Benzaldehyde → 2,4-Di(prop-1-en-2-yl)dibenzo[b,d]furan-1-amine

HRID 1750910노트

반응식

HRID 1750910 반응식
Br[C:2]1[CH:14]=[C:13](Br)[C:5]2[O:6][C:7]3[CH:12]=[CH:11][CH:10]=[CH:9][C:8]=3[C:4]=2[C:3]=1[NH2:16].[C:17](B1OC(C)(C)C(C)(C)O1)([CH3:19])=[CH2:18].O.P([O-])([O-])([O-])=O.[K+].[K+].[K+].[CH:38](=O)[C:39]1C=CC=C[CH:40]=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.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.[Pd].[Pd].C1(P(C2CCCCC2)C2C=C(C3C(OC)=CC=CC=3OC)C=CC=2)CCCCC1.O.C1(C)C=CC=CC=1>[CH2:18]=[C:17]([C:2]1[CH:14]=[C:13]([C:39]([CH3:40])=[CH2:38])[C:5]2[O:6][C:7]3[CH:12]=[CH:11][CH:10]=[CH:9][C:8]=3[C:4]=2[C:3]=1[NH2:16])[CH3:19]

참가 물질

9

반응물 4

HCID 240BenzaldehydeHCID 109974264,4,5,5-Tetramethyl-2-(prop-1-en-2-yl)-1,3,2-dioxaborolaneHCID 22031701Potassium phosphate, tribasic, monohydrateHCID 584010082,4-Dibromodibenzo[b,d]furan-1-amine

생성물 1

HCID 584010332,4-Di(prop-1-en-2-yl)dibenzo[b,d]furan-1-amine수율 99%

시약·촉매·용매 4

HCID 9811564Bis(dibenzylideneacetone)palladium촉매HCID 58401078Dicyclohexyl(2',6'-dimethoxybiphenyl-3-yl)phosphine촉매HCID 962Water용매HCID 1140Toluene용매

실험 절차

2,4-dibromodibenzo[b,d]furan-1-amine (6.5 g, 18.5 mmol), isopropenylboronic acid pinacol ester (15.5 g, 92 mmol), potassium phosphate monohydrate (17 g, 74 mmol), dicyclohexyl(2′,6′-dimethoxybiphenyl-3-yl)phosphine (0.6 g, 1.5 mmol), benzaldehyde (2 g, 18.5 mmol) were added to 170 mL 9:1 mixture of toluene and water. Reaction mixture was degassed via bubbling nitrogen for 30 minutes and Pd2 dba3 (0.34 g, 0.4 mmol) was added at this time. Reaction mixture was degassed for another 10 minutes and then refluxed for 3 h. Crude reaction mixture was filtered through a Celite pad and partitioned between brine and ethylacetate. Ethylacetate layer was washed with 1N HCl followed by saturated Na2CO3 solution and finally dried over anhydrous Na2SO4. Crude product was purified by flash chromatography over silica gel with 40% DCM/Hexanes. Target compound (4.8 g, 99% yield) was isolated as light red color oil.

후처리

  1. customReaction mixture
  2. customwas degassed
  3. customvia bubbling nitrogen for 30 minutes
  4. customReaction mixture
  5. customwas degassed for another 10 minutes
  6. temperaturerefluxed for 3 h
  7. customCrude reaction mixture
  8. filtrationwas filtered through a Celite pad
  9. custompartitioned between brine and ethylacetate
  10. washEthylacetate layer was washed with 1N HCl
  11. dry with materialfinally dried over anhydrous Na2SO4
  12. customCrude product was purified by flash chromatography over silica gel with 40% DCM/Hexanes

출처 및 근거

ORD 기록
ord-86c04fbd77c842519cbf7b89c1440774
출처 데이터셋
uspto-grants-2015_10
특허 번호
US09156870B2

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