1,1-Dibromoethane → HCID 18476046, compound

HRID 2187615Notes

Reaction equation

HRID 2187615 reaction equation
BrC(Br)C.[F:5][C:6]1[CH:13]=[CH:12][C:9]([CH2:10]Br)=[CH:8][CH:7]=1.Br[C:15]1[CH:24]=[CH:23][C:22]([N+:25]([O-:27])=[O:26])=[CH:21][C:16]=1[C:17]([O:19][CH3:20])=[O:18]>O1CCCC1.[Zn].C[Si](Cl)(C)C>[N+:25]([C:22]1[CH:21]=[C:16]([C:15]([CH2:10][C:9]2[CH:12]=[CH:13][C:6]([F:5])=[CH:7][CH:8]=2)=[CH:24][CH:23]=1)[C:17]([O:19][CH3:20])=[O:18])([O-:27])=[O:26]

Participants

7

Reactant 3

HCID 112011,1-DibromoethaneHCID 680214-Fluorobenzyl bromideHCID 245494Methyl 2-Bromo-5-nitrobenzoate

Product 1

HCID 18476046HCID 18476046, compoundYield 132.2%

Reagents, catalysts & solvents 3

HCID 6397ChlorotrimethylsilaneCatalystHCID 23994ZincCatalystHCID 8028TetrahydrofuranSolvent3×

Conditions

Temperature
67 °C

Procedure

Zinc dust (14.2 g, 217.2 mmol) and tetrahydrofuran (17 ml) were sonicated under argon for 30 minutes. Dibromoethane (2.1 ml, 24.38 mmol) was added and the mixture heated to 67° C. for 1 minute, cooled to 25° C. and trimethylsilyl chloride (2.5 ml, 19.58 mmol) added. After initial effervescence and exotherm, the mixture was stirred at ambient temperature for 30 minutes. 3M 4-Fluorobenzyl bromide (26 ml, 212 mmol) in tetrahydrofuran (70 ml) was added dropwise with exotherm and stirred at ambient temperature for 1.5 hours. To this a solution of tris(dibenzylideneacetone)palladium(0) (1.3 g, 1.42 mmol) and methyl 2-bromo-5-nitrobenzoate (44 g, 170 mmol) in tetrahydrofuran (550 ml) was added dropwise, under argon, over 30 minutes with exotherm and stirred at ambient for 18 hours. The mixture purified on silica (eluting with ethyl acetate), washed with brine (200 ml) and water (200 ml), dried (magnesium sulphate) and evaporated to give methyl 3-nitro-6-(4-fluorobenzyl)benzoate (65 g) which was used in the next step without further purification.

Workup

  1. temperaturecooled to 25° C.
  2. stirringstirred at ambient temperature for 1.5 hours
  3. stirringstirred at ambient for 18 hours
  4. customThe mixture purified on silica (eluting with ethyl acetate)
  5. washwashed with brine (200 ml) and water (200 ml)
  6. dry with materialdried (magnesium sulphate)
  7. customevaporated

Sources & evidence

ORD record
ord-900fba7ff1ad4d9eb3263531e0381334
Source dataset
uspto-grants-2002_06
Patent number
US06410539B1

Reaction notes

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