Acetylacetone → HCID 18717149, compound

HRID 1402659Notes

Reaction equation

HRID 1402659 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 1M 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): 8.14 (d, J=9.0 Hz, 2 H), ˜d, J=8.4 Hz, 2 H), 5.45 (s, 1 H), 3.06 (t, J=7.5 Hz, 2 H), 2.64 (t, J=7.8 Hz, 2 H), 2.04 (s, 3 H).

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 1M 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-4d5b81a10df9487eb99c09368ce7bb9c
Source dataset
uspto-grants-2014_12
Patent number
US08912148B2

Reaction notes

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