Preparation of Bis(trifluoromethyl)benzenes

McBee, E. T.; Hass, H. B.; Weimer, Paul J.; Rothrock, G.; Burt, William E.; Robb, R.; Dyken, A. Van

doi:10.1021/ie50447a613

Cited by 8 publications

(3 citation statements)

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“…The conversion of benzotrichloride (obtained by' direct chlorination of toluene) with hy'drogen fluoride to benzotrifluoride, without or with catalysts (SbCl3 or SbF3), was previously' established. Similarly, the xylenes and mesitydene could be chlorinated and then converted with hydrogen fluoride to bis(trifluoromethy'l)benzenes ("hexafluoroxydenes", 17) and tris(trifluoromethyl)benzenes ("nonafluoromesitylene"), respectively. All these partially fluorinated compounds can be readily' fluorinated by the two general methods (5), referred to previously, to completely' fluorinated products with much greater ydelds than the original hydrocarbons.…”

Section: Nomenclature Of Fluorocarbonsmentioning

confidence: 99%

Properties of Fluorocarbons

Grosse¹,

Cady²

1947

Ind. Eng. Chem.

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Section: Nomenclature Of Fluorocarbonsmentioning

confidence: 99%

Properties of Fluorocarbons

Grosse¹,

Cady²

1947

Ind. Eng. Chem.

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“…In comparison, trifluoromethyl arenes (ArCF 3 ) have grown into a significantly large field in chemistry and industry since their practical two-step production method was developed in the 1930s through to the 1940s. The first step was chlorination of ArCH 3 to ArCCl 3 with Cl 2 and the second step was its conversion to ArCF 3 with HF or SbF 3 [ 24 – 26 ]. A large number of trifluoromethyl arenes are currently produced on a large scale and used in many areas such as medicines, agrochemicals, dyes, materials for electronics, and others [ 27 – 30 ].…”

Section: Introductionmentioning

confidence: 99%

Discovery of practical production processes for arylsulfur pentafluorides and their higher homologues, bis- and tris(sulfur pentafluorides): Beginning of a new era of “super-trifluoromethyl” arene chemistry and its industry

Umemoto¹,

Garrick²,

Saito³

2012

Beilstein J. Org. Chem.

157

133

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SummaryVarious arylsulfur pentafluorides, ArSF5, have long been desired in both academic and industrial areas, and ArSF5 compounds have attracted considerable interest in many areas such as medicines, agrochemicals, and other new materials, since the highly stable SF5 group is considered a “super-trifluoromethyl group” due to its significantly higher electronegativity and lipophilicity. This article describes the first practical method for the production of various arylsulfur pentafluorides and their higher homologues, bis- and tris(sulfur pentafluorides), from the corresponding diaryl disulfides or aryl thiols. The method consists of two steps: (Step 1) treatment of a diaryl disulfide or an aryl thiol with chlorine in the presence of an alkali metal fluoride, and (step 2) treatment of the resulting arylsulfur chlorotetrafluoride with a fluoride source, such as ZnF2, HF, and Sb(III/V) fluorides. The intermediate arylsulfur chlorotetrafluorides were isolated by distillation or recrystallization and characterized. The aspects of these new reactions are revealed and reaction mechanisms are discussed. As the method offers considerable improvement over previous methods in cost, yield, practicality, applicability, and large-scale production, the new processes described here can be employed as the first practical methods for the economical production of various arylsulfur pentafluorides and their higher homologues, which could then open up a new era of “super-trifluoromethyl” arene chemistry and its applications in many areas.

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“…The conversion of p-bis-(trichloromethyl)benzene, 4, to p-bis-(trifluoromethyl)benzene by Cl/F exchange in anhydrous HF (AHF) is a well known process, exemplified by the conditions given below (Scheme 4) [7,8]. In spite of the considerable literature on this and related processes, there does not appear to be any significant published information related to attempts at partial fluorination of 4 that might allow preparation of the desired p-bis-(chlorodifluoromethyl)benzene 1.…”

Section: Resultsmentioning

confidence: 99%