Hydrochloric Acid → HCID 69298588, compound

HRID 2217922Notes

Reaction equation

HRID 2217922 reaction equation
Br[C:2]1[CH:6]=[CH:5][S:4][CH:3]=1.Cl.[CH2:8]1[CH2:12]O[CH2:10][CH2:9]1>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]>[CH2:10]([C:3]1[S:4][C:5]([C:2]2[CH:6]=[CH:5][S:4][CH:3]=2)=[CH:6][CH:2]=1)[CH2:9][CH2:8][CH2:12][CH2:12][CH2:8][CH2:9][CH2:10][CH2:3][CH2:2][CH2:6][CH3:5]

Participants

5

Reactant 3

HCID 313Hydrochloric AcidHCID 8028TetrahydrofuranHCID 133833-Bromothiophene

Product 1

HCID 69298588HCID 69298588, compoundYield 54%

Reagents, catalysts & solvents 1

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

Conditions

Temperature
0 °C

Procedure

Separately, diphenylphosphinoferroceneparadium dichloride (hereinafter referred to as “Pd(dppf)Cl2”) (1.7 g, 2.11 mmol, 0.01 eq) and 3-bromothiophene (41.0 g, 253 mmol, 1.2 eq) were placed in a three-necked flask, and the atmosphere in the flask was replaced by Ar. Dehydrated THF (200 ml) was added to the contents of the flask, and the mixture was cooled to 0° C. The Grignard reagent prepared above was added dropwise thereto, and the mixture was stirred for 30 min. The reaction solution was brought to room temperature and was stirred for 6 hr. A 1 N aqueous HCl solution (20 ml) was added thereto, and the mixture was stirred for 15 min. THF was removed by evaporation, and the residue was extracted with diethyl ether, followed by washing with water until pH=7. The extract was dehydrated over Na2SO4, and the solvent was removed by evaporation, and the residue was purified by chromatography on silica gel and was recrystallized from ethanol to give an objective substance 5′ dodecyl-3,2′-bithiophene as a light yellow solid (about 38.5 g, yield about 54%). 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 (d6-DMSO, TMS/ppm): 0.86 (t, 3H, J=6.83 Hz), 1.26 (m, 18H), 1.64 (m, 2H), 2.77 (t, 2H, J=7.32 Hz), 6.75 (d, 1H, J=3.42 Hz), 7.11 (d, 1H J=3.42 Hz), 7.32 (dd, 1H, J=0.97 Hz, J=5.12 Hz), 7.53 (m, 2H).

Workup

  1. customwere placed in a three-necked flask
  2. additionabove was added dropwise
  3. customwas brought to room temperature
  4. stirringwas stirred for 6 hr
  5. stirringthe mixture was stirred for 15 min
  6. customTHF was removed by evaporation
  7. extractionthe residue was extracted with diethyl ether
  8. washby washing with water until pH=7
  9. customthe solvent was removed by evaporation
  10. customthe residue was purified by chromatography on silica gel
  11. customwas recrystallized from ethanol

Sources & evidence

ORD record
ord-2fe5574c7a2c4aa1a3d805aca82ca27c
Source dataset
uspto-grants-2008_08
Patent number
US07408188B2

Reaction notes

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