Hydrochloric Acid → 2,2'-Bis-(trifluoromethyl)-4-iodo-4'-nitro-1,1'-biphenyl

HRID 2164342Notes

Reaction equation

[SH-].[Na+].N[C:4]1[CH:9]=[CH:8][C:7]([C:10]2[CH:15]=[CH:14][C:13]([N+:16]([O-:18])=[O:17])=[CH:12][C:11]=2[C:19]([F:22])([F:21])[F:20])=[C:6]([C:23]([F:26])([F:25])[F:24])[CH:5]=1.Cl.[I-:28].[K+]>>[F:24][C:23]([F:26])([F:25])[C:6]1[CH:5]=[C:4]([I:28])[CH:9]=[CH:8][C:7]=1[C:10]1[CH:15]=[CH:14][C:13]([N+:16]([O-:18])=[O:17])=[CH:12][C:11]=1[C:19]([F:22])([F:21])[F:20]

Participants

Reactant 4

HCID 313Hydrochloric Acid

HCID 4875Potassium Iodide

HCID 28015Sodium hydrosulfide

HCID 204064522,2'-Bis(trifluoromethyl)-4-nitro-4'-amino-biphenyl

Product 1

HCID 204064512,2'-Bis-(trifluoromethyl)-4-iodo-4'-nitro-1,1'-biphenyl

Procedure

Starting materials useful in the manufacture of substituted-quaterphenylene polyamides of the invention can be prepared by resort to a variety of organic synthetic routes. Preferred polyamides of the invention can be prepared, for example, by reaction of terephthaloyl chloride and/or trans-p,p'-stilbene dicarbonyl chloride with the diamino compound, 4,4'"-diamino-2,2',3",2'"-tetrakis(trifluoromethyl)-1,1':4',1'"-quaterphenyl. This novel diamine can be prepared, for example, from 2-bromo-5-nitro-benzotrifluoride by resort to the following reactions: (a) an Ullmann coupling of 2-bromo-5-nitrobenzotrifluoride utilizing active copper and dimethylformamide to provide 2,2'-bis-(trifluoromethyl)-4,4'-dinitro-1,1'-biphenyl; (b) a partial reduction utilizing aqueous sodium hydrosulfide to 4-amino-2,2'-bis-(trifluoromethyl)-4'-nitro-1,1'-biphenyl; (c) a diazotization of the resulting amine utilizing aqueous sodium nitrite and hydrochloric acid and a Sandmeyer reaction of the resulting diazonium salt with potassium iodide to provide 2,2'-bis-(trifluoromethyl)-4-iodo-4'-nitro-1,1'-biphenyl; (d) an Ullmann coupling of the resulting biphenyl compound utilizing active copper for production of 4,4'"-dinitro-2,2',3",2'"-tetrakis-(trifluoromethyl)-1,1':4',1":4",1'"-quaterphenyl; and (e) a reduction utilizing stannous chloride and hydrochloric acid for production of the desired diamine starting material. The production of this diamine starting material is illustrated by the following reaction sequence: ##STR32##

Sources & evidence

ORD record: ord-09d9c478fbb443f9a6739898a286535f
Source dataset: uspto-grants-1985_03
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US04503248

Reaction notes

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