Bromobenzene → Ethyl 3,4-dihydro-4-phenyl-2H-1,4-benzoxazine-2-carboxylate

HRID 1696294ノート

反応式

HRID 1696294 の反応式
CC1(C)C2C(=C(P(C3C=CC=CC=3)C3C=CC=CC=3)C=CC=2)OC2C(P(C3C=CC=CC=3)C3C=CC=CC=3)=CC=CC1=2.Br[C:44]1[CH:49]=[CH:48][CH:47]=[CH:46][CH:45]=1.[O:50]1[CH:55]([C:56]([O:58][CH2:59][CH3:60])=[O:57])[CH2:54][NH:53][C:52]2[CH:61]=[CH:62][CH:63]=[CH:64][C:51]1=2.C(=O)([O-])[O-].[Cs+].[Cs+]>O1CCOCC1.O.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.[Pd].[Pd]>[C:44]1([N:53]2[CH2:54][CH:55]([C:56]([O:58][CH2:59][CH3:60])=[O:57])[O:50][C:51]3[CH:64]=[CH:63][CH:62]=[CH:61][C:52]2=3)[CH:49]=[CH:48][CH:47]=[CH:46][CH:45]=1

参加物

8

反応物 4

HCID 7961BromobenzeneHCID 10796Cesium carbonateHCID 31090Ethyl 3,4-dihydro-2H-1,4-benzoxazine-2-carboxylateHCID 6360441,1'-(9,9-Dimethyl-9H-xanthene-4,5-diyl)bis(1,1-diphenylphosphine)

生成物 1

HCID 86614014Ethyl 3,4-dihydro-4-phenyl-2H-1,4-benzoxazine-2-carboxylate

試薬・触媒・溶媒 3

HCID 9811564Bis(dibenzylideneacetone)palladium触媒HCID 962Water溶媒HCID 312751,4-Dioxane溶媒

反応条件

温度
100 °C

実験手順

Tris(dibenzylideneacetone)dipalladium (0) (4.3 mg, 0.0046 mmol), xantphos (8.2 mg, 0.014 mmol), and bromobenzene (40 L, 0.381 mmol) were added to a solution of (±)-ethyl 3,4-dihydro-2H-benzo[b][1,4]oxazine-2-carboxylate (65 mg, 0.31 mmol) in dioxane (2.5 mL). The solids were allowed to dissolve, and cesium carbonate (143 mg, 0.44 mmol) was added, and the suspension was stirred at 100° C. for 24 h. The mixture was cooled to ambient temperature, diluted with water (20 mL), and the product was extracted with 67% EtOAc/hexane (3×25 mL). The organic layers were combined, dried over sodium sulfate, and concentrated. Purification of the crude concentrate by flash column chromatography using 15% EtOAc/hexane afforded the title compound. MS m/z: 284 (M+1).

後処理

  1. dissolutionto dissolve
  2. temperatureThe mixture was cooled to ambient temperature
  3. extractionthe product was extracted with 67% EtOAc/hexane (3×25 mL)
  4. dry with materialdried over sodium sulfate
  5. concentrationconcentrated
  6. customPurification of the crude
  7. concentrationconcentrate by flash column chromatography

出典と根拠

ORDレコード
ord-27473953a74f43f2816a5b7d41d3c917
出典データセット
uspto-grants-2012_04
特許番号
US08163766B2

反応ノート

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