Potassium Fluoride → 3,4-Bis(ethoxyphosphoryl)-[2,2']-bithiophene

HRID 1662871Notes

Reaction equation

HRID 1662871 reaction equation
C(O[P:4]([C:9]1[C:13]([P:14]([O:19][CH2:20][CH3:21])([O:16]CC)=O)=[C:12](I)[S:11][C:10]=1I)([O:6][CH2:7][CH3:8])=[O:5])C.[Cu]C#N.C([Sn](CCCC)(CCCC)[C:32]1[S:33][CH:34]=[CH:35][CH:36]=1)CCC.[F-].[K+]>>[CH2:20]([O:19][P:14](=[C:13]1[C:9](=[P:4]([O:6][CH2:7][CH3:8])=[O:5])[CH2:10][S:11][CH:12]1[C:32]1[S:33][CH:34]=[CH:35][CH:36]=1)=[O:16])[CH3:21]

Participants

5

Reactant 4

HCID 522689Potassium FluorideHCID 27793732-(Tri-n-butylstannyl)thiopheneHCID 866384112,5-Diiodo-3,4-bis(diethoxyphosphoryl)thiopheneHCID 178418546HCID 178418546, compound

Product 1

HCID 866384103,4-Bis(ethoxyphosphoryl)-[2,2']-bithiophene

Conditions

Temperature
70 °C

Procedure

3,4-bis(diethoxyphosphoryl)-2,5-diiodothiophene obtained in Example 7, commercially available tetrakistriphenylphosphine palladium (0.10 equivalent) and copper(I) cyanide (commercial product) in amounts indicated in Table 8 were dissolved in different types of solvents indicated in Table 8, to which 2-tributylstannylthiophene (2.2 equivalents) was added at room temperature. Thereafter, the reaction mixture was heated to 70° C. and stirred for 6 to 20 hours. After the reaction, the reaction mixture was cooled down to room temperature, to which a potassium fluoride aqueous solution was added, followed by stirring for 2 hours. Thereafter, the solid was removed by celite filtration and the filtrate was extracted with ethyl acetate. The organic phase was washed with a saturated saline solution and dried over anhydrous sodium sulfate. The solvent was removed by distilling off under reduced pressure, and the resulting product was purified with a silica gel column (ethyl acetate:methanol=15:1).

Workup

  1. dissolutionwere dissolved in different types of solvents
  2. additionwas added at room temperature
  3. customAfter the reaction
  4. additionwas added
  5. stirringby stirring for 2 hours
  6. customThereafter, the solid was removed by celite filtration
  7. extractionthe filtrate was extracted with ethyl acetate
  8. washThe organic phase was washed with a saturated saline solution
  9. dry with materialdried over anhydrous sodium sulfate
  10. customThe solvent was removed
  11. distillationby distilling off under reduced pressure
  12. customthe resulting product was purified with a silica gel column (ethyl acetate:methanol=15:1)

Sources & evidence

ORD record
ord-833783bcade544ad84eab1aee98fdc3c
Source dataset
uspto-grants-2011_10
Patent number
US08030438B2

Reaction notes

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