Sodium Chloride → 1,4-Bis(3-nitrophenyl)butane-1,4-dione

HRID 1470957Notes

Reaction equation

HRID 1470957 reaction equation
C(NCC)C.C(O)(C)(C)C.[N+:11]([C:14]1[CH:15]=[C:16]([C:20](=[O:22])[CH3:21])[CH:17]=[CH:18][CH:19]=1)([O-:13])=[O:12].Br[CH2:24][C:25]([C:27]1[CH:32]=[CH:31][CH:30]=[C:29]([N+:33]([O-:35])=[O:34])[CH:28]=1)=[O:26].[Cl-].[Na+]>C1C=CC=CC=1.O.[Cl-].[Zn+2].[Cl-].CO>[N+:11]([C:14]1[CH:15]=[C:16]([C:20](=[O:22])[CH2:21][CH2:24][C:25]([C:27]2[CH:32]=[CH:31][CH:30]=[C:29]([N+:33]([O-:35])=[O:34])[CH:28]=2)=[O:26])[CH:17]=[CH:18][CH:19]=1)([O-:13])=[O:12]

Participants

10

Reactant 5

HCID 5234Sodium ChlorideHCID 6386tert-ButanolHCID 8021DiethylamineHCID 8494m-NitroacetophenoneHCID 752132-Bromo-1-(3-nitrophenyl)ethan-1-one

Product 1

HCID 131261401,4-Bis(3-nitrophenyl)butane-1,4-dioneYield 90%

Reagents, catalysts & solvents 4

HCID 3007855ZincchlorideCatalystHCID 241BenzeneSolventHCID 887MethanolSolventHCID 962WaterSolvent2×

Procedure

Anhydrous zinc(II) chloride (5.42 g, 39.7 mmol) was stirred in dry benzene (50 mL) under nitrogen while diethylamine (3.10 mL, 29.8 mmol) and t-butanol (2.85 mL, 29.8 mmol) were added. The resulting mixture was stirred at room temperature for 90 min to give a cloudy solution. To this was added 1-(3-nitrophenyl)ethanone (4.97 g, 29.8 mmol) followed by 2-bromo-1-(3-nitrophenyl)ethanone (5.00 g, 19.87 mmol) and the resulting mixture allowed to stir at room temperature overnight. A large portion of the benzene was subsequently removed by decantation. The resulting mixture was then treated with 5% sulfuric acid (25 mL) in a separatory funnel and the aqueous phase drawn off. The organic phase was washed with water (2×25 mL). A third washing resulted in an emulsion. The contents of the funnel were emptied into a large volume of water (750 mL) to which was added sodium chloride and the oil in water mixture rapidly stirred. Methanol was added (75 mL) in portions to try and disperse the oil and promote solidification of the product. After nearly forty eight hours of stirring the product solidified and was collected by vacuum filtration. The filter cake was water washed, dried first in air and then a vacuum oven at 55° C. to provide the title compound (5.85 g, 90% yield) as a pale yellow solid that was used directly in the next step.

Workup

  1. additionwere added
  2. customto give a cloudy solution
  3. stirringto stir at room temperature overnight
  4. customA large portion of the benzene was subsequently removed by decantation
  5. additionThe resulting mixture was then treated with 5% sulfuric acid (25 mL) in a separatory funnel
  6. washThe organic phase was washed with water (2×25 mL)
  7. customA third washing resulted in an emulsion
  8. additiondisperse the oil
  9. stirringAfter nearly forty eight hours of stirring the product
  10. filtrationwas collected by vacuum filtration
  11. washwashed
  12. customdried first in air

Sources & evidence

ORD record
ord-90f7178f3b2343d2a910f2bd683addf7
Source dataset
uspto-grants-2015_04
Patent number
US09006387B2

Reaction notes

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