Cesium carbonate → tert-butyl 5'-(3-(3,5-dichlorophenyl)-4,4,4-trifluorobut-2-enoyl)-3'H-spiro[azetidine-3,1'-isobenzofuran]-1-carboxylate

HRID 1508301ノート

反応式

HRID 1508301 の反応式
[C:1]([C:4]1[CH:5]=[C:6]2[C:10](=[CH:11][CH:12]=1)[C:9]1([CH2:15][N:14]([C:16]([O:18][C:19]([CH3:22])([CH3:21])[CH3:20])=[O:17])[CH2:13]1)[O:8][CH2:7]2)(=[O:3])[CH3:2].[Cl:23][C:24]1[CH:25]=[C:26]([C:31](=O)[C:32]([F:35])([F:34])[F:33])[CH:27]=[C:28]([Cl:30])[CH:29]=1.C([O-])([O-])=O.[Cs+].[Cs+]>C1(C)C=CC=CC=1.FC(F)(F)C1C=CC=CC=1>[Cl:23][C:24]1[CH:25]=[C:26]([C:31]([C:32]([F:35])([F:33])[F:34])=[CH:2][C:1]([C:4]2[CH:5]=[C:6]3[C:10](=[CH:11][CH:12]=2)[C:9]2([CH2:13][N:14]([C:16]([O:18][C:19]([CH3:22])([CH3:21])[CH3:20])=[O:17])[CH2:15]2)[O:8][CH2:7]3)=[O:3])[CH:27]=[C:28]([Cl:30])[CH:29]=1

参加物

6

反応物 3

HCID 10796Cesium carbonateHCID 27582311-(3,5-Dichlorophenyl)-2,2,2-trifluoroethan-1-oneHCID 70663143tert-butyl 5'-acetyl-3'H-spiro[azetidine-3,1'-isobenzofuran]-1-carboxylate

生成物 1

HCID 90001161tert-butyl 5'-(3-(3,5-dichlorophenyl)-4,4,4-trifluorobut-2-enoyl)-3'H-spiro[azetidine-3,1'-isobenzofuran]-1-carboxylate収率 44%

試薬・触媒・溶媒 2

HCID 1140Toluene溶媒HCID 7368(Trifluoromethyl)benzene溶媒

反応条件

温度
110 °C

実験手順

In 100 mL two neck RBF equipped with dean-stark apparatus, the stirred solution of tert-butyl 5′-acetyl-3′H-spiro[azetidine-3,1′-isobenzofuran]-1-carboxylate (Preparation 1, 6.65 g, 21.95 mmol) in toluene (20 mL) and trifluorotoluene (20 mL) was added 1-(3,5-dichloro-phenyl)-2,2,2-trifluoro-ethanone (6.133 g, 25.24 mmol) and Cs2CO3 (0.71 g, 2.20 mmol) at room temperature. Resulting reaction mixture was stirred at 110° C. for 16 hours. After complete consumption of starting material, the reaction mixture was diluted with tert-butylmethyl ether (60 mL) and filtered through celite bed. Filtrate was concentrated to get as brown sticky oil (7.2 g, crude). Crude compound was purified by column chromatography using silica gel (230-400 mesh). Desired compound was eluted in 20% ethyl acetate in n-hexane to give light yellow solid (5.1 g, 43.97%). LC-MS (m/z): 525.9 (M−H).

後処理

  1. customResulting
  2. customreaction mixture
  3. customAfter complete consumption of starting material
  4. additionthe reaction mixture was diluted with tert-butylmethyl ether (60 mL)
  5. filtrationfiltered through celite bed
  6. concentrationFiltrate was concentrated
  7. customto get as brown sticky oil (7.2 g, crude)
  8. customCrude compound was purified by column chromatography
  9. washDesired compound was eluted in 20% ethyl acetate in n-hexane

出典と根拠

ORDレコード
ord-9b32e69de5de4989ba94334713c26026
出典データセット
uspto-grants-2015_12
特許番号
US09221835B2

反応ノート

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