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Article No : a11_349

Fluorine Compounds, Organic

GUNTER SIEGEMUND, Hoechst Aktiengesellschaft, Frankfurt, Federal Republic

of Germany

WERNER SCHWERTFEGER, Hoechst Aktiengesellschaft, Frankfurt, Federal Republic

of Germany

ANDREW FEIRING, E. I. DuPont de Nemours & Co., Wilmington, Delaware,

United States

BRUCE SMART, E. I. DuPont de Nemours & Co., Wilmington, Delaware, United States

FRED BEHR, Minnesota Mining and Manufacturing Company, St. Paul,

Minnesota, United States

HERWARD VOGEL, Minnesota Mining and Manufacturing Company, St. Paul,

Minnesota, United States

BLAINE MCKUSICK, E. I. DuPont de Nemours & Co., Wilmington, Delaware,

United States

1. Introduction. . . . . . . . . . . . . . . . . . . . . . . 444

2. Production Processes . . . . . . . . . . . . . . . . 445

2.1. Substitution of Hydrogen . . . . . . . . . . . . . 445

2.2. Halogen – Fluorine Exchange . . . . . . . . . 446

2.3. Synthesis from Fluorinated Synthons . . . 447

2.4. Addition of Hydrogen Fluoride to

Unsaturated Bonds . . . . . . . . . . . . . . . . . 447

2.5. Miscellaneous Methods . . . . . . . . . . . . . . 447

2.6. Purification and Analysis . . . . . . . . . . . . . 447

3. Fluorinated Alkanes. . . . . . . . . . . . . . . . . 448

3.1. Fluoroalkanes and Perfluoroalkanes . . . . 448

3.2. Chlorofluoroalkanes. . . . . . . . . . . . . . . . . 452

3.3. Bromofluoroalkanes . . . . . . . . . . . . . . . . . 456

3.4. Iodofluoroalkanes. . . . . . . . . . . . . . . . . . . 457

4. Fluorinated Olefins . . . . . . . . . . . . . . . . . 458

4.2. Tetrafluoroethylene . . . . . . . . . . . . . . . . . 459

4.3. Hexafluoropropene . . . . . . . . . . . . . . . . . 460

4.4. 1,1-Difluoroethylene . . . . . . . . . . . . . . . . . 461

4.5. Monofluoroethylene, Monofluoroethylene 461

4.6. 3,3,3-Trifluoropropene . . . . . . . . . . . . . . . 462

4.7. 3,3,3-Trifluoro-2-(trifluoromethyl)-

prop-1-ene . . . . . . . . . . . . . . . . . . . . . . . . . 462

4.8. Chlorofluoroolefins . . . . . . . . . . . . . . . . . 462

5. Fluorinated Alcohols . . . . . . . . . . . . . . . . 463

6. Fluorinated Ethers . . . . . . . . . . . . . . . . . 464

6.1. Perfluoroethers . . . . . . . . . . . . . . . . . . . . 464

6.1.1. Low Molecular Mass Perfluoroethers . . . . . 464

6.1.2. Perfluorinated Epoxides . . . . . . . . . . . . . . . 464

6.1.3. High Molecular Mass Perfluoroethers . . . . . 465

6.2. Perfluorovinyl Ethers. . . . . . . . . . . . . . . . 465

6.3. Partially Fluorinated Ethers . . . . . . . . . . 466

7. Fluorinated Ketones and Aldehydes . . . . 466

7.1. Fluoro- and Chlorofluoroacetones . . . . . . 466

7.2. Perhaloacetaldehydes. . . . . . . . . . . . . . . . 468

7.3. Fluorinated 1,3-Diketones . . . . . . . . . . . . 469

8. Fluorinated Carboxylic Acids and

Fluorinated Alkanesulfonic Acids . . . . . . 470

8.1. Fluorinated Carboxylic Acids . . . . . . . . . 470

8.1.1. Fluorinated Acetic Acids . . . . . . . . . . . . . . 470

8.1.2. Long-Chain Perfluorocarboxylic Acids . . . . 470

8.1.3. Fluorinated Dicarboxylic Acids . . . . . . . . . 472

8.1.4. Tetrafluoroethylene – Perfluorovinyl Ether

Copolymers with Carboxylic Acid Groups . . 472

8.2. Fluorinated Alkanesulfonic Acids . . . . . . 472

8.2.1. Perfluoroalkanesulfonic Acids . . . . . . . . . . 472

8.2.2. Fluorinated Alkanedisulfonic Acids . . . . . . 473

8.2.3. Tetrafluoroethylene – Perfluorovinyl Ether

Copolymers with Sulfonic Acid Groups . . . . 474

9. Fluorinated Tertiary Amines . . . . . . . . . . 474

10. Aromatic Compounds with Fluorinated

Side-Chains . . . . . . . . . . . . . . . . . . . . . . . 475

10.1. Properties . . . . . . . . . . . . . . . . . . . . . . . . 475

10.2. Production . . . . . . . . . . . . . . . . . . . . . . . . 476

10.3. Uses . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 477

11. Ring-Fluorinated Aromatic, Heterocyclic,

and Polycyclic Compounds . . . . . . . . . . . 477

11.1. Mono- and Difluoroaromatic Compounds 478

11.1.1. Properties . . . . . . . . . . . . . . . . . . . . . . . . . 478

11.1.2. Production. . . . . . . . . . . . . . . . . . . . . . . . . 478

11.1.3. Uses . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 481

11.2. Highly Fluorinated Aromatic Compounds 481

11.3. Perhaloaromatic Compounds. . . . . . . . . . 482

11.4. Fluorinated Heterocyclic and Polycyclic

Compounds . . . . . . . . . . . . . . . . . . . . . . . 483

11.4.1. Ring-Fluorinated Pyridines. . . . . . . . . . . . . 483

11.4.2. Trifluoromethylpyridines . . . . . . . . . . . . . . 483

11.4.3. Fluoropyrimidines . . . . . . . . . . . . . . . . . . . 483

11.4.4. Fluorotriazines . . . . . . . . . . . . . . . . . . . . . 483

11.4.5. Polycyclic Fluoroaromatic Compounds . . . . 484

12. Economic Aspects . . . . . . . . . . . . . . . . . . 484

DOI: 10.1002/14356007.a11_349

13. Toxicology and Occupational Health . . . . 484

13.1. Fluorinated Alkanes. . . . . . . . . . . . . . . . . 485

13.2. Fluorinated Olefins . . . . . . . . . . . . . . . . . 485

13.3. Fluorinated Alcohols . . . . . . . . . . . . . . . . 486

13.4. Fluorinated Ketones. . . . . . . . . . . . . . . . . 486

13.5. Fluorinated Carboxylic Acids . . . . . . . . . 486

13.6. Other Classes . . . . . . . . . . . . . . . . . . . . . . 486

References . . . . . . . . . . . . . . . . . . . . . . . . 487

1. Introduction

Organic fluorine compounds are characterized bytheir carbon – fluorine bond. Fluorine can re-place any hydrogen atom in linear or cyclicorganic molecules because the difference be-tween the van der Waals radii for hydrogen(0.12 nm) and fluorine (0.14 nm) is small com-pared to that of other elements (e.g., chlorine0.18 nm). Thus, as in hydrocarbon chemistry,organic fluorine chemistry deals with a greatvariety of species. When all valences of a carbonchain are satisfied by fluorine, the zig-zag-shapedcarbon skeleton is twisted out of its plane in theform of a helix. This situation allows the elec-tronegative fluorine substituents to envelop thecarbon skeleton completely and shield it fromchemical (especially nucleophilic) attack. Seve-ral other properties of the carbon – fluorine bondcontribute to the fact that highly fluorinatedalkanes are the most stable organic compounds.These include low polarizability and high bondenergies, which increase with increasing substi-tution by fluorine (bond energies: C – F bond inCH3F, 448 kJ/mol; C – H bond in CH4, 417 kJ/mol; C – Cl bond in CH3Cl, 326 kJ/mol; andC – F bond in CF4, 486 kJ/mol).

The cumulative negative inductive effect ofthe fluorine in perfluoroalkyl groups may reversethe polarity of adjacent single bonds (e.g., inthe pair H3C 3 I and F3C " I) or double bonds(e.g.,CH3C

dþH ¼ Cd�H2 and CF3�Cd�H¼ CdþH2). Fluorine substitution changes the re-activity of olefins and carbonyl compounds.Polyfluorinated olefins possess an electron-defi-cient double bond, which reacts preferentiallywith nucleophiles. Carboxy groups are affectedby the presence of an adjacent perfluoroalkylradical. In carboxylic acids, the acidity ismarkedly increased. In other carbonyl com-pounds, the reactivity is increased without anyfundamental change in the chemistry of thecompound. Correspondingly, the basicity ofamines is reduced by the introduction of fluorine.

Fluorine attached to the ring of aromatic com-pounds acts mainly as a para-directing substitu-ent, whereas perfluoroalkyl groups behave asmeta-directing substituents.

Naturally, the influence of fluorine is greatestin highly fluorinated and perfluorinated com-pounds. The fact that these compounds have ahigh thermal stability and chemical resistanceand are physiologically inertmakes them suitablefor many applications for which hydrocarbonsare not. Properties that are exploited commer-cially include high thermal and chemical stabili-ty, low surface tension, and good dielectric prop-erties, for example, in fluoropolymers, perfluori-nated oils and inert fluids.

Individual fluorine atoms or perfluoroalkylgroups do not change the technical propertiesof a hydrocarbon fundamentally. However, thisis not the case with physiological properties. Afluorine atom in a bioactive material may sim-ulate a hydrogen atom, and although this doesnot prevent metabolic processes from occur-ring, the end products may be ineffective ortoxic. Accordingly, such fluorine compoundsare important in, for example, pesticides andpharmaceuticals.

A bibliography of the scientific literature oforganofluorine chemistry was published in 1986[16]; commercial applications of fluorine pro-ducts are reviewed in [7], [17], and [18].

Nomenclature. Any organic fluorine com-pound can be named according to the rules of theInternational Union for Pure and Applied Chem-istry (IUPAC) [19]. However, for highly fluori-nated molecules with several carbon atoms, thisnomenclature can be confusing. Therefore, theterm ‘‘perfluoro’’ may be usedwhen all hydrogenatoms bonded to the carbon skeleton have beenreplaced by fluorine. The designation of hydro-gen atoms belonging to functional groups (e.g.,CHO or COOH), of the functional groups them-selves, and of other substituents is not affected[19]. Examples are given in Table 1.

444 Fluorine Compounds, Organic Vol. 15

In the case of highly fluorinated compoundswith few hydrogen atoms (1 – 4), the perfluorocompound can be taken as the parent compound.The hydrogen atoms are named according to theirnumber and position; the letter H or the prefixhydryl (hydro) are used for hydrogen. The sym-bol F was approved by the American ChemicalSociety as abbreviation for perfluoro [20].

Historical Development. The pioneeringwork in organofluorine chemistry dates from1835 to 1940 [21]. Controlled production oforganic fluorine compounds was started in1892 by exchanging halogen for fluorine in hy-drocarbons, using antimony(III) fluoride. Theindustrial phase began in 1929 in the UnitedStates with the discovery of the nonflammable,nontoxic refrigerants CCl3F and CCl2F2 [22]. InGermany, commercial production of aromaticfluorine compounds started in 1930.

The first fluoropolymer, polychlorotrifluor-oethylene, was synthesized in 1934 in Germany,followed by the discovery of polytetrafluoroethy-lene in 1938 in the United States. During WorldWar II, thermally and chemically stable workingmaterials for the separation of uranium isotopeswere investigated by the United States Manhat-tan Project [23]. After World War II, numerousnovel applications were discovered. The devel-opment of new organic fluorine compounds withnovel applications continues undiminished.

2. Production Processes

The four principal methods for the preparation oforganic fluorine compounds are as follows [1],[2], [24], [25]:

1. substitution of hydrogen in hydrocarbonsusing fluorine, high-valencymetal or nonmet-al fluorides, or electrochemical fluorination

2. halogen – fluorine exchange with hydrogenfluoride, hydrogen fluoride-base complexes,or metal fluorides

3. synthesis of higher molecular mass fluorinecompounds from reactive fluorinatedsynthons

4. addition of fluorine, hydrogen fluoride, orreactive nonmetal fluorides to unsaturatedbonds

Only a few of the many possibilities in eachgroup have been developed commercially, withvarying degrees of success.

2.1. Substitution of Hydrogen

Fluorination with Elemental Fluorine [26],[27]. The action of elemental fluorine on organiccompounds normally leads to violent, mainly ex-plosive, reactions. The substrate fragments intounits with a varying degree of fluorination becausethe heats of formation of the C – F bond (ca.460 kJ/mol) and the H – F bond (566 kJ/mol) aregreater than the heat of formation of the C – Cbond (ca. 348 kJ/mol).

Therefore, direct fluorinationsmust take placewith strict control of the reaction and removal ofthe heat generated. This may be achieved bydilution of the fluorine with inert gases (e.g.,N2 or CO2), dilution of the organic substrateswith inert solvents [28], intensive mixing, andreduction of the temperature to as low as� 150 �C.

Direct fluorination can also be carried out inthe gas phase in a tubular reactor packed withsilver- or gold-plated copper turnings [29]. Spe-cialized methods are based on LaMar fluorina-tion [26], aerosol fluorination [30], porous-tubefluorination [31], and jet fluorination [32]; highproduct selectivities are achieved at a laboratory

Table 1. Nomenclature of organic fluorine compounds

Formula CAS IUPAC designation Perfluoro designation

registry no.

CF3CF3 [76-16-4] hexafluoroethane perfluoroethane, F-ethane

CF3CF2CF2CHO [375-02-0] Heptafluoro-n-butyraldehyde Perfluoro-n-butyraldehyde, F-n-butyraldehyde

CF3(CF2)6COOH [335-67-1] Pentadecafluoro-n-octanoic acid Perfluoro-n-octanoic acid, F-n-octanoic acid

CF3(CF2)2CHF2 [375-17-7] 1,1,1,2,2,3,3,4,4-Nonafluoro-n-butane 1H-Perfluoro-n-butane, 1-hydryl-F-n-butane

CF3(CF2)4CH2OH [423-46-1] 2,2,3,3,4,4,5,5,6,6,6-Undecafluoro-n-hexanol 1H,1H-Perfluoro-n-hexanol,

1,1-dihydroperfluoro-n-hexanol

Vol. 15 Fluorine Compounds, Organic 445

scale. Commercial operation remains to bedeveloped.

Fluorination with Metal Fluorides [33].Metal fluorides that can transfer fluorine to or-ganic substrates by changing the oxidative stateof the metal, such as cobalt(III) fluoride (CoF3)and silver(II) fluoride (AgF2), serve as fluorinat-ing agents in an oxidizing fluorination. The spentmetal fluoride is regenerated with elementalfluorine.

Fluorination and regeneration can be cyclical,permitting a commercial operation.

Electrochemical Fluorination. The Simonsprocess [34], [35] is used commercially for theproduction of perfluorinated compounds. Solu-tions of organic compounds (mainly carboxylicacids, sulfonic acids, and tertiary amines) areelectrolyzed in anhydrous hydrogen fluoride in asingle cell without intermediate formation of freefluorine. Fluorination takes place at a nickel anodeby a free-radical mechanism at current densities of10 – 20 mA/cm2 [36]. Selectivity decreasessharply as the number of carbons increases.

Volatile, hydrogen-containing compounds(hydrocarbons and chlorohydrocarbons) can beelectrofluorinated on porous graphite anodes inKF-containing hydrogen fluoride in a processdeveloped by Phillips Petroleum [37], [38],[39] and nowreferred to asCAVE(CarbonAnodeVapor Phase Electrochemical Fluorination), inoperation at 3 M [40]. The organic compound isintroduced into the cell through the anode. In thepores of the anode, i.e., at the phase boundary,partial or complete exchange of the hydrogen, butnot the chlorine, takes place. To date this processhas been used only on a small scale.

2.2. Halogen – Fluorine Exchange

Exchange of chlorine with hydrogen fluo-ride is used inmany commercial processes bothfor the production of chlorofluoroalkanes and forthe side-chain fluorination of aromatic and N-heterocyclic compounds [41]. The method in-volves exchange of chlorine for fluorine in poly-

halogenated compounds using hydrogen fluoride[42]:

Whether the process takes place with or with-out a catalyst depends on the reactivity of thechlorine atoms to be exchanged. With com-pounds containing several chlorine atoms ofdiffering reactivity, selective fluorination canbe achieved by selecting suitable processconditions.

Fluorinations without a catalyst such as

are carried out in liquid, anhydrous hydrogenfluoride at 100 – 150 �C in pressure vesselsmade of steel, alloy steels, or nickel. The processcan be carried out by batch (e.g., autoclave) orcontinuous methods (autoclaves in series or atubular reactor). In either case, the hydrogenchloride that is generated during fluorination isremoved from the reactor to maintain the desiredpressure.

Most liquid-phase fluorinations, e.g., of CCl4,CHCl3, CCl3CCl3, CCl3CHCl2, or CCl3CH2Cl,are carried out in the presence of a catalyst [43] topromote the exchange, which becomes increas-ingly difficult as fluorination progresses. Themain catalysts used are antimony(III) and anti-mony(V) halides with low volatility. Addition ofchlorine oxidizes the antimony to the pentavalentstate.

In addition to the liquid-phase processes,many commercially important gas-phase fluor-inations employ hydrogen fluoride [43]. Thecomponents in the gas phase are passed througha tubular reactor containing the catalyst. Thecomposition of the product can be controlledwithin wide limits by varying temperature, pres-sure, residence time, catalyst, and the proportionsof the reactants. Various metal fluorides aresuitable catalysts, e.g., aluminum fluoride [44]or basic chromium fluoride [45].

For further processing of the mixture pro-duced by gas- or liquid-phase fluorination, thefollowing criteria should be satisfied [46]:

1. The hydrogen chloride generated should beseparated in a pure form to permit further use.


2. Unreacted hydrogen fluoride should berecovered.

3. Acid residues, water, and other impuritiesmust be removed from the product.

Usually, the hydrogen chloride is separatedfrom the crude fluorination mixture by fractionaldistillation. The bulk of the hydrogen fluoridemay then be separated from the residue. Furthertreatment includes washing to remove traces ofacid, drying, and fractional distillation.

Exchange of Chlorine with NonoxidizingMetal Fluorides [41]. Alkali fluorides, espe-cially potassium fluoride, are often used toexchange chlorine in carboxylic acid chlorides,sulfonic acid chlorides,a-chlorocarboxylic acidderivatives (esters, amides, and nitriles), ali-phatic monochloro compounds, or activatedaromatic chloro compounds (Halex process)[47].

The dry, finely powdered metal fluoride isemployed in a solvent-free process at 400 –600 �C, e.g., with polychlorinated aromatic com-pounds, or, inmost other cases, in the presence ofa solvent. For slow reactions, polar, aprotic sol-vents are used.

2.3. Synthesis from FluorinatedSynthons

The variety of organic fluorine compounds canbe greatly increased by the use of easily accessi-ble, low molecular mass fluoroalkanes and ole-fins to synthesize higher molecular mass pro-ducts. Halofluoromethanes add to halogenatedethylenes to form halogenated fluoropropanes[48]. An industrially applied reaction is the ad-dition of iodopentafluoroethane to tetrafluor-oethylene yielding a homologous series oflong-chain 1-iodoperfluoroalkanes (see Section3.4). The pyrolysis of chlorodifluoromethane isthe industrial source of tetrafluoroethylene, hex-afluoropropene, and the corresponding oligo-mers and polymers (see Sections 4.2 and 4.3).These examples illustrate the importance of thissynthetic method, especially for the productionof organic fluorine compounds containing morethan two carbon atoms where the above-men-tioned fluorination methods fail to give highyields of the desired products.

2.4. Addition of Hydrogen Fluoride toUnsaturated Bonds

Addition of hydrogen fluoride to alkenes andalkynes takes place below 0 �C with formationof mono- or difluoroalkanes; ethylene and acety-lene are exceptions [24]. Ethyl fluoride is pro-duced from ethylene and hydrogen fluoride at90 �C; catalytic processes have been developedfor the addition of hydrogen fluoride to acetyleneto produce vinyl fluoride or 1,1-difluoroethane.Unsymmetrical olefins obeyMarkovnikov’s rule.Chloroolefins can undergo chlorine – fluorineexchange after addition of hydrogen fluoride.Addition of hydrogen fluoride to the electron-deficient double bond of perfluoroolefins can beperformed using trialkylamine trishydrofluoridesat moderate temperatures [49].

2.5. Miscellaneous Methods

Substitution of Amino Groups in AromaticCompounds [50]. Introduction of one or twofluorine atoms into aromatic rings is carried outcommercially by diazotization of aromaticamines in anhydrous hydrogen fluoride withsolid sodium nitrite and decomposition of thedissolved diazonium salt (see Section 11.1.2).

Fluorination with Nonmetal Fluorides.Reactions of nonmetal fluorides with certain sub-strates are predominantly restricted to laboratoryoperations. Sulfur tetrafluoride and the followingcompounds can be used for the controlled introduc-tion of fluorine into organic compounds: dialkyla-minosulfur(IV) fluorides (R2NSF3) [51–53],fluoroalkylamines (e.g., 2-chloro-1,1,2-trifluor-oethyldiethylamine or 1,1,2,3,3,3-hexafluoropro-pyldiethylamine), tetra-n-butylammonium fluoride,trialkylamine trishydrofluorides, nitrosyl fluoride,perchloryl fluoride, fluoroxyfluoroalkanes (e.g.,CF3OF) [54], xenon difluoride [55], or CH3COOF[56]. They are of commercial value for the fluori-nation of complex organic compounds such aspharmaceuticals.

2.6. Purification and Analysis

Impurities are usually removed from organicfluorine compounds by fractional distillation,


fractional crystallization, or chromatographicmethods. This does not apply to fluoropolymersand high-boiling perfluorinated oils, which re-quire special measures, i.e., the use of extremelypure starting materials.

Quantitative determination of fluorine is pos-sible in most cases by combustion and subse-quent analysis of the hydrogen fluoride generat-ed. Wet chemical methods are used to determinefluoride ions [57].

Because of the high volatility of organic fluo-rine compounds, purity can be readily deter-mined by gas chromatography. 19F-Nuclearmag-netic resonance spectroscopy is a valuable toolfor determining the structure of organic fluorinecompounds. Structure determinations, even ofmixtures, are often easier using this method thanwith 1H-NMR spectra due to the larger chemicalshifts of 19F-NMR spectra. The 19F signals can beintegrated and used for quantitative analysis [58].

3. Fluorinated Alkanes

The hydrogen atoms of alkanes may be partiallyor totally replaced by fluorine. Partially fluori-nated alkanes are hydrofluorocarbons (HFCs);fully fluorinated alkanes (perfluoroalkanes) areperfluorocarbons (PFCs). In chlorofluorocarbons(CFCs) and hydrochlorofluorocarbons (HCFCs),the alkane hydrogens are replaced by both chlo-rine and fluorine.

A special nomenclature [59] has been intro-duced to identify smaller chain length fluoroalk-anes (up to four carbon atoms) used in refriger-ants. It consists of a three-digit number combinedwith various letters. The first figure of the three-digit number indicates the number of carbonatoms minus one (for methane derivatives, thefigure 0 is omitted); the second figure indicatesthe number of the hydrogen atoms plus one; andthe third figure indicates the number of fluorineatoms. All other bonds are saturated with chlo-rine. The letter R before the code number is anabbreviation for refrigerant; the letter C indicatesa cyclic compound. The complete number iscalled the refrigerant number. The AmericanSociety of Heating, Refrigerating, and Air Con-ditioning Engineers (Atlanta, Georgia) ASH-RAE Standard 34 – 78 describes the method ofcoding. The abbreviation F is sometimes usedand stands for fluorohydrocarbon.

This system does not allow isomerisms to beexpressed for ethane derivatives; for such cases, aletter (a, b, . . . etc.) is added to isomers as theirasymmetry increases, e.g.,

CF2Cl��CCl2F ¼ CFC 113 ðR 113Þ

CF3 ��CCl3 ¼ CFC 113 a ðR 113 aÞThe compound with the highest degree of

symmetry is not given a letter.A special isomer in the series of propane

derivatives is designated by adding two lettersto the numbers derived from the standard rules[60]. The first letter attached to the number refersto the central carbon atom, coding the totalatomic mass of the two substituents attached(a ¼ CCl2, b ¼ CFCl, c ¼ CF2, d ¼ CHCl, e ¼CHF, f ¼ CH2). The second appended letter isderived from the symmetry rule applied to thetwo terminal carbon atoms combined to an imag-inary ethane unit. This unit is then treated like anethane derivative with the difference that theletter a is given to the most symmetric combina-tion. Examples for the codes of the isomericpropane derivatives C3HCl2F5 are:

CF3–CF2–CHCl2 HCFC 225 ca

CF2Cl–CF2–CHFCl HCFC 225 cb

CF3–CHCl–CF2Cl HCFC 225 da

CF3–CHF–CFCl2 HCFC 225 eb.

Codes for the butane derivatives contain threeletters appended to the numeral (e.g., CF3–CH2–CF2–CH3 is coded as HFC 365 mfc [61]).

3.1. Fluoroalkanes andPerfluoroalkanes

Properties. Monofluoroalkanes are at-tacked by bases and sometimes by heat; however,chemical resistance increases with increasingfluorine substitution, especially multiple substi-tution at the same carbon atom.

Perfluoroalkanes have distinct properties[62], [63]. Their physical properties differ fromthose of the corresponding hydrocarbons: densi-ties and viscosities are higher, whereas surfacetensions, refractive indices, and dielectric con-stants are lower. At room temperature perfluor-oalkanes are attacked only by sodium in liquidammonia. At 400 – 500 �C, they are degraded


by alkali metals and silicon dioxide; the formerproduce a metal fluoride and carbon, while thelatter produces silicon tetrafluoride and carbondioxide. Thermal decomposition starts above800 �C (compounds with tertiary carbon atomsabove 600 �C) with the formation of saturatedand unsaturated decomposition products andsome carbon. In addition to their chemical andphysical stability, perfluoroalkanes are charac-terized by nonflammability and physiologicalinertness.

Whereas partially fluorinated alkanes dissolvein many common solvents, perfluoroalkaneshave low solubility, which decreases with theirchain length. Only ethers, ketones, esters, chlor-ohydrocarbons, and chlorofluorocarbons havethe power to dissolve perfluoroalkanes [62].Boiling points, melting points, and densities offluoroalkanes and perfluoroalkanes are listed inTable 2. For other physical properties of HFCs,see Table 3. Physical data for liquid perfluoralk-anes are given in Tables 4 and 5.

Production. Mono- and difluoroalkanes canbe produced by addition of hydrogen fluoride toolefins or alkynes (e.g., CF2H–CH3,HFC 152 a).Another synthetic pathway is the exchange ofchlorine (or bromine) for fluorine using hydrogen

fluoride or metal fluorides such as antimonyfluoride. Monohydroperfluoroalkanes can be ob-tained by adding hydrogen fluoride to perfluor-oalkenes (e.g., CF3–CHF–CF3, HFC 227 ea) orby decarboxylation of perfluorocarboxylates inthe presence of proton donors. The novel com-mercially interesting hydrofluorocarbons areproduced by processes, that have been developedfor the production of chlorofluorocarbons andhydrofluorocarbons and optimized during the lastdecades (see Section 3.2).

Higher temperatures and higher hydrogen fluo-ride : substrate ratios are necessary to achievecomplete replacement of all chlorine atoms in thestarting chlorocompounds by fluorine. Both liquid-phasehalogenexchange in thepresenceof catalystssuch as antimony(V) or tin(IV) chlorofluorides andvapor phase reactions using solid-phase catalystsbased on chromium are employed. Preferred start-ingmaterials are chloroform forHFC 23 [45], [65],dichloromethane for HFC 32 [66] and 1,1,1-tri-chloroethane for HFC 143 a [67]. The conversionof tetrachloroethylene to HFC 125 [68] andtrichloroethylene to HFC 134 a [69] involvesinitial HF-addition across the double bond fol-lowed by a series of chlorine – fluorine ex-change reactions. Vapor-phase hydrogenolysisof chlorofluorocarbons and hydrochlorofluoro-

Table 2. Boiling points, melting points, and densities of fluoroalkanes and perfluoroalkanes

Compound CAS registry

no.

Formula Mr Refrigerant

no.

Code no. bp, �C mp, �C dq4 , g/cm3

(q, �C)

Fluoromethane [593-53-3] CH3F 34.03 R 41 HFC 41 � 78.5 � 141.8 0.8428 (� 60)

Difluoromethane [75-10-5] CH2F2 52.03 R 32 HFC 32 � 51.7 � 136 1.100 (20)

Trifluoromethane [75-46-7] CHF3 70.02 R 23 HFC 23 � 82.1 � 160 1.246 (� 34)

Tetrafluoromethane [75-73-0] CF4 88.01 R 14 PFC 14 � 128 � 183.6 1.33 (� 80)

Fluoroethane [353-36-6] CH3CH2F 48.06 R 161 HFC 161 � 37.1 � 143.2 0.8176 (� 37)

1,2-Difluoroethane [624-72-6] CH2FCH2F 66.05 R 152 HFC 152 30.7 0.913 (19)

1,1-Difluoroethane [75-37-6] CH3CHF2 66.05 R 152a HFC 152a � 24.7 � 117 0.966 (19)

1,1,2-Trifluoroethane [430-66-0] CHF2CH2F 84.04 R 143 HFC 143 5.0 � 84

1,1,1-Trifluoroethane [420-46-2] CH3CF3 84.04 R 143a HFC 143a � 47.6 � 111 0.942 (30)

1,1,2,2-Tetrafluoroethane [359-35-3] CHF2CHF2 102.03 R 134 HFC 134 � 19.7 � 89

1,1,1,2-Tetrafluoroethane [811-97-2] CF3CH2F 102.03 R 134a HFC 134a � 26.3 � 101 1.2078 (25)

Pentafluoroethane [354-33-6] CF3CHF2 120.03 R 125 HFC 125 � 48.5 � 103 1.250 (20)

Hexafluoroethane [76-16-4] CF3CF3 138.02 R 116 PFC 116 � 78.1 � 100.6 1.607 (� 78)

1,1,2,2,3-Pentafluoropropane [679-86-7] CHF2CF2CH2F 134.05 R 245ca HFC 245ca 26 � 82

1,1,1,2,2-Pentafluoropropane [1814-88-6] CF3CF2CH3 134.05 R 245cb HFC 245cb � 18

1,1,1,3,3-Pentafluoropropane [460-73-1] CF3CH2CHF2 134.05 R 245fa HFC 245fa 15.3 1.320 (25)

1,1,1,2,3,3,3-Heptafluorpropane [431-89-0] CF3CHFCF3 170.03 R 227ea HFC 227ea � 16.5 � 131 1.394 (25)

Octafluoropropane [76-19-7] CF3CF2CF3 188.03 R 218 PFC 218 � 36.7 � 183 1.350 (20)

Octafluorocyclobutane [115-25-3] 200.04 RC 318 PFCC 318 � 6.06 � 40.7 1.5241 (20)

1,1,1,3,3-Pentafluoro-n-butane [406-58-6] CF3CH2CF2CH3 148.07 R 365mfc HFC 365mfc 40.2 1.264 (20)

Decafluoro-n-butane [355-25-9] CF3CF2CF2CF3 283.02 R 610 � 22 � 128.2 1.517 (20)


carbons is also proposed for the production ofhydrofluorocarbons [70], [71].

Perfluoroalkanes canbeproducedbyavarietyofroutes. Indirect fluorination of hydrocarbons withcobalt(III) fluoride or silver(II) fluoride is carriedout in a steel or nickel tube with stirring. Thehydrocarbon vapors are passed at 150 – 450 �Cover the fluorinating agent, which is regenerated in

a fluorine stream [72], [73]. This process is suitablefor the production of perfluoroalkanes containingup to 20 carbon atoms. It affords better processcontrol and yields than the direct gas-phase fluori-nation using dilute fluorine and a metal catalyst,especially for longer-chain compounds [74].

Fluoroalkanes and perfluoroalkanes can alsobe produced electrochemically by the Phillips

Table 3. Physical properties of hydrofluorocarbons

Property CH2F2 CHF3 CHF2CH3 CF3CH3 CF3CH2F CF3CHF2 CF3CH2CHF2 CF3CHFCF3 CF3CH2CF2CH3

Critical temperature, �C 78.2 26.3 113.3 73.6 101.1 66.3 154.1 101.8 187.7

Critical pressure, MPa 5.80 4.87 4.52 3.83 4.06 3.63 2.93 2.75

Critical density, g/cm3 0.527 0.365 0.434 0.515 0.517 0.582

Heat of evaporation

at bp, kJ/kg

240.8 326.0 230.0 213.46 177.03 208.96 131.8

Specific heat,

kJ/kg�1 K�1

876

Refractive index, nD 1.200

(� 50)

1.442

(� 80)

1.023

(� 30)

1.53

(� 48.5)

1.407 (25)

Surface tension, N/cm 6.93 �10�5

9.94 �10�5

4.60 �10�5

8.02 �10�5

3.70 �10�5

Vapor pressure (kPa) at

� 120 �C 5.9

� 100 �C 31.5

� 80 �C 113.9

� 60 �C 314.0

� 40 �C 177.3 712.0 141.7 52.0 148.4 32.4

� 20 �C 405.8 1403.0 120.7 316.4 134.0 337.6 19.7 86.7 6.3

0 �C 813.4 2504.3 264.2 620.2 293.0 670.6 53.6 196.2 18.8

20 �C 1474.6 4184.3 513.4 1104.3 572.0 1204.6 123.8 390.2 46.7

40 �C 2477.4 909.7 1831.5 1017.0 2008.1 251.8 702.9 100.9

60 �C 3933.4 1501.0 2884.7 1681.0 463.5 1174.7 194.9

80 �C 2344.1 2631.0 788.8 1857.2 344.6

100 �C 3511.4 3970.0 1261.0 2824.6 567.3

120 �C 1920.0 880.2

140 �C 1300.2

Lower ignition limit

(25 �C), vol %,

12.7 none 3.1 7.1 none none none none 3.5

Atmospheric lifetime, a 15.6 40.5 7.4 40 10.8

HGWP* (CFC 11 ¼ 1) 0.15 8.4 0.03 1.0 0.29 0.67 0.69

*HGWP ¼ Halogen Global Warming Potential

Table 4. Boiling points, melting points, and densities of liquid perfluorocarbons

Compound (also mixtures) CAS registry no. Molecular formula Mr Commercial designationa bp, �C pour point, �C d254 , g/cm3

F-pentanesb [678-26-2] C5F12 288 PP50 29 � 120 1.604

F-methylcyclopentanes C6F12 300 PP1C 48 � 70 1.707

F-hexanes [355-42-0] C6F14 338 PP1 57 � 90 1.682

F-methylcyclohexanes C7F14 350 PP2 76 � 30 1.778

F-decalin (cis/trans) [306-94-5] C10F18 462 PP5/PP6 142 � 8 1.917

F-perhydrofluorene C13F22 574 PP10 194 � 40 1.984

F-perhydrophenanthrene [306-91-2] C14F24 624 PP11 215 � 20 2.03

F-perhydrofluoranthene C16F26 686 PP24 244 0 2.052

F-cyclohexylmethyldecalin C17F30 774 PP25 260 � 10 2.049

aFlutec notation (BNFL Fluorochemicals)bF ¼ perfluoro


Petroleum process or the electrochemical fluori-nation of alcohols, amines, carboxylic acids, andnitriles by the Simons process (see Section 2.1).

Tetrafluoromethane (carbon tetrafluoride,CF4) can be produced by reaction of CCl2F2 orCCl3F and hydrogen fluoride in the gas phase[75] or by direct fluorination of carbon [76].Hexafluoroethane (PFC 116) is often obtainedas a byproduct in the production of CFC 115.Octafluoropropane (PFC 218) can be producedby direct [77], electrochemical [78], or CoF3-fluorination [79] of commercially availablehexafluoropropene (see Section 4.3). Octafluor-ocyclobutane is obtained by dimerization oftetrafluoroethylene [80] or by passing 1,2-di-chloro-1,1,2,2-tetrafluoroethane, CClF2CClF2,over a nickel catalyst at 590 �C [81].

Uses. Hydrofluorocarbons have been gainingincreasing commercial interest as substitutes forchlorofluoro- and hydrochlorofluorocarbons sincegovernmental regulations banned the worldwideproduction and consumption of CFCs by 1996 andintroduced a specific timetable for the phase out ofHCFCs [82]. In contrast to CFCs hydrofluorocar-bons have no adverse effect on the ozone layer andonly a low contribution to global warming (seebelow).The latter effect couldbe furtherminimizedby avoiding leakages in refrigeration and air-con-ditioning equipment and by refrigerant recycling.

In all applications involving considerable emis-sions to the atmosphere, e.g., as propellants inaerosols (except medicinal aerosols), in open cellfoams, or in extruded foamsCFCswill be replacedby nonhalogenated compounds in the future.

Due to the presence of hydrogen in the mole-cule, the stability of HFCs is reduced. In theatmosphere they are degraded below the strato-

spheric level, leading to zero ozone depletionpotentials (ODP ¼ 0) and to reduced halogenglobal warming potentials (HGWPs). However,depending on the structure of the HFCs thisreduced stability can entail an increased flamma-bility and thus make safe handlingmore difficult.Therefore, alternatives to the CFCs need to retainthe attractive properties of CFCs like low toxici-ty, nonflammability, good thermodynamic prop-erties, and accessibility via economically andecologically viable manufacturing processes, butavoid any adverse effect to the environment.

In refrigeration and air-conditioning systemsCFC 12 is replaced by HFC 134 a, HCFC 22 bythe azeotropic mixtures HFC 507 (HFC 125/HFC 143 a 1 : 1) or HFC 410 (HFC 32/HFC 1251 : 1) and CFC 13 by HFC 23. HFC 134 a andHFC 227 ea can be used as propellants in medici-nal aerosols instead of CFC 114. HFC 245 fa andHFC 365 mfc are proposed as blowing agents forfoams in replacing CFC 11, CFC 113 andHCFC 141 b [83]. Until now no HFC candidatefor replacement of CFC 11 and CFC 113 as sol-vents, degreasing agents, or cleaning agents fortextiles ormetal surfaces has been identified. In theperiod 1990 – 1995 159.5 x 103 t of HFC 134 ahave been produced [84].

Gaseous perfluorocarbons (PFC 14, PFC 116,PFC 218) are used in plasma etching processes inthe microelectronic industry [85] and as gaseousdielectrics. Liquid perfluorocarbons [64] serveas heat-transfer media in transformers and incapacitors, as lubricants and hydraulic fluids, orin vapor-phase soldering [86] and vapor-phasesterilization [64].

Perfluoroalkanes, e.g., perfluorodecalin [306-94-5], are used in the production of blood sub-stitutes [87].

Table 5. Further physical properties of liquid perfluoroalkanes [64]

Property PP50 PP1C PP1 PP2 PP5/6 PP10 PP11 PP24 PP25

Critical temperature, �C 148.7 180.8 177.9 212.8 292.0 357.2 377 388.7 400.4

Critical pressure, MPa 2.05 2.26 1.83 2.02 1.75 1.62 1.46 1.51 1.13

Critical volume, L/kg 1.626 1.567 1.582 1.522 1.521 1.59 1.58 1.606 1.574

Heat of evaporation

at bp, kJ/kg

90.8 75.8 85.5 85.9 78.7 71 68 65.8 67.9

Specific heat, kJ/kg�1 K�1 1.05 0.878 1.09 0.963 1.05 0.92 1.07 0.93 0.957

Refractive index, n20D 1.283 1.2650 1.2509 1.2781 1.3130 1.3289 1.3348 1.3462 1.3376

Surface tension, N/cm 9.4 � 10�5 12.6 � 10�5 11.1 � 10�5 15.4 � 10�5 17.6 � 10�5 19.7 � 10�5 19 � 10�5 22.2 � 10�5

Viscosity (dynamic),

mPa � s0.465 1.049 0.656 1.561 5.10 9.58 28.4 31.5 114.5

Vapor pressure (kPa)

at 25 �C8.62 3.68 2.94 1.41 0.09 < 0.01 < 0.01 < 0.01 < 0.01


Trade Names. Hydrofluorocarbons substi-tuting chlorofluorocarbons and hydrochloro-fluorocarbons are marketed worldwide underprotected trade names. The individual productis characterized by the HFC code number fol-lowing the trade name. Some worldwide appliedtrade names are:

France

Rhone-Poulenc Isceon

Elf Atochem Forane

Germany

Hoechst Reclin

Solvay Solkane

United Kingdom

ICI Klea

Italy

Montefluos Algogrene

Japan

Asahi Glass Asahiflon

Daikin Daiflon

United States

Allied Signal Genetron

DuPont Suva

Great Lakes Chemical FM

3 M 3M Brand

Perfluorocarbons are offered under tradenames such as Freon C-51–12; Perfluorokero-sene FCX-329, FCX-330;Perfluorolube oil FCX-512, FCX-412 (DuPont); Flutec PP-1, PP-2, PP-3, PP-9, etc. (BNFL Fluorochemicals), Multi-fluor Inert Fluids (Air Products and Chemicals).

3.2. Chlorofluoroalkanes

For more than 50 years chlorofluorocarbons andhydrochlorofluorocarbons have been the mostimportant organic fluorine compounds commer-cially. The five products listed in Table 6 havebeen by far the most important of these withregard to the field of applications and to theamount produced [84].

The results of the investigation on postulatedatmospheric changes caused by CFCs [88] with

respect to the ozone balance and the greenhouseeffect [89], [90] verified the adverse impact onthe stratospheric ozone layer and the significantcontributions to global warming due to the longatmospheric lifetimes of the CFCs. In 1987, aUnited Nations agreement, called the MontrealProtocol – revised in 1992 during the Copenha-gen Intergovernmental Conference – set thedeadline for the phase out of CFCs in developedcountries. Since 1996 production and consump-tion of CFCs are prohibited, except as intermedi-ates in the production of fluorine chemicals,especially fluoropolymers. For HCFCs with re-duced atmospheric stabilities a timetable hasbeen introduced for their phase out. HCFCs areallowed to be used as drop-in alternatives forCFCs until suitable HFC substitutes (see Section3.1) will have been developed, but no longer thanuntil 2015 to 2030 [82].

High molecular mass chlorofluorocarbons, asmall but significant class of CFCs will not beaffected by the ban.

Properties. Chlorofluoroalkanes are char-acterized by high chemical and thermal stabili-ties, which increase with their fluorine content.Low flammability (or nonflammability) and lowtoxicity are additional commercial advantages.Most of these compounds have a pleasant, weakodor; some are mild anesthetics [91].

Boiling points, freezing points, and densitiesof formerly commercially important chloro-fluoroalkanes are shown in Table 7; other phys-ical properties are listed in Table 8. Physicalproperties of some high molecular mass CFCsproduced from chlorotrifluoroethylene aregiven in Table 9.

Production. Commercial production ofchlorofluoroalkanes employs halogen exchange,with hydrogen fluoride in the liquid phase in thepresence of a catalyst. The production scheme fordichlorodifluoromethane shown in Figure 1 is

Table 6. Economically most important organic fluorine compounds

Compound Total production

through 1995, 106t

Maximum annual

production (year), 103 t

Trichlorofluoromethane (R 11, CFC 11) 8.62 382 (1987)

Dichlorodifluoromethane (R 12, CFC 12) 11.28 425 (1987)

Chlorodifluoromethane (R 22, HCFC 22) 3.85 243 (1995)

1,2,2-Trichloro-1,1,2-trifluoroethane (R 113, CFC 113) 2.97 251 (1989)

1,2-Dichloro-1,1,2,2-tetrafluoroethane (R 114, CFC 114) 0.51 19 (1986)


typical [93]:

CCl4þ2 HF!CCl2F2þ2 HCl

A steam-heated steel autoclave (a) lined withstainless steel (V2A) serves as the reactor. Theseals are made from aluminum or copper. Theautoclave (capacity 2 – 5 m3) is filled with500 kg of hydrogen fluoride, 1540 kg of carbontetrachloride, 220 kg of antimony(III) chloride,and 20 kg of chlorine, and the mixture is heatedto 100 �C. After ca. 2 h and an increase inpressure to ca. 3 MPa, the fluorination productswith lower boiling points are removed togetherwith the hydrogen chloride that is generated andsome hydrogen fluoride; higher-boiling productsin the exit gases are condensed and recycled. Thelow-boiling fraction is first washed with water ina tower (e) lined with poly(vinyl chloride) andpacked with graphite; it is then washed withcaustic in a tower (f) filled with porcelain pack-ing. After beingwashed to neutrality, the productis dried in a tower (i) containing concentratedsulfuric acid, compressed to a liquid, and fed intoan intermediate storage tank (m). Each batchtakes ca. 24 h to process. The antimony catalystremains in the reactor and is regenerated beforeeach subsequent batch by adding a small amount

of chlorine to convert it to the catalytically activeSb(V) form.

The crude product is fractionally distilledunder pressure (0.6 – 0.8 MPa). The lower-boiling fraction contains some chlorotrifluoro-methane and most of the dichlorodifluorometh-ane (yield 90% based on carbon tetrachloride,80% based on hydrogen fluoride). The higher-boiling fraction consists of trichlorofluoromethane(5 – 10% based on carbon tetrachloride), whichcan be recycled. The distilled product is passedthrough a caustic filter (s). Steel bottles, pressurevessels, tank cars, and tank trucks are used fortransport.

More recently developed exchange processesare carried out continuously in the gas phase at100 – 400 �C, using catalysts based on chromi-um [45], aluminum [44], or iron [94]. Startingmaterials, which include carbon tetrachloride,chloroform, tetrachloroethylene, and trichloro-ethylene, are passed over the catalyst with excesshydrogen fluoride and, where necessary, chlo-rine. Further processing follows the same prin-ciples as in the liquid-phase process.

In the Montedison chlorofluorination process,reaction of C1- and C2-hydrocarbons with chlo-rine and hydrogen fluoride takes place in a singlestep in a fluidized-bed reactor. A suitable catalyst

Table 7. Boiling points, melting points, and densities of chlorofluoroalkanes

Compound CAS

registry no.

Formula Mr Refrigerant

number

Code no.�C

bp,�C

mp,

g/cm3

dq4 ,

(q, �C)

Trichlorofluoromethane [75-69-4] CCl3F 137.38 R 11 CFC 11 23.7 � 111 1.490 (20)

Dichlorodifluoromethane [75-71-8] CCl2F2 120.93 R 12 CFC 12 � 29.8 � 155 1.328 (20)

Chlorotrifluoromethane [75-72-9] CClF3 104.47 R 13 CFC 13 � 81.1 � 181 0.924 (20)

Dichlorofluoromethane [75-43-4] CHCl2F 102.93 R 21 HCFC 21 8.9 � 135 1.366 (20)

Chlorodifluoromethane [75-45-6] CHClF2 86.48 R 22 HCFC 22 � 40.8 � 160 1.213 (20)

Tetrachloro-1,2-difluoroethane [76-12-0] CCl2FCCl2F 203.85 R 112 CFC 112 92 27.4 1.634 (30)

Tetrachloro-1,1-difluoroethane [76-11-9] CClF2CCl3 203.85 R 112 a CFC 112 a 91.5 40.8 1.649 (20)

1,1,2-Trichlorotrifluoroethane [76-13-1] CCl2FCClF2 187.39 R 113 CFC 113 47.7 � 33 1.582 (20)

1,1,1-Trichlorotrifluoroethane [354-58-5] CF3CCl3 187.39 R 113 a CFC 113 a 45.9 14 1.579 (20)

1,2-Dichlorotetrafluoroethane [76-14-2] CClF2CClF2 170.94 R 114 CFC 114 3.8 � 94 1.473 (20)

1,1-Dichlorotetrafluoroethane [374-07-2] CF3CCl2F 170.94 R 114 a CFC 114 a � 2 � 56.6 1.478 (21)

Chloropentafluoroethane [76-15-3] CF3CClF2 154.48 R 115 CFC 115 � 38 � 106 1.291 (25)

1,1,2-Trichloro-2,2-difluoroethane [354-21-2] CClF2CHCl2 169.39 R 122 HCFC 122 71.9 � 140 1.544 (25)

1,1-Dichlor-2,2,2-trifluoroethane [306-83-2] CF3CHCl2 152.94 R 123 HCFC 123 28.7 � 107 1.475 (15)

1-Chloro-1,2,2,2-tetrafluoroethane [2837-89-0] CF3CHClF 136.48 R 124 HCFC 124 � 12 � 199 1.364(25)

1,2-Dichloro-1,1-difluoroethane [1649-08-7] CClF2CH2Cl 134.94 R 132 b HCFC 132 b 46.8 � 101.2 1.4163 (20)

1-Chloro-2,2,2-trifluoroethane [75-88-7] CF3CH2Cl 118.49 R 133 a HCFC 133 a 6.9 � 101 1.389 (0)

1,1-Dichloro-1-fluoroethane [1717-00-6] CCl2FCH3 116.95 R 141 b HCFC 141 b 32 � 103.5 1.250 (10)

1-Chloro-1,1-difluoroethane [75-68-3] CClF2CH3 100.49 R 142 b HCFC 142 b � 9.2 � 130.8 1.120 (25)

1,1-Dichloro-2,2,3,3,3-

pentafluoropropane

[422-56-0] CF3CF2CHCl2 202.9 R 22 5ca HCFC 225

ca

51.1 � 94 1.550 (25)

1,3-Dichloro-1,2,2,3,3-

pentafluoropropane

[507-55-1] CClF2CF2CHClF 202.9 HCFC

225 cb

56.1 � 97 1.560 (25)


is a combination of aluminum chloride and othermetals [95–97]:

Commercial production of chlorofluoroalk-anes is also possible by the electrochemical

Table 8. Physical properties of chlorofluoroalkanes [92]

Property CCl3F CCl2F2 CClF3 CHClF2 CCl2FCClF2 CClF2CClF2 CF3CHCl2 CF3CHClF CCl2FCH3 CClF2CH3

Critical temperature,�C

198.0 112.0 28.8 96.0 214.1 145.7 185 122.2 210.3 137.1

Critical pressure,

MPa

4.40 4.21 3.86 4.94 3.41 3.27 3.79 3.57 4.64 4.12

Critical density,

g/cm3

0.548 0.558 0.581 0.525 0.576 0.578

Heat of evaporation

at bp, kJ/kg

182.16 166.88 148.50 234.12 145.70 139.42 174.17 167.9 223.15 223.15

Specific heat at

101.3 kPa,

J kg�1 K�1 871 854 850 1088 946 971 1017.4 1130 1155.6 1297.9

Refractive index,

n26:5D

1.384 1.285 1.263 1.252 1.355 1.290 1.3322 (15) 1.3600 (10)

Surface tension,

N/cm

19�10�5 9�10�5 9�10�5 19�10�5 13�10�5 19�10�5

Solubility in water,

g/100 g

at 0 �C 0.0036 0.0025 0.0019 0.060 0.0036 0.0026

at 30 �C 0.013 0.0125 0.0065 0.15 0.013 0.011 0.39

(25 �C)1.71

(25 �C)0.021

(25 �C)0.14

(25 �C)Dielectric strength

at 101.3 kPa,

23 �C, nitrogen ¼ 1 3.1 2.4 1.4 1.3 2.6 (39.2 kPa) 2.8

Dielectric constant

liquid at 25 �C* 2.5 2.1 2.3

(� 30 �C)6.6 2.6 2.2

vapor (t, �C) 1.0019

(26)

1.0016

(29)

1.0013

(29)

1.0035

(25.4)

1.0024 (27.5) 1.0021

(26.8)

7.9 (20 �C)

Vapor pressure

(kPa) at

� 120 �C 6.96

� 100 �C 1.18 33.14

� 80 �C 6.12 109.8

� 60 �C 22.7 282.5 3.6

� 40 �C 5.1 64.3 607 13.0

� 20 �C 15.7 151.0 1146 246 5.08 37.0

0 �C 40.2 308.7 1969 500 14.79 87.9 28

20 �C 89.0 566.9 3177 917 36.4 182 65

40 �C 176 958.5 1549 78.3 340 184 (50 �C)60 �C 316 1518.7 2459 151.3 583

80 �C 528 2284.7 268.0 935

100 �C 830 3297.5 442.2 1423

120 �C 1242 2083

140 �C 1785 2964

Atmospheric

lifetime, a

55 116 15.8 110 220 1.71 7.0 10.8 22.4

ODP 1.00 1.00 0.055 1.07 0.80 0.02 0.022 0.11 0.065

HGWP (CFC11 ¼ 1) 1.00 3.00 0.33 1.6 7.1 0.02 0.11 0.14 0.41

*Except where otherwise stated.

Table 9. Physical data of highmolecular mass CFCswith the structure

Cl(CF2CFCl)nCl

n ¼ 2 3 4 5

Mr 304 420.5 537 653.5

bp, �C 136 205 255 300

Density, d37:84 1.713 1.808 1.865 1.902

Viscosity (dynamic),

mPa � s (37.8 �C)1.35 3.4 10.8 48.9


fluorination process developed by Phillips Petro-leum (see Section 2.1).

High molecular mass chlorofluoroalkanes areproduced by fluorinationwith chlorine trifluoride[98], [99].

Other important processes for production ofhigh molecular mass CFCs are based on thetelomerization of chlorotrifluoroethylene (seeSection 4.8) with carbon tetrachloride [100] orCFC 113 [101] as telogens. Stabilization andend-group fluorination are achieved using cobalttrifluoride as fluorinating agent [102], [103].

Specifications. Chlorofluoroalkanes (andalso the alternative HCFCs and HFCs) producedon an industrial scale are subject to stringentstandards. Impurities must not exceed the fol-lowing limits (vol %):

acids 0

moisture < 0.001

higher-boiling fractions < 0.05

other gases 2

Uses. Up to the ban in the USA in 1978chlorofluoroalkanes had been used mainly asaerosol propellants and as spraying and foamblowing agents (R 11, R 12, R 114). Furtherimportant applications up to 1996 had been in

the area of refrigerants, where R 11, R 12, R 13,R 22, R 113, R 114, R 115, and the chlorine-freecompounds R 23 and RC 318 were preferred. Ofthe drop-in alternatives to CFCs HCFC 22 is themost important compound, used as refrigerant(annual production in 1995 243 � 103 t [84]),followed by HCFC 141 b (113 � 103 t in 1995[84]) and HCFC 142 b (38 � 103 t in 1995 [84])used as blowing agents for closed cell foams. ForHFCs as alternatives see Section 3.1.

Chlorofluoroalkanes, especially R 11 andR 113, were also employed as solvents and de-greasing and cleaning agents for textiles;HCFC 22, CFC 113, and HCFC 142 b will beimportant intermediates for the production offluoroolefins also in the future.

Higher molecular mass perchlorofluoroalk-anes are used as oils, greases, and waxes, aslubricants, hydraulic fluids, damping oils, heat-transfer media, impregnating agents, and plasti-cizers. Oligomers of chlorotrifluoroethylenehave achieved special importance in this area[104].

Trade Names. Chlorofluoroalkanes weresold worldwide under protected trade names; therefrigerant numbers describing the chemicalcomposition (see Table 7) are included to specifyindividual compounds. Some of the trade namesthat were applied worldwide are:

Figure 1. Manufacture of dichlorodifluoromethane (R 12) by fluorination of carbon tetrachloride in the liquid phasea) Autoclave; b) Reflux condenser; c) Separator; d) Pressure valve; e)Wash column (water); f)Wash column (NaOH); g) Pumpfor NaOH; h) Gasometer; i) Wash column (H2SO4); j) Pump for H2SO4; k) Compressor; l) Condenser; m) Receiver for crudeproduct; n) Distillation pot; o) Dephlegmator; p) Condenser; q) Forerun receiver; r) Tank for pure product; s) Caustic filter


Australia

Australian Fluorine Chemicals Isceon

Czechoslovakia

Slovek Pro Chemickov Ledon

Federal Republic of Germany

Hoechst Frigen

Kali-Chemie Kaltron

France

Rhone-Poulenc Flugene

Ugine Kuhlmann Forane

German Democratic Republic

Volkseigener Betrieb Chemiewerk Nunchritz Fridohna

Volkseigener Betrieb Fluorwerke Dohna Frigedohn

Italy

Montedison Algofrene

Japan

Asahi Glass Asahiflon

Daikin Kogyo Daiflon

Mitsui Fluorochemicals Flon

North America

Allied Chemical Genetron

DuPont Freon

Kaiser Chemicals Kaiser

Pennwalt Isotron

Racon Racon

Union Carbide Ucon

Soviet Union

Khladon

Eskimon

The Netherlands

AKZO FCC

United Kingdom

ICI Arcton

Imperial Smelting Corporation Isceon

Trade names of higher molecular mass chloro-fluoroalkanes include Florubes (ICI), Fluorolubeoils, Fluorolube greases (Hooker Industrial Che-micals Division), Halocarbon oils, greases, andwaxes (Halocarbon Products), Kel-F oils, greases,and waxes (3M), and Voltalef (Atochem).

3.3. Bromofluoroalkanes

Bromofluoro compounds of practical importanceare foundmainly in the methane and ethane series.

In the refrigerant (R) numbering system forbromofluoroalkanes, the corresponding chloro-fluoroalkanes are taken as the basic structures (seealso Section 3); the substitution of chlorine bybromine is expressed by the addition of B1, B2,etc. For example, bromotrifluoromethane is de-noted asR 13B1and1,2-dibromotetrafluoroethaneas R 114B2. In fire-fighting applications the Halonnumbering system is used, specifying the numberof carbon, fluorine, chlorine, and bromine atoms inthe molecules when reading from left to right (e.g.,

Halon 1301 denotes CF3Br; Halon 1211 isCF2ClBr; and Halon 2402 denotes CF2BrCF2Br).

Bromofluorocarbons (BFCs) and hydrobro-mofluorocarbons (HBFCs) are involved in thedepletion of stratospheric ozone and globalwarming like the CFCs and HCFCs; howeverthe contributions of the bromine-containingcompounds are distinctly higher. Therefore, the1992 Copenhagen meeting agreed to phase outthe production of BFCs and HBFCs by 1994,with the exception of Halon for some essentialfire-fighting applications. HFC 125 andHCFC 123 (DuPont) or HFC 227 ea (GreatLakes) are announced as alternatives though theyare significantly less efficient as fire extinguish-ing agents than the BFC Halons

Properties. Fully halogenated compoundswith a high fluorine content have excellent ther-mal stability; they are nonflammable and some(e.g.,CF3Br) are physiologically inert [92].At hightemperature, thermal cleavage of the C – Br bondinto radicals occurs, which is responsible for theutility of some of these compounds in extinguish-ing fires (! Fire Extinguishing Agents) [105].Their chemical stability is slightly lower than thatof the corresponding chlorofluoroalkanes. Howev-er, as with the chlorofluoroalkanes, stability in-creases with the fluorine : bromine ratio. Somecompounds have a marked anesthetic effect[91]. Physical properties are listed in Table 10.

Production. Bromofluoromethanes are ob-tained by bromination of a stream of the appropri-ate fluoromethane [106] or chlorofluoromethane[107] at 300 – 600 �C.Ethane derivatives can alsobe obtained by thermal bromination [108] or byaddition of bromine or hydrogen bromide [109] tofluoroolefins. In some cases hydrogen bromide canbe used to exchange a chlorine atom in a chloro-fluoroalkane for a bromine atom [110]. Iodine –bromine exchange in a fluoroiodoalkane can beeffected with bromine [111].

Uses. The lower-boiling compounds CBrF3(R 13B1; Halon 1301) and CBrClF2 (R 12B1;Halon 1211) had been used as fire extinguishingagents. Producers were Atochem, ICI, and Solvayin Europe, DuPont and Great Lakes in the USAand Asahi Glass, Daikin, and Nippon Halon inJapan. The total worldwideHalon productionwasestimated to be 25 � 103 t in 1986.


Perfluoro-1-bromo-n-octane [423-55-2] isphysiologically inert and is useful as an X-raycontrast agent, especially for lung examinations[112]. With its low surface tension it penetratessmall spaces and evenly wets healthy lung tissue.

2-Bromo-2-chloro-1,1,1-trifluoroethane [151-67-7], also known as halothane, has been usedworldwide since 1956 as an effective, nonflam-mable inhalation anesthetic (! Anesthetics,General). It is commonly produced by the ICIprocess:

or the Hoechst process [43, pp. 208 – 210]:

As alternatives for halothane a series offluorinated ethers (containing in addition hydro-gen and chlorine atoms or exclusively hydrogenatoms) have been developed, that retain or evensurmount the desirable properties of halothaneas inhalation anesthetic [113]. However, alsothese compounds have an adverse effect on theozone layer.

Trade Names. Fluothane (ICI), Halothane‘‘HOECHST’’ (Hoechst).

3.4. Iodofluoroalkanes

Iodofluoroalkanes have become important inter-mediates in the commercial production of com-pounds containing a perfluorinated moiety.

Properties. In contrast to chloro- and bro-mofluoroalkanes, iodofluoroalkanes readily un-dergo chemical reactions [24, Chap. 6], reactingpreferentially by homolytic cleavage of the C – Ibond.

The radical intermediates CnF2nþ1. and I . can

add to double bonds; thus, reaction with ethyleneyields 1H,1H,2H,2H-1-iodoperfluoroalkanes,which are commercially important intermediates[114]:

CnF2nþ1IþCH2 ¼ CH2!CnF2nþ1CH2CH2I

Control of the reaction between iodofluor-oalkanes and fluoroolefins, especially tetrafluor-oethylene, can result in oligomerization (telo-merization) of the olefin [115]:

CF3IþnCF2 ¼ CF2!CF3ðCF2CF2ÞnI

This reaction is employed commercially andis initiated by free radicals, UV irradiation, orheat [116].

Iodofluoroalkanes also form organometalliccompounds, some of which are useful intermedi-ates, e.g., for Grignard reactions [117].

Iodoperfluoroalkanes cannot be used as alky-lating agents and their applications are thereforelimited. However, derivatives of the FITS-typereagent are alkylating agents [118]:

Physical constants of some iodofluoroalkanesare shown in Table 11.

Table 10. Boiling points, melting points, and densities of bromofluoroalkanes

Compound CAS Formula Mr Halon no. bp, mp, d 4q, g/m3 ODP Atmospheric

registry no. �C �C (q,�C) R 11 ¼ 1 lifetime,a

Tribromofluoromethane [353-54-8] CBr3F 270.76 1103 106 � 74.5 2.7648 (20)

Dibromodifluoromethane [75-61-6] CBr2F2 209.84 1202 24.5 � 110 2.3063 (15)

Dibromochlorofluoromethane [353-55-9] CBr2ClF 226.30 1112 80

Bromotrifluoromethane [75-63-8] CBrF3 148.93 1301 � 57.8 � 168 1.58 (21) 16 67

Bromochlorodifluoromethane [353-59-3] CBrClF2 165.38 1211 � 4 � 160.5 1.850 (15) 4 19

Bromodifluoromethane [1511-62-2] CHBrF2 130.92 1201 � 15.5 � 145 1.825 (20) 1.4 5.6

1,2-Dibromotetrafluoroethane [124-73-2] CBrF2CBrF2 259.85 2402 47.5 � 110.4 2.18 (20) 6

1-Bromo-2-chloro-1,1,2-

trifluoroethane

[354-06-3] CHClFCBrF2 197.40 2311 a 51.7 1.864 (20)

2-Bromo-2-chloro-1,1,1-

trifluoroethane

[151-67-7] CF3CHBrCl 197.40 2311 50.2 1.861 (25)


Production. Iodofluoroalkanes can beproduced by heating the silver salts of the per-fluorocarboxylic acids with iodine [119] or thecorresponding sodium salts with iodine in di-methylformamide [120]. Of commercial impor-tance is the production of pentafluoroiodoethane(CF3CF2I) by reactionof tetrafluoroethylenewith amixture of iodine pentafluoride and iodine [121]:

5 CF2 ¼ CF2þIF5þ2 I2!5 CF3CF2I

Heptafluoro-2-iodopropane (CF3CFICF3) isobtained similarly from hexafluoropropene.

The higher homologues CnF2nþ1I (n ¼ 4 – 12)are produced commercially by reaction of the lowermemberswith tetrafluoroethylene (telomerization).

a,w-Diiodoperfluoroalkanes are obtainedfrom tetrafluoroethylene and iodine [122]:

Uses. 1-Iodoperfluoroalkanes and1H,1H,2H,2H-1-iodoperfluoroalkanes are inter-mediates in the production of surfactants andtextile finishes [123]. Perfluorocarboxylic acids,especially perfluorooctanoic acid, are obtainedfrom perfluoroiodoalkanes [124], and perfluori-nated dicarboxylic acids are obtained from a,w-diiodoperfluoroalkanes [125].

4. Fluorinated Olefins

The commercial importance of fluoro- and chlor-ofluoroolefins lies in the production of fluorinat-ed plastics and inert fluids.

Properties. The chemical behavior of fluor-oolefins [126] is governed by the number ofvinylic fluorine atoms. In contrast to their hydro-carbon analogues, fluoroolefins are attacked byelectrophiles only with difficulty [127], whichincreases with the degree of fluorination. How-ever, fluoroolefins react readily with nucleo-philes [128], [129], because as the number ofvinylic fluorine atoms increases, the p-electronsystem of the double bond is destabilized. Ther-modynamic calculations have shown that thestrength of the C – C p-bond in tetrafluoroethy-lene

CF2 ¼ CF2�.CF2 ��CF

.

2

is only ca. 160 kJ/mol as opposed to 241 kJ/molin ethylene [130]. In unsymmetrically substitut-ed fluoroolefins, the nucleophile attacks thecarbon atom that is made strongly positive bythe neighboring fluorine atoms and is shieldedonly weakly (sp2 hybridization). The reactivityof fluoroolefins toward nucleophiles increasesas follows:

CF2 ¼ CF2 < CF2 ¼ CF��CF3 < CF2 ¼ CðCF3Þ2

Fluoroolefins are slightly to highly toxic andmust be handled with care. The toxicity of fluo-rinated olefins is apparently proportional to theirreactivity toward nucleophiles [131]. Perfluoroi-sobutene, CF2¼C(CF3)2 [382-21-8], for exam-ple, is far more toxic than its lower homologues.

Physical properties of commercial fluoro- andchlorofluoroolefins are given in Table 12.

Fluoroolefins also differ from hydrogen-con-taining olefins in their marked tendency to un-dergo cycloaddition [132].

Table 11. Boiling points, melting points, and densities of iodoperfluoroalkanes

Compound CAS registry no. Formula Mr bp, �C mp, �C d4q, g/cm3 (q, �C)

Trifluoroiodomethane [2314-97-8] CF3I 195.9 � 22.5 2.3608 (� 32)

Pentafluoroiodoethane [354-64-3] CF3CF2I 245.9 12.5 � 92 2.0850 (20)

Perfluoro-1-iodopropane [27636-85-7] CF3(CF2)2I 295.9 41.2 � 95 2.0626 (20)

Perfluoro-2-iodopropane [677-69-0] CF3CFICF3 295.9 38

Perfluoro-1-iodo-n-butane [423-39-2] CF3(CF2)3I 345.9 67 � 88 2.07 (15)

Perfluoro-1-iodo-n-pentane [638-79-9] CF3(CF2)4I 395.9 94.4 � 50 2.0349 (27.8)

Perfluoro-1-iodo-n-hexane [355-43-1] CF3(CF2)5I 445.9 117 � 45 2.06 (20)

Perfluoro-1-iodo-n-heptane [335-58-0] CF3(CF2)6I 495.9 137 – 138

Perfluoro-1-iodo-n-octane [507-63-1] CF3(CF2)7I 545.9 163 20.8 2.008 (25)

Perfluoro-1-iodo-n-decane [423-62-1] CF3(CF2)9I 645.9 195 – 200 65.5 1.940 (70)

1,2-Diiodotetrafluoroethane [354-65-4] CF2ICF2I 353.8 112 2.629 (25)

1,4-Diiodooctafluoro-n-butane [375-50-8] I(CF2)4I 453.8 150 � 9.0 2.4739 (27)


Production. Fluoroolefins are produced bydehalogenation of chlorofluoro-, bromofluoro-,or iodofluoroalkanes with zinc and alcohol, bydehydrohalogenation of hydrogen-containinghaloalkanes with alcoholic alkali, or by heating.Other common methods include addition of hy-drogen halides to alkynes, decarboxylation offluorocarboxylic acid salts, and pyrolysis offluorohydrocarbons [133–135].

4.2. Tetrafluoroethylene

Properties. Tetrafluoroethylene (TFE), per-fluoroethylene, CF2¼CF2, a colorless, odorlessgas, is flammable in oxygen, producing tetra-fluoromethane and carbon dioxide. For physicalproperties, see Table 12. At low temperature inthe presence of oxygen, explosive peroxides areformed [136], [137]. Tetrafluoroethylenemust behandledwith great care since, even in the absenceof oxygen, it can decompose explosively intocarbon and tetrafluoromethane under pressureabove � 20 �C (DH ¼ � 276 kJ/mol at298 K). If the polymerization to polytetrafluor-oethylene (PTFE) (DH ¼ � 172 kJ/mol at298 K) is uncontrolled, a more strongly exother-mic decomposition reaction can occur. Polymer-ization inhibitors include dipentene [138-86-3],a-pinene [80-56-8], which are added to liquidtetrafluoroethylene during purification and stor-age (at � 30 �C) [138]. In the United States, thetransportation of liquid TFE containing stabili-zers is permitted.

In the gas phase at ca. 300 – 500 �C, tetra-fluoroethylene dimerizes to perfluorocyclobu-tane [139]. Above 600 �C, hexafluoropropylene

(see Section 4.3) and the highly toxic perfluor-oisobutene are formed [139].

Production. Many commercial processesfor the production of tetrafluoroethylene areknown, e.g., reaction of tetrafluoromethane inan electric arc [140], dechlorination of CF2Cl �CF2Cl with a metal [141], and thermal decom-position of trifluoroacetic acid [142]:

2 CF3COOH!CF2 ¼ CF2þ2 HFþ2 CO2

The two principal commercial methods arepyrolysis of trifluoromethane [143]:

and pyrolysis of chlorodifluoromethane [144]:

In the second method (Fig. 2), the chlorodi-fluoromethane gas is passed at atmospheric orreduced pressure through a heated platinum,silver, or carbon tubular reactor (a). The 28%conversion obtained under these conditions islow (yield, 83%), but can be increased to ca.65% with the same yield by adding steam [145].In modification of this method, chlorodifluoro-methane is treated with superheated steam at ca.700 �C, which results in a conversion rate of60 – 80% and a selectivity of 84 – 93% [146].The pyrolysis gas iswashedwithwater (b) to coolit and to remove HCl. After being washed withcaustic soda (c) and dried with concentratedsulfuric acid (d), the crude product can be stored

Table 12. Physical properties of fluoroolefins and chlorofluoroolefins

Property Tetrafluoro- Hexafluoro- 1,1-Difluoro- Fluoro- Chlorotri- 3,3,3-Tri-

ethylene propene ethylene ethylene fluoroethylene fluoro-

prop-1-ene

[116-14-3] [116-15-4] [75-38-7] [75-02-5] [359-29-5] [677-21-4]

Mr 100.02 150.02 64.03 46.04 116.47 96.05

bp, �C � 75.6 � 29.4 � 82 � 72.2 � 28.36 � 27

mp, �C � 142.5 � 156.2 � 144 � 160.5 � 158.2

d4q, g/cm3 (q, �C) 1.519 (� 76.3) 1.292 (� 29.4) 0.617 (23.6) 0.775 (� 30) 1.51 (� 40)

Critical temperature, �C 33.3 86.2 30.1 54.7 105.8 107

Critical pressure, MPa 3.82 2.75 4.29 5.43 3.93 4.14

Critical density, g/cm3 0.58 0.417 0.320 0.55

Heat of evaporation, 16 821 (� 75.6) 20 100 (� 29) 13 189 (� 40) 13 494 (� 20) 20 893 (� 28.4)

J/mol (t, �C)


in liquid or gaseous form (e). It is a complexmixture from which tetrafluoroethylene is sepa-rated by distillation in the presence of dipenteneor a similar stabilizer to prevent polymerization.An overhead fraction containing inert gases andtrifluoromethane is obtained in a low-boilingfractionation column (f) before isolating pureTFE (column g).

The higher-boiling fractions are processed (i)to recover unreacted CHCl2F and to isolatehexafluoropropene, a byproduct. Extractantssuch as methanol are added because of theformation of azeotropes during distillation[147]. Methanol also reacts with the toxicperfluoroisobutene, (CF3)2C¼CF2, to give anaddition product.

Uses. Currently, tetrafluoroethylene is themost important fluoroolefin; it is used mainly forthe production of fluoropolymers (! Fluoropo-lymers, Organic). It reacts with perfluoronitro-soalkanes to produce so-called nitroso rubbers[148]. Tetrafluoroethylene is also used in theproduction of low molecular mass compoundsand intermediates, e.g., for the manufacture ofiodoperfluoroalkanes (see Section 3.4).

Polytetrafluoroethylene [9002-84-0], (PTFE)is a homopolymer sold under the trade namesAlgoflon (Montefluos), Fluon (ICI), Halon (Al-lied Chemical), Hostaflon TFE (Hoechst), TeflonPTFE (DuPont), Fluon (Asahi Glass), and Poly-flon TFE (Daikin). Copolymers with fluorinatedor fluorine-free olefins or vinyl ethers are alsocommercially available.

4.3. Hexafluoropropene

Properties. Hexafluoropropene (HFP),CF3CF¼CF2, a colorless, odorless gas, is non-flammable in air at room temperature. For physi-cal properties, see Table 12. It exhibits no specialtendency toward radical homopolymerization[149], but like other fluoroolefins, it reacts readi-ly with nucleophiles [128], [129].

Liquid hexafluoropropene has unlimited stor-age life under pressure at room temperature insteel containers, even without stabilizers. Inmany countries the liquid can be transported insteel cylinders or tank cars. Hexafluoropropene istoxic (LC50 3000 ppm) and can decompose ther-mally to form highly toxic perfluoroisobutene.

Figure 2. Flow sheet for tetrafluoroethylene productiona) Pyrolysis reactor; b) Quench column (water); c)Wash column (NaOH); d) Drier (conc. H2SO4); e) Intermediate storage tankfor crude tetrafluoroethylene; f) Fractionation column for low-boiling constituents; g) Product distillation column;h) Tetrafluoroethylene storage tank; i) Fractionation column


Production. Hexafluoropropene is pro-duced commercially by temperature-controlledpyrolysis of chlorodifluoromethane (cf. produc-tion of tetrafluoroethylene, see Section 4.2)[150]. Hexafluoropropene can also be obtainedfrom tetrafluoroethylene by heating at normal orreduced pressure, preferably in the presence of aninert gas (e.g., CO2) or water vapor [151]:

Uses. An important application of hexa-fluoropropene is the production of copolymers,e.g., with tetrafluoroethylene or 1,1-difluoroethy-lene (! Fluoropolymers, Organic, Section 2.3.,! Fluoropolymers, Organic, Section 3.2.). Theversatile epoxide, hexafluoropropylene oxide[428-59-1] (see Section 6.1.2), can be obtainedfrom hexafluoropropene by oxidation.

4.4. 1,1-Difluoroethylene

vinylidene fluoride (VDF) CH2¼CF2, is a com-mercially important, partially fluorinated olefin.It is a colorless, flammable gas that undergoeshomopolymerization and copolymerization. Forphysical properties, see Table 12.

Production. Currently, three basic methodsare used for the commercial production of vinyl-idene fluoride:

1. Dechlorination of 1,2-dichloro-1,1-difluor-oethane [1649-08-7], R 132 b in the gasphase and on a metal catalyst [142], [152]:

2. Dehydrochlorination of 1-chloro-1,1-difluor-oethane [75-68-3], R 142 b [144], [153]:

In the presence of steam the temperature canbe reduced to 500 – 650 �C [154].

3. Dehydrofluorination of 1,1,1-trifluoroethane[420-46-2], R 143 a [155]:

Vinylidene fluoride is transported as a liquidin steel cylinders without stabilizers.

Uses. 1,1-Difluoroethylene is the startingmaterial for the commercially important homo-polymer poly(vinylidene fluoride) [24937-79-9],(PVDF) (! Fluoropolymers, Organic, Section2.8.).

Trade Names (PVDF). Kynar (AtochemUSA), Florafon (Atochem), Solef (Solvay), Neo-flon (Daikin), KF (Kureha Chem.), Vidar(S€uddeutsche Kalkstickstoffwerke). Worldwideannual production (1988): 7.4 � 103 t.

The copolymer with hexafluoropropene [116-15-4] is marketed as Viton (DuPont) and Fluorel(3M).

4.5. Monofluoroethylene,Monofluoroethylene

vinyl fluoride (VF), CH2¼CHF, is a colorless,highly flammable gas; up to 0.2% of polymeri-zation inhibitors are added for stabilization dur-ing transport and storage. For physical proper-ties, see Table 12.

Production. In the past, vinyl fluoride wasproduced by dehydrofluorination of 1,1-difluor-oethane [75-37-6], obtained in two steps byaddition of hydrogen fluoride to acetylene [24,p. 59 – 66], [156]:

However, with mercury catalysts, vinyl fluo-ride can be produced directly from acetylene andhydrogen fluoride [24, p. 59 – 66], [157]:

The dehydrochlorination of 1-chloro-1-fluor-oethane [1615-75-4], CHClFCH3, and 1-chloro-2-fluoroethane [762-50-5], CH2FCH2Cl, are alsoutilized commercially [158].

Uses. The main use of monofluoroethyleneis in the production of poly(vinyl fluoride)[24981-14-4] (PVF) (! Fluoropolymers,Organic,


Section 2.8.,! Fluoropolymers, Organic, Section2.9.).

Trade Names (PVF). Tedlar (DuPont),Dalbon (Diamond Shamrock, USA). Worldwideannual production (1988): 1.6 � 103 t

4.6. 3,3,3-Trifluoropropene

3,3,3-Trifluoropropene, CF3CH¼CH2 (TFP), isproduced almost exclusively by fluorination anddehalogenation of 1,1,1,3-tetrachloropropane[1070-78-6] (TCP), CCl3CH2CH2Cl. With sodi-um fluoride at 400 – 475 �C, trifluoropropene isobtained in a single step, involving chlorine –fluorine exchange and dehydrochlorination[159]. Using hydrogen fluoride and oxygen, thereaction can be carried out at 300 �C over achromium fluoride catalyst [160]. Liquid-phasefluorination of 1,1,1,3-tetrachloropropane withhydrogen fluoride in the presence of an antimonycatalyst yields 1,1,1-trifluoro-3-chloropropane,CF3CH2CH2Cl, which gives 3,3,3-trifluoropro-pene when treated with a base [161]. The con-version is effected in a single operation with amixture of hydrogen fluoride and a tertiary amine[162].

A multistep synthesis starts from vinylidenefluoride (CF2¼CH2) [163].

Uses. The main use of trifluoropropene is inthe production of fluorine-containing siliconesused in hydraulic fluids [159], [164].

4.7. 3,3,3-Trifluoro-2-(trifluoromethyl)-prop-1-ene

3,3,3-Trifluoro-1-(trifluoromethyl)prop-1-ene[382-10-5], hexafluoroisobutene, (HFIB),(CF3)2C¼CH2, is a colorless, toxic gas (4-h LC50

1700 ppm) with a bp of 14.1 �C at 101.3 kPa. Anumber of processes for its production have beendescribed; the most important use hexafluoroa-cetone [165] or perfluoroisobutene [166] as thestarting material.

Acetic anhydride can be used with hexafluor-oacetone instead of ketene. The multistep reac-tion takes place in a single operation in a copperreactor above 300 �C [167]. Presumably, pro-cesses based on the highly toxic perfluoroisobu-tene are designed to remove it as a harmfulbyproduct of tetrafluoroethylene or hexafluoro-propene production.

Hexafluoroisobutene is used for the produc-tion of fluoropolymers. The trade name of thecopolymer [34149-71-8] with vinylidene fluo-ride is CM-X (Ausimont) [168].

4.8. Chlorofluoroolefins

Among the numerous known chlorofluoroolefins[134], [134], 1,1-dichloro-2,2-difluoroethylene[79-35-6] has some importance as a startingmaterial in the production of methoxyflurane[76-38-0], an inhalation anesthetic. However,chlorotrifluoroethylene is the most importantmember of this class.

Chlorotrifluoroethylene [359-29-5](CTFE), CF2¼CFCl, a colorless, flammable gas,is less reactive than tetrafluoroethylene. Forphysical properties, see Table 12. Althoughchlorotrifluoroethylene is more stable than tetra-fluoroethylene, stabilizers such as tributylamineare used during transportation and storage in steelcylinders [169]. Chlorotrifluoroethylene is toxic.

Production. Chlorotrifluoroethylene is pro-duced commercially by dechlorination of 1,1,2-trichloro-1,2,2-trifluoroethane [76-13-1], (R 113)with zinc in methanol [170]:

An alternative route is dechlorination in thegas phase, e.g., on an aluminumfluoride – nickelphosphate catalyst; this catalyst is highly stable[171].


Uses. Chlorotrifluoroethylene is a startingmaterial for homopolymers and copolymers(PCTFE) (! Fluoropolymers, Organic, Section2.6.,! Fluoropolymers, Organic, Section 2.7.).In addition, chlorotrifluoroethylene is an inter-mediate in the production of the inhalation anes-thetic halothane. (2-Chloro-1,1,2-trifluor-oethyl)-diethylamine [357-83-5], ClFHCCF2N(C2H5)2 (an addition product of chlorotrifluor-oethylene with diethylamine), is used as a fluori-nating agent to replace hydroxyl groups in ster-oids and carbohydrates with fluorine [54], [172].Another use of chlorotrifluoroethylene is in tel-omerization with carbon tetrachloride or chloro-form. The products are stabilized with fluorine orCoF3 and are used as inert fluids, hydraulic fluids,or lubricants [104], [173].

Trade Names (PCTFE). Aclon (Allied-Signal), Daiflon (Daikin), Kel-F (3M), Voltalef(Atochem). Worldwide annual production(1988): 103 t.

5. Fluorinated Alcohols [174]

Primary and secondary alcohols that havefluorineand hydroxyl groups on the same carbon atom areunstable, and readily lose hydrogen fluoride toform carbonyl compounds. Primary and second-ary perfluoroalkoxides, however, can be preparedin polar solvents under aprotic conditions fromcarbonyl compounds and a source of ionic fluo-ride [175]; typical counterions are alkali-metal,tetraalkylammonium, or tris(dialkylamino)sulfo-nium cations. The perfluoroalkoxides are moder-ately nucleophilic and are used in situ to preparecompounds containing perfluoroalkoxy groups(see Section 6.3). Tris(dialkylamino)sulfoniumperfluoroalkoxides are unusually stable and, insome cases, have been isolated as crystallinesolids [176]. Tertiary perfluoro alcohols, e.g.,perfluoro-tert-butanol (1,1,1,3,3,3-hexafluoro-2-trifluoromethyl-2-propanol) [2378-02-1] [177]and alcohols containing CH2 groups between thefluorinated segment and the OH group are alsostable. Fluorinated alcohols are more acidic thantheir nonfluorinated analogues because fluorine ishighly electronegative (see Table 13) [178].

Short-Chain Fluoroalcohols. Of the short-chain fluorinated alcohols (C2– C4), only 2,2,2-

trifluoroethanol [75-89-8], bp 73.6 �C, and1,1,1,3,3,3-hexafluoro-2-propanol [920-66-1],bp 58.2 �C, have achieved commercial impor-tance. The former is prepared by catalytic hydro-genation of trifluoroacetamide [179], trifluoroa-cetyl chloride [180], or trifluoroacetic acid esters[181], or by reduction of trifluoroacetic acid withmetal hydrides [182]. Similar processes are usedto prepare the latter from hexafluoroacetone[183]. Because of their strong tendency to formhydrogen bonds, the fluorinated alcohols formstable complexes with hydrogen bond acceptorsand are excellent solvents for polar polymers[184]. Ethers derived from these alcohols areused as inhalation anesthetics (see Section6.3). 2-Aryl-1,1,1,3,3,3-hexafluoro-2-propanolsare prepared by alkylation of aromatic com-pounds with hexafluoroacetone [185]. Tertiarydiols, e.g., 1,3-bis(2-hydroxyhexafluoro-2-pro-pyl) benzene [802-93-7] are used to preparefluoroepoxy resins [186].

Long-Chain Fluoroalcohols. The uniquehydro- and oleophobic properties of long per-fluoroalkyl chains lead to many applications oflong-chain fluoroalcohols and their derivativesas surfactants, antisoilants, and surface-treat-ment agents [187]. Structures can be repre-sented by,

where X is typically F, H, or CH3, n is 6 – 12,and m is 1 or 2. The most important compoundsare the 1H,1H-perfluoroalcohols (X ¼ F, m ¼1), prepared by reduction of the correspondingperfluorinated carboxylic acids [188], and the1H,1H,2H,2H-perfluoroalcohols (X ¼ F, m ¼2); the latter are prepared by treatment of thecorresponding 1-iodo-1H,1H,2H,2H-perfluor-oalkanes with oleum [189]. Alcohols of theformula H(CF2)nCH2OH, where n is an even

Table 13. pKa values of alcohols [178]

Alcohol R ¼ H R ¼ F

CR3CH2OH 15.9 12.8

(CR3)2CHOH 17.1 9.3

(CR3)3COH 19.2 5.4


number, are prepared by telomerization of tet-rafluoroethylene with methanol [190].

For use as soil-repellent finishes, the long-chain fluoroalcohols are converted into deriva-tives to adjust the hydrophobicity, solubility inaqueous and organic solutions, surface retention,and stability for each specific application. Thesederivatives include esters, phosphates, carboxy-lates, and polyoxyethylenes. Polymeric alcoholsare prepared by esterification with (meth)acry-loyl chloride, followed by polymerization.

Trade Names. Teflon, Zepel, and Zonyl(DuPont), Scotchgard (3M), and Oleophobal(Chemische Fabrik Pfersee, Ciba-Geigy).

6. Fluorinated Ethers [191]

6.1. Perfluoroethers

Perfluorinated ethers are less basic than theirhydrogen-containing analogues [192]. The satu-rated aliphatic and cycloaliphatic perfluoroethersare noncombustible, and, with the exception ofthe perfluorinated epoxides, display high chemi-cal and thermal stability. Other properties of thestable ethers, such as a large difference betweenthe melting and boiling points at ambient pres-sure, and a low pour point, surface tension, anddielectric constant, are the basis of applicationssuch as dielectric and heat-exchange fluids in, forexample, high power transformers. Higher mo-lecular mass perfluoroethers are used as lubri-cants and hydraulic fluids in extreme serviceconditions, i.e., at high temperature and/or in acorrosive environment.

6.1.1. Low Molecular MassPerfluoroethers

The low molecular mass perfluoroethers are usu-ally prepared by electrochemical fluorination ofaliphatic ethers, alcohols, or carboxylic acids[193]. Typical empirical formulas are C6F12O,C7F14O, andC8F16O; these ethers often consist ofisomer mixtures. Compound FC-75 [11072-16-5] (3M), mostly perfluorobutyltetrahydrofurans,is a useful solvent that has been explored as anoxygen-transport agent in artificial blood [194].Perfluorinated ethers can also be prepared from

partially fluorinated or nonfluorinated ethers byfluorination with cobalt fluoride or elementalfluorine under carefully controlled conditions[195].

Trade Names. Fluorinert liquids (3M) andGalden fluorinated fluids (Montedison).

6.1.2. Perfluorinated Epoxides

In contrast to other perfluorinated cyclic ethers,ring strain in perfluorinated epoxides results inhigh reactivity, making them versatile precursorsto other fluorinated compounds [196]. The mostimportant is hexafluoropropylene oxide [428-59-1] (HFPO), trifluoro(trifluoromethyl)oxirane[197]. It is prepared from hexafluoropropene byreaction with elemental oxygen [198], by elec-trochemical oxidation [199], or by reaction withhypochlorites [200] or hydrogen peroxide [201]in alkaline media.

Hexafluoropropylene oxide (bp� 27.4 �C) isstable at room temperature, but decomposesabove 150 �C to form trifluoroacetyl fluoride anddifluorocarbene [202]. In the presence of strongBrønsted or Lewis acids, such as alumina oraluminum chloride, HFPO undergoes catalyticrearrangement to hexafluoroacetone, constitut-ing a convenient synthesis of this compound[203]. Most significantly, HFPO reacts readilywith nucleophiles. Attack usually occurs at thecentral carbon atom [204], resulting in formationof an acid fluoride by loss of a fluoride ion fromthe intermediate perfluoroalkoxide, which canreact further with HFPO to form higher oligo-mers. Acid fluorides are precursors to the com-mercially important perfluorovinyl ethers andhigher molecular mass perfluoroethers.

where X ¼ nucleophile, e.g., fluoride ion.Both tetrafluoroethylene oxide [694-17-7]

(TFEO), also called tetrafluorooxirane [205], andepoxides of longer chain-length perfluoroolefins[206] are known; however, the former is unstableat room temperature and rearranges to form


trifluoroacetyl fluoride, whereas the latter areprepared from inaccessible perfluoroolefins. On-ly HFPO has achieved commercial significancebecause it is used for the synthesis of hexafluor-oacetone (see Hexafluoroacetone), high molecu-lar mass perfluoroethers, Section 6.1.3, and fluo-rinated vinyl ethers (Section 6.2).

6.1.3. High Molecular MassPerfluoroethers

High molecular mass perfluorinated ethers areprepared by fluoride-catalyzed oligomerizationof HFPO [207]. The resulting terminal acidfluoride group is removed by hydrolysis anddecarboxylative fluorinationwith elemental fluo-rine. Chemically inert ethers are produced whichhave the formula,

These ethers are obtained in various molecu-lar mass and viscosity ranges by controllingoligomerization conditions or by partial distilla-tion of the oligomeric mixture. In an alternativemethod [208], perfluorinated olefins (e.g., tetra-fluoroethylene or hexafluoropropene) react pho-tochemically with oxygen to form oligomericperfluoroethers with terminal acid fluoridegroups and peroxide bonds [209]. These endgroups and the unstable peroxide linkages areeliminated by fluorination. Perfluoroethers withmolecular masses of ca. 500 – 6000 are used asinert fluids, lubricants, and hydraulic fluids inapplications that require resistance to high tem-perature or strongly corrosive environments.

Trade Names. Krytox (DuPont), Aflunox(SCM Specialty Chemicals), and Fomblin(Montedison).

6.2. Perfluorovinyl Ethers

Perfluorovinyl ethers are comonomers used inthe preparation of melt-processable perfluoro-plastics, fluorinated elastomers, and perfluoro-polymers containing functional groups [210] (!Fluoropolymers, Organic, Section 3.3.). Theethers are synthesized by reaction of a fluorinated

alkoxide generated in situ, or of other nucleo-philes with HFPO. The resulting acid fluoridesare converted to acid salts, which lose carbondioxide and metal fluoride when heated in anaprotic environment. For example, HFPO istreated with cesium trifluoromethoxide (fromcesium fluoride and carbonyl fluoride). Hydroly-sis and decarboxylation of the resulting acidfluoride gives perfluoro(methyl vinyl ether)[1187-93-5].

This compound is a comonomerwith tetrafluor-oethylene in a perfluorinated elastomer [211].

Perfluoro(propyl vinyl ether) [1623-05-8],CF3CF2CF2OCF¼CF2, prepared from the dimerof HFPO [212], is copolymerized with tetrafluor-oethylene to a melt-processable perfluoroplastic.

Perfluorovinyl ethers containing specificfunctional groups and usually two or more molesof hexafluoropropylene oxide are prepared in asimilar fashion. These compounds have the struc-ture RO(C3F6O)CF¼CF2; they are used as func-tional groups in perfluoroelastomers which canundergo a crosslinking reaction, i.e., cure-sitemonomers (R ¼ CF2CF2CN or pentafluorophe-nyl) [213] and asmonomers that provide the ionicgroups in perfluorinated ion-exchange resins(R ¼ CF2CF2SO2F, CF2CF2CF2CO2CH3, orCF2CF2CO2CH3) [214]. Synthesis of the sulfo-nyl fluoride-substituted vinyl ether is illustrative.Reaction of tetrafluoroethylene with sulfur triox-ide gives a sultone, which rearranges to fluoro-sulfonyldifluoroacetyl fluoride. The anionformed after addition of fluoride ion to this acidfluoride gives a 2 : 1 adduct with HFPO [215].Pyrolysis of the sodium salt over sodium carbon-ate gives the functional monomer [216].


Perfluorovinyl ethers can also be prepared bydeiodofluorination of iodine-containing ethers,XRfCF2OCF2CF2I, where X is hydrogen, halo-gen, CO2R, CONR2, SO2F, or PO(OR)2 (R ¼alkyl) and Rf is a perfluoroalkyl group. Initially,an organometallic derivative of the iodide isformed by reaction with metals, such as Mg, Cu,Zn, Sn, or Sb. Heating in the absence of a protonsource affords the vinyl ethers [217].

6.3. Partially Fluorinated Ethers

Partially fluorinated ethers are synthesized byseveral methods. Fluoroalkyl alkyl or fluoroalkylaryl ethers are prepared from alkoxides or phen-oxides and fluoroolefins [218]; for example,1,1,2,2-tetrafluoro-1-methoxyethane [425-88-7]is prepared from tetrafluoroethylene and sodiummethoxide – methanol. Higher perfluoroolefinscan also be employed [219]. The methyl ethersare valuable intermediates, which can be con-verted to acid fluorides with sulfur trioxide [220]or other Lewis acids [221]. Primary and second-ary perfluorinated alkoxides (seeChap. 5) are notsufficiently nucleophilic to react with fluorinatedor nonfluorinated olefins. However, they reactwith a variety of olefins in the presence of halo-gen to give ethers [222], e.g.,

Perfluoroalkoxides react with benzyl halidesto give perfluoroalkyl benzyl ethers [223].

In contrast to the physiological inertness ofperfluoroethers, some partially fluorinated ethersact as inhalation anesthetics. Many cyclic andacyclic ethers containing varying amounts offluorine, hydrogen, and sometimes other halo-gens have been evaluated as anesthetics in searchof the ideal combination of potency, volatility,lack of short- and long-term toxicity, and non-flammability [224]. Some ethers have achievedclinical significance (! Anesthetics, General,Section 2.5.).

The first fluorinated ether anesthetic to beintroduced clinically was2,2,2-trifluoro-1-viny-loxyethane [406-90-6] [trade name: Fluromar(Anaquest)] [225]. It is prepared by addition of2 mol of trifluoroethanol to acetylene, followedby thermolysis:

The flammability behavior of the compound isnot significantly better than that of nonfluori-nated anesthetics, and it behaves as a mutagenin the Ames test [226]; therefore, the compoundis not currently produced commercially.

2-Chloro-1-(difluoromethoxy)-1,1,2-trifluoro-ethane [13838-16-9] [trade name: Ethrane (Ana-quest)], which is nonflammable, is prepared bysuccessive chlorination and fluorination of thehydrocarbon ether [227]. 1-Chloro-1-(difluoro-methoxy)-2,2,2-trifluoroethane [26675-46-7][trade name: Forane (Anaquest)] is prepared in asimilar fashion [228]. Other possible anestheticsinclude 2,2-dichloro-1,1-difluoro-1-methox-yethane [76-38-0] [229] and 1,1,1,3,3,3-hexa-fluoro-2-(fluoromethoxy)propane [28523-86-6][230].

7. Fluorinated Ketones andAldehydes

The carbonyl groups in partially or perfluorinatedketones and aldehydes are electron deficientowing to the inductive effect of the highly elec-tronegative fluorine atom. Compared with theirhydrocarbon counterparts, fluorinated ketonesand aldehydes are, consequently, much morereactive toward nucleophilic reagents. Stableaddition compounds with water, alcohols, andamines are commonly formed. By contrast, fluo-rinated ketones and aldehydes are relatively un-reactive toward electrophilic reagents. An ex-treme case is hexafluoroacetone, which is notprotonated by the FSO3H – SbF5 superacid[231].

A wide variety of fluoroalkyl ketones andaldehydes has been synthesized, often by specialmethods that are unique to polyfluorinated com-pounds [232]. Of the many known examples, afew fluorinated acetones, aldehydes, and 1,3-diketones are of practical importance.

7.1. Fluoro- and Chlorofluoroacetones

Several fluoro- and chlorofluoroacetones (propa-nones) are listed in Table 14. Hexafluoroacetone


and, to a lesser extent, chloropentafluoroacetoneand sym-dichlorotetrafluoroacetone are commer-cially important. Hexafluoroacetone is manufac-tured by DuPont in the United States and byHoechst in the Federal Republic of Germany.The two chlorofluoroacetones were made in pi-lot-plant quantities by Allied in the 1960s [233],but their production has been discontinued.

Hexafluoroacetone, 1,1,1,3,3,3-hexafluoro-2-propanone, is made industrially by the vapor-phase reaction of hexachloroacetone with hydro-gen fluoride in the presence of a chromiumcatalyst [234], [235]. The rearrangement of hex-afluoropropylene oxide induced by Lewis acids[203] is an attractive new route that avoids thehighly toxic sym-dichlorotetrafluoro- and chlor-opentafluoroacetones. A convenient laboratorysynthesis uses hexafluoropropylene as a startingmaterial [236]:

Hexafluoroacetone is used mainly for themanufacture of the solvent hexafluoro-2-propa-nol and high-performance fluoropolymers. Forthe properties, chemistry, and uses of hexafluor-oacetone, see ! Acetone.

Chloropentafluoroacetone, 1-chloro-1,1,3,3,3-pentafluoro-2-propanone [trade name:5FK (Allied)] and sym-dichlorotetrafluoroace-tone, 1,3-dichloro-1,1,3,3-tetrafluoro-2-propa-none (4FK, Allied) can be made by the incom-

plete exchange of chlorine in hexachloroacetone,using hydrogen fluoride and a Cr3þ or Cr5þ

catalyst [234], [235], [237]. Their properties andchemical reactivities are similar to those of hex-afluoroacetone [238]. Like hexafluoroacetone,chloropentafluoroacetone and sym-dichlorotetra-fluoroacetone form stable, acidic hydrates andhemiacetals, e.g., CClF2COCF3� 3 H2O [34202-28-3], bp 105 �C, and CClF2COCClF2� 2 H2O[34202-29-4], bp 106 �C. The hydrates are pow-erful solvents for acetal resins and various polarpolymers [239], [240]. These chlorofluoroace-tones and some of their derivatives possess her-bicidal or fungicidal activity [241–243] and areuseful intermediates for synthesizing repellantsfor textile fibers [244], [245], specialty polycar-bonates [246], [247], and inhalation anesthetics[248].

1,1,1-Trifluoro-2-propanone can be pre-pared in quantitative yield by the acid hydro-lysis of ethyl trifluoroacetoacetate, the ethylester of 4,4,4-trifluoro-3-oxobutanoic acid[372-31-6], which is made by the alkali-pro-moted condensation of ethyl trifluoroacetatewith ethyl acetate [249]. 1,1,1-Trifluoro-2-pro-panone is easily made in the laboratory by thereaction of trifluoroacetic acid with methyl-magnesium iodide [250]. Its aryl hydrazonederivatives show nematocidal and acaricidalactivity [251].

1,1,3,3-Tetrafluoro-2-propanone is madeby the acid hydrolysis of the ethyl esterof 2,2,4,4-tetrafluoro-3-oxobutanoic acid,CHF2COCF2CO2C2H5 [249]. The ketone is usedas an intermediate in the synthesis of inhalationanesthetics [252], [253].

Table 14. Molecular masses and boiling points of fluoro- and chlorofluoropropanones

Name CAS Formula Mr bp, �Cregistry no. (101.3 kPa)

1,1,1-Trifluoro-2-propanone [421-50-1] CF3COCH3 112.05 21.5 – 22.5

1,1,3,3-Tetrafluoro-2-propanone [360-52-1] CHF2COCHF2 130.05 58

1,1,1,3,3,3-Hexafluoro-2-propanone [684-16-2] CF3COCF3 166.03 � 27.4

1-Chloro-1,1,3,3,3-pentafluoro-2-propanone [79-53-8] CClF2COCF3 182.48 7.8

1,3-Dichloro-1,1,3,3-tetrafluoro-2-propanone [127-21-9] CClF2COCClF2 198.93 45.2

1,1,3-Trichloro-1,3,3-trifluoro-2-propanone [79-52-7] CCl2FCOCClF2 215.38 84.5

1,1,3,3-Tetrachloro-1,3-difluoro-2-propanone [79-51-6] CCl2FCOCCl2F 231.83 123.9

1,1,1,3,3-Pentachloro-3-fluoro-2-propanone [2378-08-7] CCl3COCCl2F 248.28 163.7

1,1,1,3,3,3-Hexachloro-2-propanone [116-16-5] CCl3COCCl3 264.73 203.6


7.2. Perhaloacetaldehydes

Perchlorfluoroacetaldehydes. Some phys-ical properties of the perchlorofluoroacetalde-hydes are shown in Table 15. Their chemicalreactivities are similar to those of the per-chlorofluoroacetones.

Chlorodifluoroacetaldehyde and dichloro-fluoroacetaldehyde can be prepared by the lithiumaluminumhydride reduction of the correspondingmethyl chlorofluoroacetates [254], [255].

Trifluoroacetaldehyde (fluoral) and someof its derivatives have found practical importanceas monomers and intermediates for biologicallyactive compounds.

Properties. Trifluoroacetaldehyde is a col-orless gas at ambient temperature and pressure.Like hexafluoroacetone, it reacts with water toform a stable, solid hydrate – 1,1-dihydroxy-2,2,2-trifluoroethane [421-53-4], CF3CH(OH)2,mp 69 – 70 �C. It reacts in a manner similar tohexafluoroacetone with alcohols to give stablehemiacetals: 2,2,2-trifluoro-1-methoxyethanol[431-46-9], CF3CH(OH)OCH3, bp 96 –96.5 �C; and 2,2,2-trifluoro-1-ethoxyethanol[433-27-2], CF3CH(OH)OC2H5, bp 104 –105 �C (99.3 kPa). Unlike hexafluoroacetone, itreadily homopolymerizes upon cationic, anionic,or free-radical initiation [254], [255].

Production. Several laboratory syntheses oftrifluoroacetaldehyde have been developed, in-cluding reduction of trifluoroacetic acid and itsalkyl esters, trifluoroacetic anhydride, and trifluor-oacetyl chloride [256]. Trifluoroacetaldehyde canbemanufactured on a large scale by the reaction oftrichloroacetaldehyde (chloral) with hydrogenfluoride in the presence of chromium catalysts[235]. The product is a CF3CHO � HF complex,bp 38 �C (133.3 kPa), which requires treatmentwith a hydrogen fluoride acceptor (e.g., sodium

fluoride) to give free trifluoroacetaldehyde.Hydro-lysis of the inhalation anesthetic Halothane,CF3CHBrCl, by a mixture of 65% oleum, mercu-ric oxide, and silver oxide also produces trifluor-oacetaldehyde in high yield [257].

Trifluoroacetaldehyde is commercially avail-able as its hydrate or methyl and ethyl hemiace-tals, which liberate the pure aldehyde in polypho-sphoric acid at 150 – 180 �C. AHoechst processfor the manufacture of its hemiacetals involvestreating the product from the gas-phase fluorina-tion of chloral with tetraalkoxyl silanes, or withalcohols and silicon tetrachloride. This processavoids the need to isolate or handle free trifluor-oacetaldehyde [258], [259].

Uses of Perhaloacetaldehydes. Certainoximes [260] and hydrazones [251] of trifluor-oacetaldehyde have insecticidal or acaricidalactivity. Its hemiacetal, 2,2,2-trifluoro-1-meth-oxyethanol, has been used as a starting materialfor the preparation of fluoroether inhalation an-esthetics [261] (see Section 6.3), including iso-flurane, CF3CHClOCHF2 [262], and its isomerCF3CHFOCHClF [263], [264].

The stereoregularity of perchlorofluoroacetal-dehyde polymerizations has been an area ofactive research, although no commercial uses ofthe polymers have yet appeared.

Trifluoroacetaldehyde can be homopolymer-ized to give insoluble crystalline, or soluble,amorphous, polyoxymethylene polymers de-pending upon the polymerization conditions[254], [255]. This is in contrast with trichloroa-cetaldehyde which can only be polymerized toa crystalline, apparently isotactic polymer.Copolymers of perhaloacetaldehydes have beenprepared [254], [255].

Table 15. Molecular mass and boiling points of perchlorofluoroacetaldehydes

Name Formula Mr CAS registry no. bp, �C (101.3 kPa)

Trichloroacetaldehyde CCl3CHO 147.38 [75-87-6] 97.8

Dichlorofluoroacetaldehyde CCl2FCHO 130.93 [63034-44-6] 56

Chlorodifluoroacetaldehyde CClF2CHO 114.48 [811-96-1] 17.8

Trifluoroacetaldehyde CF3CHO 98.03 [75-90-1] � 18 to � 19a

*At 99.7 kPa


7.3. Fluorinated 1,3-Diketones

Fluorinated 1,3-diketones in which the two car-bonyl groups are separated by a methylene ormethine group form complexes with a widevariety of metal ions. This property is the basisof their utility in chromatographic analysis ofmetals, laser technology, NMR spectroscopy,and hydrometallurgical separations. The proper-ties, preparation, and uses of fluorinated 1,3-diketones and theirmetal complexes have beenextensively reviewed [265–267].

Properties and Production. Some physicalproperties of the industrially important fluorinat-ed 1,3-diketones are shown in Table 16. Thesecompounds are considerably more acidic thantheir nonfluorinated analogues, i.e., 1,3-pentane-

dione [123-54-6], CH3COCH2COCH3 (pKa ¼8.9), CF3COCH2COCH3 (pKa ¼ 6.7), andCF3COCH2COCF3 (pKa ¼ 4.6) [267]. Fluori-nated 1,3-diketones have a high enolic content,typically 92 – 100%, in comparison with ca.80% for 1,3-pentanedione. Their enolic protonscan be readily replaced bymetals ormetal salts toform 1,3-diketonates of the type

Fluorinated 1,3-diketones form hydrates withwater and hemiketals with shorter alcohols. Theyare usually obtained by aClaisen condensation of

Table 16. Molecular masses and boiling points of fluorinated 1,3-diketones

Name CAS Formula Mr bp, �C (kPa)

registry no.

1,1,1-Trifluoro-2,4-

pentanedione

[367-57-7] CF3COCH2COCH3 154.09 105 – 107 (101.3)

1,1,1,5,5,5-Hexafluoro-

2,4-pentanedione

[1522-22-1] CF3COCH2COCF3 208.06 70 – 71 (101.3)

1,1,1-Trifluoro-5,5-di-

methyl-2,4-hexanedione

[22767-90-4] CF3COCH2COC(CH3)3 196.17 138 – 141 (101.3)

1,1,1,2,2,3,3-Hepta-

fluoro-7,7-dimethyl-4,6-

octanedione

[17587-22-3] CF3CF2CF2COCH2COC(CH3)3 296.19 46 – 47 (0.67)

4,4,4-Trifluoro-1-phenyl-

1,3-butanedione

[326-06-7] 216.16 224 (101.3)a

4,4,4-Trifluoro-1-(2-thie-

nyl)-1,3-butanedione

[326-91-0] 222.18 96 – 98 (1.07)b

3-(Trifluoroacetyl)cam-

phor, 1,7,7-trimethyl-3-

(trifluoroacetyl)-bicyclo

[2.2.1]heptan-2-one

[51800-98-7] 248.25 100 – 101 (2.13)

3-(Heptafluorobutyryl)

camphor, 3-

(2,2,3,3,4,4,4-hepta-

fluoro-1-oxo-butyl)-bicy-

clo[2.2.1]heptan-2-one

[51800-99-8] 348.26 60 – 70 (0.03)

amp 38 – 40 �C.bmp 42 – 43 �C.


a fluorinated carboxylic acid ester with a ketone,using a strong base such as a sodium alkoxide orsodium hydride.

Uses. The1,3-diketonesRCOCH2COR0 (R¼

CF3, n-C3F7 and R0 ¼ t-C4H9, CF3) that formvolatile, thermally and hydrolytically stable com-plexes are useful for liquid or gas chromatographicanalysis of metals. These diketones, especially1,1,1,2,2,3,3-heptafluoro-7,7-dimethyl-4,6-octa-nedione are widely used for the extraction ofmetalions from aqueous solutions at variable pH [268].

4,4,4-Trifluoromethyl- 1-(2-thienyl)-1,3-bu-tanedione is especially suited for the analysis ofuranium and other radioactive elements. Thetetrakis-chelates of 4,4,4-trifluoro-1-phenyl-1,3-butanedione with rare-earth elements arepotential laser materials.

The paramagnetic lanthanide complexes ofheptafluoro-7,7-dimethyl-4,6-octanedione havegained considerable importance as NMR shiftreagents for simplifying the interpretation ofcomplex NMR spectra [269]; the europium com-plex is the most widely used.

The chiral-shift reagents derived from 3-hep-tafluorobutyryl-(þ)- or -(�)-camphor and 3-tri-fluoroacetyl-(þ)- or -(�)-camphor are very use-ful for the NMR assay of enantiomeric purity insolution [269].

8. Fluorinated Carboxylic Acids andFluorinated Alkanesulfonic Acids

8.1. Fluorinated Carboxylic Acids

8.1.1. Fluorinated Acetic Acids

Fluorination increases the strength of acetic acidas seen in the pKa values of monofluoroacetic

acid (2.66), difluoroacetic acid (1.24), and tri-fluoroacetic acid (0.23) compared to the pKa of4.74 for acetic acid [270].

Production. Trifluoroacetic acid has beenprepared by the electrochemical fluorination ofacetyl chloride or acetic anhydride in anhydroushydrogen fluoride using the Simons process (Sec-tion 2.1) followed by hydrolysis of the resultingtrifluoroacetyl fluoride. The yield is excellent(> 90%) [271], [272]. The Phillips Petroleumelectrochemical process (Section 2.1) employsacetyl fluoride as feed to produce trifluoroacetylfluoride along with mono and difluoroacetyl fluo-ride [273]. Sulfur trioxide treatment of CF3CCl3,obtained by isomerization of Freon 113,CF2ClCFCl2, yields CF3COCl [274]. The acid ispurified by hydrolysis of the acyl halide withalkali, followed by acidification and distillation.

Uses. Most uses of fluorinated acetic acidsare confined to trifluoroacetic acid, its anhydride,and its derivative, 1,1,1-trifluoroethanol. Mono-fluoroacetic acid derivatives (salts, esters,amides, and alcohols) are toxic because they aremetabolized to fluorocitric acid which inhibitsrespiration (see Section 13.5) [275]. w-Fluoroacids of the formula F(CH2)nCOOH, where n isan odd number, are extremely toxic, because ofdegradation in vivo tomonofluoroacetic acid andfinally to fluorocitric acid [275]. Sodium mono-fluoroacetate has been used as a rodenticide, butis now banned.

8.1.2. Long-Chain PerfluorocarboxylicAcids

Properties. The boiling points and densitiesof straight-chain perfluorocarboxylic acids areshown in Table 17.

Production. Long-chain perfluorocarbo-xylic acids are prepared by the Simons electro-chemical fluorination (see Section 2.1.) of thecorresponding acyl halide:

The acids are obtained by hydrolysis of theperfluoroacyl fluoride, followed by distillation.Some carbon – carbon bond scission occurs to


form lower homologous acids along with inertfluorocarbons and cyclic ethers. The acid yielddecreases with increasing chain length; for ex-ample, perfluorobutyric acid yields are ca. 36%compared to ca. 20% for the industrially impor-tant perfluorooctanoic acid [271], [272]. Trifluor-oacetic acid is also prepared by the Phillipselectrochemical method, employing a KF � HFmolten salt electrolyte [273]. Acids with higherboiling points are not easily or efficiently pre-pared by the Phillips process.

Perfluorocarboxylic acids are also preparedby nonelectrochemical methods. Treatment ofperfluoroalkyl iodides (RfI) with sulfur trioxide[276] or chlorosulfonic acid [277] gives thecarboxylic acid in good yield. Another methodemploys fuming sulfuric acid (oleum) [278].Another process involves the preparation of per-fluorotetrahydroalkyl iodides, RfCH2CH2I, ob-tained by the free-radical addition of ethylene toperfluoroalkyl iodides, followed by dehydroio-dination and oxidation by dichromate [279] orozonolysis [280]:

This process produces carboxylic acids hav-ing one more carbon atom than the startingperfluoroalkyl iodide, in contrast to the electro-chemical and oleum routes, which produceacids containing the same number of carbonatoms as the original acyl halide or telomericiodide. In all processes utilizing fluorinatediodine-containing telomers, it is important tofind uses for the telomers and to recover theexpensive iodine.

Polyfluoroalkoxyacyl fluorides of the type

are prepared by the addition of perfluoroacylfluorides and hexafluoropropylene oxide cata-lyzed by alkali-metal fluorides [281]. Acids,salts, or esters are obtained by hydrolysis, neu-tralization, or esterification, respectively.

Addition reactions of perfluorodiacyl fluor-ides with hexafluoropropylene oxide [282] giveether-containing diacyl fluorides, such as

where n is usually 2 – 4, and at least two units arederived from hexafluoropropylene oxide (i.e.,m � 2) [282]. The addition reaction may occurat one or both acyl groups of the starting diacylfluoride. Selectivity can be maintained by esteri-fying one of the acyl fluoride groups. Thus,CH3OCO(CF2)2COF, prepared by addition ofmethanol to perfluoro-g-butyrolactone or per-fluorosuccinyl fluoride, reacts with hexafluoro-propylene oxide to give ester acyl fluorides of theformula

[283], [284]. The acyl halides are converted toacids or salts by hydrolysis or neutralization,respectively.

Uses. Long-chain perfluoroalkanecarboxylicacids and their salts are surface-active chemicals(surfactants), which greatly reduce the surface

Table 17. Boiling points and densities of perfluorocarboxylic acids

Acid CAS registry no. Formula bp, �C (kPa) d204 , g/cm3

Perfluoroacetic [76-05-1] CF3CO2H 72.4 1.489

Perfluoropropionic [422-64-0] C2F5CO2H 96 1.561

Perfluorobutyric [375-22-4] C3F7CO2H 120 1.651

Perfluorovaleric [2706-90-3] C4F9CO2H 130

Perfluorocaproic [307-24-4] C5F11CO2H 157 1.762

Perfluoroheptanoic [375-85-9] C6F13CO2H 175 1.792

Perfluorocaprylic [335-67-1] C7F15CO2H 189

Perfluorononanoic [375-95-1] C8F17CO2H 110 (2.1)

Perfluorocapric [335-76-2] C9F19CO2H 121 (2.0

Perfluoroundecanoic [2058-94-8] C10F21CO2H 245

Perfluorododecanoic [307-55-1] C11F23CO2H 270


tension (surface energy) of water, aqueous solu-tions, and organic liquids even at low concentra-tions. These acids (C6– C12) and derivatives areused as wetting, dispersing, emulsifying, andfoaming agents.

Ammonium perfluorooctanoate (FC-143,3M) is used as an emulsifier in the polymerizationof fluorinated monomers, especially tetrafluor-oethylene. It has exceptional chemical stabilityand lowers the surface tension of water to ca.3 mN � m at 0.5 wt %. In contrast with hydrocar-bon emulsifiers, ammonium perfluorooctanoatedoes not interfere with the emulsion polymeriza-tion of tetrafluoroethylene.

Trade Names. Fluorad FC-26, 126, 143(3M), Fluorowet CP (Hoechst), RM 350, 370(Rimar), and Surflon S-111P (Asahi Glass).

8.1.3. Fluorinated Dicarboxylic Acids

Properties. The boiling points and densitiesof perfluorodicarboxylic acids are shown in Ta-ble 18.

Production. a,w-Perfluoroalkanedicarbo-xylic acids are prepared by the electrochemicalmethod, followed by hydrolysis, acidification,and extraction. Other methods include the oxi-dation of the appropriate chlorofluoroolefin orperfluoroolefin. Perfluoroglutaric acid is pre-pared from hexachlorocyclopentadiene by halo-gen exchange, followed by oxidation and acidi-fication [285]. Perfluoroadipic acid is preparedby an analogous method from hexachloroben-zene [286]. The cyclic anhydrides from perfluor-osuccinic and perfluoroglutaric acid are preparedby dehydration of the acids with phosphoruspentoxide. They are used to prepare the corre-sponding alcohols by reduction.

8.1.4. Tetrafluoroethylene – PerfluorovinylEther Copolymers with Carboxylic AcidGroups

Ion-exchange membranes, used in fuel cells andchloralkali production, are copolymers of tetra-fluoroethylene and perfluorovinyl ethers thatcontain esters or other acid precursor groups[287]. These membranes have excellent thermaland chemical resistance to hot concentratedalkali (up to 40%).

Production. The vinyl ethers are preparedby the reaction of hexafluoropropylene oxide andmethyl-3-fluorocarbonyl perfluoropropionate[285], followed by pyrolysis to give:,

Copolymerization with tetrafluoroethylenefollowed by saponification produces a polymerwith terminal carboxylic acid groups.

Trade Names. Flemion (Asahi Glass), Na-fion (DuPont), Neosepta (Tokuyama Soda), andAciplex (Asahi Chemical).

8.2. Fluorinated Alkanesulfonic Acids

8.2.1. Perfluoroalkanesulfonic Acids

Properties. The first member of the series,trifluoromethanesulfonic acid, was reported in1954 [288]. Perfluoroalkanesulfonic acids areamong the strongest acids known. Conductivitymeasurements in acetic acid show that the acidstrength of trifluoromethanesulfonic acid is com-parable to that of fluorosulfonic and perchloricacids [289]. Boiling points are listed in Table 19.Because of their ability to lower surface energy,

Table 18. Physical properties of perfluorodicarboxylic acids

Acid CAS registry no. Formula mp, �C bp, �C (kPa)

Perfluoromalonic [1514-85-8] CF2(CO2H)2 117 – 118

Perfluorosuccinic [377-38-8] (CF2)2(CO2H)2 86 – 87 150 (2.0)

Perfluoroglutaric [376-73-8] (CF2)3(CO2H)2 88 134 – 138 (0.4)

Perfluoroadipic [336-08-3] (CF2)4(CO2H)2 132 – 134 138 (0.5)

Perfluorosuberic [678-45-5] (CF2)6(CO2H)2 154 – 158


the longer-chain perfluoroalkanesulfonic acidsand sulfonyl fluoride derivatives have foundutility as surface-active agents and water repel-lents and for antisoiling treatment of textiles andfabrics.

Production. Perfluoroalkanesulfonyl fluor-ides are usually made by the Simons electro-chemical fluorination process (see Section 2.1),in which a hydrocarbon sulfonyl fluoride is elec-trolyzed in anhydrous hydrogen fluoride at nickelelectrodes:

The electrochemical yield is excellent for thefirst member of the series and decreases progres-sively with the increasing length of the carbonchain; the yield for octanesulfonyl fluoride is ca.40% [271], [290]. Alkaline hydrolysis of per-fluoroalkanesulfonyl fluorides gives the corre-sponding salts, which when acidified and dis-tilled from concentrated sulfuric acid yield theanhydrous sulfonic acids [288].

A nonelectrochemical method for the prepa-ration of trifluoromethanesulfonic acid deriva-tives is shown below:

Alkaline hydrolysis, followed by acidificationof the sulfonate salt, gives the acid [291].

Uses. Short-chain perfluoroalkanesulfonylfluorides are used to prepare sulfonamides,whichare employed as plant growth regulators andherbicides. Trifluoromethanesulfonic acid isused as an esterification catalyst (FC-24, 3M),and the lithium salt has been investigated as a fuelcell and battery electrolyte (FC-124, 3M). Per-fluorobutanesulfonate salts are used as antistatic

agents [292], [293]. The higher homologuesexhibit good surfactant properties; the deriva-tives of perfluorohexanesulfonyl fluoride areemployed in fire extinguishing formulations.Useful derivatives containing the sulfonamidogroup can be prepared by reaction of the sulfonylfluoride with a diamine, followed by quaterniza-tion with alkylating agents such as methyl iodideto give a cationic surfactant. As an example,reaction of perfluorohexanesulfonyl fluoridewith 3-dimethylaminopropylamine gives

The properties related to the low surface energyof the perfluorooctanesulfonyl fluoride,C8F17SO2F, areutilized inmanyderivatives.Thesederivatives include alcohols and their acrylate andmethacrylate esters; they are used as comonomersin polymers that impart oil-, water-, and soil-repellent properties to porous substrates such aspaper and textiles [294], [295]. A typical reactionsequence for the synthesis of a perfluoroalkane-sulfonamide acrylate monomer is shown below:

Perfluoroalkanesulfonamido alcohols are alsoused as mold-release agents. Esterification withphosphoric acid gives phosphate ester salts of thetype

which are useful oil repellents for paper products[296].

Trade Names. Paper Treatment FC-807,808 (3M), Textile Treatment Dic-Guard (Dai-nippon Ink), and Scotchgard (3M).

8.2.2. Fluorinated Alkanedisulfonic Acids

a,w-Perfluoroalkanedisulfonyl fluorides areprepared by the electrochemical fluorination of

Table 19. Boiling points of perfluoroalkanesulfonic acids

Acid Formula CAS registry no. bp, �C (kPa)

CF3SO3H [1493-13-6] 60 (0.4)

C2F5SO3H [354-88-1] 81 (0.29)

n-C4F9SO3H [59933-66-3] 76 – 84 (0.13)

n-C5F11SO3H [3872-25-1] 110 (0.67)*

n-C6F13SO3H [355-46-4] 95 (0.46)

n-C8F17SO3H [1763-23-1] 133 (0.8)

* n-C5F11SO3H � H2O


hydrocarbon disulfonyl fluorides. The corre-sponding acids are prepared by alkaline hydro-lysis of the fluoride and acidification, or byaqueous permanganate oxidation of the disul-fone, CH3SO2(CF2CF2)nSO2CH3 [297]. Distilla-tion of the acids from phosphorus pentoxideyields the cyclic anhydrides [298].

8.2.3. Tetrafluoroethylene – PerfluorovinylEther Copolymers with Sulfonic AcidGroups

Ion-exchange membranes are prepared by thecopolymerization of tetrafluoroethylene withperfluorovinyl ethers containing sulfonyl halidegroups, followed by hydrolysis to yield sulfonicacids. Thesemembranes have excellent chemicaland thermal properties similar to those of ion-exchange membranes with terminal carboxylicacid groups (see Section 8.1.4) [299–301].

Production. These ethers are prepared bythe condensation of hexafluoropropylene oxidewith fluorosulfonyldifluoroacetyl fluoride,FSO2CF2COF, which is prepared from C2F4 andSO3, followed by isomerization [302], [303].Condensation of hexafluoropropylene oxidewithg-fluorosulfonylperfluoroalkyl carbonyl fluor-ides, FSO2(CF2)nCOF (prepared by electro-chemical fluorination of the respective aliphaticsulfone [304], [305]) gives perfluoroether fluor-osulfonyl acyl fluorides, e.g., [306]

Subsequent conversion to the vinyl ether

followed by copolymerization with tetrafluor-oethylene gives polymers with fluorosulfonylside chains, which are hydrolyzed to sulfonategroup side-chains [307].

9. Fluorinated Tertiary Amines

Physical Properties. Relative to their mo-lecular mass, perfluoroalkyl-tert-amines, like theperfluoroethers, have low boiling points and lowfreezing or pour points, as shown in Table 20.Low polarity and weak intermolecular forces areresponsible for other unusually low values forproperties such as viscosity, solubility, heat ofvaporization, refractive index, dielectric con-stant, and surface tension [308]. Some perfluor-obis(dialkylaminoalkyl) ethers have even lowerpour points and liquid ranges as broad as 250 �C.These ethers exhibit increased internal flexibilitythrough the combined effect of the nitrogen andoxygen atoms [311].

Chemical Properties. Perfluorinated tert-amines are chemically inert and thermally stable[308], [312]. The electron-withdrawing nature ofthe perfluoroalkyl substituents deprives the ni-trogen atom of its basic character and reactivity.Fluorinated tert-amines do not form salts orcomplexes with strong acids and are not attackedby most oxidizing or reducing agents. Withaluminum chloride they form chlorinated imines[313]. Because of their nonpolar nature, fluori-nated tert-amines are poor solvents and are im-miscible with water and alcohols [308]. Gasessuch as oxygen, nitrogen, and carbon dioxidehave unusually high solubility in perfluorinatedtert-amines. For example, perfluorotributyla-mine dissolves 40 vol % of oxygen at ambientconditions and has been used in artificial blood asan effective oxygen-transport medium [313].

Table 20. Physical properties of fluorinated tert-amines [308–310]

Compound CAS registry no. Formula Mr bp, �C Pour point, �C d254

Perfluorotrimethylamine [432-03-1] N(CF3)3 221 �11

Perfluorotriethylamine [359-70-6] N(C2F5)3 371 69 1.74

Perfluorotripropylamine [338-83-0] N(C3F7)3 521 130 � 52 1.82

Perfluorotributylamine [311-89-7] N(C4F9)3 671 178 � 50 1.88

Perfluorotriamylamine [338-84-1] N(C5F11)3 821 215 � 25 1.93

Perfluorotrihexylamine [432-08-6] N(C6F13)3 971 256 33* 1.90**

*Freezing point.**d354


Production. Electrochemical fluorinationvia the Simons process (see Section 2.1) is thepreferred route to fluorinated tertiary alkyla-mines. The hydrogen atoms are completely re-placed by fluorine atoms. Perfluorotributyla-mine, for example, is synthesized as follows:,

The crude product contains a significantamount of perfluorinated isomers and cleavageproducts because of molecular rearrangementduring electrolysis; it is purified by fractionaldistillation and treatment with base.

Uses. The combination of unusual physicaland chemical properties, excellent dielectricproperties, nonflammability, and lack of toxicitymake the perfluorinated tert-amines useful formany fluid applications that involve direct con-tact with sensitive materials [308], [313]. Theelectronic industry relies heavily on these fluidsin reliability testing of electronic components, asdirect-contact coolants for integrated circuits,and as heating media in vapor-phase reflowsoldering. Perfluorinated tributylamine, triamy-lamine, and trihexylamine are the main consti-tuents of Fluorinert electronic liquids FC-43, FC-70, and FC-71 (3M).

Information on the preparation and utility ofother nitrogen-containing fluoroaliphatic com-pounds can be found in the general references[1–15].

10. Aromatic Compounds withFluorinated Side-Chains

The first aromatic compound with a fluorinatedside-chain, benzotrifluoride [98-08-8], trifluoro-methylbenzene, was synthesized in 1898 [314].

The perfluoroalkyl substituents of aromatic com-pounds are meta-directing; this influence can, ofcause, be overcome by a stronger ortho- or para-directing substituent. These compounds are usu-ally prepared from iodoperfluoroalkanes and ha-logenated aromatic compounds in the presence ofa copper catalyst [315–317]. Except for the ben-zotrifluorides, aromatic compounds with fluori-nated side-chains have only scientific interest[318]. Araliphatic compounds with one or twotrifluoromethyl substituents on the benzene ringgained commercial importance in the early 1930sfor two reasons: 1) the recognition of the advan-tageous properties of aromatic dyes with CF3substituents, and 2) the development of an eco-nomical production process [4]. Since then, theirimportance in the production of dyes, pharma-ceuticals, and pesticides has increased.

10.1. Properties

The physical properties of benzotrifluorides areshown in Table 21.

If no other substituents are present in thebenzene ring, the trifluoromethyl group is ther-mally stable up to 350 �C and resistant to basesup to 130 �C. It is inert toward reducing agents[319], [320] and inhibits oxidation of the benzenering. However, in the presence of aluminumchloride the trifluoromethyl group undergoeschlorolysis to produce a trichloromethyl group[321], and acid hydrolysis forms a carboxy group[322]. Substituents such as amino or hydroxylgroups destabilize the trifluoromethyl group[323].

The characteristic reaction of benzotrifluor-ides is electrophilic substitution of the benzenering; chlorination and nitration are commerciallyimportant. Chlorination of benzotrifluoride at65 �C with FeCl3 as a catalyst yields 83%

Table 21. Physical properties of benzotrifluorides

Compound CAS registry Empirical Mr bp, �C d4q (q, �C) nD

q (q, �C)number formula

Benzotrifluoride [98-08-8] C7H5F3 146.11 102.03 1.188 (20) 1.4114 (25)

2-Chlorobenzotrifluoride [88-16-4] C7H4ClF3 180.56 152.5 1.367 (20) 1.4550 (20)

4-Chlorobenzotrifluoride [98-56-6] C7H4ClF3 180.56 140 1.35 (15) 1.4444 (25)

2,4-Dichlorobenzotrifluoride [320-60-5] C7H3Cl2F3 215.0 117 – 118 1.377 (20) 1.4802 (20)

1,3-Bis(trifluoromethyl)benzene [402-31-3] C8H4F6 214.11 116.1 1.379 (25) 1.3791 (20)

1,4-Bis(trifluoromethyl)benzene [433-19-2] C8H4F6 214.11 117.1 1.381 (25) 1.3792 (20)

3-Trifluoromethylbenzoyl fluoride [328-99-4] C8H4F4O 192.11 159 – 163 1.4350 (20)


3-chlorobenzotrifluoride [98-15-7] [324]; chlo-rination of 4-chlorobenzotrifluoride gives 3,4-dichlorobenzotrifluoride [328-84-7].Nitration ofbenzotrifluoride results in a 6 : 3 : 91 mixture of2-nitro- [384-22-5], 4-nitro- [402-54-0], and 3-nitrobenzotrifluoride [98-46-4] [325]. Othercommercially important nitrations are the con-version of 2-chlorobenzotrifluoride [88-16-4] to2-chloro-5-nitrobenzotrifluoride [777-37-7] andthe conversion of 4-chlorobenzotrifluoride toyield 99% 4-chloro-3-nitrobenzotrifluoride[121-17-5] or 4-chloro-3,5-dinitrobenzotrifluor-ide [393-75-9] [326]. These derivatives are re-duced to amines or are further processed.

10.2. Production

Benzotrifluorides are prepared on a laboratoryscale by the reaction of aromatic compoundswithiodotrifluoromethane [315]; by the reaction ofaromatic carboxylic acids and their derivativeswith sulfur tetrafluoride [51–53]; or by chlo-rine – fluorine exchange in trichloromethyl aro-matic compounds with metal fluorides [327].

In the commercial process, known since 1931,chlorine is exchanged for fluorine with use ofanhydrous hydrogen fluoride in the presence orabsence of catalyst [328]:

This reaction can be carried out as a batchprocess in autoclaves or continuously in a seriesof autoclaves [329] (Fig. 3) or tubular reactors[330]. Typical conditions for the production ofbenzotrifluoride are a temperature of 80 –110 �C, pressure of 1.2 – 1.4 MPa, and a molarratio of HF : benzotrichloride of 4 : 1. A yield of70% is obtained within 3 – 4 h [331]. In contin-uous processing, a yield of over 90% is obtainedin a nickel flow tube with a residence time of 1 hat 90 – 130 �C and at 3 – 5 MPa [332]. Yieldsare increased by using additives such as hexam-ethylenetetraamine [333] or by employing chlo-rine – fluorine exchange in the gas phase in thepresence of a transition metal – aluminum oxidecatalyst [334]. Corrosion is reduced by loweringthe reaction temperature (< 60 �C) and addingiron or iron compounds [335], [336].

Thismethod isused toproducebenzotrifluoride,2-chlorobenzotrifluoride, 4-chlorobenzotrifluor-ide, 2,4-dichlorobenzotrifluoride, 1,3-bis(trifluoro-methyl)benzene, 1,4-bis(trifluoromethyl)benzene,3-(trifluoromethyl)benzoyl fluoride, and 4-(tri-fluoromethyl)benzoyl fluoride [368-94-5] from thecorresponding trichloromethyl compounds.

Figure 3. Production of benzotrifluorides in a series of autoclaves [329]a) Reactor; b) Pressure distillation column; c) Separator; d) Product distillation column; e) Product storage tank


The trifluoromethyl group can also be intro-duced into aromatic compounds by the Friedel –Crafts reaction with carbon tetrachloride in thepresence of hydrogen fluoride [337].

10.3. Uses

Benzotrifluoride and 4-chlorobenzotrifluorideare key intermediates for the synthesis of dyes,pharmaceuticals, and pesticides.

Dyes. Trifluoromethyl aromatic compoundswere first used in dyes [4] and are still importantintermediates for azo, anthraquinone, and triphe-nylmethane dyes. The strongly electronegativetrifluoromethyl group improves color clarity andfastness to light and washing; it also shifts lightabsorption to the visible and ultraviolet ranges.

Some of these dye intermediates [338] for theproduction of anthraquinone and azo dyes(Naphtol AS, Hoechst AG) and azo pigmentsare still used, especially for polyesters and poly-amides. These compounds include 2-aminoben-zotrifluoride [88-17-5] for C.I. Pigment Yellow154 [63661-02-9]; 3-amino-4-chlorobenzotri-fluoride [121-50-6] for C.I. Pigment Orange 60[68399-99-5]; 3-(trifluoromethyl)benzoyl fluo-ride for Indanthren Blue CLB [6492-78-0](BASF) as well as 2-amino-5-chlorobenzotri-fluoride [445-03-4], 3,5-bis(trifluoromethyl)ani-line [328-74-5], and 3-amino-4-ethylsulfonyl-benzotrifluoride [382-85-4].

Pharmaceuticals. The trifluoromethyl sub-stituent is highly lipophilic; it increases the lipidsolubility of pharmaceuticals and thus acceler-ates their absorption and transport in a livingorganism [339], [340]. In some cases, introduc-tion of the CF3 group also increases drug effec-tiveness and reduces undesirable side effects;therefore, benzotrifluorides are used in thesynthesis of many pharmaceuticals [341]. Theseinclude the analgesics flufenamic acid [530-78-9] and niflumic acid [4394-00-7], the antidepres-

sant fluoxetine [54910-89-3], themuscle relaxantflumetramide [7125-73-7], the appetite depres-sants fenfluramine [458-24-2] and fludorex[15221-81-5], and the tranquilizers trifluproma-zine [146-54-3] and fluphenazine [69-23-8].Bendroflumethiazide [73-48-3] is an effectivediuretic and antihypertensive agent.

Pesticides. Benzotrifluorides are also im-portant in the production of pesticides [342]. Thekey intermediate, 4-chloro-3,5-dinitrobenzotri-fluoride [393-75-9], is obtained by dinitration of4-chlorobenzotrifluoride. Reaction with second-ary amines gives trifluralin [1582-09-8], proflur-alin [26399-36-0], and benfluralin [1861-40-1].4-Chlorobenzotrifluoride and 3,4-dichlo-roben-zotrifluoride are intermediates for herbicideswith a diphenyl ether structure – fluorodifen[15457-05-3] and acifluorfen [50594-66-6] andthe insecticide fluvalinate [69409-94-5]. 3-Ami-nobenzotrifluoride [98-16-8] is obtained frombenzotrifluoride by nitration and hydrogenation.It is used to make the selective herbicide fluo-meturon [2164-17-2] or is used as a component ofthe herbicide norflurazon [27314-13-2].

11. Ring-Fluorinated Aromatic,Heterocyclic, and PolycyclicCompounds

The compounds discussed in this chapter containone or more fluorine atoms that are directlyattached to aromatic, heterocyclic, or polycyclicrings. Unlike chlorination and bromination,fluorination with elemental fluorine is rarelyemployed for their production because its vio-lence produces many side reactions (ring-open-ing, coupling, polymerization, and charring).Therefore, indirect methods are used, distribut-ing the reaction enthalpy over several controlla-ble steps [318].

Diazonium salts are suitable for introducingup to three fluorine atoms per ring. Chlorine –fluorine exchange (halogen exchange, Halex pro-cess) with alkali – metal fluorides is suitable incases where activating substituents are present.

Ring-fluorinated aromatic, heterocyclic, andpolycyclic compounds are predominantly usedas intermediates for pharmaceuticals, pesti-cides, dyes and other products. The exceptional


properties of fluorinated cyclic compounds (bio-activity spectrum, effectiveness, and solublity)justify the higher production costs compared tothose of fluorine-free compounds.

11.1. Mono- and DifluoroaromaticCompounds

Research on ring-substituted aromatic fluorinecompounds began in 1870. The fluorine atomattached to the benzene ring is strongly electro-negative; it preferentially directs new substitu-ents into the para position and rarely, if ever, intothe ortho position [343]. Important aspects, es-pecially for biological applications, are (1) theinfluence of the strongly electronegative fluorinesubstituent on adjacent groups, (2) its participa-tion in the resonance system of the aromaticcompound by returning electron density, and(3) the simulation of hydrogen or hydroxy sub-stituents that is due to the similarity in spacerequirements and has led to the synthesis of aseries ofmonofluoro aromatic enzyme inhibitors.The varying lability of the carbon – fluorinebond in mono- and difluoro aromatic compoundshas been exploited to prepare indicators andanalytical reagents, especially for biogenic andmetabolic studies.

11.1.1. Properties

Replacement of aromatic hydrogen by fluorinehas only aminor effect on boiling points. Densityincreases, whereas refractive index and surfacetension decrease. Physical constants are shown inTable 22.

The reactivity of fluorine in benzene deriva-tives depends on the nature of the other ringsubstituents. Nucleophilic substitution occursonly where activating groups (e.g. nitro) arepresent in the ortho or para position. In othercases, e.g., with 1-bromo-4-fluorobenzene [460-00-4], the carbon – fluorine bond is stronger;hydrolysis gives 4-fluorophenol [371-41-5][344], [345].

11.1.2. Production

Among the published processes for the produc-tion of mono- or difluoroaromatic compounds,ring fluorination with dilute fluorine or fluorinat-ing agents such as xenon difluoride [346–349]does not follow a clear course (i.e., without sidereactions) and has no commercial value. Fluor-obenzene itself can be prepared by pyrolysis ofchlorodifluoromethane or chlorotrifluoroethy-lene in the presence of cyclodipentadiene at300 – 800 �C [350] and by anodic fluorinationof benzene with tetraethylammonium fluoride inacetonitrile [351]. Promising methods are thedecarbonylation of benzoyl fluorides in the pres-ence of tris(triphenylphosphine)rhodium(I) chlo-ride in boiling xylene [352] and the thermaldecarboxylation of aryl fluoroformates [353].

Diazotization. Aromatic compounds con-taining one or two fluorine substituents are pro-duced commercially by diazotization of aromaticamines and decomposition of the resulting dia-zonium fluorides [318], [354]. In one process,aromatic amines are diazotized with dry sodiumnitrite in anhydrous hydrogen fluoride at 0 –20 �C [355] (see Fig.4).

Table 22. Physical properties of ring-fluorinated aromatic compounds

Compound CAS registry Empirical Mr bp, �C d4q (q, �C) nD

q (q, �C)number formula (101.3 kPa)

Fluorobenzene [462-06-6] C6H5F 96.1 84.7 1.083 (25) 1.4629 (25)

2-Fluorotoluene [95-52-3] C7H7F 110.13 113 – 114 1.003 (21) 1.4727 (20)

3-Fluorotoluene [352-70-5] C7H7F 110.13 115 0.991 (25) 1.4691 (20)

4-Fluorotoluene [352-32-9] C7H7F 110.13 116 0.991 (25) 1.4688 (20)

4,40-Difluorodiphenylmethane [457-68-1] C13H10F2 204.22 263.5* 1.145 (20) 1.5362 (20)

1,3-Difluorobenzene [372-18-9] C6H4F2 114.09 82 – 83 1.1572 (20) 1.4410 (20)

1,4-Difluorobenzene [540-36-3] C6H4F2 114.09 88 – 89 1.176 (20) 1.4421 (20)

*At 100.5 kPa


The temperature is increased to 30 – 120 �C,and the formed diazonium fluorides decomposeto form fluoroaromatic compounds. A yield ofover 90% of mono- and difluorinated com-pounds is obtainable. Yields of ca. 81% arereported for batch operations on a 1-t scale.

In a continuous process the three exothermicsteps are controlled by separation; i.e., hydro-fluorination of the aromatic amine, diazotization,and thermal decomposition [356]. This permitssafe operation on a large scale. Diazotizationwith nitrosyl chloride [357] and nitrosyl fluo-ride – HF complexes [358] is also possible. Pro-blems associated with these processes are hydro-gen fluoride recovery and waste gas treatment.

In another method (Balz – Schiemann reac-tion), water-insoluble diazonium fluoroboratesare prepared by diazotization of aromatic amineswith sodium nitrite in the presence of 40%fluoroboric acid or sodium or ammonium tetra-fluoroborate in HCl [327], [359]. After filtrationthe diazonium salts are dried and thermolyzed[360] (Fig. 5):

This thermal decomposition must be strictlycontrolled, especially when nitro substituents arepresent, to avoid an explosion. Diazonium tetra-fluoroborates usually decompose at a highertemperature than the corresponding diazoniumfluorides. The Balz – Schiemann process hasrarely been used on a large scale because of thedifficulties in handling diazonium tetrafluorobo-rates. However, it is convenient as a laboratoryprocess because it does not require specializedapparatus. A plant of several 100 t/a has beenreported [361].

A large number of fluoroaromatic compoundshave been produced by using the two diazotiza-tion routes described [327], [362]. Those ofcommercial interest include fluorobenzene fromaniline; 2-, 3-, and 4-fluorotoluene from the appro-priate toluidines; 4,40-difluorodiphenylmethanefrom 4,40-diaminodiphenylmethane; 1,3-difluoro-benzene from m-phenylenediamine; and 1,4-di-fluorobenzene from p-phenylenediamine.

The reaction sequence of nitration, reduction,diazotization, and thermal decomposition can be

Figure 4. Production of fluoroaromatics by the HF diazotization – dediazoniation method [354]a) Diazotation reactor; b) Dediazoniation vessel; c) Condenser; d) Separator; e) Distillation column; f) HF purification column;g) Product storage tank


repeated to introduce up to four fluorine atomsinto the benzene ring.

Chlorine – Fluorine Exchange. Of similarcommercial importance to diazotization is thereplacement of activated chlorine atoms with theaid of alkali-metal fluorides [318], [354]. Theusual activating groups are ortho and para nitro,cyano, and trifluoromethyl groups [363]. Apro-tic – polar solvents are preferred, such as di-methylformamide, dimethylacetamide, dimethylsulfoxide, N-methyl-2-pyrrolidone, and tetrahy-drothiophene-1,1-dioxide (sulfolane).

Phase-transfer catalysts are sometimes used[364]. The effectiveness of the fluoride sourcedecreases in the order CsF > KF > NaF > LiF.

In commercial batch or semicontinuousoperations, the Halex process (Fig. 6), potassiumfluorideand theactivatedchloroaromatic compound

Figure 5. Production of fluoroarmatics by the Balz – Schiemann methoda) Stirred diazotization reactor; b) Storage for 50%HBF4; c) Filter; d) Drier; e)Mixer; f) Dediazoniation reactor; g) Condenser;h) Separation column; i) Product distillation column; k) Product storage tank

Figure 6. Flow sheet of the Halex process for the manufacture of fluoronitrobenzene [363]a) Reactor; b) Distillation column; c) Condenser; d) Drier; e) Product distillation column; f) Product storage tank; g) Condenserfor off-gas


are thoroughly mixed (1 : 1) with a large volume ofan aprotic solvent (dimethyl sulfoxide or sulfolane)and are heated to 150 – 250 �C [363], [365]. Thereaction is 90% complete within 48 h. Removal ofKCl and distillation of the product present nodifficulty, but efficient solvent recovery is importantto reduce costs.

Cost is also reduced by regenerating the potas-sium fluoride by treating the KCl with HF [366].The Halex process has the clear advantage ofreadily accessible raw materials, simplicity of asingle-step procedure, and structural specificity.Certain products are accessible in no other way.

The following commercially important inter-mediates are obtained by the Halex process: 1-fluoro-2-nitrobenzene [1493-27-2] and 1-fluoro-4-nitrobenzene [350-46-9] from the correspond-ing chloronitrobenzenes;1-chloro-2-fluoro-5-ni-trobenzene [350-30-1] from 1,2-dichloro-4-ni-trobenzene;1-chloro-4-fluoro-3-nitrobenzene[345-18-6] from 1,4-dichloro-2-nitrobenzene;1-fluoro-2,4-dinitrobenzene [70-34-8] from 1-chloro-2,4-dinitrobenzene;5-fluoro-2-nitroben-zotrifluoride [393-09-9] from 5-chloro-2-nitro-benzotrifluoride [118-83-2]; 1,3-difluoro-4-ni-trobenzene [446-35-5] from 1,3-dichloro-4-ni-trobenzene; and 2,6-difluorobenzonitrile [1897-52-5] from2,6-dichlorobenzonitrile. These inter-mediates are mostly used for substituted anilinesand compounds with carbonyl and carboxyfunctions.

11.1.3. Uses

Fluorobenzene, difluorobenzenes, and their de-rivatives are used widely in the synthesis ofpharmaceuticals and pesticides, and as fine che-micals. Fluoroaromatics have played a specialrole in the development of drugs that act on thecentral nervous system [367]. The increase inlipid solubility due to fluorine atoms facilitatesthe absorption and transport of drugs through theblood – brain barrier into the central nervoussystem.

Fluorobenzene derivatives are used in neuro-leptics such as haloperidol [52-86-8], tranquili-zers such as fluspirilene [1841-19-6], sedativessuch as flurazepam [17617-23-1], and antide-pressants such as fluroxamin [54739-18-3].

Pesticidal [342] and fungicidal fluorobenzenederivatives [368] include the insecticide diflu-

benzuron [35367-38-5] (made from 2,6-difluor-obenzonitrile), the herbicides flamprop [58677-63-3] and fluoronitrofen [13738-63-1], and thefungicides nuarimol [63284-71-9] and flurimid[41205-21-4].

4,40-Difluorobenzophenone [345-92-6], astarting material for aromatic polycondensates,is produced by oxidation of 4,40-difluorodiphe-nylmethane, which is obtained by diazotizationof the corresponding diamine. 4,40-Difluoroben-zophenone undergoes polycondensationwith hy-droquinone, yielding a polyetherether ketone(PEEK) resin, a thermoplastic. 4-Fluoroaniline[371-40-4], 4-fluorobenzaldehyde [459-57-4],and 4-fluorobenzoic acid [456-22-4] are inter-mediates for liquid crystal polymers [369].

Aromatic compounds with reactive fluorinesubstituents are used for the characterization ofamino acids (Sanger’s reagent, 1-fluoro-2,4-di-nitrobenzene [70-34-8]), the immobilization ofenzymes (4-fluoro-3-nitrophenylazide [28166-06-5]), and peptide cross-linkage (1,5-difluoro-2,4-dinitrobenzene [327-92-4]).

Aromatic fluorine compounds have been de-veloped for medical applications, such as 19F-magnetic resonance imaging (MRI) and in 18F-positron emission tomography (PET) [370].

11.2. Highly Fluorinated AromaticCompounds

Compounds in which an aromatic ring is substi-tuted by three to five fluorine atoms have littlecommercial importance. 1,2,4-Trifluoroben-zene [367-23-7], bp 88 �C, and 1,3,5-trifluoro-benzene [372-38-3], bp 75.5 �C, are producedby the Balz – Schiemann reaction (see Section11.1.2) from 2,4-difluoroaniline [367-25-9] and3,5-difluoroaniline [372-39-4], respectively.1,3,5-Tricyano-2,4,6-trifluorobenzene [3638-97-9], mp 148 – 150 �C, is used as an interme-diate for pesticides; it is obtained by chlorine –fluorine exchange from 1,3,5-tricyano-2,4,6-tri-chlorobenzene [371].

1,2,3,5-Tetrafluorobenzene [2367-82-0], bp83 �C, is obtained by the Balz – Schiemannreaction from 2,3,5-trifluoroaniline [363-80-4],and 1,2,4,5-tetrafluorobenzene [327-54-8], bp90 �C, from 2,4,5-trifluoroaniline [57491-45-9]. 1,2,3,4-Tetrafluorobenzene [551-62-2], bp95 �C, pentafluorobenzene [363-72-4], bp


85 �C, and hexafluorobenzene are produced bythe CoF3 method (see Section 11.3).

The Halex process (Section 11.1.2) is usedcommercially to produce 1,4-dicyano-2,3,5,6-tetrafluorobenzene [1835-49-0], mp 197 –199 �C, from the corresponding tetrachloro de-rivative [372]. This compound is used as amonomer for thermostable polymers.

11.3. Perhaloaromatic Compounds

Hexafluorobenzene [392-56-3], bp 80.3 �C, hasbeen thoroughly investigated [373]. Nucleophilicsubstitution produces pentafluoroaromatic com-pounds such as

bromopentafluorobenzene [344-04-7], bp135.6 �C

pentafluorophenol [771-56-2], bp 117 – 118 �Cpentafluoroaniline [771-60-8], bp 153 �Cpentafluorobenzene [771-61-9], bp 143 �Cpentafluorotoluene [771-56-2], bp 117 �Cpentafluorobenzaldehyde [653-37-2], bp 164 –

166 �Cpentafluorobenzoic acid [602-94-8], bp 220 �C

Production. Hexafluorobenzene was firstproduced in 1955 by pyrolysis of tribromofluor-omethane [353-54-8] in a platinum tube at640 �C under atmospheric pressure [374]:,

Of greater commercial interest is the pyrolysisof an equimolar mixture of dichlorofluoro-methane [75-43-40] and chlorofluoromethane[593-70-4] at 600 – 800 �C [375]:

For many years a commercial multistep pro-cess employed CoF3 as the fluorinating agent[376]. For example, at 150 �C benzene gives amixture of cyclohexanes containing 8 – 11 fluo-rine atoms.

TheCoF2 formed in this reaction is fluorinatedto CoF3 with elemental fluorine, and reused. Theorganic products are heated with an alkali-metalhydroxide to form a mixture of polyfluorocyclo-hexenes and polyfluorocyclohexadienes. Theseproducts are aromatized by passage over iron oriron compounds at 400 – 600 �C to give hexa-fluorobenzene, pentafluorobenzene, and tetra-fluorobenzenes. Octafluorotoluene [434-64-0]and the three perfluoroxylenes are also obtainedby this method.

The disadvantages of this process are thetechnological difficulties and the low utilizationof fluorine, of which a large part is converted tohydrogen fluoride and alkali-metal fluorides. Asa consequence, aromatic fluorine compoundscontaining other halogens are currently producedby the Halex method (Section 11.1.2). Reactionof hexachlorobenzene [365] with potassiumfluo-ride at 450 �C and 1.03 MPa gives a yield of21% hexafluorobenzene together with chloro-pentafluorobenzene [344-07-0] (20%), 1,3-di-chloro-2,4,5,6-tetrafluorobenzene [1198-61-4](14%), and 1,3,5-trichloro-2,4,6-trifluoroben-zene [319-88-0] (12%).

The yield of hexafluorobenzene can be in-creased by recycling the other products for fur-ther reaction with potassium fluoride. A yield of42% hexafluorobenzene is obtained from chlor-opentafluorobenzene with the more reactive, butmore expensive, cesium fluoride [377].

Hexachlorobenzene reacts with KF in aproticsolvents such as dimethylformamide, dimethylsulfoxide, N-methyl-2-pyrrolidone, and sulfo-lane to give not hexafluorobenzene, but theabove-mentioned mixed products. The reactiontemperature is 150 – 250 �C and the residencetime 5 – 36 h. Detailed discussions of the pro-cess are given in [363], [365].

Uses. Hexafluorobenzene has been investi-gated as an inhalation anesthetic in veterinarymedicine [378] and as a working fluid in Ran-kine-cycle engines for temperatures above350 �C [379]. Derivatives such as pentafluoro-benzaldehyde or pentafluorophenyl dimethylsi-lyl ether are used in the chromatographic analysisof steroids [380] and catecholamines [381], andas intermediates for the production of liquid


crystal polymers [382]. Pentafluorophenoxy per-fluorovinyl ethers are cross-linking comonomersfor perfluorinated elastomers [383].

11.4. Fluorinated Heterocyclic andPolycyclic Compounds

Fluorinated pyridines, pyrimidines, and triazinesare heterocycles with commercial importance.Only some representative polycyclic fluorinecompounds are discussed as examples.

11.4.1. Ring-Fluorinated Pyridines

Introduction of fluorine into the pyridine ringreduces the basicity of the latter [384]. 2-Fluor-opyridine [372-48-5], bp 126 �C (100.4 kPa), hasa labile fluorine substituent. It is produced in 74%yield by reaction of 2-chloropyridine with potas-sium bifluoride at 315 �C in 4 h [385]. 3-Fluor-opyridine [372-47-4], bp 105 – 107 �C(100.3 kPa), is produced in 50% yield from 3-aminopyridine using the Balz – Schiemann pro-cess (see Diazotization). 4-Fluoropyridine [694-52-0], bp 108 �C (100 kPa) is produced in 54%yield by diazotization of 4-aminopyridine in an-hydrous hydrogen fluoride [386].

2,4-Difluoropyridine [34941-90-7], bp 104 –105 �C, is obtained by the Halex process (seeChlorine – Fluorine Exchange) from 2,4-di-chloropyridine and potassium fluoride in sulfo-lane [387]. 2,6-Difluoropyridine [1513-65-1], bp124.5 �C (99.1 kPa), is obtained by the reactionof 2,6-dichloropyridine with potassium fluoridein the absence of solvent. The yield is 80% after18 h at 400 �C [388].

For pentafluoropyridine [700-16-3], bp 83 �C,the preferredmethod is the reaction of pentachlor-opyridine with KF at 480 – 500 �C; the yield is83% [389]. Nucleophilic substitution reactionshave been thoroughly investigated [390].

Uses. Fluoropyridines are intermediates forpesticides. For example, 2-fluoro-4-hydroxypyr-idine [22282-69-5] is a precursor of 2-fluoro-3,5-dihalo-4-hydroxypyridine herbicides [391]; 2-fluoro-6-hydroxypyridine [55758-32-2] is usedfor insecticides and nematocides [392] and vari-ous derivatives of fluorinated pentahalogenpyr-idine herbicides [393]. Pentafluoropyridine in

mixtures with hexafluorobenzene is used as theworking fluid in Rankine-cycle engines up to382 �C [379].

11.4.2. Trifluoromethylpyridines

2-Trifluoromethyl- [368-48-9], 3-trifluoro-methyl- [3796-23-4], and 4-trifluoromethylpyr-idine [3796-24-5] can be obtained by the reactionof picolinic, nicotinic, or isonicotinic acid, re-spectively, with sulfur tetrafluoride [394]. Com-mercial processes use side-chain chlorination ofthemethylpyridines followed by chlorine – fluo-rine exchange with antimony chlorofluorides oranhydrous hydrogen fluoride [395]. 2-Chloro-5-trifluoromethylpyridine, bp 190 �C, is producedcommercially from 2-chloro-5-trichloromethyl-pyridine and hydrogen fluoride at 180 – 200 �Cand at a pressure of 3 – 4.5 MPa. It is an inter-mediate for the synthesis of the selective herbi-cide fluazifop [69335-91-7], [396].

11.4.3. Fluoropyrimidines

Certain fluoropyrimidines have gained commer-cial importance [397]. 5-Fluoropyrimidines areemployed in cancer chemotherapy; their bio-chemistry and pharmacology have been inten-sively studied [398]. 5-Fluorouracil [51-21-8] isobtained in a 80 – 92% yield by the fluorinationof 2,4-dihydroxypyrimidine with fluorine or tri-fluoromethyl hypofluorite [399], [400].

5-Chloro-2,4,6-trifluoropyrimidine [697-83-6], bp 114.5 �C (100 kPa), is produced commer-cially from 2,4,5,6-tetrachloropyrimidine bychlorine – fluorine exchange, using sodium fluo-ride at 300 �C [401] or anhydrous hydrogenfluoride in the liquid phase [402] or gas phase[403].

The 5-chloro-2,4-difluoropyrimidinyl radicalacts as the reactive group in reactive dyes [397]for cellulose and cotton fibers such as Levafix EA(Bayer) and Drimarene K (Sandoz) and for wool,e.g., Verofix (Bayer) and Drimalene (Sandoz).

11.4.4. Fluorotriazines

2,4,6-Trifluoro-1,3,5-triazine [675-14-9], bp72.4 �C (101.7 kPa), is produced commercially


from 2,4,6-trichloro-1,3,5-triazine (cyanuricchloride) with either anhydrous hydrogen fluo-ride [404] or sodium fluoride in sulfolane [405].It is used to manufacture reactive dyes by reac-tion between one or two fluorine substituentswith amino groups of chromophores; the remain-ing fluorine binds to the fiber [406]. The reactiveintermediates can be synthesized e.g., from thecorresponding 6-substituted 2,4-dichlorotria-zines and an alkali-metal fluoride or by reactionof cyanuric fluoride with anilines or phenols inorganic solvents [406], [407]. Like the pyrimi-dine reactive dyes, the fluorotriazines are used oncellulose, polyesters, polyamides, and wool[397]. See also ! Reactive Dyes.

11.4.5. Polycyclic FluoroaromaticCompounds

Polycyclic fluoroaromatic compounds areused as intermediates for the production ofpharmaceuticals.

4-Fluoro- [324-74-3] and 4,40-difluorobiphe-nyl [398-23-2] are obtained by diazotizationfrom the corresponding amines in yields of upto 80% [408]. Other biphenyl derivatives areprepared from fluorobenzenes. The analgesicdiflunisal [22494-42-4] is produced from 2,4-difluoroaniline [367-25-9] by diazotization andcoupling with salicylic acid. The anti-inflamma-tory drugsflurbiprofen [5104-49-4] and fluprofen[17692-38-5] are prepared from 2-fluoroaniline[348-54-9].

The anti-inflammatory drug sulindac [38194-50-2] is a monofluorinated indole-3-acetic acid.

12. Economic Aspects

The compounds discussed in Chapters 10 and 11are not produced in large quantities and oftencommand high prices. 4-Chlorobenzotrifluoride,3,4-dichlorobenzotrifluoride, 3-trifluoromethyl-phenyl isocyanate, and benzotrifluoride are pro-duced in the United States by Occidental Chemi-cal, in Western Europe by Hoechst, Rhone-Pou-lenc, MitEni and Dow-Elanco, and in Japan byDaikin. Theworldwide production capacity is ca.35 000 – 40 000 t/a.

Heterocyclic fluorine compounds have eco-nomic importance in the production of reactive

dyes. The main producers in Western Europe areBayer AG, Ciba-Geigy, ICI, and Sandoz.

Fluorobenzene and its derivatives are pro-duced in Western Europe by AlliedSignal –Riedel-de-Ha€en (production capacity 1600 t/a),Zeneca (2000 – 2500 t/a), Rhone-Poulenc(1000 t/a), MitEni (1000 t/a) in Europe, DuPont(1400 t/a), Mallinckrodt (1200 t/a) in the USAand Asahi Glass (1000 t/a) in Japan. Fluoroni-trobenzenes and fluoroanilines are produced bythe Halex process by Hoechst, MitEni, Rhone-Poulenc, Asahi Glass, and others. The total ca-pacity for fluoroaromatic intermediates is esti-mated to be several thousand tons per year.

13. Toxicology and OccupationalHealth

With few exceptions, organic fluorine com-pounds are physiologically inert and displayinsignificant toxicity. This is a consequence ofthe chemical stability of the carbon – fluorinebond and the increased stability of hydrogen andhalogen bonds attached to a fluorinated carbonatom. Low toxicity is an important factor inmanyapplications of these compounds.

The difference in toxicity between a chloro orbromo compound and the corresponding fluorocompound is often striking. Thus, carbon tetra-chloride [56-23-5] is a powerful liver and kidneytoxin and a weak carcinogen, as reflected in itsTLV of 5 ppm. However, the product obtainedby replacing one chlorine atom with fluorine,trichlorofluoromethane [75-69-4], has no ad-verse effects on the liver, kidney, or other organs,and no carcinogenic effects on animals exposedto high concentrations for a lifetime; the TLV is1000 ppm. Another example is the chemicalwarfare agent mustard gas, S(CH2CH2Cl)2[505-60-2], which is a strong alkylating agentand notorious vesicant. The fluoro analog, bis(2-fluoroethyl) sulfide [373-25-1], is chemicallyand physiologically inert, with no vesicant prop-erties [409].

The few highly toxic organofluorine com-pounds usually have easily replaceable fluorineatoms. Examples are diisopropyl fluoropho-sphate [55-91-4], a potent cholinesterase inhibi-tor, and perfluoroisobutylene [382-21-8], whichcauses pulmonary edema at low concentrations.Sodium fluoroacetate [62-74-8], a potent roden-


ticide, is an exception; it does not liberate fluo-rine, but interferes with metabolism by mimick-ing acetic acid.

13.1. Fluorinated Alkanes

Fluoroalkanes [410], [411]. Perfluoroalk-anes have very low toxicity. Thus, rats exposedto an 80 : 20 mixture of perfluorocyclobutane[115-25-3] and oxygen for 4 h survived with noill effects. Likewise, no ill effects were seen infour species of animals exposed to a 10% con-centration in air 6 h/d for 90 d. Partially fluori-nated alkanes have similarly low toxicity, asshown by similar experiments with difluoro-methane [75-10-5] and1,1-difluoroethane [75-37-6].

Chlorofluoroalkanes are more toxic thanthe corresponding fluoroalkanes; nevertheless,most chlorofluoroalkanes have low toxicity[410–412]. High concentrations (10 – 50% inair) ofmany of them, like lower concentrations ofmany hydrocarbon and chlorohydrocarbon sol-vents, can cause cardiac sensitization, i.e., sen-sitization of the heart to the body’s adrenalin.This can lead to cardiac arrhythmia (heartbeatirregularity) and sometimes cardiac arrest.Deaths have been caused by ‘‘aerosol sniffing’’.

The toxicity of dichlorodifluoromethane [75-71-8] has been thoroughly investigated. Ratssurvived a 6-h exposure to an 80% mixture withoxygen. Five species of animals continuouslyexposed to 810 ppm for 90 d showed no effectsexcept for slight liver damage in guinea pigs.Rats and dogs showed no significant health ef-fects when fed a diet containing 0.3% for 2 years.Teratogenic and reproductive tests in rats werealso negative. Repeated exposure caused little orno irritation to rat skin or the rabbit eye. In ascreening test, dogs injected with adrenalinshowed cardiac sensitization on exposure to50 000 ppm in air, but not to 25 000. On thebasis of animal data and human experience, aTLV of 1000 ppm has been selected to providean ample margin of safety against cardiac sensi-tization and other injury [413]. The MAK is also1000 ppm [414].

Compared to dichlorodifluoromethane, tri-chlorofluoromethane [75-69-4] and 1,1,2-tri-chloro-1,2,2-trifluoroethane [76-13-1] are slight-

ly more toxic, whereas 1,2-dichloro-1,1,2,2-tet-rafluoroethane [76-14-2] is slightly less toxic.However, for all three a TLV of 1000 ppm isjudged to provide an adequate margin of safety.On the other hand, 1,1,1,2-tetrachloro-2,2-di-fluoroethane [76-11-9] and 1,1,2,2-tetrachloro-1,2-difluoroethane [76-12-0] cause liver and lungdamage to rats subjected to repeated exposure at1000 ppm; therefore, a TLV of 500 ppm is re-commended for these compounds. These dataindicate that the toxicity of chlorofluorocarbonstends to increase with the chlorine : fluorine ratioand the number of carbon atoms.

Although the toxicity of most chlorofluor-oalkanes bearing hydrogen (chlorofluorohydro-carbons) is also low, it tends to be higher than thatof the closely related chlorofluorocarbons. Thedifference is usually slight, as in the case of 2-chloro-1,1,1,2-tetrafluoroethane [2837-89-0],which is a slightly stronger cardiac sensitizerthan 1,2-dichloro-1,1,2,2-tetrafluoroethane, butis otherwise similar to it in toxic properties.Chlorodifluoromethane [75-45-6] is similar intoxicity to dichlorodifluoromethane in most re-spects, and has the same TLV of 1000 ppm. At50 000 ppm it has a weak carcinogenic effect inmale rats, but not at lower concentrations or inmice or female rats; therefore, this is consideredof no practical significance [415].

The toxicity of dichlorofluoromethane [75-43-4] is more like that of chloroform than ofdichlorodifluoromethane or chlorotrifluoro-methane [75-72-9], especially with respect toinjury on repeated exposure; its TLV, 10 ppm,is low for a chlorofluoroalkane.

Bromofluoroalkanes, some of which arefire extinguishing agents and anesthetics, aremore toxic than the corresponding chlorofluor-oalkanes, but generally are low in toxicity com-pared to other fire extinguishing agents andanesthetics [409], [413]. Trifluorobromo-methane [75-63-8] produced no adverse effectson dogs and rats exposed to 23 000 ppm 6 h/d,5 d/week, for 18 weeks; its TLV is 1000 ppm[413].

13.2. Fluorinated Olefins

Most fluorinated olefins have halogen atoms oflow reactivity and a correspondingly low-to-


moderate toxicity [409], [412]. The toxicities ofthe five most common members of the class,typical in these respects, are shown in Table 23.

In perfluoroisobutylene and 2,3-dichloro-1,1,1,4,4,4-hexafluoro-2-butene [303-04-8], ha-logens are readily displaced by nucleophilicreactants; thus, these two compounds exhibithigh acute toxicity. Perfluoroisobutene, with aLC50 of 0.5 ppm, acts much like phosgene incausing death by pulmonary edema. However,perfluoroisobutene is ca. 10 times as toxic asphosgene, so exposure to it must be carefullyavoided. Pyrolysis of tetrafluoroethylene or itspolymers above 400 �C is one of its sources.

13.3. Fluorinated Alcohols

2-Fluoroethanol [371-62-0] has a high acutetoxicity (LD50 10 mg/kg), a consequence of itsready biological oxidation to fluoroacetic acid(see Section 13.6). Thus, contact with the skinand inhalation of vaporsmust be avoided. The di-and trifluoroethanols ([359-13-7] and [75-89-8],respectively) have relatively low acute toxicity,similar to the corresponding acetic acids [412].The acute toxicity of 1,1,1,3,3,3-hexafluoro-2-propanol [920-66-1] is also low, but the sub-stance is a strong skin and eye irritant.

13.4. Fluorinated Ketones

In 90-d inhalation studies in animals, hexafluor-oacetone [684-16-2] caused severe damage tokidneys and other organs at 12 ppm, moderatedamage at 1 ppm, and no damage at 0.1 ppm.Repeated skin exposure led to testicular damagein rats. These data and plant experience led toselection of a TLV of 0.1 ppm, with a warningagainst skin exposure [413]. Studies of hexa-

fluoroacetone and three fully halogenated chlor-ofluoroketones indicatedmoderate acute toxicity[416].

13.5. Fluorinated Carboxylic Acids

Fluoroacetic acid [144-49-0] is highly toxic tomammals; its sodium salt is an effective, butindiscriminate, rodenticide; in rats the LD50 ofthe salt is only 1.7 mg/kg [413]. In contrast,difluoroacetic acid [381-73-7] and perfluoroalk-anoic acids have low acute toxicity.

The unusually high toxicity of fluoroaceticacid compared to the more highly fluorinatedacids is due to its unique ability to interferewith the citric acid cycle, the oxidation path-way used for energy production from aminoacids, fatty acids, and carbohydrates. Fluoroa-cetic acid enters the cycle at the same site asacetic acid and is converted to fluorocitric acid[387-89-1] analogously to the conversion ofacetic acid to citric acid. The fluorocitric acidinhibits aconitase, a key enzyme for the break-down of citric acid, with the result that thecitric acid concentration soon rises to lethallevels [417].

Substances that yield fluoroacetic acid onbiochemical oxidation, such as straight-chain,even-numbered, w-fluoro alcohols or alkanoicacids, are also very toxic.

13.6. Other Classes

Simple perfluoroethers, and the oily oligomers ofhexafluoropropylene oxide with modified endgroups, have the low toxicity expected from theirchemical inertness. Hexafluoropropylene oxideitself, a reactive substance, is moderately toxic torats (4-h LC50, 3700 ppm) [418]. Several partial-ly fluorinated ethers are used as anesthetics, e.g.,Enflurane [13838-16-9], F2CHOCF2CHFCl, andMethoxyflurane [76-38-0], CH3OCF2CHCl2.Their toxicity is low compared to that of mostanesthetics (! Anesthetics, General).

Perfluorinated tertiary aliphatic amines areinert both chemically and biologically. This isillustrated by perfluorotripropylamine [338-83-0]; in emulsionwith perfluorodecalin [306-94-5],it has shown promise as a blood substitute inclinical trials [419].

Table 23. Toxicities of fluorinated olefins*

Compound CAS Lethal conc.,

registry no. ppm

Vinyl fluoride [75-02-5] > 800 000 (ALC)**

Vinylidene fluoride [75-38-7] > 800 000 (ALC)**

Tetrafluoroethylene [116-14-3] 40 000 (LC50)

Hexafluoropropene [116-15-4] 3 000 (LC50)

Chlorotrifluoroethylene [79-38-9] 1 000 (LC50)

* Inhalation by rats, 4-h exposure.**Approximate lethal concentration.


Fluorine substituents usually have little effecton the toxicity of aromatic compounds, whethermonocyclic, polycyclic or heterocyclic [416].

References

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Further Reading

W.X. Bajzer: Fluorine Compounds, Organic, ‘‘Kirk Othmer

Encyclopedia of Chemical Technology’’, 5th edition,

John Wiley & Sons, Hoboken, NJ, online DOI:

10.1002/0471238961.0914201802011026.a01.pub2.

J.-P. B�egu�e, D. Bonnet-Delpon: Bioorganic and Medicinal

Chemistry of Fluorine, JohnWiley & Sons, Hoboken, NJ

2008.

W. R.Dolbier:Guide to FluorineNMR forOrganicChemists,

Wiley, Hoboken, NJ 2009.

I. Ojima (ed.): Fluorine in Medicinal Chemistry and Chemi-

cal Biology, Wiley-Blackwell, Chichester 2009.

V. A. Petrov: Fluorinated Heterocyclic Compounds, Wiley,

Hoboken, NJ 2009.

V. A. Soloshonok, K. Mikami, T. Yamazaki, J. T. Welch, J.

Honek (eds.): Current Fluoroorganic Chemistry, Ameri-

can Chemical Society, Washington, DC 2007.

K. Uneyama: Organofluorine Chemistry, Blackwell, Oxford

2006.


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