4-Fluoroiodobenzene → 4-Acetyl-4'-fluoro-2-nitrobiphenyl

HRID 1580289Notes

Reaction equation

HRID 1580289 reaction equation
[F:1][C:2]1[CH:7]=[CH:6][C:5](I)=[CH:4][CH:3]=1.[CH3:9][C:10]([C:12]1[CH:17]=[CH:16][C:15](Br)=[C:14]([N+:19]([O-:21])=[O:20])[CH:13]=1)=[O:11]>>[C:10]([C:12]1[CH:17]=[CH:16][C:15]([C:5]2[CH:6]=[CH:7][C:2]([F:1])=[CH:3][CH:4]=2)=[C:14]([N+:19]([O-:21])=[O:20])[CH:13]=1)(=[O:11])[CH3:9]

Participants

3

Reactant 2

HCID 96054-FluoroiodobenzeneHCID 877371-(4-Bromo-3-nitrophenyl)ethan-1-one

Product 1

HCID 213205554-Acetyl-4'-fluoro-2-nitrobiphenyl

Procedure

The starting material was prepared as follows. An Ullmann reaction using p-fluoroiodobenzene and 4-bromo-3-nitroacetophenone gave 4-acetyl-4'-fluoro-2-nitrobiphenyl, m.p. 88°-90°C., which was reduced with stannous chloride/hydrochloric acid to give 4-acetyl-2-amino-4'-fluorobiphenyl, m.p. 88°-91°C. This was subjected to the Schiemann reaction to give 4-acetyl-2,4'-difluorobiphenyl, m.p. 80°-82.5°C., which was subjected to the Willgerodt reaction using morpholine and sulphur, followed by hydrolysis, to give 2,4'-difluoro-4-biphenylylacetic acid, m.p. 144°-146°C. This was esterified to give the ethyl ester, b.p. 142°-146°C./0.35 mm., which was treated conventionally with diethyl carbonate, and then with dimethyl sulphate, to yield the required ethyl 2-(2,4'-difluoro-4-biphenylyl)-2-methylmalonate, b.p. 164°-166°C./0.05 mm.

Workup

  1. customThe starting material was prepared
  2. customAn Ullmann reaction

Sources & evidence

ORD record
ord-89781946357b4dfca8f138d66664edd9
Source dataset
uspto-grants-1976_01
Patent number
US03932499

Reaction notes

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