Hydrochloric Acid → 3-(2,6-Dimethylmorpholino)benzaldehyde

HRID 85178

反応式

HRID 85178 の反応式
Br[C:2]1[CH:3]=[C:4]([CH:8]2[O:13]CCCO2)[CH:5]=[CH:6][CH:7]=1.[CH3:14][CH:15]1[O:20][CH:19]([CH3:21])[CH2:18][NH:17][CH2:16]1.CC([O-])(C)C.[Na+].Cl.[OH-].[Na+]>C1(C)C=CC=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.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.[Pd].[Pd].C1C=CC(P(C2C(C3C(P(C4C=CC=CC=4)C4C=CC=CC=4)=CC=C4C=3C=CC=C4)=C3C(C=CC=C3)=CC=2)C2C=CC=CC=2)=CC=1>[CH3:21][CH:19]1[CH2:18][N:17]([C:2]2[CH:3]=[C:4]([CH:5]=[CH:6][CH:7]=2)[CH:8]=[O:13])[CH2:16][CH:15]([CH3:14])[O:20]1

参加物

9

反応物 5

HCID 313Hydrochloric AcidHCID 14798Sodium HydroxideHCID 1108622,6-DimethylmorpholineHCID 101058152-(3-Bromophenyl)-1,3-dioxaneHCID 23676156Sodium t-butoxide

生成物 1

HCID 767394383-(2,6-Dimethylmorpholino)benzaldehyde収率 75.4%

試薬・触媒・溶媒 3

HCID 634876Binap, (A+-)-触媒HCID 9811564Bis(dibenzylideneacetone)palladium触媒HCID 1140Toluene溶媒

実験手順

A mixture containing 2-(3-bromophenyl)-1,3-dioxane (136; 2.0 g, 8.23 mmol), 2,6-dimethylmorpholine (122; 1.14 g, 9.88 mmol), Pd2(dba)3 (50 mg), NaOt-Bu (1.39 g, 14.0 mmol) and BINAP (100 mg) in 20 mL of toluene was stirred at reflux for 5 h. Upon cooling to room temperature, enough cold 1N HCl (50 mL) was added to adjust the pH The resulting reaction mixture was stirred at room temperature for 1 h. NaOH(aq) was added to adjust the pH=11. The aqueous mixture was extracted with CH2Cl2 (3×50 mL). The combined organic layers were dried (MgSO4) and concentrated under reduced pressure. Purification by chromatography (petroleum ether:EtOAc=10:1) afforded 3-(2,6-dimethylmorpholino)benzaldehyde 137 as a yellow oil (1.36 g, yield: 72%).

後処理

  1. temperatureat reflux for 5 h
  2. customThe resulting reaction mixture
  3. stirringwas stirred at room temperature for 1 h
  4. extractionThe aqueous mixture was extracted with CH2Cl2 (3×50 mL)
  5. dry with materialThe combined organic layers were dried (MgSO4)
  6. concentrationconcentrated under reduced pressure
  7. customPurification by chromatography (petroleum ether:EtOAc=10:1)

出典と根拠

ORDレコード
ord-246fa3323393435ca51916887adbf9e1
出典データセット
uspto-grants-2014_09
特許番号
US08846947B2

関連ノート

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