4-Bromothioanisole → Dimethyl 2-thioanisylterepthalate

HRID 1493852

Reaction equation

HRID 1493852 reaction equation
Br[C:2]1[CH:7]=[CH:6][C:5]([S:8][CH3:9])=[CH:4][CH:3]=1.[Li][C:11](C)(C)C.[CH3:15][O:16][C:17](=[O:29])[C:18]1[CH:27]=[CH:26][C:21]([C:22]([O:24][CH3:25])=[O:23])=[CH:20][C:19]=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>[CH3:11][C:2]1[CH:7]=[CH:6][C:5]([S:8][CH3:9])=[CH:4][C:3]=1[C:19]1[CH:20]=[C:21]([C:22]([O:24][CH3:25])=[O:23])[CH:26]=[CH:27][C:18]=1[C:17]([O:16][CH3:15])=[O:29]

Participants

7

Reactant 3

HCID 660374-BromothioanisoleHCID 87741Dimethyl 2-bromoterephthalateHCID 178418306HCID 178418306, compound

Product 1

HCID 86744855Dimethyl 2-thioanisylterepthalate

Reagents, catalysts & solvents 3

HCID 3007855ZincchlorideCatalystHCID 178418751HCID 178418751, compoundCatalystHCID 8028TetrahydrofuranSolvent2×

Procedure

4-Bromothioanisole (7.1 g) was dissolved in tetrahydrofuran (23 ml). To this solution at -78° C. under nitrogen was added over a ten minute period 1.7M tBuLi (48 ml). After 45 minutes at room temperature, 1M ZnCl2 (41 ml) was added dropwise over a ten minute period. After one half hour at room temperature, bis(triphenylphosphine)nickel(II) chloride (1.4 g) was added followed by dimethyl-2-bromoterepthalate (4.67 g) in tetrahydrofuran (47 ml). The reaction mixture was stirred at room temperature for 45 minutes. The THF 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 gave the crude product. Chromatography on silica gel using 15% ethyl acetate/hexanes gave the desired product (3.92 g).

Workup

  1. waitAfter one half hour at room temperature
  2. customThe THF was removed under reduced pressure
  3. additionThe residue was treated with ethyl acetate and 1N HCl
  4. customthe layers separated
  5. washThe organic phase was washed with water, brine
  6. dry with materialdried over magnesium sulfate
  7. customevaporated
  8. customgave the crude product

Sources & evidence

ORD record
ord-34d2e9b246ad404a807df43f1ee17ec8
Source dataset
uspto-grants-1991_06
Patent number
US05025007

Linked notes

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