Hydrochloric Acid → 3-Tetradecylthiophene

HRID 523435Notes

Reaction equation

HRID 523435 reaction equation
Br[C:2]1[CH:6]=[CH:5][S:4][CH:3]=1.[CH2:7]([Mg]Br)[CH2:8][CH2:9][CH2:10][CH2:11][CH2:12][CH2:13][CH2:14][CH2:15][CH2:16][CH2:17][CH2:18][CH2:19][CH3:20].Cl>C(OCC)C.Cl[Ni]Cl.C1(P(C2C=CC=CC=2)CCCP(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1>[CH2:20]([C:2]1[CH:6]=[CH:5][S:4][CH:3]=1)[CH2:19][CH2:18][CH2:17][CH2:16][CH2:15][CH2:14][CH2:13][CH2:12][CH2:11][CH2:10][CH2:9][CH2:8][CH3:7]

Participants

6

Reactant 3

HCID 313Hydrochloric AcidHCID 133833-BromothiopheneHCID 178418320HCID 178418320, compound

Product 1

HCID 149008163-TetradecylthiopheneYield 75.9%

Reagents, catalysts & solvents 2

HCID 2724937Dichloro(1,1'-(1,3-propanediyl)bis(1,1-diphenylphosphine-kappaP))nickelCatalystHCID 3283Diethyl EtherSolvent

Procedure

To a mixture of 3-bromothiophene (81.5 g, 0.5 mol) and [1,3-bis(diphenylphosphino)propane]-dichloronickel(II) (dppp) in 300 mL of dry ethyl ether, tetradecylmagnesium bromide (560 mL, 0.56 mol) was added dropwise. The mixture was then refluxed overnight and cooled in an ice bath. A 5% HCl solution was added to destroy the unreacted Grignard reagents. The organic layer was separated from the water layer in a separation funnel. The ether solution was then washed with NaHCO3 solution (100 mL), brine (2×100 mL), and water (100 mL) and dried over anhydrous MgSO4. After the ether was removed, the organic residue was vacuum distilled (101° C./3 mmHg) to give 3-tetradecylthiophene: 85 g, yield 75.9%. 1H NMR: ä 7.23 (m, 1H), 6.93 (m, 1H), 2.62 (t, 2H), 1.64-1.26 (m, 16H), 0.88 (t, 3H).

Workup

  1. additionwas added dropwise
  2. temperatureThe mixture was then refluxed overnight
  3. temperaturecooled in an ice bath
  4. customto destroy the unreacted Grignard reagents
  5. customThe organic layer was separated from the water layer in a separation funnel
  6. washThe ether solution was then washed with NaHCO3 solution (100 mL), brine (2×100 mL), and water (100 mL)
  7. dry with materialdried over anhydrous MgSO4
  8. customAfter the ether was removed
  9. distillationdistilled (101° C./3 mmHg)

Sources & evidence

ORD record
ord-54e4b27e919d4bdba882ab8bc45a4bb7
Source dataset
uspto-grants-2016_05
Patent number
US09337358B2

Reaction notes

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