Sodium Carbonate → 4-Bromo-3',5'-dimethoxy-biphenyl-2,3-diamine

HRID 43111

反応式

HRID 43111 の反応式
[CH3:1][O:2][C:3]1[CH:4]=[C:5](B(O)O)[CH:6]=[C:7]([O:9][CH3:10])[CH:8]=1.[Br:14][C:15]1[CH:20]=[CH:19][C:18](Br)=[C:17]([NH2:22])[C:16]=1[NH2:23].C([O-])([O-])=O.[Na+].[Na+]>CCO.C1(C)C=CC=CC=1.CCOC(C)=O.O.C1C=CC(P(C2C=CC=CC=2)[C-]2C=CC=C2)=CC=1.C1C=CC(P(C2C=CC=CC=2)[C-]2C=CC=C2)=CC=1.Cl[Pd]Cl.[Fe+2]>[Br:14][C:15]1[CH:20]=[CH:19][C:18]([C:5]2[CH:4]=[C:3]([O:2][CH3:1])[CH:8]=[C:7]([O:9][CH3:10])[CH:6]=2)=[C:17]([NH2:22])[C:16]=1[NH2:23]

参加物

9

反応物 3

HCID 10340Sodium CarbonateHCID 4374257(3,5-Dimethoxyphenyl)boronic acidHCID 118215323,6-Dibromobenzene-1,2-diamine

生成物 1

HCID 592928784-Bromo-3',5'-dimethoxy-biphenyl-2,3-diamine収率 37.9%

試薬・触媒・溶媒 5

HCID 178418228Bis(cyclopenta-1,4-dien-1-yl(diphenyl)phosphane);dichloropalladium;iron(2+)触媒HCID 702Ethanol溶媒HCID 962Water溶媒HCID 1140Toluene溶媒HCID 8857Ethyl Acetate溶媒

反応条件

温度
105 °C

実験手順

A mixture of 3,5-dimethoxyphenylboronic acid (15.1 g, 82.7 mmol, 1.1 equiv) (Step 1.8) in EtOH (50 mL) was added dropwise to a mixture of 3,6-dibromo-benzene-1,2-diamine (20 g, 75.2 mmol) (Step 1.6), PdCl2(dppf) (6.1 g, 7.5 mmol, 0.1 equiv), Na2CO3 (2 M solution in H2O, 150 mL, 300.8 mmol, 4 equiv) in toluene (300 mL) at 105° C., under an argon atmosphere. The reaction mixture was stirred at 105° C. for 3 h, allowed to cool to rt, diluted with EtOAc and H2O and extracted with EtOAc. The organic phase was washed with H2O and brine, dried (Na2SO4), filtered and concentrated. The crude product was purified by silica gel column chromatography (DCM) followed by trituration in EtOH to afford 9.2 g of the title compound as a white solid: ES-MS: 323.0/325.0 [M+H]+; tR=4.43 min (System 1); Rf=0.15 (DCM).

後処理

  1. temperatureto cool to rt
  2. extractionextracted with EtOAc
  3. washThe organic phase was washed with H2O and brine
  4. dry with materialdried (Na2SO4)
  5. filtrationfiltered
  6. concentrationconcentrated
  7. customThe crude product was purified by silica gel column chromatography (DCM)

出典と根拠

ORDレコード
ord-99b0390f550b43afa7312b65ce2d7fbd
出典データセット
uspto-grants-2013_09
特許番号
US08536175B2

関連ノート

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