Benzene → 1-(p-Nitrophenoxy)-bicyclo[2,2,2]octane

HRID 259354Notes

Reaction equation

HRID 259354 reaction equation
[H-].[Na+].[CH:3]1[CH:8]=[CH:7][CH:6]=[CH:5][CH:4]=1.Cl[C:10]1[CH:15]=[CH:14][C:13]([N+:16]([O-:18])=[O:17])=[CH:12][CH:11]=1.Cl[C:20]1C=CC=C[C:21]=1[N+]([O-])=O.CN(C=[O:33])C>>[N+:16]([C:13]1[CH:14]=[CH:15][C:10]([O:33][C:3]23[CH2:21][CH2:20][CH:6]([CH2:7][CH2:8]2)[CH2:5][CH2:4]3)=[CH:11][CH:12]=1)([O-:18])=[O:17]

Participants

6

Reactant 5

HCID 241BenzeneHCID 6228DimethylformamideHCID 69451-Chloro-2-nitrobenzeneHCID 74741-Chloro-4-nitrobenzeneHCID 24758Sodium hydride

Product 1

HCID 122483561-(p-Nitrophenoxy)-bicyclo[2,2,2]octane

Procedure

A mixture of 10 g. of [2,2,2]bicyclo-1-octanol and 3.37 g. of 56% sodium hydride in mineral oil in 163 ml. each of benzene and DMF was heated at gentle reflux for 45 min. The mixture was cooled to room temperature and 12.4 g. of p-chloronitrobenzene was added. The mixture was again brought to reflux. Following 15 hrs heating the dark mixture was allowed to cool and washed thoroughly with water and then brine. The residue which remained when the solution was taken to dryness was chromatographed on 1 l. of silica gel. Elution with 20% benzene in Skellysolve B afforded 2.38 g. of recovered chloronitrobenzene; elution with benzene gave crude product and 1:1 benzene ethyl acetate afforded recovered carbinol.

Workup

  1. additionA mixture of 10 g
  2. temperatureat gentle reflux for 45 min
  3. temperatureto reflux
  4. temperatureheating the dark mixture
  5. temperatureto cool
  6. washwashed thoroughly with water
  7. customwas chromatographed on 1 l
  8. washElution with 20% benzene in Skellysolve B
  9. customafforded 2.38 g
  10. washelution with benzene
  11. customgave crude product and 1:1 benzene ethyl acetate
  12. customafforded
  13. customrecovered carbinol

Sources & evidence

ORD record
ord-b89e593468ec4d4f8cf32b81b65eb14e
Source dataset
uspto-grants-1977_07
Patent number
US04036977

Reaction notes

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