Benzene → 2,4-Difluoro-1,1'-biphenyl

HRID 1580287Notes

Reaction equation

HRID 1580287 reaction equation
[F:1][C:2]1[CH:8]=[C:7]([F:9])[CH:6]=[CH:5][C:3]=1N.N(OCCCC)=O.[CH:17]1[CH:22]=[CH:21][CH:20]=[CH:19][CH:18]=1>>[F:1][C:2]1[CH:8]=[C:7]([F:9])[CH:6]=[CH:5][C:3]=1[C:17]1[CH:22]=[CH:21][CH:20]=[CH:19][CH:18]=1

Participants

4

Reactant 3

HCID 241BenzeneHCID 97092,4-DifluoroanilineHCID 10996Butyl nitrite

Product 1

HCID 1699742,4-Difluoro-1,1'-biphenyl

Procedure

The starting material was prepared as follows. 2,4-Difluoroaniline and butyl nitrite were reacted with benzene in a modified Gomberg reaction to give 2,4-difluorobiphenyl, m.p. 63°-65°C. which was reacted with acetyl chloride in a Friedel-Crafts reaction to give 4-acetyl-2',4'-difluorobiphenyl, m.p. 82.5°-83.5°C. This was subjected to the Willgerodt reaction using morpholine and sulphur, followed by hydrolysis, to give 2',4'-difluoro-4-biphenylylacetic acid, m.p. 143°-145°C., which was esterified to give ethyl 2',4'-difluoro-4-biphenylylacetate, b.p. 129°-130°C./0.2 mm. This ester 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. 172°-175°C./0.5 mm.

Workup

  1. customThe starting material was prepared

Sources & evidence

ORD record
ord-e3077787ae6248ffb6bdd1d8e9386aae
Source dataset
uspto-grants-1976_01
Patent number
US03932499

Reaction notes

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