Hydrogen Peroxide → HCID 20136519, compound

HRID 579736Notes

Reaction equation

HRID 579736 reaction equation
[CH3:1][O:2][C:3]1[CH:8]=[CH:7][C:6]([C:9]2[S:10][CH:11]=[CH:12][C:13]=2[C:14]2[CH:19]=[CH:18][C:17]([O:20][CH3:21])=[CH:16][CH:15]=2)=[CH:5][CH:4]=1.[CH2:22]([Li])[CH2:23][CH2:24][CH3:25].C(B(C(CC)C)C(CC)C)(CC)C.BrBr.[OH-].[Na+].OO>C1(C)C=CC=CC=1.C(OCC)C>[CH3:22][CH:23]([C:11]1[S:10][C:9]([C:6]2[CH:5]=[CH:4][C:3]([O:2][CH3:1])=[CH:8][CH:7]=2)=[C:13]([C:14]2[CH:19]=[CH:18][C:17]([O:20][CH3:21])=[CH:16][CH:15]=2)[CH:12]=1)[CH2:24][CH3:25]

Participants

9

Reactant 6

HCID 784Hydrogen PeroxideHCID 14798Sodium HydroxideHCID 24408BromineHCID 102559Borane, tris(1-methylpropyl)-HCID 114037172,3-Bis(4-methoxyphenyl)thiopheneHCID 178418339Butyllithium

Product 1

HCID 20136519HCID 20136519, compoundYield 41%

Reagents, catalysts & solvents 2

HCID 1140TolueneSolventHCID 3283Diethyl EtherSolvent2×

Procedure

A solution of 2,3-bis(4-methoxyphenyl)thiophene (5.92 g, 20 mmole) in toluene (40 ml)/diethyl ether (130 ml) was treated with 1.6M n-butyl lithium (14 ml, 1.1 equiv.) and heated at reflux for 1.5 hours. The reaction mixture was cooled to -76° and treated dropwise with 1M tri-s-butylboron (22 ml, 1.1 equiv.). After 0.5 hours at -76°, the reaction mixture was stirred at 0° for 0.5 hours, recooled to -76° and treated with bromine (1 ml, 20 mmole) in 20 ml diethyl ether. The mixture was allowed to warm to room temperature, and then after 2 hours was treated sequentially with 50% (w/w) sodium hydroxide (2.3 ml) and 30% hydrogen peroxide (8 ml). The mixture was stirred overnight, and then extracted with ethyl acetate. The organic extracts were washed with water and brine, dried and concentrated in vacuo. Chromatography on a Waters Prep 500 (hexane/ethyl acetate, 9:1) provided the title compound (2.9 g, 41%) as an oil. Proton NMR was consistent with the assigned structure. Mass Spec. (MS): m/z 352 (M+), 323 (M--C2H5).

Workup

  1. temperatureheated
  2. temperatureat reflux for 1.5 hours
  3. temperatureThe reaction mixture was cooled to -76°
  4. customrecooled to -76°
  5. stirringThe mixture was stirred overnight
  6. extractionextracted with ethyl acetate
  7. washThe organic extracts were washed with water and brine
  8. customdried
  9. concentrationconcentrated in vacuo

Sources & evidence

ORD record
ord-16db53b36520447ab9bd579916159426
Source dataset
uspto-grants-1988_06
Patent number
US04749712

Reaction notes

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