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

HRID 1010784노트

반응식

HRID 1010784 반응식
[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]

참가 물질

7

반응물 3

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

생성물 1

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

시약·촉매·용매 3

HCID 74236Tetrabutylammonium Bromide촉매HCID 167845palladium(II) acetate촉매HCID 6228Dimethylformamide용매

실험 절차

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.

후처리

  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

출처 및 근거

ORD 기록
ord-b6a68d1a79704dd6bae4dad4303f7abc
출처 데이터셋
uspto-grants-2011_07
특허 번호
US07977329B2

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