Hydrochloric Acid → 5-Decyl-2,2'-bithiophene

HRID 545982Notes

Reaction equation

HRID 545982 reaction equation
[Mg].Br[C:3]1[S:4][CH:5]=[CH:6][CH:7]=1.Br[C:9]1[S:10][C:11]([CH2:14][CH2:15][CH2:16][CH2:17][CH2:18][CH2:19][CH2:20][CH2:21][CH2:22][CH3:23])=[CH:12][CH:13]=1.Cl>C1COCC1>[CH2:14]([C:11]1[S:10][C:9]([C:3]2[S:4][CH:5]=[CH:6][CH:7]=2)=[CH:13][CH:12]=1)[CH2:15][CH2:16][CH2:17][CH2:18][CH2:19][CH2:20][CH2:21][CH2:22][CH3:23]

Participants

6

Reactant 4

HCID 313Hydrochloric AcidHCID 138512-BromothiopheneHCID 5462224MagnesiumHCID 588928162-Bromo-5-decylthiophene

Product 1

HCID 588928175-Decyl-2,2'-bithiopheneYield 65,934.5%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent3×

Procedure

Magnesium (8.90 g, 0.365 mmol) and THF (100 ml) were placed in a 300-ml flask equipped with a reflux tube. A solution of 2-bromothiophene (54.0 g, 0.332 mmol) in THF (100 ml) was slowly added drowpwise thereto, and the mixture was heated under reflux for about 2 hr to prepare a Grignard reagent. This Grignard reagent was added dropwise to a mixed solution composed of [1,1′-bis(diphenylphosphino)ferrocene]palladium(II) dichloride dichloromethane complex (1:1) (1.80 g, 2.21 mmol), 2-bromo-5-decylthiophene (67.0 g, 221 mmol) prepared above, and THF (100 ml) at about 0° C. After the completion of the dropwise addition, the mixture was stirred at room temperature overnight. After the completion of the reaction, 1 N HCl (200 ml) was added to the reaction solution, and the organic layer was extracted with chloroform, was dried over sodium sulfate, and was applied to column chromatography (n-hexane) to give an objective compound 5-decyl-2,2′-bithiophene as a light yellow solid (67.1 g, yield 99.1%). An NMR spectrum of the compound thus obtained was measured at room temperature with an NMR spectrometer (model JNM-LA400W, manufactured by Japan Electric Optical Laboratory). 1H-NMR (CDCl3, TMS/ppm): 0.88 (t, 3H, J=6.83 Hz), 1.31 (m, 14H), 1.67 (m, 2H), 2.78 (t, 2H, J=7.32 Hz), 6.67 (d, 1H, J=3.90 Hz), 6.98 (m, 2H), 7.09 (d, 1H, J=3.90 Hz), 7.15 (d, 1H, J=4.88 Hz)

Workup

  1. customequipped with a reflux tube
  2. temperaturethe mixture was heated
  3. temperatureunder reflux for about 2 hr
  4. additionAfter the completion of the dropwise addition
  5. additionwas added to the reaction solution
  6. extractionthe organic layer was extracted with chloroform
  7. dry with materialwas dried over sodium sulfate

Sources & evidence

ORD record
ord-98f6ed1420244e34aea5f8df36c7dda3
Source dataset
uspto-grants-2011_05
Patent number
US07935828B2

Reaction notes

Loading…