3,4-Ethylenedioxythiophene → HCID 59593876, compound

HRID 2262330Notes

Reaction equation

HRID 2262330 reaction equation
[CH2:1]1[CH2:9][O:8][C:7]2[C:3](=[CH:4][S:5][CH:6]=2)[O:2]1.C([Li])CCC.[CH3:15][Si:16]([C:19]#[C:20][C:21]1[CH:26]=[CH:25][C:24](I)=[CH:23][CH:22]=1)([CH3:18])[CH3:17]>O1CCCC1.[Br-].[Zn+2].[Br-].Cl[Pd](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>[O:8]1[CH2:9][CH2:1][O:2][C:3]2=[C:4]([C:24]3[CH:25]=[CH:26][C:21]([C:20]#[C:19][Si:16]([CH3:15])([CH3:18])[CH3:17])=[CH:22][CH:23]=3)[S:5][CH:6]=[C:7]12

Participants

7

Reactant 3

HCID 44218643,4-EthylenedioxythiopheneHCID 11808725(4-Iodophenylethynyl)trimethylsilaneHCID 178418339Butyllithium

Product 1

HCID 59593876HCID 59593876, compoundYield 58%

Reagents, catalysts & solvents 3

HCID 10421208Zinc bromideCatalystHCID 178418476HCID 178418476, compoundCatalystHCID 8028TetrahydrofuranSolvent

Procedure

As shown in the following Reaction 3, 580 mg (4.08 mmol) of 3.4-ethylenedioxythiophene was melted in 10 mL of tetrahydrofuran under nitrogen atmosphere at the temperature of −78° C., and 2.45 mL (6.12 mmol, 1.5 eq) of n-butyllithium was added thereto, and then the reaction solution was stirred for 1 hour. After completion of stirring, 1.37 g (6.12 mmol, 1.5 eq) of zinc bromide was again added to the reaction solution at the temperature of 0° C., and then the reaction solution was stirred for 1 hour. Next, 1.22 g (4.08 mmol, 1 eq) of 4-trimethylsilylethynyl iodobenzene and 110 mg (0.16 mmol, 0.04 eq) of dichlorobis-(triphenylphosphine)palladium(II) were added to the reaction solution, and then the reaction solution was stirred for 12 hours at room temperature. After solvents of the reaction solution were removed by distillation under reduced pressure, the compound distilled under reduced pressure was purified with an alumina column chromatography (mobile phase volume ratio: methylene chloride:n-hexane=2:3) to obtain 740 mg of [4-(2,3-Dihydro-thieno[3,4-b][1,4]dioxin-5-yl)-phenylethynyl]-trimethyl-silane with the yield of 58%. NMR data of the obtained compound is as follows. [1H NMR (400 MHz, CDCl3): δ 0.25 (s, 9H), 4.23-4.24 (m, 2H), 4.30-4.32 (m, 2H), 6.32 (s, 1H), 7.44 (d, 2H), 7.64 (d, 2H)].

Workup

  1. additionwas added
  2. stirringAfter completion of stirring
  3. stirringthe reaction solution was stirred for 1 hour
  4. stirringthe reaction solution was stirred for 12 hours at room temperature
  5. customAfter solvents of the reaction solution were removed by distillation under reduced pressure
  6. distillationthe compound distilled under reduced pressure
  7. customwas purified with an alumina column chromatography (mobile phase volume ratio: methylene chloride:n-hexane=2:3)

Sources & evidence

ORD record
ord-72dc48a4fb1548bd9522d5d6b55be128
Source dataset
uspto-grants-2010_12
Patent number
US07850872B2

Reaction notes

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