1-Bromooctane → 4,4,9,9-Tetraoctyl-4,9-dihydro-s-indaceno[1,2-b:5,6-b']dithiophene

HRID 1473810Notes

Reaction equation

HRID 1473810 reaction equation
[S:1]1[CH:5]=[CH:4][C:3]2[CH2:6][C:7]3[C:18]([C:2]1=2)=[CH:17][C:10]1[CH2:11][C:12]2[CH:16]=[CH:15][S:14][C:13]=2[C:9]=1[CH:8]=3.C[C:20]([CH3:23])([O-])[CH3:21].[Na+].Br[CH2:26][CH2:27][CH2:28][CH2:29][CH2:30][CH2:31][CH2:32][CH3:33]>CS(C)=O>[CH2:26]([C:11]1([CH2:17][CH2:18][CH2:2][CH2:3][CH2:4][CH2:21][CH2:20][CH3:23])[C:12]2[CH:16]=[CH:15][S:14][C:13]=2[C:9]2[C:10]1=[CH:17][C:18]1[C:2]3[S:1][CH:5]=[CH:4][C:3]=3[C:6]([CH2:13][CH2:12][CH2:11][CH2:10][CH2:9][CH2:8][CH2:7][CH3:6])([CH2:26][CH2:27][CH2:28][CH2:29][CH2:30][CH2:31][CH2:32][CH3:33])[C:7]=1[CH:8]=2)[CH2:27][CH2:28][CH2:29][CH2:30][CH2:31][CH2:32][CH3:33]

Participants

5

Reactant 3

HCID 81401-BromooctaneHCID 23676156Sodium t-butoxideHCID 584350184,9-Dihydro-s-indaceno[1,2-b:5,6-b']dithiophene

Product 1

HCID 584350134,4,9,9-Tetraoctyl-4,9-dihydro-s-indaceno[1,2-b:5,6-b']dithiophene

Reagents, catalysts & solvents 1

HCID 679Dimethyl SulfoxideSolvent

Conditions

Temperature
80 °C

Procedure

To a 3-necked flask is added 4,9-dihydro-s-indaceno[1,2-b:5,6-b′]dithiophene (3.0 g, 11.3 mmol) and anhydrous DMSO (60 cm3) and the mixture is degassed for 20 minutes. To this mixture is added sodium tert-butoxide (6.69 g, 68.9 mmol) portion wise and the mixture is heated to 80° C. 1-Bromooctane (12 cm3, 69.5 mmol) is added dropwise over 30 minutes ensuring the reaction mixture temperature did not rise above 90° C. The mixture is then heated at 85° C. for 3 hours. The mixture allowed to cool to 70° C. and poured into ice-water (100 cm3). The product is extracted with DCM (2×200 cm3) and the combined organics washed with water (3×200 cm3), dried over anhydrous magnesium sulfate, filtered and the solvent removed in vacuo. The crude product is purified by column chromatography (eluent: petroleum ether 40-60) to yield the product as a yellow oil, which crystallised to a yellow solid (2.83 g, 28%). 1H NMR (300 MHz, CDCl3): δ(ppm) 7.27 (s, 2H, Ar—H), 7.25 (d, J=4.9 Hz, 2H, Ar—H), 6.96 (d, J=4.9 Hz, 2H, Ar—H), 1.79-2.02 (m, 8H, CH2), 1.02-1.34 (m, 40H, CH2), 0.71-0.93 (m, 20H, CH3 & CH2). 13C NMR (75 MHz; CDCl3): δ(ppm) 155.1, 153.2, 141.6, 135.6, 126.1, 121.7, 113.1, 53.7, 39.2, 31.8, 30.0, 29.33, 29.25, 24.2, 22.6, 14.1.

Workup

  1. customthe mixture is degassed for 20 minutes
  2. customdid not rise above 90° C
  3. temperatureThe mixture is then heated at 85° C. for 3 hours
  4. temperatureto cool to 70° C.
  5. extractionThe product is extracted with DCM (2×200 cm3)
  6. washthe combined organics washed with water (3×200 cm3)
  7. dry with materialdried over anhydrous magnesium sulfate
  8. filtrationfiltered
  9. customthe solvent removed in vacuo
  10. customThe crude product is purified by column chromatography (eluent: petroleum ether 40-60)

Sources & evidence

ORD record
ord-81ed4624f7164064a04da0fed974d691
Source dataset
uspto-grants-2015_04
Patent number
US09017577B2

Reaction notes

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