Acetanilide → N-(4′-Iodo-3,3′-dimethyl[1,1′-biphenyl]-4-yl)-N-phenylacetamide

HRID 725741Notes

Reaction equation

HRID 725741 reaction equation
[C:1]([NH:4][C:5]1[CH:10]=[CH:9][CH:8]=[CH:7][CH:6]=1)(=[O:3])[CH3:2].[CH3:11][C:12]1[CH:13]=[C:14]([C:19]2[CH:24]=[CH:23][C:22](I)=[C:21]([CH3:26])[CH:20]=2)[CH:15]=[CH:16][C:17]=1[I:18].C(=O)([O-])[O-].[K+].[K+]>[Cu].[N+](C1C=CC=CC=1)([O-])=O>[CH3:26][C:21]1[CH:20]=[C:19]([C:14]2[CH:15]=[CH:16][C:17]([I:18])=[C:12]([CH3:11])[CH:13]=2)[CH:24]=[CH:23][C:22]=1[N:4]([C:1](=[O:3])[CH3:2])[C:5]1[CH:10]=[CH:9][CH:8]=[CH:7][CH:6]=1

Participants

6

Reactant 3

HCID 904AcetanilideHCID 11430Potassium CarbonateHCID 223236094,4'-Diiodo-3,3'-dimethyl-1,1'-biphenyl

Product 1

HCID 19708499N-(4′-Iodo-3,3′-dimethyl[1,1′-biphenyl]-4-yl)-N-phenylacetamideYield 69.3%

Reagents, catalysts & solvents 2

HCID 23978CopperCatalystHCID 7416NitrobenzeneSolvent

Procedure

16.2 g (0.12 mol) of acetanilide, 56.4 g (0.13 mol) of 3,3'-dimethyl-4,4'-diiodobiphenyl, 18.0 g (0.13 mol) of anhydrous potassium carbonate, 1.71 g (0.027 mol) of copper powder, and 30 ml of nitrobenzene were mixed. The reaction mixture was then allowed to undergo reaction at a temperature of 192° C. to 203° C. for 13 hours. The reaction product was then extracted with 160 ml of toluene. The insoluble contents were removed by filtration. The filtrate was then concentrated to dryness. The concentrate was then purified by column chromatography (carrier: silica gel; elute: 7/1 mixture of toluene and ethyl acetate) to obtain 36.7 g (yield: 69.3%) of N-(3,3'-dimethyl-4'-iodo-4-biphenylyl)acetanilide. Subsequently, 13.2 g (0.030 mol) of N-(3,3'-dimethyl-4'-iodo-4-biphenylyl)acetanilide thus obtained, 6.09 g (0.036 mol) of diphenylamine, 5.11 g (0.037 mol) of anhydrous potassium carbonate, 0.44 g (0.007 mol) of copper powder, and 10 ml of nitrobenzene were mixed. The reaction mixture was then allowed to undergo reaction at a temperature of 198° to 211° C. for 13 hours. The reaction product was then extracted with 100 ml of toluene. The insoluble contents were then removed by filtration. The filtrate was then concentrated to obtain an oily matter. The oily matter thus obtained was then dissolved in 50 ml of isoamyl alcohol. The material was then hydrolyzed with 1 ml of water and 2.38 g (0.036 mol) of 85% potassium hydroxide at a temperature of 130° C. The reaction solution was then subjected to steam distillation to distill off isoamyl alcohol. The residue was extracted with 200 ml of toluene, washed with water, and then concentrated to dryness. The concentrate was then purified by column chromatography (carrier: silica gel; elute: 1/3 mixture of toluene and n-hexane) to obtain 9.27 g (yield: 70.1%) of 3,3'-dimethyl-N,N,N'-triphenylbenzidine. The melting point of the product was from 104.0° C. to 105.0° C.

Workup

  1. customreaction at a temperature of 192° C. to 203° C. for 13 hours
  2. extractionThe reaction product was then extracted with 160 ml of toluene
  3. customThe insoluble contents were removed by filtration
  4. concentrationThe filtrate was then concentrated to dryness
  5. customThe concentrate was then purified by column chromatography (carrier: silica gel; elute: 7/1 mixture of toluene and ethyl acetate)

Sources & evidence

ORD record
ord-6370d03cc200425b880ec14f00b2c867
Source dataset
uspto-grants-1998_01
Patent number
US05707747

Reaction notes

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