HCID 59560812, compound → HCID 15534927, compound

HRID 1176966Notes

Reaction equation

HRID 1176966 reaction equation
Br[C:2](Br)=[CH:3][C:4]1[CH:9]=[CH:8][C:7]([O:10][CH2:11][CH2:12][CH2:13][CH2:14][CH2:15][CH2:16][CH2:17][CH2:18][CH2:19][CH2:20][CH2:21][CH3:22])=[C:6]([O:23][CH2:24][CH2:25][CH2:26][CH2:27][CH2:28][CH2:29][CH2:30][CH2:31][CH2:32][CH2:33][CH2:34][CH3:35])[CH:5]=1.[Li]CCCC>C1COCC1>[CH2:11]([O:10][C:7]1[CH:8]=[CH:9][C:4]([C:3]#[CH:2])=[CH:5][C:6]=1[O:23][CH2:24][CH2:25][CH2:26][CH2:27][CH2:28][CH2:29][CH2:30][CH2:31][CH2:32][CH2:33][CH2:34][CH3:35])[CH2:12][CH2:13][CH2:14][CH2:15][CH2:16][CH2:17][CH2:18][CH2:19][CH2:20][CH2:21][CH3:22]

Participants

4

Reactant 2

HCID 59560812HCID 59560812, compoundHCID 178418339Butyllithium2×

Product 1

HCID 15534927HCID 15534927, compoundYield 65.2%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Conditions

Temperature
-78 °C

Procedure

4-(2,2-Dibromo-vinyl)-1,2-bis-dodecyloxy-benzene (JYC-II-003-A) (9.0 g, 14.3 mmol) in 150 mL of dry THF was cooled down to −78° C. under Ar atmosphere. nBuLi (11.4 mL of 2.5 M solution in hexanes, 28.5 mmol) was added dropwise to the mixture and the resulting mixture was stirred at −78° C. for 1 h. The reaction mixture was allowed to warm up to room temperature and stirred at room temperature for additional 2 h. The reaction was quenched with a saturated NH4Cl aqueous solution and extracted with diethyl ether. The organic layer was dried over anhydrous MgSO4. The solvent was removed under reduced pressure. (The reaction did not go to completion and the product has very similar Rf value to that of the starting material.) The crude mixture was re-dissolved in dry THF and nBuLi (11.4 mL of 2.5 M solution in hexanes, 28.5 mmol) was added dropwise to the mixture. The mixture was stirred at room temperature for 2 h. The workup procedure was repeated. The product was further purified by column chromatography (silica gel, hexanes, then hexanes:dichloromethane=50:1 (v/v)) to give a white solid (4.38 g, 65.2%). 1H NMR (300 MHz, CDCl3, δ): 7.04 (dd, J=8.2 Hz, J=1.9 Hz, 1H), 6.97 (d, J=1.9 Hz, 1H), 6.77 (d, J=8.2 Hz, 1H), 3.97 (t, J=6.6 Hz, 2H), 3.95 (t, J=6.6 Hz, 2H), 2.96 (s, 1H), 1.74-1.84 (m, 4H), 1.20-1.50 (m, 36H), 0.87 (t, J=6.6 Hz, 6H). 13C{1H} NMR (75 MHz, CDCl3, δ): 149.87, 148.45, 125.36, 116.91, 113.93, 112.91, 83.92, 75.39, 69.18, 69.05, 32.00, 29.78, 29.73, 29.70, 29.48, 29.45, 29.22, 26.08, 22.78, 14.22. HRMS-EI (m/z): [M]+ calcd for C32H54O2, 470.4124; found, 470.4113. Anal. Calcd for C32H54O2,: C, 81.64; H, 11.56. Found: C, 81.36; H, 11.70.

Workup

  1. temperatureto warm up to room temperature
  2. stirringstirred at room temperature for additional 2 h
  3. customThe reaction was quenched with a saturated NH4Cl aqueous solution
  4. extractionextracted with diethyl ether
  5. dry with materialThe organic layer was dried over anhydrous MgSO4
  6. customThe solvent was removed under reduced pressure
  7. dissolution) The crude mixture was re-dissolved in dry THF
  8. stirringThe mixture was stirred at room temperature for 2 h
  9. customThe product was further purified by column chromatography (silica gel, hexanes

Sources & evidence

ORD record
ord-107cadd9a78e421c809ca010a6533983
Source dataset
uspto-grants-2010_11
Patent number
US07842830B2

Reaction notes

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