Acetylacetone → HCID 18717149, compound

HRID 2111517Notes

Reaction equation

HRID 2111517 reaction equation
C([N-]C(C)C)(C)C.[Li+].[CH3:9][C:10](=[O:15])[CH2:11][C:12](=[O:14])[CH3:13].[N+:16]([C:19]1[CH:26]=[CH:25][C:22]([CH2:23]Br)=[CH:21][CH:20]=1)([O-:18])=[O:17]>O1CCCC1>[N+:16]([C:19]1[CH:26]=[CH:25][C:22]([CH2:23][CH2:9][C:10](=[O:15])[CH2:11][C:12](=[O:14])[CH3:13])=[CH:21][CH:20]=1)([O-:18])=[O:17]

Participants

5

Reactant 3

HCID 31261AcetylacetoneHCID 660114-Nitrobenzyl bromideHCID 2724682Lithium diisopropylamide

Product 1

HCID 18717149HCID 18717149, compoundYield 52.1%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Conditions

Temperature
-78 °C

Procedure

To a reaction vessel (heat and vacuum dried and equipped with a magnetic spin bar) was added tetrahydrofuran and lithium diisopropylamide (2M heptane/ethylbenzene/tetrahydrofuran; 69.4 mL, 138.9 mmol). The solution cooled to −78° C. Pentane-2,4-dione (7.13 mL, 69.4 mmol) was added dropwise and the solution stirred 30 minutes at −78° C. 4-nitrobenzyl bromide (15.0 g, 69.4 mmol) was added in one portion. The solution was removed from the dry-ice/acetone bath, allowed to warm to room temperature and stirred 16 hours. The solution was cooled to approximately 0° C. and the reaction quenched with 1 M HCl. Tetrahydrofuran was removed under reduced pressure. The crude material was taken up into dichloromethane and washed with 1M HCl and brine. The aqueous layers were again washed with dichloromethane. The combined dichloromethane layers were dried (Na2SO4) and removed under reduced pressure. Gradient flash column chromatography (FCC) was performed using 5% to 15% ethyl acetate/hexanes to afford title compound (8.5 g, 52%; yellow solid). 1H NMR (CDCl3): δ 8.14 (d, J=9.0 Hz, 2 H), δ 7.43 (d, J=8.4 Hz, 2 H), δ 5.45 (s, 1H), δ 3.06 (t, J=7.5 Hz, 2H), δ 2.64 (t, J=7.8 Hz, 2H), δ 2.04 (s, 3H).

Workup

  1. temperatureTo a reaction vessel (heat and vacuum dried and equipped with a magnetic spin bar)
  2. customThe solution was removed from the dry-ice/acetone bath
  3. temperatureto warm to room temperature
  4. stirringstirred 16 hours
  5. temperatureThe solution was cooled to approximately 0° C.
  6. customthe reaction quenched with 1 M HCl
  7. customTetrahydrofuran was removed under reduced pressure
  8. washwashed with 1M HCl and brine
  9. washThe aqueous layers were again washed with dichloromethane
  10. dry with materialThe combined dichloromethane layers were dried (Na2SO4)
  11. customremoved under reduced pressure

Sources & evidence

ORD record
ord-9d554c8459cf41eeb5ca0bb739b0a791
Source dataset
uspto-grants-2009_04
Patent number
US07521425B2

Reaction notes

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