Tetrahydrofuran → HCID 90410938, compound

HRID 2282338Notes

Reaction equation

HRID 2282338 reaction equation
[CH2:1]([C:12]1[CH:20]=[CH:19][C:15]([N:16]([CH3:18])[CH3:17])=[CH:14][C:13]=1Br)[C:2]1[CH:10]=[CH:9][C:5]([N:6]([CH3:8])[CH3:7])=[CH:4][C:3]=1Br.[Li]C(CC)C.[Ge:27](Cl)(Cl)([CH3:29])[CH3:28].C1C[O:35]CC1>>[CH3:17][N:16]([CH3:18])[C:15]1[CH:19]=[CH:20][C:12]2[C:1](=[O:35])[C:2]3[CH:10]=[CH:9][C:5]([N:6]([CH3:8])[CH3:7])=[CH:4][C:3]=3[Ge:27]([CH3:29])([CH3:28])[C:13]=2[CH:14]=1

Participants

5

Reactant 4

HCID 8028Tetrahydrofuran2×HCID 73724DichlorodimethylgermaneHCID 13317682HCID 13317682, compoundHCID 178418400CID 53628100

Product 1

HCID 90410938HCID 90410938, compound

Procedure

To the solution of 4,4′-methylene-bis(3-bromo-N,N-dimethylaniline) (2.0 g, 4.85 mmol) in anhydrous THF (50 mL), 1.4 M sec-BuLi (12.13 mmol) at −78° C. was added, and the mixture stirred for 30 min. At the same temperature, a solution of GeMe2Cl2 (1.26 g, 7.28 mmol) in anhydrous THF (15 mL) was slowly added. The mixture was warmed to room temperature and stirred for 1 h. The reaction was quenched by addition of 2 N HCl (7 ml), and the mixture neutralized with NaHCO3 and extracted with CH2Cl2. The organic layer was washed with brine and dried over Na2SO4. To this solution, the sufficient chlorinil (5 eq.) was added, and the resultant mixture stirred for 2 hours. Acetone/saturated NaHCO3 (50 mL/100 ml) were added, and the mixture stirred overnight. The mixture was then diluted with CH2Cl2 (200 mL), filtered through glass wool, and the filtrate extracted three times with methylene chloride and evaporated to dryness. The residue was purified by silica column chromatography using heptane/methylene chloride/ethyl acetate as eluent to give light yellow compound. 1HNMR (300 MHz, CD2Cl2): δ 8.32 (d, 2H), 6.7-6.90 (m, 4H), 3.20 (s, 12H, NCH3), 0.6 (d, 6H, CH3); MS (m/e): calculated 370.11. found 371.0 for [M+H]+.

Workup

  1. stirringstirred for 1 h
  2. customThe reaction was quenched by addition of 2 N HCl (7 ml)
  3. extractionextracted with CH2Cl2
  4. washThe organic layer was washed with brine
  5. dry with materialdried over Na2SO4
  6. additionTo this solution, the sufficient chlorinil (5 eq.) was added
  7. stirringthe resultant mixture stirred for 2 hours
  8. additionAcetone/saturated NaHCO3 (50 mL/100 ml) were added
  9. stirringthe mixture stirred overnight
  10. additionThe mixture was then diluted with CH2Cl2 (200 mL)
  11. filtrationfiltered through glass wool
  12. extractionthe filtrate extracted three times with methylene chloride
  13. customevaporated to dryness
  14. customThe residue was purified by silica column chromatography
  15. customto give light yellow compound

Sources & evidence

ORD record
ord-130483b7496a42c3a6a66330e8fcc0c3
Source dataset
uspto-grants-2015_09
Patent number
US09139868B2

Reaction notes

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