4-Nitrobenzoyl chloride → HCID 21932475, compound

HRID 634581Notes

Reaction equation

HRID 634581 reaction equation
C([N-]C(C)C)(C)C.[Li+].[C:9]([O:12][C:13]([CH3:22])([CH2:15][CH2:16][CH2:17][CH:18]([CH3:21])[CH:19]=[CH2:20])[CH3:14])(=[O:11])[CH3:10].[N+:23]([C:26]1[CH:34]=[CH:33][C:29]([C:30](Cl)=[O:31])=[CH:28][CH:27]=1)([O-:25])=[O:24]>C1COCC1>[N+:23]([C:26]1[CH:27]=[CH:28][C:29]([C:30](=[O:31])[CH2:10][C:9]([O:12][C:13]([CH3:22])([CH2:15][CH2:16][CH2:17][CH:18]([CH3:21])[CH:19]=[CH2:20])[CH3:14])=[O:11])=[CH:33][CH:34]=1)([O-:25])=[O:24]

Participants

5

Reactant 3

HCID 85024-Nitrobenzoyl chlorideHCID 1038262,6-Dimethyloct-7-en-2-yl acetateHCID 2724682Lithium diisopropylamide

Product 1

HCID 21932475HCID 21932475, compound

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent2×

Conditions

Temperature
-20 °C

Procedure

Lithium diisopropylamide (121.0 mL of a 2.0 M solution, 0.243 mol) is placed into a 500 mL three-necked round-bottomed flask fitted with a magnetic stirrer, internal thermometer, argon inlet, and addition fimnel. The flask is placed in a dry ice-acetone bath. 2,6-Dimethyl-7-octen-2-yl acetate (22.66 g, 0.114 mol) is dissolved in THF (5 mL) and the resulting solution added to the flask over 45 min. Once addition is complete, the mixture is stirred for an additional 15 min. before being treated with a solution of 4-nitrobenzoyl chloride (20.00 g, 0.108 mol) dissolved in THF (25 niL) over 30 min. The mixture is warmed to −20° C. and stirred at that temperature for 18 h. After warming to 0° C., the mixture is quenched with 20% HCl (70 mL). The mixture is poured into a separatory fumnel containing ether (150 mL) and water (250 mL). The aqueous layer is extracted with ether (150 mL). The combined organic layers are washed with saturated NaHCO3 solution (2×100 mL), water (2×150 mL and brine (150 mL), dried over MgSO4 and filtered. The solvent is removed by rotary evaporation to give an orange/red oil. The oil is purified by column chromatography (elution with 2% ethyl acetate/petroleum ether) to yield a colorless oil having 1H and 13C NMR spectra consistent with the desired product.

Workup

  1. customfitted with a magnetic stirrer
  2. additioninternal thermometer, argon inlet, and addition fimnel
  3. customThe flask is placed in a dry ice-acetone bath
  4. additionthe resulting solution added to the flask over 45 min
  5. additionOnce addition
  6. stirringstirred at that temperature for 18 h
  7. temperatureAfter warming to 0° C.
  8. customthe mixture is quenched with 20% HCl (70 mL)
  9. additionThe mixture is poured into a separatory fumnel
  10. additioncontaining ether (150 mL) and water (250 mL)
  11. extractionThe aqueous layer is extracted with ether (150 mL)
  12. washThe combined organic layers are washed with saturated NaHCO3 solution (2×100 mL), water (2×150 mL and brine (150 mL)
  13. dry with materialdried over MgSO4
  14. filtrationfiltered
  15. customThe solvent is removed by rotary evaporation
  16. customto give an orange/red oil
  17. customThe oil is purified by column chromatography (elution with 2% ethyl acetate/petroleum ether)
  18. customto yield a colorless oil

Sources & evidence

ORD record
ord-45f2b4f6567c445ba81b271ae3874903
Source dataset
uspto-grants-2001_02
Patent number
US06184188B2

Reaction notes

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