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Cesium carbonate → Methyl 2,6-diamino-3-[2-(tert-butyldimethylsilanyloxymethyl)furan-3-yl]benzoate

HRID 927927
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HRID 927927 반응식
Br[C:2]1[C:3]([NH2:13])=[C:4]([C:9]([NH2:12])=[CH:10][CH:11]=1)[C:5]([O:7][CH3:8])=[O:6].[Si:14]([O:21][CH2:22][C:23]1[O:24][CH:25]=[CH:26][C:27]=1B(O)O)([C:17]([CH3:20])([CH3:19])[CH3:18])([CH3:16])[CH3:15].C(=O)([O-])[O-].[Cs+].[Cs+].F[B-](F)(F)F.C([PH+](C(C)(C)C)C(C)(C)C)(C)(C)C>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]>[NH2:13][C:3]1[C:2]([C:27]2[CH:26]=[CH:25][O:24][C:23]=2[CH2:22][O:21][Si:14]([C:17]([CH3:20])([CH3:19])[CH3:18])([CH3:15])[CH3:16])=[CH:11][CH:10]=[C:9]([NH2:12])[C:4]=1[C:5]([O:7][CH3:8])=[O:6]
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참가 물질

8

반응물 4

HCID 10796Cesium carbonateHCID 2734635Tri-tert-butylphosphine tetrafluoroborateHCID 66685632Methyl 2,6-diamino-3-bromobenzoate2회HCID 709840592-(Tert-butyldimethylsilanyloxymethyl)furan-3-boronic acid2회

생성물 1

HCID 90071951Methyl 2,6-diamino-3-[2-(tert-butyldimethylsilanyloxymethyl)furan-3-yl]benzoate수율 59.8%

시약·촉매·용매 3

HCID 9811564Bis(dibenzylideneacetone)palladium촉매HCID 962Water용매HCID 312751,4-Dioxane용매

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온도
70 °C

실험 절차

A mixture of methyl 3-bromo-2,6-diaminobenzoate (Intermediate 25, 2.6 g), 2-(tert-butyldimethylsilanyloxymethyl)furan-3-boronic acid (Intermediate 37, 3.5 g), cesium carbonate (11.35 g), tri-tert-butylphosphonium tetrafluoroborate (0.334 g) and tris-(dibenzylideneacetone)dipalladium (0.529 g) in dioxane (72 mL) and water (18 mL) was degassed and purged with nitrogen then heated at 70° C. for 75 minutes. After cooling, ethyl acetate and water were added and the mixture was filtered through Celite. The filtrate was separated and the organic layer was washed with brine, dried (MgSO4) and filtered. The filtrate was evaporated to dryness and the residue was purified by chromatography on silica eluting with a mixture of ethyl acetate and cyclohexane with a gradient of 5-20% to give methyl 2,6-diamino-3-[2-(tert-butyldimethylsilanyloxymethyl)furan-3-yl]benzoate (2.39 g) as a viscous oil which was used without further characterization.

후처리

  1. customwas degassed
  2. custompurged with nitrogen
  3. temperatureAfter cooling
  4. additionethyl acetate and water were added
  5. filtrationthe mixture was filtered through Celite
  6. customThe filtrate was separated
  7. washthe organic layer was washed with brine
  8. dry with materialdried (MgSO4)
  9. filtrationfiltered
  10. customThe filtrate was evaporated to dryness
  11. customthe residue was purified by chromatography on silica eluting with a mixture of ethyl acetate and cyclohexane with a gradient of 5-20%

출처 및 근거

ORD 기록
ord-f97f597d5bf64360b34dfa84ab211726
출처 데이터셋
uspto-grants-2016_03
DOI
10.6084/m9.figshare.5104873.v1
특허 번호
US09290472B2

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