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

HRID 43111

반응식

HRID 43111 반응식
[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]

참가 물질

9

반응물 3

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

생성물 1

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

시약·촉매·용매 5

HCID 178418228Bis(cyclopenta-1,4-dien-1-yl(diphenyl)phosphane);dichloropalladium;iron(2+)촉매HCID 702Ethanol용매HCID 962Water용매HCID 1140Toluene용매HCID 8857Ethyl Acetate용매

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온도
105 °C

실험 절차

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).

후처리

  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)

출처 및 근거

ORD 기록
ord-99b0390f550b43afa7312b65ce2d7fbd
출처 데이터셋
uspto-grants-2013_09
특허 번호
US08536175B2

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