methyl 7-(2-bromo-4-fluorobenzenesulfonylamino]-4H-benzo[b]pyrrolo[1,2-d][1,4]oxazine-6-carboxylate → methyl 7-[2-((Z)-3-diethylaminoprop-1-enyl)-4-fluorobenzenesulfonylamino]-4H-benzo[b]pyrrolo[1,2-d][1,4]oxazine-6-carboxylate

HRID 595110ノート

反応式

HRID 595110 の反応式
Br[C:2]1[CH:7]=[C:6]([F:8])[CH:5]=[CH:4][C:3]=1[S:9]([NH:12][C:13]1[C:25]([C:26]([O:28][CH3:29])=[O:27])=[C:17]2[O:18][CH2:19][C:20]3[N:21]([CH:22]=[CH:23][CH:24]=3)[C:16]2=[CH:15][CH:14]=1)(=[O:11])=[O:10].[CH2:30]([N:32]([CH2:49][CH3:50])[CH2:33]/[CH:34]=[CH:35]\[Sn](CCCC)(CCCC)CCCC)[CH3:31]>O1CCOCC1.CS(C)=O>[CH2:30]([N:32]([CH2:49][CH3:50])[CH2:33]/[CH:34]=[CH:35]\[C:2]1[CH:7]=[C:6]([F:8])[CH:5]=[CH:4][C:3]=1[S:9]([NH:12][C:13]1[C:25]([C:26]([O:28][CH3:29])=[O:27])=[C:17]2[O:18][CH2:19][C:20]3[N:21]([CH:22]=[CH:23][CH:24]=3)[C:16]2=[CH:15][CH:14]=1)(=[O:11])=[O:10])[CH3:31]

参加物

5

反応物 2

HCID 70983589methyl 7-(2-bromo-4-fluorobenzenesulfonylamino]-4H-benzo[b]pyrrolo[1,2-d][1,4]oxazine-6-carboxylate2 回HCID 86684726N,N-diethyl-N-((Z)-1-tributylstannanylprop-1-en-3-yl)amine2 回

生成物 1

HCID 86712813methyl 7-[2-((Z)-3-diethylaminoprop-1-enyl)-4-fluorobenzenesulfonylamino]-4H-benzo[b]pyrrolo[1,2-d][1,4]oxazine-6-carboxylate収率 64.8%

試薬・触媒・溶媒 2

HCID 679Dimethyl Sulfoxide溶媒HCID 312751,4-Dioxane溶媒

反応条件

温度
95 °C

実験手順

A mixture of methyl 7-(2-bromo-4-fluorobenzenesulfonylamino]-4H-benzo[b]pyrrolo[1,2-d][1,4]oxazine-6-carboxylate (Intermediate 16, 0.107 g) and N,N-diethyl-N—((Z)-1-tributylstannanylprop-1-en-3-yl)-amine (Intermediate 3, 0.179 g) in dioxane (3 mL) and DMSO (0.3 mL) was degassed and purged with nitrogen. Tris-(dibenzylideneacetone)dipalladium (0) (0.01 g) and tri-tert-butylphosphonium tetrafluoroborate (0.006 g) were added and the mixture was degassed and purged with nitrogen again, then the mixture was heated to 95° C. for 1 hour. After cooling, the mixture was partitioned between ethyl acetate and water. The aqueous layer was extracted with more ethyl acetate and the combined organic layers were dried (MgSO4) and filtered. The filtrate was concentrated in vacuo and the residue was purified by chromatography on silica, eluting with a mixture of methanol and DCM with a gradient of 0-5% to give methyl 7-[2-((Z)-3-diethylaminoprop-1-enyl)-4-fluorobenzenesulfonylamino]-4H-benzo[b]pyrrolo[1,2-d][1,4]oxazine-6-carboxylate (0.074 g) as a sticky yellow oil.

後処理

  1. customwas degassed
  2. custompurged with nitrogen
  3. additionTris-(dibenzylideneacetone)dipalladium (0) (0.01 g) and tri-tert-butylphosphonium tetrafluoroborate (0.006 g) were added
  4. customthe mixture was degassed
  5. custompurged with nitrogen again
  6. temperatureAfter cooling
  7. customthe mixture was partitioned between ethyl acetate and water
  8. extractionThe aqueous layer was extracted with more ethyl acetate
  9. dry with materialthe combined organic layers were dried (MgSO4)
  10. filtrationfiltered
  11. concentrationThe filtrate was concentrated in vacuo
  12. customthe residue was purified by chromatography on silica
  13. washeluting with a mixture of methanol and DCM with a gradient of 0-5%

出典と根拠

ORDレコード
ord-5d279f218f06492c8ac45c9c0064c942
出典データセット
uspto-grants-2016_01
特許番号
US09242997B2

反応ノート

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