:19])[CH:17]=[CH:18][C:13]=2[CH2:12][CH2:11]1)=[O:10]

参加物

7

反応物 3

HCID 11776TriphenylphosphineHCID 517044Potassium AcetateHCID 24773729N-Allyl,N-trifluoroacetyl-2-iodo-4-chlorophenethylamine

生成物 1

HCID 22292831N-Trifluoroacetyl-8-chloro-1-methylene-2,3,4,5-tetrahydro-1H-3-benzazepine収率 43.7%

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-4-chlorophenethylamine (0.76 g, 1.8 mmol) in dimethylformamide (20 mL) was treated with KOAc (0.53 g, 5.4 mmol), n-Bu4NBr (0.58 g, 1.8 mmol), PPh3 (0.047 g, 0.18 mmol), Pd(OAc)2 (0.041 g, 0.18 mmol) and stirred overnight at 105 C. The product mixture was cooled to 20 C, filtered, diluted with water (100 mL), extracted with ether (3×100 mL), the combined organic phases washed with water (100 mL), brine (100 mL), dried with Na2SO4 and concentrated. Flash chromatography (10% EtOAc in hexane, silica) resulted in 0.228 g of a clear oil. 1H NMR (400 MHz, CDCl3) d 7.29 (s, 1H), 7.18 (m, 1H), 7.04 (m, 1H), 5.38 (m, 2H), 5.40 (d, J=16 Hz, 2H), 3.80 (m, 2H), 3.00 (m, 2H). MS calculated for C13H11ClF3NO+H: 290, observed: 290.

後処理

  1. temperatureThe product mixture was cooled to 20 C
  2. filtrationfiltered
  3. additiondiluted with water (100 mL)
  4. extractionextracted with ether (3×100 mL)
  5. washthe combined organic phases 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-2dc1ce41c65442fbb49f0c4683f0d6dd
出典データセット
uspto-grants-2009_04
特許番号
US07514422B2

反応ノート

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