Ethylene Glycol → 4-(2-(4-Fluorophenyl)-1,3-dioxolan-2-yl)-2-nitroaniline

HRID 437792Notes

Reaction equation

HRID 437792 reaction equation
[NH2:1][C:2]1[CH:7]=[CH:6][C:5]([C:8]([C:10]2[CH:15]=[CH:14][C:13]([F:16])=[CH:12][CH:11]=2)=[O:9])=[CH:4][C:3]=1[N+:17]([O-:19])=[O:18].[CH2:20](O)[CH2:21][OH:22].CC1C=CC(S(O)(=O)=O)=CC=1.C(O)CCC>O.C1C=CC=CC=1>[F:16][C:13]1[CH:12]=[CH:11][C:10]([C:8]2([C:5]3[CH:6]=[CH:7][C:2]([NH2:1])=[C:3]([N+:17]([O-:19])=[O:18])[CH:4]=3)[O:22][CH2:21][CH2:20][O:9]2)=[CH:15][CH:14]=1

Participants

7

Reactant 4

HCID 174Ethylene GlycolHCID 2631-ButanolHCID 6101p-Toluenesulfonic acid2×HCID 30155674-Amino-4'-fluoro-3-nitrobenzophenone

Product 1

HCID 64548864-(2-(4-Fluorophenyl)-1,3-dioxolan-2-yl)-2-nitroanilineYield 33.2%

Reagents, catalysts & solvents 2

HCID 241BenzeneSolventHCID 962WaterSolvent2×

Procedure

A mixture of 26 parts of (4-amino-3-nitrophenyl)(4-fluorophenyl)methanone, 12 parts of 1,2-ethanediol, 10 parts of 4-methylbenzenesulfonic acid, 32 parts of butanol and 360 parts of benzene is stirred and refluxed for 96 hours with water-separator. Another 5 parts of 4-methylbenzenesulfonic acid are added and stirring at reflux is continued for 72 hours. The reaction mixture is cooled, water is added and the layers are separated. The organic phase is dried, filtered and evaporated. The residue is purified twice by column-chromatography over silica gel using first a mixture of trichloromethane and 2% of methanol and then trichloromethane as eluent. The pure fractions are collected and the eluent is evaporated, yielding 10.1 parts (33.2%) of 4-[2-(4-fluorophenyl)-1,3-dioxolan-2-yl]-2-nitrobenzenamine; mp. 105° C.

Workup

  1. stirringstirring
  2. temperatureat reflux
  3. temperatureThe reaction mixture is cooled
  4. customthe layers are separated
  5. customThe organic phase is dried
  6. filtrationfiltered
  7. customevaporated
  8. customThe residue is purified twice by column-chromatography over silica gel using first
  9. additiona mixture of trichloromethane and 2% of methanol
  10. customThe pure fractions are collected
  11. customthe eluent is evaporated

Sources & evidence

ORD record
ord-8cd9cabfb2b0492ba5dc2a0be96da42b
Source dataset
uspto-grants-1977_06
Patent number
US04032536

Reaction notes

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