3,4-Dibromothiophene → HCID 59155817, compound

HRID 1662863Notes

Reaction equation

HRID 1662863 reaction equation
[Br:1][C:2]1[C:6](Br)=[CH:5][S:4][CH:3]=1.[P:8]([O-])([O:13][CH2:14][CH3:15])([O:10][CH2:11][CH3:12])=[O:9].C(N(C(C)C)CC)(C)C.P([O-])([O-])(O)=O.[Na+].[Na+].P([O-])(O)(O)=O.[Na+]>C1C=CC(P(C2C=CC=CC=2)[C-]2C=CC=C2)=CC=1.C1C=CC(P(C2C=CC=CC=2)[C-]2C=CC=C2)=CC=1.Cl[Pd]Cl.[Fe+2].CN(C=O)C>[Br:1][C:2]1[C:6]([P:8]([O:13][CH2:14][CH3:15])([O:10][CH2:11][CH3:12])=[O:9])=[CH:5][S:4][CH:3]=1

Participants

7

Reactant 4

HCID 184523,4-DibromothiopheneHCID 81531DiisopropylethylamineHCID 5166299Diethyl phosphoric acidHCID 86630341Sodium phosphate (Na3(PO4)2)

Product 1

HCID 59155817HCID 59155817, compound

Reagents, catalysts & solvents 2

HCID 178418228Bis(cyclopenta-1,4-dien-1-yl(diphenyl)phosphane);dichloropalladium;iron(2+)CatalystHCID 6228DimethylformamideSolvent

Procedure

Under nitrogen, 0.0968 g (0.4 mmols) of 3,4-dibromothiophene and 0.0131 g (0.016 mmols) of commercially available Pd(dppf)2Cl2 were added to DMF (4 ml) and were dissolved under stirring at room temperature for 5 minutes. To the thus obtained solution, 0.1326 g (0.96 mmols) of commercially available diethyl phosphate and 0.1241 g (0.96 mmols) of diisopropylethylamine were added at room temperature. Thereafter, the reaction mixture was heated to 110° C. and stirred for 4 hours. After the reaction, the reaction mixture was cooled down to room temperature, to which a disodium hydrogen phosphate/sodium dihydrogen phosphate buffer solution, adjusted to pH=7.0, was added, followed by extraction with ethyl acetate. The resulting organic phase was washed with a saturated saline 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 PTLC plate (developed with ethyl acetate:hexane=1:1) to obtain a specified substance 1 in the form of a brown solid and the specified substance 2 in the form of a yellow oil. The thus obtained substances were used for the reaction of Example 2(2) as they are. The yields of the compounds 1 and 2 are shown in Table 1.

Workup

  1. dissolutionwere dissolved
  2. temperatureThereafter, the reaction mixture was heated to 110° C.
  3. stirringstirred for 4 hours
  4. customAfter the reaction
  5. additionwas added
  6. extractionfollowed by extraction with ethyl acetate
  7. washThe resulting organic phase was washed with a saturated saline
  8. dry with materialdried over anhydrous sodium sulfate
  9. customThe solvent was removed
  10. distillationby distilling off under reduced pressure
  11. customthe resulting crude product was purified with a PTLC plate (developed with ethyl acetate:hexane=1:1)
  12. customto obtain a specified substance 1 in the form of a brown solid
  13. customThe thus obtained substances were used for the reaction of Example 2(2) as they

Sources & evidence

ORD record
ord-d836505e5324441dbd8148b63d109013
Source dataset
uspto-grants-2011_10
Patent number
US08030438B2

Reaction notes

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