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Tri-tert-butylphosphine tetrafluoroborate → methyl 7-[2-((Z)-3-diethylaminoprop-1-enyl)-4-fluorobenzenesulfonyl-amino]-10H-9-oxa-1,2-diazaphenanthrene-8-carboxylate

HRID 2200332
ノート
印刷プレビュー

反応式

HRID 2200332 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:26]([C:27]([O:29][CH3:30])=[O:28])=[C:25]2[C:16]([C:17]3[CH:18]=[CH:19][N:20]=[N:21][C:22]=3[CH2:23][O:24]2)=[CH:15][CH:14]=1)(=[O:11])=[O:10].[CH2:31]([N:33]([CH2:50][CH3:51])[CH2:34]/[CH:35]=[CH:36]\[Sn](CCCC)(CCCC)CCCC)[CH3:32].F[B-](F)(F)F.C([PH+](C(C)(C)C)C(C)(C)C)(C)(C)C>O1CCOCC1.CS(C)=O.C(OCC)(=O)C.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]>[CH2:31]([N:33]([CH2:50][CH3:51])[CH2:34]/[CH:35]=[CH:36]\[C:2]1[CH:7]=[C:6]([F:8])[CH:5]=[CH:4][C:3]=1[S:9]([NH:12][C:13]1[C:26]([C:27]([O:29][CH3:30])=[O:28])=[C:25]2[C:16]([C:17]3[CH:18]=[CH:19][N:20]=[N:21][C:22]=3[CH2:23][O:24]2)=[CH:15][CH:14]=1)(=[O:11])=[O:10])[CH3:32]
参加物反応条件実験手順後処理出典と根拠反応ノート

参加物

8

反応物 3

HCID 2734635Tri-tert-butylphosphine tetrafluoroborate2 回HCID 86684726N,N-diethyl-N-((Z)-1-tributylstannanylprop-1-en-3-yl)amine4 回HCID 89705396methyl 7-(2-bromo-4-fluorobenzenesulfonylamino)-10H-9-oxa-1,2-diazaphenanthrene-8-carboxylate2 回

生成物 1

HCID 89705427methyl 7-[2-((Z)-3-diethylaminoprop-1-enyl)-4-fluorobenzenesulfonyl-amino]-10H-9-oxa-1,2-diazaphenanthrene-8-carboxylate
収率 58.9%

試薬・触媒・溶媒 4

HCID 9811564Bis(dibenzylideneacetone)palladium触媒2 回HCID 679Dimethyl Sulfoxide溶媒HCID 8857Ethyl Acetate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)-10H-9-oxa-1,2-diazaphenanthrene-8-carboxylate (Intermediate 5, 0.403 g), N,N-diethyl-N—((Z)-1-tributylstannanylprop-1-en-3-yl)-amine (Intermediate 2, 0.656 g), tris(dibenzylidene-acetone)dipalladium(0) (0.037 g) and tri-tert-butylphosphonium tetrafluoroborate (0.024 g) in dioxan (10 mL) and DMSO (1 mL) was stirred and heated at 95° C. under nitrogen for 90 minutes. Further N,N-diethyl-N—((Z)-1-tributylstannanylprop-1-en-3-yl)-amine (Intermediate 2, 0.656 g), tris(dibenzylideneacetone)dipalladium(0) (0.037 g) and tri-tert-butylphosphonium tetrafluoroborate (0.024 g) were added and the mixture was heated at 95° C. under nitrogen for a further 45 minutes. After cooling, the mixture was diluted with ethyl acetate and washed three times with water. The combined aqueous extracts were extracted with DCM and the combined organic layers were filtered through a phase separator. The filtrate was evaporated in vacuo and the residue was purified by chromatography on silica, eluting with a mixture of methanol and DCM with a gradient of 0-20% to give methyl 7-[2-((Z)-3-diethylaminoprop-1-enyl)-4-fluorobenzenesulfonylamino]-10H-9-oxa-1,2-diazaphenanthrene-8-carboxylate (0.253 g) as a sandy coloured solid.

後処理

  1. temperaturethe mixture was heated at 95° C. under nitrogen for a further 45 minutes
  2. temperatureAfter cooling
  3. washwashed three times with water
  4. extractionThe combined aqueous extracts were extracted with DCM
  5. filtrationthe combined organic layers were filtered through a phase separator
  6. customThe filtrate was evaporated in vacuo
  7. customthe residue was purified by chromatography on silica
  8. washeluting with a mixture of methanol and DCM with a gradient of 0-20%

出典と根拠

ORDレコード
ord-615f058410a745a2adb3a45b25e601c3
出典データセット
uspto-grants-2016_06
DOI
10.6084/m9.figshare.5104873.v1
特許番号
US09359369B2

反応ノート

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