2,2'-Bithiophene → HCID 59207321, compound

HRID 2242776Notes

Reaction equation

HRID 2242776 reaction equation
[S:1]1[CH:5]=[CH:4][CH:3]=[C:2]1[C:6]1[S:7][CH:8]=[CH:9][CH:10]=1.C([Li])CCC.[Cl:16][CH2:17][CH2:18][CH2:19][CH2:20][CH2:21][CH2:22]I>C1COCC1>[Cl:16][CH2:17][CH2:18][CH2:19][CH2:20][CH2:21][CH2:22][C:5]1[S:1][C:2]([C:6]2[S:7][CH:8]=[CH:9][CH:10]=2)=[CH:3][CH:4]=1

Participants

5

Reactant 3

HCID 681202,2'-BithiopheneHCID 1187131-Chloro-6-iodohexaneHCID 178418339Butyllithium

Product 1

HCID 59207321HCID 59207321, compoundYield 54.3%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Procedure

To a stirred solution of 2,2′-bithiophene (10.0 g, 60.24 mmol) in anhydrous THF (150 ml) is added n-butyllithium (2.5 M in hexanes, 20.0 ml, 50.0 mmol) dropwise at −78° C. under nitrogen. After complete addition, the mixture is allowed to warm to room temperature, with stirring, over 2 h, followed by the addition of 1-chloro-6-iodohexane (14.55 g, 50.0 mmol). The resultant mixture is stirred overnight at room temperature. The reaction is quenched with sat. aq. NH4Cl, and the reaction mixture is extracted with ethyl acetate (3×100 ml). The combined organic extracts are washed with water, brine, and dried over sodium sulphate. The solvent is removed under reduced pressure and the residue is purified by column chromatography on silica, eluting with petroleum ether, to give 5-(6-chlorohexyl)-2,2′-bithiophene as a white solid (7.73 g, 54%). 1H NMR (300 MHz, CDCl3): δ (ppm) 7.14 (d, J=5.3 Hz, 1.3 Hz, 1H, Ar—H), 7.08 (dd, J=3.5 Hz, 1.1 Hz, 1H, Ar—H), 6.97 (m, 2H, Ar—H), 6.66 (d, J=3.5 Hz, 1H, Ar—H), 3.51 (d, J=6.6 Hz, 2H, ClCH2), 2.78 (t, J=7.1 Hz 2H, ArCH2), 1.61-1.81 (m, 4H, CH2), 1.35-1.51 (m, 4H, CH2); MS (m/e): 282 (M+, 2%), 166 (8), 123 (39), 110 (22), 97 (100).

Workup

  1. additionAfter complete addition
  2. customThe reaction is quenched with sat. aq. NH4Cl
  3. extractionthe reaction mixture is extracted with ethyl acetate (3×100 ml)
  4. washThe combined organic extracts are washed with water, brine
  5. dry with materialdried over sodium sulphate
  6. customThe solvent is removed under reduced pressure
  7. customthe residue is purified by column chromatography on silica
  8. washeluting with petroleum ether

Sources & evidence

ORD record
ord-9d063d834cbd4d01b503eecacc9ca3bb
Source dataset
uspto-grants-2010_03
Patent number
US07674397B2

Reaction notes

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