3-Methylpyridine → HCID 24778107, compound

HRID 243584Notes

Reaction equation

HRID 243584 reaction equation
[Li+].C[CH:3]([N-:5][CH:6](C)C)C.[N:9]1[CH:14]=[CH:13][CH:12]=[C:11]([CH3:15])[CH:10]=1.Br[CH2:17][CH2:18][CH2:19][CH2:20][CH2:21][CH2:22][CH2:23][CH2:24][CH2:25][CH2:26]Br.[NH4+].[Cl-].[CH2:30]1[CH2:34]O[CH2:32][CH2:31]1>>[N:9]1[CH:14]=[CH:13][CH:12]=[C:11]([CH2:15][CH2:17][CH2:18][CH2:19][CH2:20][CH2:21][CH2:22][CH2:23][CH2:24][CH2:25][CH2:26][CH2:32][C:31]2[CH:3]=[N:5][CH:6]=[CH:34][CH:30]=2)[CH:10]=1

Participants

6

Reactant 5

HCID 79703-MethylpyridineHCID 8028Tetrahydrofuran2×HCID 25517Ammonium ChlorideHCID 2214831,10-DibromodecaneHCID 2724682Lithium diisopropylamide

Product 1

HCID 24778107HCID 24778107, compoundYield 75%

Procedure

LDA (2M) (20.40 mL, 40.80 mmol) was added drop-wise to a solution of 3-picoline (3.80 g, 40.80 mmol) in THF (60 mL) at −78° C. The mixture was stirred for 30 min and then 1,10-dibromodecane (6.43 g, 16.32 mmol) in THF (10 mL) was added drop-wise. The resulting mixture was warmed to room temperature and stirred for 4 hrs. Fifty percent saturated NH4Cl was added to the reaction mixture. The aqueous phase was extracted with ethylacetate (2×40 mL), and the combined organic liquors were washed with 50% saturated brine (3×40 mL) and saturated brine (40 mL), dried over anhydrous Na2SO4, and concentrated under reduced pressure. The crude product was purified by column chromatography (hexanes:ethylacetate 2:1 to 1:1) to afford 3.98 g of the title compound. Yield: 75%. 1H NMR (300 MHz, CDCl3) δ 1.17-1.40 (m, 16H), 1.53-1.68 (m, 4H), 2.60 (t, J=7.5 Hz, 4H), 7.20 (dd, J=7.8, 1.8 Hz, 2H), 7.48 (dt, J=7.8, 1.8 Hz, 2H), 8.43 (d, J=5.1 Hz, 2H), 8.44 (s, 2H) ppm; 13C NMR (75 MHz, CDCl3) δ 29.4, 29.7, 29.8, 29.9, 31.4, 33.3, 123.3, 135.8, 138.4, 147.2, 150.0 ppm.

Workup

  1. stirringstirred for 4 hrs
  2. extractionThe aqueous phase was extracted with ethylacetate (2×40 mL)
  3. washthe combined organic liquors were washed with 50% saturated brine (3×40 mL) and saturated brine (40 mL)
  4. dry with materialdried over anhydrous Na2SO4
  5. concentrationconcentrated under reduced pressure
  6. customThe crude product was purified by column chromatography (hexanes:ethylacetate 2:1 to 1:1)

Sources & evidence

ORD record
ord-b9f1564d537a4706870aada7b1df88d6
Source dataset
uspto-grants-2014_02
Patent number
US08653275B2

Reaction notes

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