Hydrochloric Acid → 3',4'-Bis(diethoxyphosphoryl)-[2,2':5',2'']-terthiophene

HRID 1662872Notes

Reaction equation

HRID 1662872 reaction equation
[CH2:1]([O:3][P:4]([C:9]1[C:13]([P:14]([O:19][CH2:20][CH3:21])([O:16][CH2:17][CH3:18])=[O:15])=[C:12](I)[S:11][C:10]=1I)([O:6][CH2:7][CH3:8])=[O:5])[CH3:2].C([Sn](CCCC)(CCCC)[C:29]1[S:30][CH:31]=[CH:32][CH:33]=1)CCC.Cl>CN(C=O)C.[Cu]>[CH2:1]([O:3][P:4]([C:9]1[C:13]([P:14]([O:19][CH2:20][CH3:21])([O:16][CH2:17][CH3:18])=[O:15])=[C:12]([C:10]2[S:11][CH:12]=[CH:13][CH:9]=2)[S:11][C:10]=1[C:31]1[S:30][CH:29]=[CH:33][CH:32]=1)([O:6][CH2:7][CH3:8])=[O:5])[CH3:2]

Participants

6

Reactant 3

HCID 313Hydrochloric AcidHCID 27793732-(Tri-n-butylstannyl)thiopheneHCID 866384112,5-Diiodo-3,4-bis(diethoxyphosphoryl)thiophene

Product 1

HCID 591559493',4'-Bis(diethoxyphosphoryl)-[2,2':5',2'']-terthiophene

Reagents, catalysts & solvents 2

HCID 23978CopperCatalystHCID 6228DimethylformamideSolvent

Conditions

Temperature
80 °C

Procedure

3,4-bis(diethoxyphosphoryl)-2,5-diiodothiophene obtained in Example 7, and different types of copper reagents (2.2 equivalents, commercial products) indicated in Table 9 were dissolved in DMF, to which 2-tributylstannylthiophene (2.2 equivalents) was added at room temperature. Thereafter, the reaction mixture was heated to 80° C. and stirred for 11 to 13 hours. After the reaction, the reaction mixture was cooled down to room temperature, to which a 0.6 M hydrochloric acid aqueous solution was added, 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 product was purified with a silica gel column (ethyl acetate:methanol=15:1) to obtain the specified substance.

Workup

  1. additionwas added at room temperature
  2. customAfter the reaction
  3. additionwas added
  4. extractionfollowed by extraction of the resulting product with ethyl acetate
  5. washThe organic phase was washed with a saturated saline solution
  6. dry with materialdried over anhydrous sodium sulfate
  7. customThe solvent was removed
  8. distillationby distilling off under reduced pressure
  9. customthe resulting product was purified with a silica gel column (ethyl acetate:methanol=15:1)
  10. customto obtain the specified substance

Sources & evidence

ORD record
ord-05b45716e4a740d8ab33aeba37c60287
Source dataset
uspto-grants-2011_10
Patent number
US08030438B2

Reaction notes

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