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

HRID 1040739ノート

反応式

HRID 1040739 の反応式
[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]

参加物

6

反応物 3

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

生成物 2

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

試薬・触媒・溶媒 1

HCID 6342Acetonitrile溶媒

実験手順

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).

後処理

  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%)

出典と根拠

ORDレコード
ord-bfe89bf7038847d68cbc80de01e8769b
出典データセット
uspto-grants-2013_10
特許番号
US08552186B2

反応ノート

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