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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
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인쇄 미리보기

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HRID 2200332 반응식
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]
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참가 물질

8

반응물 3

HCID 2734635Tri-tert-butylphosphine tetrafluoroborate2회HCID 86684726N,N-diethyl-N-((Z)-1-tributylstannanylprop-1-en-3-yl)amine4회HCID 89705396methyl 7-(2-bromo-4-fluorobenzenesulfonylamino)-10H-9-oxa-1,2-diazaphenanthrene-8-carboxylate2회

생성물 1

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

시약·촉매·용매 4

HCID 9811564Bis(dibenzylideneacetone)palladium촉매2회HCID 679Dimethyl Sulfoxide용매HCID 8857Ethyl Acetate용매HCID 312751,4-Dioxane용매

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온도
95 °C

실험 절차

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.

후처리

  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%

출처 및 근거

ORD 기록
ord-615f058410a745a2adb3a45b25e601c3
출처 데이터셋
uspto-grants-2016_06
DOI
10.6084/m9.figshare.5104873.v1
특허 번호
US09359369B2

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