2,2'-Bithiophene → (6-[2,2']Bithiophenyl-5-yl-hexyloxy)-tert-butyl-dimethylsilane

HRID 644110

Reaction equation

HRID 644110 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.Br[CH2:17][CH2:18][CH2:19][CH2:20][CH2:21][CH2:22][O:23][Si:24]([C:27]([CH3:30])([CH3:29])[CH3:28])([CH3:26])[CH3:25]>C1COCC1>[S:1]1[C:5]([CH2:17][CH2:18][CH2:19][CH2:20][CH2:21][CH2:22][O:23][Si:24]([C:27]([CH3:28])([CH3:30])[CH3:29])([CH3:25])[CH3:26])=[CH:4][CH:3]=[C:2]1[C:6]1[S:7][CH:8]=[CH:9][CH:10]=1

Participants

5

Reactant 3

HCID 681202,2'-BithiopheneHCID 4260352(6-Bromohexyloxy)-tert-butyldimethylsilaneHCID 178418339Butyllithium

Product 1

HCID 58807316(6-[2,2']Bithiophenyl-5-yl-hexyloxy)-tert-butyl-dimethylsilaneYield 79.2%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Procedure

To a stirred solution of 2,2′-bithiophene (10.0 g, 60.24 mmol) in dry THF (150 ml) was 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 was allowed to warm to room temperature, with stirring, over 2 h, followed by the addition of 6-bromohexyloxy-tert-butyldimethylsilane (14.75 g, 50.0 mmol). The resultant mixture was stirred overnight at room temperature. The reaction was quenched with sat. aq. ammonium chloride, and the reaction mixture was extracted with ethyl acetate (3×70 ml). The combined organic extracts were washed with water, brine, and dried over magnesium sulphate. The solvent was removed under reduced pressure and the residue was chromatographyed (silica gel, petroleum/ethyl acetate from 100:0 to 20:1), to afford the product as a pale green oil (15.07 g, 79%). 1H NMR (300 MHz, CDCl3): δ (ppm) 7.08 (m, 1H, Ar—H), 7.03 (m, 1H, Ar—H), 6.92 (m, 2H, Ar—H), 6.61 (d, J=3.6 Hz, 1H, Ar—H), 3.55 (t, J=6.2 Hz, 2H, OCH2), 3.34 (t, J=6.8 Hz, 2H, ArCH2), 1.25-1.85 (m, 8H, CH2), 0.86 (s, 9H, CH3), 0.01 (s, 6H, CH3); 13C NMR (75 MHz, CDCl3): δ (ppm) 145.1 (quat.), 138.0 (quat.), 134.8 (quat.), 127.6 (CH), 124.7 (CH), 123.7 (CH), 123.4 (CH), 122.9 (CH), 63.0 (OCH2), 33.8 (CH2), 32.9 (CH2), 32.7 (CH2), 28.0 (CH2), 26.0 (CH3) 25.1 (CH2), 18.4 (quat.), −5.2 (CH3); MS (m/e): 380 (M+, 27%), 323 (63), 179 (100), 75 (37).

Workup

  1. additionAfter complete addition
  2. customThe reaction was quenched with sat. aq. ammonium chloride
  3. extractionthe reaction mixture was extracted with ethyl acetate (3×70 ml)
  4. washThe combined organic extracts were washed with water, brine
  5. dry with materialdried over magnesium sulphate
  6. customThe solvent was removed under reduced pressure

Sources & evidence

ORD record
ord-415b52a16c2b4074a7e34292b001b2ad
Source dataset
uspto-grants-2010_04
Patent number
US07700643B2

Linked notes

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