Tetrahydrofuran → HCID 16103459, compound

HRID 1513842Notes

Reaction equation

HRID 1513842 reaction equation
Br[C:2]1[S:6][C:5]2[C:7]([Br:11])=[C:8](Br)[S:9][C:4]=2[C:3]=1[Br:12].[C:13]1([Li])[CH:18]=[CH:17][CH:16]=[CH:15][CH:14]=1.C([O:24][CH2:25][CH2:26][CH2:27][CH3:28])CCC.[C:29](Cl)(=[O:40])[CH2:30][CH2:31][CH2:32][CH2:33][CH2:34][CH2:35][CH2:36][CH2:37][CH2:38][CH3:39].[CH2:42]1COCC1>>[Br:12][C:3]1[C:4]2[S:9][C:8]([C:25](=[O:24])[CH2:26][CH2:27][CH2:28][CH2:42][CH2:14][CH2:15][CH2:16][CH2:17][CH2:18][CH3:13])=[C:7]([Br:11])[C:5]=2[S:6][C:2]=1[C:29](=[O:40])[CH2:30][CH2:31][CH2:32][CH2:33][CH2:34][CH2:35][CH2:36][CH2:37][CH2:38][CH3:39]

Participants

6

Reactant 5

HCID 8028TetrahydrofuranHCID 8909Butyl etherHCID 87287Undecanoyl chlorideHCID 27625682,3,5,6-Tetrabromothieno[3,2-b]thiopheneHCID 178506676HCID 178506676, compound

Product 1

HCID 16103459HCID 16103459, compoundYield 41.3%

Conditions

Temperature
-78 °C

Procedure

Di-acylation (Step A) A suspension of (2,3,5,6-tetrabromothieno[3,2,b]thiophene (10 g, 21.9 mmol) in anhydrous THF (200 mL) was cooled to −78° C. Phenyl lithium solution in n-butyl ether (1.8 mol/L, 25 mL, 45 mmol) was added dropwise and the reaction mixture was stirred at −78° C. for 4 h. Undecanoyl chloride (9.2 g, 44.9 mmol) was added to the reaction mixture via syringe while maintaining the temperature of the mixture as close to −78° C. as possible. The reaction was allowed to warm to RT over about three hours and then stirred overnight at RT. The reaction mixture was then quenched by the addition of crushed ice (200 g). The reaction mixture was stirred while the ice was allowed to melt. Most (greater than about 90%) of the THF was then removed under reduced pressure and the solid was filtered from the residual solution. The solid was suspended in water (100 mL) and stirred for 1 hr then filtered. The solid was resuspended in methanol (100 mL), stirred for 1 hr then filtered to give the product 1-{3,6-dibromo-5-undecanoylthieno[3,2-b]thiophen-2-yl}undecan-1-one as a white solid (5.75 g, 41.3% yield). 1H NMR (CD2Cl2) δ 0.90 (6H, t, J=6.3 Hz), 1.20-1.48 (28H, m), 1.68-1.73 (4H, m), and 3.11 (4H, t, J=7.2 Hz).

Workup

  1. temperaturewhile maintaining the temperature of the mixture
  2. customas close to −78° C. as possible
  3. temperatureto warm to RT over about three hours
  4. stirringstirred overnight at RT
  5. customThe reaction mixture was then quenched by the addition of crushed ice (200 g)
  6. stirringThe reaction mixture was stirred while the ice
  7. customMost (greater than about 90%) of the THF was then removed under reduced pressure
  8. filtrationthe solid was filtered from the residual solution
  9. stirringstirred for 1 hr
  10. filtrationthen filtered
  11. stirringstirred for 1 hr
  12. filtrationthen filtered

Sources & evidence

ORD record
ord-a23fbabe24ba411c978c9f70056fc197
Source dataset
uspto-grants-2012_07
Patent number
US08217183B2

Reaction notes

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