Hydrochloric Acid → HCID 10576414, compound

HRID 1774090Notes

Reaction equation

HRID 1774090 reaction equation
[Mg].Br[C:3]1[S:4][CH:5]=[CH:6][C:7]=1[CH2:8][CH2:9][CH2:10][CH2:11][CH2:12][CH2:13][CH2:14][CH3:15].Br[CH:17](Br)[CH3:18].Br[C:21]1[S:22][C:23](Br)=[CH:24][CH:25]=1.Cl>C(OCC)C.Cl[Ni]1(Cl)[P](C2C=CC=CC=2)(C2C=CC=CC=2)CCC[P]1(C1C=CC=CC=1)C1C=CC=CC=1>[CH2:8]([C:7]1[CH:6]=[CH:5][S:4][C:3]=1[C:21]1[S:22][C:23]([C:3]2[S:4][CH:5]=[CH:6][C:7]=2[CH2:8][CH2:9][CH2:10][CH2:11][CH2:12][CH2:13][CH2:17][CH3:18])=[CH:24][CH:25]=1)[CH2:9][CH2:10][CH2:11][CH2:12][CH2:13][CH2:14][CH3:15]

Participants

8

Reactant 5

HCID 313Hydrochloric AcidHCID 112011,1-DibromoethaneHCID 184532,5-DibromothiopheneHCID 5462224MagnesiumHCID 107548542-Bromo-3-n-octylthiophene

Product 1

HCID 10576414HCID 10576414, compoundYield 134.5%

Reagents, catalysts & solvents 2

HCID 178418745HCID 178418745, compoundCatalystHCID 3283Diethyl EtherSolvent3×

Procedure

0.53 g (21.8 mmol) of magnesium turnings were introduced in a 100 ml flask and suspended in 30 ml of anhydrous diethyl ether. To the resulting suspension, maintained under an argon (Ar) atmosphere, was slowly added a solution of 3.0 g (3.9 mmol) of 2-bromo-3-octylthiophene having formula (1) and 0.93 ml (10.9 mmol) of dibromoethane in 20 ml of anhydrous diethyl ether. The obtained reaction mixture was sonicated for 30 minutes and subsequently heated at the boiling point of the solvent, for 1.5 hours. After the elimination of the excess of magnesium turnings by filtration, the solution containing 2-(3-octylthienyl)magnesium bromide having formula (2), was slowly added, at 0° C., to a mixture of 0.4 ml (3.6 mmol) of 2,5-dibromothiophene and 0.18 g (0.3 mmol) of [1,3-bis(diphenylphosphino)propane]dichloronickel(II) [Ni(DPPP)Cl2] in 30 ml of anhydrous diethyl ether. The resulting reaction mixture was heated at the boiling point of the solvent, for 18 hours, and poured into a mixture of crushed ice and hydrochloric acid (HCl) (2 M) obtaining an organic phase and an aqueous phase which were separated. The aqueous phase was then extracted with diethyl ether (3×20 ml). The overall organic phase (obtained by joining the organic phases obtained as described above) was dried over anhydrous magnesium sulfate (MgSO4), at room temperature (25° C.), for 3 hours. The solvent was subsequently evaporated at reduced pressure and the obtained residue was purified by chromatography on silica gel using petroleum ether as eluent obtaining 1.24 g (67% yield) of 3,3″-dioctyl-2,2′:5′,2″-terthiophene having formula (3), as yellow liquid, which was characterized by 1H NMR (300 MHz, CDCl3) obtaining the following spectrum: 7.18 (d, 2H), 7.05 (s, 2H), 6.94 (d, 2H), 2.77 (t, 4H), 1.65-1.59 (m, 4H), 1.39-1.26 (m, 20H), 0.87 (t, 6H).

Workup

  1. temperatureTo the resulting suspension, maintained under an argon (Ar) atmosphere
  2. customThe obtained reaction mixture
  3. customwas sonicated for 30 minutes
  4. temperaturesubsequently heated at the boiling point of the solvent, for 1.5 hours
  5. filtrationAfter the elimination of the excess of magnesium turnings by filtration
  6. additionthe solution containing 2-(3-octylthienyl)magnesium bromide having formula (2)
  7. customThe resulting reaction mixture
  8. temperaturewas heated at the boiling point of the solvent, for 18 hours
  9. customobtaining an organic phase
  10. customan aqueous phase which were separated
  11. extractionThe aqueous phase was then extracted with diethyl ether (3×20 ml)
  12. customThe overall organic phase (obtained
  13. customobtained
  14. dry with materialwas dried over anhydrous magnesium sulfate (MgSO4), at room temperature (25° C.)
  15. customThe solvent was subsequently evaporated at reduced pressure
  16. customthe obtained residue was purified by chromatography on silica gel

Sources & evidence

ORD record
ord-db7e2b943bab4343a47c9c586e625171
Source dataset
uspto-grants-2016_02
Patent number
US09257236B2

Reaction notes

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