Toluene → HCID 86762221、化合物

HRID 338132

反応式

HRID 338132 の反応式
[C:1]([NH:9][C:10]1[S:11][CH2:12][C@@H:13]2[CH2:18][N:17]([C:19]([O:21][CH2:22][C:23]3[CH:28]=[CH:27][CH:26]=[CH:25][CH:24]=3)=[O:20])[CH2:16][C@:14]2([C:29]2[S:30][C:31](Br)=[CH:32][CH:33]=2)[N:15]=1)(=[O:8])[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.[CH2:35]([N:39]1C=CN=C1)CCC.C1(C)C=CC=CC=1>C(OCC)(=O)C.O.[C-]#N.[C-]#N.[C-]#N.[C-]#N.[C-]#N.[C-]#N.[K+].[K+].[K+].[K+].[Fe+6].[Cu]I>[C:1]([NH:9][C:10]1[S:11][CH2:12][C@@H:13]2[CH2:18][N:17]([C:19]([O:21][CH2:22][C:23]3[CH:28]=[CH:27][CH:26]=[CH:25][CH:24]=3)=[O:20])[CH2:16][C@:14]2([C:29]2[S:30][C:31]([C:35]#[N:39])=[CH:32][CH:33]=2)[N:15]=1)(=[O:8])[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1

参加物

8

反応物 3

HCID 1140TolueneHCID 61347ButylimidazoleHCID 86762219Benzyl(4aR,7aR)-2-(benzoylamino)-7a-(5-bromothiophen-2-yl)-4a,5,7,7a-tetrahydropyrrolo[3,4-d][1,3]thiazine-6(4H)-carboxylate

生成物 1

HCID 86762221HCID 86762221、化合物収率 74%

試薬・触媒・溶媒 4

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)触媒HCID 11963580Ferrate(4-), hexakis(cyano-C)-, tetrapotassium, (OC-6-11)-触媒HCID 962Water溶媒HCID 8857Ethyl Acetate溶媒

反応条件

温度
145 °C

実験手順

Benzyl (4aR,7aR)-2-(benzoylamino)-7a-(5-bromothiophen-2-yl)-4a,5,7,7a-tetrahydropyrrolo[3,4-d][1,3]thiazine-6(4H)-carboxylate (3.88 g, 6.97 mmol), anhydrous potassium hexacyanoferrate (II) (2.57 g, 6.97 mmol) (prepared as cited in Schareina, T.; et al Synthesis, 2008, 20, 3351-3355), copper (I) iodide (398 mg, 2.09 mmol), 1-butylimidazole (2.8 mL, 20.9 mmol), and toluene (23 mL) are added to a 60 mL glass pressure tube fitted with a stirrer bar. A stream of nitrogen is passed over the mixture for a few minutes and the pressure tube is then sealed. The stirred mixture is heated at 145° C. for 18 hours. The resulting dark mixture is cooled to room temperature. The mixture is diluted with ethyl acetate (100 mL) and water (15 mL) and vacuum filtered through a pad of diatomaceous earth while rinsing with ethyl acetate (100 mL) and water (15 mL). The layers of the filtrate are separated and the organic layer is further washed with water (2×30 mL) and brine (30 mL). The organic phase is dried over sodium sulfate, filtered, and concentrated under reduced pressure. The residue is purified by silica gel flash chromatography eluting with a hexanes/ethyl acetate, gradient from 80:20 to 0:100, to give the title compound (2.59 g, 74%) as a white foam: ES/MS (m/z): 503.2 (M+H).

後処理

  1. customfitted with a stirrer bar
  2. waitA stream of nitrogen is passed over the mixture for a few minutes
  3. customthe pressure tube is then sealed
  4. temperatureThe resulting dark mixture is cooled to room temperature
  5. filtrationfiltered through a pad of diatomaceous earth
  6. washwhile rinsing with ethyl acetate (100 mL) and water (15 mL)
  7. customThe layers of the filtrate are separated
  8. washthe organic layer is further washed with water (2×30 mL) and brine (30 mL)
  9. dry with materialThe organic phase is dried over sodium sulfate
  10. filtrationfiltered
  11. concentrationconcentrated under reduced pressure
  12. customThe residue is purified by silica gel flash chromatography
  13. washeluting with a hexanes/ethyl acetate, gradient from 80:20 to 0:100

出典と根拠

ORDレコード
ord-b4764b344aac40128a11ce0aaf2b7c0f
出典データセット
uspto-grants-2014_11
特許番号
US08889856B2

関連ノート

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