Water → HCID 67006176, compound

HRID 1513840Notes

Reaction equation

HRID 1513840 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:47])[CH2:30][CH2:31][CH2:32][CH2:33][CH2:34][CH2:35][CH2:36][CH2:37][CH2:38][CH2:39][CH2:40][CH2:41][CH2:42][CH2:43][CH2:44][CH2:45][CH3:46].O>O1CCCC1>[Br:12][C:3]1[C:4]2[S:9][C:8]([C:25](=[O:24])[CH2:26][CH2:27][CH2:28][CH2:29][CH2:30][CH2:31][CH2:32][CH2:33][CH2:34][CH2:35][CH2:36][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:47])[CH2:30][CH2:31][CH2:32][CH2:33][CH2:34][CH2:35][CH2:36][CH2:37][CH2:38][CH2:39][CH2:40][CH2:41][CH2:42][CH2:43][CH2:44][CH2:45][CH3:46]

Participants

7

Reactant 5

HCID 962WaterHCID 8212Stearoyl chlorideHCID 8909Butyl etherHCID 27625682,3,5,6-Tetrabromothieno[3,2-b]thiopheneHCID 178506676HCID 178506676, compound

Product 1

HCID 67006176HCID 67006176, compoundYield 44%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent2×

Conditions

Temperature
-78 °C

Procedure

Di-acylation (Step A) A suspension of 2,3,5,6-tetrabromothieno[3,2,b]thiophene (9.1 g, 0.2 mol) in anhydrous THF (500 mL) was cooled to −78° C. Phenyl lithium solution in n-butyl ether (1.8 mol/L, 24 mL, 2.16 eq.) was added dropwise and the reaction mixture was stirred at −78° C. After 1 hr, an aliquot was removed and quenched, then tested by GC-MS. This test revealed that the di-anion was formed in 100% yield. Stearoyl chloride (13.6 g, 0.045 mol) was dissolved in tetrahydrofuran (THF) and added as quickly as possible while maintaining the reaction temperature as close to −78° C. as possible. The reaction was allowed to warm to RT over a few hours and then stirred overnight at RT. The reaction mixture was then quenched with water (2.5 to 3 eq.). The solvent was then removed under reduced pressure and the residual solid was washed with water (2×300 mL) and methanol (2×300 mL), filtered, then dried. The crude product was recrystallized from hot to cold hexane to give the desired product, 1-{3,6-dibromo-5-octadecanoylthieno[3,2-b]thiophen-2-yl}octadecan-1-one (7.3 g, 44% yield) as an off white solid. 1H NMR (CD2Cl2) δ 0.88 (6 H, t, J=6.6 Hz), 1.20-1.48 (56 H, m), 1.69-1.82 (4 H, m), and 3.07 (4 H, t, J=7.2 Hz).

Workup

  1. customan aliquot was removed
  2. customquenched
  3. customwas formed in 100% yield
  4. additionadded as quickly as possible
  5. temperaturewhile maintaining the reaction temperature
  6. customas close to −78° C. as possible
  7. temperatureto warm to RT over a few hours
  8. stirringstirred overnight at RT
  9. customThe solvent was then removed under reduced pressure
  10. washthe residual solid was washed with water (2×300 mL) and methanol (2×300 mL)
  11. filtrationfiltered
  12. customdried
  13. customThe crude product was recrystallized from hot to cold hexane

Sources & evidence

ORD record
ord-16ee5c3285104c2b9d8be48e0eaa9f0a
Source dataset
uspto-grants-2012_07
Patent number
US08217183B2

Reaction notes

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