Hydrochloric Acid → 3,3'-Bis(diethoxyphosphoryl)-[2,2']-bithiophene

HRID 1662881Notes

Reaction equation

HRID 1662881 reaction equation
[CH2:1]([O:3][P:4]([C:9]1[CH:13]=[CH:12][S:11][C:10]=1I)([O:6][CH2:7][CH3:8])=[O:5])[CH3:2].C([Sn](CCCC)(CCCC)[C:20]1[S:21][CH:22]=[CH:23][C:24]=1[P:25]([O:30][CH2:31][CH3:32])([O:27][CH2:28][CH3:29])=[O:26])CCC.Cl>CN(C=O)C.[Cu]Cl>[CH2:1]([O:3][P:4]([C:9]1[CH:13]=[CH:12][S:11][C:10]=1[C:20]1[S:21][CH:22]=[CH:23][C:24]=1[P:25]([O:30][CH2:31][CH3:32])([O:27][CH2:28][CH3:29])=[O:26])([O:6][CH2:7][CH3:8])=[O:5])[CH3:2]

Participants

6

Reactant 3

HCID 313Hydrochloric AcidHCID 59155833HCID 59155833, compoundHCID 591558362-Iodo-3-diethoxyphosphorylthiophene

Product 1

HCID 866384143,3'-Bis(diethoxyphosphoryl)-[2,2']-bithiopheneYield 71%

Reagents, catalysts & solvents 2

HCID 6228DimethylformamideSolventHCID 62652Cuprous chlorideSolvent

Conditions

Temperature
80 °C

Procedure

At room temperature, 0.6790 g (1.96 mmols) of the 3-(diethoxyphosphoryl)-2-iodothiophene obtained in Example 12(1) and 0.9982 g (1.96 mmols) of the 2-(tributylstannyl)-3-(diethoxyphosphoryl)thiophene obtained in Example 12(2) were dissolved in DMF, to which 0.2326 g (2.35 mmols) of commercially available copper(I) chloride was added at room temperature. Thereafter, the reaction mixture was heated to 80° C. and stirred for 10 hours. After the reaction, the reaction mixture was cooled down to room temperature, to which a 10% hydrochloric acid aqueous solution, followed by extraction of the resulting product 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 crude product was purified with a silica gel column (gradiated from ethyl acetate:hexane=1:1 with acetone) to obtain the specified substance in the form of white crystals at a yield of 0.6101 g (yield: 71%).

Workup

  1. additionwas added at room temperature
  2. customAfter the reaction
  3. extractionfollowed by extraction of the resulting product with ethyl acetate
  4. washThe organic phase was washed with a saturated saline solution
  5. dry with materialdried over anhydrous sodium sulfate
  6. customThe solvent was removed
  7. distillationby distilling off under reduced pressure
  8. customthe resulting crude product was purified with a silica gel column (gradiated from ethyl acetate:hexane=1:1 with acetone)
  9. customto obtain the specified substance in the form of white crystals at a yield of 0.6101 g (yield: 71%)

Sources & evidence

ORD record
ord-71582fc1bd6a4b4aaac1ff2b4eb1c85c
Source dataset
uspto-grants-2011_10
Patent number
US08030438B2

Reaction notes

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