Dichloromethane → 2,6-Dibromodithieno[3,2-b:2',3'-d]thiophene

HRID 2414992Notes

Reaction equation

HRID 2414992 reaction equation
[Br:1][C:2]1[S:13][C:5]2[C:6]3[S:11][C:10]([Br:12])=[CH:9][C:7]=3[S:8][C:4]=2[CH:3]=1.C(N([CH2:19][CH3:20])CC)C.[CH2:21]([C:26]1[CH:31]=[CH:30][C:29]([C:32]#[CH:33])=[CH:28][CH:27]=1)[CH2:22][CH2:23][CH2:24][CH3:25].ClCCl>O1CCCC1.[Cl-].[Cl-].C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.[Pd+2].[Cu](I)I>[Br:12][C:10]1[S:11][C:6]2[C:5]3[S:13][C:2]([Br:1])=[CH:3][C:4]=3[S:8][C:7]=2[CH:9]=1.[CH2:21]([C:26]1[CH:27]=[CH:28][C:29]([C:32]#[C:33][C:2]2[S:13][C:5]3[C:6]4[S:11][C:10]([C:33]#[C:32][C:29]5[CH:30]=[CH:31][C:26]([CH2:21][CH2:22][CH2:23][CH2:19][CH3:20])=[CH:27][CH:28]=5)=[CH:9][C:7]=4[S:8][C:4]=3[CH:3]=2)=[CH:30][CH:31]=1)[CH2:22][CH2:23][CH2:24][CH3:25]

Participants

9

Reactant 4

HCID 6344DichloromethaneHCID 8471TriethylamineHCID 27751311-Ethynyl-4-pentylbenzeneHCID 113826492,6-Dibromodithieno[3,2-b:2',3'-d]thiophene

Product 2

HCID 113826492,6-Dibromodithieno[3,2-b:2',3'-d]thiopheneHCID 22639416HCID 22639416, compound

Reagents, catalysts & solvents 3

HCID 83717Copper iodideCatalystHCID 84124Bis(triphenylphosphine)palladium chlorideCatalystHCID 8028TetrahydrofuranSolvent2×

Conditions

Temperature
60 °C

Procedure

2,6-Dibromo-dithieno[3,2-b;2′,3′-d]thiophene was prepared according to a procedure described in G. F. Pedulli, M. Tiecco, M. Guera, G. Martelli and P. Zanirato, J. C. S. Perkin II, 1978, 212. 2,6-Dibromo-dithieno[3,2-b;2′,3′-d]thiophene (0.5 g, 1.4 mmol), triethylamine (15 ml), and a catalytic amount of palladium bis(triphenylphosphine) dichloride and copper iodide were stirred under nitrogen in tetrahydrofuran. The solution was warmed to 60° C. and 4-pentylphenylacetylene (1.1 g, 6.4 mmol) dissolved in tetrahydrofuran (30 ml) was added dropwise over a period of 2 hours. The solution was heated under reflux overnight. The brown solution was poured in to dichloromethane, washed with water, the chlorinated phase was removed, dried over sodium sulphate and evaporated to dryness. The residue was purified by flash column chromatography using petroleum (80-100) followed by dichloromethane as eluant. Evaporation of the appropriate fractions yielded (1) as a bright yellow solid (320 mg). 1H NMR and 13C NMR showed expected signals.

Workup

  1. additionwas added dropwise over a period of 2 hours
  2. temperatureThe solution was heated
  3. temperatureunder reflux overnight
  4. washwashed with water
  5. customthe chlorinated phase was removed
  6. dry with materialdried over sodium sulphate
  7. customevaporated to dryness
  8. customThe residue was purified by flash column chromatography
  9. customEvaporation of the appropriate fractions

Sources & evidence

ORD record
ord-2b5b4369a49a40d8aebe4578e6e5c826
Source dataset
uspto-grants-2004_11
Patent number
US06818260B2

Reaction notes

Loading…