Trifluoroacetic anhydride → 2,2,2-Trifluoro-1-(7-methoxy-8-nitro-1,2,4,5-tetrahydro-benzo[d]azepin-3-yl)-ethanone

HRID 1040739노트

반응식

HRID 1040739 반응식
[CH3:1][O:2][C:3]1[CH:13]=[CH:12][C:6]2[CH2:7][CH2:8][NH:9][CH2:10][CH2:11][C:5]=2[CH:4]=1.[F:14][C:15]([F:26])([F:25])[C:16](O[C:19](=[O:24])[C:20]([F:23])([F:22])[F:21])=[O:17].[N+:27]([O-:30])([O-:29])=[O:28].[K+]>C(#N)C>[F:14][C:15]([F:26])([F:25])[C:16]([N:9]1[CH2:10][CH2:11][C:5]2[CH:4]=[C:3]([O:2][CH3:1])[C:13]([N+:27]([O-:29])=[O:28])=[CH:12][C:6]=2[CH2:7][CH2:8]1)=[O:17].[F:23][C:20]([F:21])([F:22])[C:19]([N:9]1[CH2:10][CH2:11][C:5]2[C:4]([N+:27]([O-:30])=[O:28])=[C:3]([O:2][CH3:1])[CH:13]=[CH:12][C:6]=2[CH2:7][CH2:8]1)=[O:24]

참가 물질

6

반응물 3

HCID 9845Trifluoroacetic anhydrideHCID 24434Potassium NitrateHCID 138533487-Methoxy-2,3,4,5-tetrahydro-1h-3-benzazepine

생성물 2

HCID 866338662,2,2-Trifluoro-1-(7-methoxy-8-nitro-1,2,4,5-tetrahydro-benzo[d]azepin-3-yl)-ethanone수율 38%HCID 866338672,2,2-Trifluoro-1-(7-methoxy-6-nitro-1,2,4,5-tetrahydro-benzo[d]azepin-3-yl)-ethanone수율 25%

시약·촉매·용매 1

HCID 6342Acetonitrile용매

실험 절차

Into a 1-neck round-bottom flask 7-methoxy-2,3,4,5-tetrahydro-1H-benzo[d]azepine (17.00 g, 0.096 mol) was dissolved in acetonitrile (100 mL). Trifluoroacetic anhydride (47.4 mL, 0.34 mol) was added at −20° C. After 10 minutes potassium nitrate (9.7 g, 0.096 mol) was added at the same temperature, and the reaction mixture was stirred for 1.5 hours. The reaction was quenched by addition of diluted NaHCO3, and allowed to warm to room temperature. Partition between saturated aqueous Na2CO3 and dichloromethane, extraction, drying (MgSO4), filtration, and concentration, provided the crude product. Flash chromatography separation on SiO2 with dichloromethane (100%) provided 2,2,2-trifluoro-1-(7-methoxy-8-nitro-1,2,4,5-tetrahydro-benzo[d]azepin-3-yl)-ethanone (11.5 g, 38%) and 2,2,2-trifluoro-1-(7-methoxy-6-nitro-1,2,4,5-tetrahydro-benzo[d]azepin-3-yl)-ethanone (7.5 g, 25%). 2,2,2-Trifluoro-1-(7-methoxy-8-nitro-1,2,4,5-tetrahydro-benzo[d]azepin-3-yl)-ethanone: 1H-NMR (CDCl3; amide rotamers observed) δ 7.72 (1H), 6.89 (1H), 3.95 (3H), 3.65-3.85 (4H), 2.95-3.07 (4H); LC/MS (ESI+): 319.20 (M+H). 2,2,2-Trifluoro-1-(7-methoxy-6-nitro-1,2,4,5-tetrahydro-benzo[d]azepin-3-yl)-ethanone: 1H-NMR (CDCl3; amide rotamers observed) δ 7.24 (1H), 6.85 (1H), 3.88 (s, 3H), 3.65-3.81 (4H), 2.80-3.05 (4H).

후처리

  1. customThe reaction was quenched by addition of diluted NaHCO3
  2. customPartition between saturated aqueous Na2CO3 and dichloromethane, extraction
  3. customdrying
  4. filtration(MgSO4), filtration, and concentration
  5. customprovided the crude product
  6. customFlash chromatography separation on SiO2 with dichloromethane (100%)

출처 및 근거

ORD 기록
ord-bfe89bf7038847d68cbc80de01e8769b
출처 데이터셋
uspto-grants-2013_10
특허 번호
US08552186B2

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