4-Bromotoluene → [1,1'-Biphenyl]-2,5-dicarboxylic acid, 4'-methyl-, 2,5-dimethyl ester

HRID 1087027

반응식

HRID 1087027 반응식
Br[C:2]1[CH:7]=[CH:6][C:5]([CH3:8])=[CH:4][CH:3]=1.[Li]C(C)(C)C.[CH3:14][O:15][C:16](=[O:28])[C:17]1[CH:26]=[CH:25][C:20]([C:21]([O:23][CH3:24])=[O:22])=[CH:19][C:18]=1Br>O1CCCC1.[Cl-].[Cl-].[Zn+2].Cl[Ni](Cl)([P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1)[P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1>[CH3:14][O:15][C:16](=[O:28])[C:17]1[CH:26]=[CH:25][C:20]([C:21]([O:23][CH3:24])=[O:22])=[CH:19][C:18]=1[C:2]1[CH:7]=[CH:6][C:5]([CH3:8])=[CH:4][CH:3]=1

참가 물질

7

반응물 3

HCID 78054-BromotolueneHCID 87741Dimethyl 2-bromoterephthalateHCID 178418306HCID 178418306, 화합물

생성물 1

HCID 105655[1,1'-Biphenyl]-2,5-dicarboxylic acid, 4'-methyl-, 2,5-dimethyl ester수율 85.3%

시약·촉매·용매 3

HCID 3007855Zincchloride촉매HCID 178418751HCID 178418751, 화합물촉매HCID 8028Tetrahydrofuran용매2회

반응 조건

온도
0 °C

실험 절차

4-Bromotoluene (6 g) was dissolved in tetrahydrofuran (20 ml). To this solution at -78° C. under N2 was added over a ten minute period, 1.7M tBuLi (42 ml). After two hours at room temperature, the reaction mixture was cooled to 0° C. and 1M ZnCl2 (36 ml) was added over a ten minute period. After one-half hour at room temperature, bis(triphenylphosphine)nickel(II) chloride (1.32 g) was added followed by dimethyl-2-bromo-terephthalate (6 g) in tetrahydrofuran 920 ml) dropwise over a five minute period. The reaction mixture was stirred at room temperature for two hours. The tetrahydrofuran was removed under reduced pressure. The residue was treated with ethyl acetate and 1N HCl and the layers separated. The organic phase was washed with water, brine, dried over magnesium sulfate and evaporated which gave the crude product. Chromatography on silica gel using 5% hexanes/methylene chloride gave the desired product (5.33 g).

후처리

  1. additionTo this solution at -78° C. under N2 was added over a ten minute period
  2. waitAfter one-half hour at room temperature
  3. customdropwise over a five minute
  4. customThe tetrahydrofuran was removed under reduced pressure
  5. additionThe residue was treated with ethyl acetate and 1N HCl
  6. customthe layers separated
  7. washThe organic phase was washed with water, brine
  8. dry with materialdried over magnesium sulfate
  9. customevaporated which
  10. customgave the crude product

출처 및 근거

ORD 기록
ord-44e17e1e10bc416cb8f76554c663ea8c
출처 데이터셋
uspto-grants-1991_07
특허 번호
US05034384

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