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

HRID 1750910ノート

反応式

HRID 1750910 の反応式
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]

参加物

9

反応物 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

生成物 1

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

試薬・触媒・溶媒 4

HCID 9811564Bis(dibenzylideneacetone)palladium触媒HCID 58401078Dicyclohexyl(2',6'-dimethoxybiphenyl-3-yl)phosphine触媒HCID 962Water溶媒HCID 1140Toluene溶媒

実験手順

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.

後処理

  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

出典と根拠

ORDレコード
ord-86c04fbd77c842519cbf7b89c1440774
出典データセット
uspto-grants-2015_10
特許番号
US09156870B2

反応ノート

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