UNITED STATES PATENT Office

Patented Nov. 4, 1952 es 2,616,927 UNITED STATES PATENT oFFICE

Edward A. Kauck, St. Paul, Minn., and Joseph H. Simons, State College, Pa., assignors to Minne- - - sota Mining & Manufacturing Company, St. Paul, Minn., a corporation of Delaware No Drawing. Application May 12, 1950, . . . Serial No. 161,71 10 Claims. (CI. 260-563) 1. This application is a continuation-in-part of ing material, and is described in more detail our copending application Ser. No. 29,955, filed hereafter. On May 28, 1948 (now abandoned). Those compounds which contain five or more This invention relates to our discovery of a carbon atoms in the molecule have boiling points new and useful class of fluorinated carbon com above room temperature and hence are normally pounds, namely, the saturated fluorocarbon ter non-gaseous. Compounds containing eight or tiary amines. In these novel compounds the more carbon atoms have boiling points near to molecules contain only carbon, fluorine and ni or above that of water and may be referred to as trogen atoms and each nitrogenatom is directly high-boiling compounds...... bonded to three carbon atoms. 0 These fluorocarbon tertiary amine compounds These compounds constitute the family of fully are water-insoluble; they have a high degree of fluorinated analogues of the family of Saturated chemicalinertness; they are non-flammable; and hydrocarbon tertiary amines, the carbon-nitro they can be heated to moderately elevated tem gen skeletal structures being the same but all peratures in "Pyrex' laboratory type glassware hydrogen atoms being replaced by fluorine 5 without reacting or decomposing. They do not atoms. These compounds are termed fluorocar react with metallic sodium or potassium at room bon "amines' merely as a matter of expediency temperatures. Making comparisons with non in order to conform with commonly used nomen fluorine compounds on the basis of molecular clature practice. The tertiary amines of conven weights, these new compounds have exceptionally tional organic chemistry are regarded as derived 20 low boiling points, low refractive indices, low from ammonia, NH3, by replacement of the three viscosities and low surface tensions. They are hydrogen atoms by three hydrocarbon radicals. colorless and are apparently odorless when in The present compounds may be correspondingly pure form...... regarded as derived from nitrogen trifluoride, These compounds have properties which per NF3, by replacement of the three fluorine atoms 25 mit of use for many of the purposes for which by three fluorocarbon radicals. The present saturated fluorocarbons can be used. They can compounds have physical and chemical proper be employed as refrigerants, inert diluents for ties which are entirely different from those of chemical reactions, solvents, hydraulic mecha the corresponding hydrocarbon tertiary amines, nism fluids, heat transfer media, turbine impel as will be indicated in more detail hereafter. 30 lants, transformer liquids, dielectrics, and lubri They are members of a disparate class of tertiary cants. They can also be used as intermediates. “amine' compounds which is Sui generis. in the manufacture of other compounds. The present family of compounds embraces Various illustrative sub-classes of our novel cyclic as well as non-cyclic compounds, and poly compounds will now be indicated and exemplary amines as well as monoamines, all of which have 35 compounds will be mentioned, following which a their structural analogues in the hydrocarbon number of experimental examples will be set system of tertiary amines. It is our discovery forth to illustrate the general utility of the proc that the electrochemical process which We employ ess and to provide detailed data on various of is a general process capable of producing the fully the compounds. . . fluorinated analogues of all of the Saturated hy 40 The saturated aliphatic trifluorocarbon mono drocarbon tertiary amines, as distinguished from amines (containing a single nitrogen atom) are special processes capable of preparing particular derivable from the corresponding trialkyl amines, species or types of compounds only. and have the same structure except that the We have found that the compounds of the drogen atoms have been entirely replace present class can be directly made from the 45 fluorine atoms. The nitrogenatom of the mo) corresponding hydrocarbon amine compounds cule is directly bonded to each of three saturated as starting materials by employing the novel aliphatic fluorocarbon groups. These compounds electrochemical process broadly described and claimed in the copending application of one of have the formula: ...... us, J. H. Simons, Ser. No. 62,496, filed November 50 29, 1948 (which replaced Ser. No. 677,407, filed where the R's represent saturated aliphatic fluo June 17, 1946, and since abandoned), now Patent rocarbon groups which may be the same or dif No. 2,519,983, issued on August 22, 1950. This ferent, having the generic formula: -CF2n+1. process involves electrolyzing a solution of liquid A fluorocarbon group which contains three or hydrogen fluoride containing the organic start 55 more carbon atoms may be present either, as a 2,616,927 3 4. “normal' (straight chain) group or as an iso cyclohexylmethylamine; (C6F11CF2CF2)3N, corre meric group having a branched structure. sponding to tricyclohexylethylamine; The simplest illustration of these compounds is provided by tri-trifluoromethyl amine, having (CF3) gNC6F11 the structural formula: 5 corresponding to dimethylcyclohexylamine; (CE) 2NCF3 CFa corresponding to dicyclohexylmethylamine; and CF-N (C6F11)an, corresponding to tricyclohexylamine. CF's In these cyclohexyl compounds the molecules Con O tain only acyclic nitrogen atoms, that is, the rings The following table shows how the boiling are carbocyclic and the nitrogen atons are not points of these compounds vary with the number present in the rings. The nitrogen atom can be of carbon atoms, and has been simplified by in in a ring (which may be regarded as formed by cluding only the normal (straight chain) con 5 the closure of two nitrogen-bonded fluorocarbon pounds wherein the three fluorocarbon groups chains), as illustrated by the heterocyclic fluor are the same. Boiling points at 760 mm. preS inated N-alkylpiperidines, such as C5F10NCF3, sure are given. These listed compounds are all corresponding to N-methylpiperidine, and fluid (gaseous or liquid) at room temperature. Compounds: B. P. ( C.) 20 corresponding to N-ethylpiperidine, etc., wherein (CF3)3N ------il C5EoN is a fluoropiperidine group. A further (C2Fs)3N ------70 illustration is C5F10NC6F11, corresponding to N (C3F)3N ------130 cyclohexylpiperidine. The previously mentioned (CAF9) 3N ------178 25 electro-chemical process is adapted to the produc (C5F11)3N ------28 tion of such cyclic compounds from the corre (C6F13)3N ------258 sponding hydrocarbon amine compounds, the (CF15)3N ------2.94 hydrogen atoms being replaced by fluorine atoms. (CaF17)3N ------32 The invention embraces tertiary polyamine compounds, which contain more than one ter It will be noted that these boiling points are 30 tiary nitrogen atom. These can be made by the substantially lower than those of the correspond aforesaid electrochemical proceSS. An example ing compounds of the hydrocarbon trialkyl amine is the diamine compound: series (despite the fact that the molecular weights are much higher). Thus the B. P. of (C2F5)3N is 70° C. as compared with 89 C. for (C2H5)3N. corresponding to N,N,N',N'-tetramethyltrimeth The B. P. of (C6F13)3N is 258 C. as compared yenedianine. With 300° C. for (C6H13)3N. A further example is: The boiling points of these compounds are (C2F5) 2N-CF2CF, N(C2F5)2 higher than those of the saturated aliphatic 40 fuorocarbons having the same number of carbon corresponding to N,N,N',N'-tetraethylethylenedi atoms, as is illustrated by the fact that the B. P. amine. These diamine compounds have the ge of normal C6F14 is about 55° C. as compared to aeric formula: 70° C. for (C2Fs)3N. Unsymmetrical as well as Symmetrical Con pounds are included. The lack of symmetry may where the primed R's represent Saturated ter arise from different numbers of carbon atoms minal fluorocarbon groups and R represents a in the fluorocarbon groups, as in the case of nitrogen-linking Saturated fluorocarbon group. (CF3)2N (C5E11). Another type of non-symmetry An example of a triamine compound is: exists when the groups differ as to branching, as when one group is branched and the others 50 (CF).N-CF-N-CF-N(CF3) are normal straight chains. Both types of non F3 symmetry may be present, as in the case of A further example is: (CE) 2N (iSO-C5F1), Unlike the trialkyl amines, even the lowest 5 5 trifluorocarbon amines are not only Water-in wherein C6F9 is a fluorocyclohexyl ring. soluble but do not react with, and are not soluble In respect to the Warious types of Saturated in, the mineral acids. They are not miscible with fluorocarbon tertiary amine compounds claimed the trialkyl amines. They separate out when herein, an important category consists of com mixed with liquid hydrogen fluoride, although 60 pounds wherein two or all of the three nitrogen the trialkyl amines are highly soluble in the bonded carbon atoms are constitutents of latter. -CF2- groups. Each of these groups is also Tests made both at room temperature and at bonded either to a fluorine atom or to a carbon the temperature of boiling water (100° C.) in atom of a Saturated fluorocarbon group. In the dicate that these compounds do not react with 65 latter case the nitrogen-bonded initial carbon any of the following: concentrated HCl, concen atom of the group is necessarily a 'primary' car trated H2SO4, concentrated NaOH, 30% H2O2, bon atom (only one other carbon atom being HNO2, and methyl iodide. directly bonded to it). Previously mentioned ex The invention is not limited to the aliphatic amples include (CF3)3N, normal (CAF9)3N, and Series of compounds. The nitrogen-bonded Satu (CF3) NC6F11. rated carbon-chain groups need not be of the The electrochemical process produces as by Open-chain type; since One, two or all three may products various fragmentation products con be allicyclic, containing a saturated fluorocarbon taining fewer carbon atoms than the parent ring (closed chain). Examples of such com compound, due to cleavage of Carbon-nitrogen pounds are (CsIF11CF2)3M, corresponding to trir 75 and even carbon-carbon bonds in the case of

2,616,927 5 6 tions; and the hydrogen atoms offer points of some molecules. Thus some CF4 will be recov attack for chemical reactions. Some or all of ered from (CH3)3N, and some CF4 and CF's from the hydrogen atoms thereof can be replaced (C2H5)3N.Another type of by-product consists of fluoro. . . . by chlorine or bromine atoms by the thermal carbon tertiary amine compounds which contain 5 chlorination and bromination process which, a greater number of carbon atoms and which as applied to fluorocarbon hydrides, was de have higher boiling points than the fluorocarbon scribed by J. H. Simons, 'et al., in the Jour tertiary amine which corresponds to the starting inal of the American Chemical Society, vol. 68, compound. These are presumably formed by pp. 968-969 (June, 1946). The procedure con the combining of free radicals in the electrolyte 0. sists in passing a gaseous mixture of the starting Solution. These high-boilers, range from free compound, and chlorine or bromine, through a flowing liquids up through viscous oily liquids, tube which is heated to a high temperature by greases, tacky solids, and brittle resinous solids. a furnace, and separating the chlorinated or Still another type of by-product consists of brominated reaction product from the resultant amine compounds wherein less than all of the 5 reaction mixture, as by fractional distillation. hydrogen atoms have been replaced by fluorine Despite the formation of by-products, the elec atoms. These have higher boiling points than tro-chemicals process is capable of providing the corresponding fully fluorinated amines hav igood yields of the fully fluorinated tertiary amine ing the same number of carbon atoms. Included corresponding to the hydrocarbon amine start in this category are high-boilers containing a 20 lag COmpOund. greater number of carbon atoms than the start ing compound, which evidently are formed by ELECTROCHEMICAL METHOD OF MAKING the combining of free radicals in the electrolyte As previously stated, the compounds of this in Solution. These hydrogen-containing high-boil yention can be conveniently made by electrolyz ers range from free-flowing liquids up to brittle ing. Solutions of the corresponding hydrocarbon Solids and contain, generally, a fraction of one nine compounds in liquid hydrogen fluoride, the percent of conbined hydrogen. end result of which is to replace hydrogen atoms The complex mixture of fugrocarbon tertiary With fluorine atoms. The formation of by-prod amines (which are fully fluorinated) and the tacts has been discussed above. It is not eSSential above-mentioned hydrogen-containing amines to use a hydrocarbon amine (containing only hy (which are partially fluorinated), as obtained drogen atoms to be replaced by fluorine atoms) from the electrochemical cell, can be fractionally as equivalent tertiary amines can be employed distilled to obtain cuts of differing consistencies which contain one or more other carbon-bonded and boiling ranges, ranging from free-flowing atoms or groups which are replaceable by fluorine liquids to brittle Solids. For instance, the high atoms in the operation of the proceSS. Thus an boilers from the treatment of triethylamine, amine having one or more carbon-bonded hy (C2Fs)3N, yield fractions having boiling points droxyl groups (-OH) can be used, as illustrated as high as 150° C. and higher. The high-boilers by triethanolamine, in which case the hydroxyl from the treatment of tributylamine, (C3F).3N, groups as Well as the carbon-bonded hydrogen yield fractions which have the consistency at 40 atoms will be replaced by fluorine atoms. Un room temperature of oils, greases, and brittle Saturated and aromatic amine Starting com Solids, with vacuum boiling points at 4 mm. pres pounds can be employed, which have the Sale sure ranging as high as 285° C. and with the carbon-nitrogen skeleton structures as the de number of carbon atoms per molecule ranging sired Saturated end products, saturation result as high as forty or more. These high-boiler 45 ing from fluorine addition in the operation of the cuts are very soluble in liquid fuorocarbons and process. Thus (CF3)2NC6F11 can be made from in liquid fluorocarbon amines. . . , dimethylaniline, (CH3)2NC6H5. The lower-boiling compounds of the two types when the starting compound is a mixture of (fully fluorinated and incompletely fluorinated) Soleric Species (such as a mixture of normal can be separated from each other by fractional 50 and branched-chain forms of the Compound), a The fully fluorinated compounds Sorresponding mixture of isomeric species of the distillation.can be further purified by refluxing with 25% fluorocarbon amine product will be obtained. NaOH solution for a period of several hours to " .. A. simple type of electrolytic cell can be used, eliminate any remaining hydrogen-containing employing a nickel anode and an iron or steel contaminants. Purification can also be effected 55 cathode, for example. An iron or steel container by selective adsorption of the hydrogen-contain can be used, which may be employed as a cath ing compounds, using silica gel, activated alu ode, With a cover of iron or steel which is bolted mina, or activated carbon. The hydrogen-con in place. Anode and cathode plates, in closely taining fluoroamines can also be effectively re Spaced, alternating array, can be SUSpended from moved from the high-boiler mixtures by selec 60 the cover. A suitable gasket material, and in tive adsorption so as to obtain high-boiler com Sulating material for electrode mountings and positions consisting of substantially pure fluoro leads, is “Teflon' (polytetrafluoroethylene). An carbon tertiary amines. In this way fluorocar upper outlet for gaseous products, an upper in bon tertiary amine fractions can be obtained let for charging materials, and a bottom outlet Which contain as many as forty or more carbon 65 for liquid products, may be provided. The cell atoms in the molecule and which are brittle may be provided with a cooling jacket for main Solids at room temperature. taining a desired Operating temperature. Although these hydrogen-containing... fluoro Commercial anhydrous liquid hydrogen fluo amines have a relatively good degree of thermal ride can be used. This normally contains a trace stability and chemical inertness, they lack the of water, but water need not be present and high stability and inertness characteristic of the fully ly anhydrous hydrogen fluoride can be used. fluorinated compounds. In particular, they Additional Water can be present, but more than undergo dehydrofluorination at elevated tem a few percent will seriously reduce the Operating peratures, giving off HF'; they decompose when eficiency. The amine starting compounds are refluxed with boiling sodium hydroxide solu 75 Soluble in this material. 2,616,927 8 A cell potential of about 4 to 8 volts D. C. has square foot of anode Surface, operating at at been found suitable. A current density of about mospheric pressure and a temperature of 0° C. 20 amperes per Square foot of anode Surface can At the end of 25 hours an immiscible liquid, be obtained. Voltages sufficiently high to result weighing 172 grams, was withdrawn from the in the formation of free fluorine are avoided. bottom of the cell. This was washed with base The process does not depend upon the genera (potassium hydroxide solution) and with Sull tion of free fluorine and the latter, if produced, furic acid and was fractionally distilled to yield would result in explosions, electrode corrosion, a liquid main fraction which was identified as and undesirable reactions. relatively pure (C2F5)3N, tri-pentafluoroethyl The preferred operating pressure is atmos 0. amine. pheric pressure or a moderately elevated pres That this compound was not a fluorocarbon, sure, and the preferred operating temperature was made apparent from the differences in phys range is about 0 to 20° C.; but higher and lower ical properties relative to the boiling point value. operating pressures and temperatures can be en In fact the only fluorocarbon of comparable boil ployed. 15 ing point that might be expected to have been When (CF3)3N or other gaseous amine product formed from the particular amine Starting Com is being made, it can be withdrawn. With and pound is C6F14, having a molecular Weight of separated from the other gaseous products of the 338 and having a boiling point of about 55° C. for cell. Liquid amine product compounds separate the normal form. These values differ from those as a constituent of a liquid which is imniscible 20 determined for the found compound by many with the electrolyte and 'settles to the bottom of times the probable experimental error. In addi the cell from which it can be withdrawn. The tion, analytical determinations Were made for latter can be washed with a base and with dilute fluorine and nitrogen Which checked With the sulfuric acid, and fractionally distilled to yield calculated values for (C2F5)3N to Within a close the desired fully fluorinated amine product. The 25 experimental margin of error, and Still further desired fully fluorinated amine product can be confirmation was provided by the infra-red ab further purified by refluxing with 25% NaOH so Sorption Spectrum. lution for a period of several hours. This effec The measured properties of this (C2F5)3N tively eliminates any hydrogen-containing by fraction were as followS: product contaminants. Higher product com 30 pounds are also formed and can be recovered and Boiling point (at 743 mm.) ------C 68-69 purified as previously mentioned. Refractive index (at 25 C.) ------1258 Density (grams/cC. at 35 C.) ------1708 Eacample 1 Dielectric constant (at 20° C.) ------1.86 175 grams of trimethylamine was dissolved in 3 5 Molecular Weight (from vapor density) - 370 1800 grams of commercial anhydrous liquid hy Per cent nitrogen ------3.93 drogen fluoride and electrolyzed in an iron lab Per cent fluorine ------76.0 oratory cell containing nickel electrodes. The The calculated values for pure (C2F5)3N are: mixture of gaseous products of the cell was led molecular weight 371, per cent nitrogen 3.77, per through a low-temperature condenser (-40 C.) 40 cent fluorine 76.7. to condense out most of the HF present in the In another experiment employing triethyl mixture (which was returned to the cell), then amine as the Starting compound, distillation of through an aqueous calcium chloride bubbler to the cell drainings resulted in the obtaining of a remove remaining traces of HF, then through an main fraction of distillation bottoms which was aqueous potassium-sulfite-iodide bubbler to re 45 fractionally redistilled to yield the following move traces of OF2, then through an aqueous p0 tassium hydroxide bubbler to remove traces of CutS all of which showed the presence of com CO2, then through a dry potassium hydroxide bined hydrogen upon analysis: tower to remove traces of Water, and then through a liquid air trap to separate the hydro CutNo. Weight(grams) (B.P. C.) Percent" | N. W. n.() Density- gen from the therein condensed compounds. 50 The traces of CO2 and OF2 result When there is a 1------200 71-75 0.24 347 .267 1689 2------25 75-82 0.42 339 .272 1656 trace of water in the electrolyte of the cell. At 3------40 - 82-88 0.418 364 1.277 ... 6SO the end of 19 hours, 400 grams of material had 4------221 88-153 ------been condensed in the liquid air trap and this was 55 5------545 Residue 0.16 ------1.31 1706 subjected to fractional distillation. In addition to normally gaseous fractions identified as CF4, Cuts 2 and 3 were identified as mixtures of CF3H and NF3, there Was obtained a normally partially fluorinated triethylamines containing gaseous fraction identified as relatively pure an average of about one to two atoms of hydro (CF3)3N, tri-trifluoromethylamine, having the 60 gen per molecule. following properties: In another similar experiment also using tri ethylamine as the starting compound, fractiona Boiling point (at 735 mm.).------minus 11° C. Molecular weight (found).------224 tion of the liquid product resulted in obtaining Molecular weight (calc.) ------221 a recognized fraction of (C2F5)2CF3N, di-penta 65 fluoroethyl-trifluoromethylamine, having the fol The identification was additionally confirmed lowing properties: by the infra-red absorption spectrum. Boiling point (at 734 mm.) ------C- 45 Eacd.imple 2 Refractive index (at 25° C.) ------1.253 Molecular weight (found) ------320 175 grams of triethylamine was dissolved in 70 1800 grams of commercial anhydrous liquid hy Molecular Weight (calc.) ------32. drogen fluoride and the solution Was placed in an This illustrates that some molecular fragmen iron laboratory cell containing nickel anodes. tation takes place to produce trifluorocarbon The applied potential was 5.6 volts D. C., which amine end products having fewer carbon atoms resulted in a current flow of 20 amperes per 75 than the starting compound. 2,816,927 9. 10. . . . Eacample 3 and wash washed and fractionated to yield a liquid main fraction which was identified as Using tri-n-propylamine as the starting com relatively pure (CsIF1)3N, tri-undecafluoroamyl pound in the electrochemical process there was amine. This fraction was an isomeric mixture obtainedrelatively a pureliquid normalfraction (CF)3N,which was tri-n-hepta-identified as and had the following properties: fluoropropylamine, which was found to have the Boiling range (at 26m -----C- 215-216.5 following properties: - Refeaty ind (at ...) ------3. s. s ' -- ensity (grams/cc. at 25 C.).------1923 Boiling point (at 760 mm.). ------' C. 130. iny . Refractive index (at 25 C.) ------1.279 0. M: WE: y ------E. Density (grams/CC. at 25 C.). ------1821 TT ------Eacample 4 150 to: 8 150 grams of tri-n-butylamine was dissolved in in So". EYity 1800 grams of commercial anhydrous liquid hy- hydrogen fluoride and electrol F. C drogenpreviously fluoride indicated. and electrolyzedAn additional in the 285 manner grams 15 nyd previouslyOg i.art- described.ae . . . ele At rolyzed the end in of the 58 hours,man of digitalthe amine was added during of innisibleiaithe run. At the 250SER.E. grams of cell drainings were remgved, wasWEEEEEE removed from the bottom of the cell and was 20 EENilesiolohexylamine,Ant., 4-as-isiana R. - fractionormal which(CF).N. was identifiedtinnonafluorobutylamine. as relatively pure EEE Stre-----C-- ThisEli, fraction ESTC had the following properties: PensityEyes, cerams/eet------Cat. 9. ------19223. Refractive index (at 25°C.) ------, 1.290 - Eacample 7 Density (grams/cc. at 23. C.)------1856 Using di-n-propylethylamine as the starting Dielectric constant. (at 20 C.). ------2.15 compound in the electrochemical process there Molecular weight ------670 was obtained a liquid fraction which was identi Per cent nitrogen ------2.0 fied as relatively pure normal (C3F)2N(C2Fs), Per cent fluorine. ------4.8 din heptafluoropropyl-pentafluoroethylamine, The calculated values for pure (CaF).N are: Which was found to have the following proper molecular weight 671, per cent nitrogen 209, es: . : . . per cent fluorine. 76.5. . . l. Boiling point (at 732 mm.).------C 111 In another experiment employing tri-n- 35 Refractive index (at 24°C).------1273 butylamine as the starting. material, the primary Density (grams/cc. at 24. C.).------1794. distillation bottoms were fractionated under Molecular Weight (found) ------468 vacuum to give the following cuts: Molecular weight (calc.)------47. B.P. Cutin No. Weight55. - . PercentEI o' Appearance'inture at Roon , (°C.). (mm) 1 98 65-85 2 0.07 - 1.308 Clear olly liquid. 2 89 88-95 2 : 0.08 - 1.310 Do. 3 83,96-106; ; ; 2. 0.09, i. 312 Do. 4. 92 109-128. 2 0.11, 1.315 Light oil. 5 13 130-43. 2. 0.4.319. Medium oil. 6 109's 146-152, 2. 0.17 1.32 Heavy oil...... - - - - 7 89 154-164. 2 0.18 1,322. Wery heavy oil - - 8 29. , 169 2. 0.19. 1325. Light grease...... 9 5860, 220-250191-220 ! 3,4------0.22. 1.331.329.9ease. Very heavy grease. li. 6: 240-285. 4: . 0.231.35: Brown brittle solid; 2- 3 285. 4. 0.25 1,35 Do. Cut 12 was estimated to contain an average Ecample: 8. andof forty 9, werecarbon subsequently atoms per molecule.refluxed withCuts, 25%5, 6 55 102 gramssyner OfF : disopropylethylamine,i.e. s.v. aqueous sodium... hydroxide. for four hours, . . . (i-C3H)2NCHs washed, and redistilled; and the cuts as thus was dissolved in 1800 grams of commerci treated were found to have the percent H val hydrous liquid higi and ues reduced to 0.100.10 and 0.14% respectively. lyzed in the manner previously indicated. After Theseof fully high-boiler fluorinated fractions and incompletely contained fluorinatimixtures 34product hours was of operation,removed from 187 thegrams bottom of a liquidE. ed tertiary amines. As previously mentioned, cell and, washed and distilled to yield a liquid the hydrogen-containing compoundsgan be re fraction which was identified as relatively pure moved by selective adsorption methods. (i-CaF)2NC2F5, di-heptafluoroisopropyl-penta : Eacample: 5 (55 Eyre, resulting from complete fluo 1800150 grams grams of of commercial, triamylamine anhydrous was dissolved liquid hy- in tionE.E.E.E.E.E. had the following properties: This drogen fluoride and electrolyzed in a similar Boiling point (at 736-mm.). or, essee manner. The starting compound was a com- 70, Refractive index (at 28°C.) mercial product consisting of a mixture of nor- Molecular Weight (found).------mal and branched chain isomeric species of tri- Molecular weight (calc.). ------theamyl end amine, of 94having hours, different, 392 grams boiling of points.immiscible At , EcampleS-a - - - - -72. 9 liquid was removed from the bottom of the cell 75 . Using diethyl-n-propylamine. as the starting 2,616,927 a 11 - . 12 compound in the electrochemical process there fied as relatively pure (C2F5)N(C6F11), di-penta was obtained a liquid fraction which was identi fluoroethyl-undecafiuorocyclohexylamine, which fied as relatively pure normal (C2F5) 2N (CgF), was found to have the following properties: di-pentafluoroethyl - n-heptafluoropropylamine, Which was found to have the following proper Boiling range (at 738 mm.).------C 145-149 Refractive index (at 21.5° C.).------.300 ties: Density (grams/cC. at 30.5°. C.) ------1854 Boiling point (at 760 nm.) ------C. 93 Molecular Weight (found) ------537 Refractive index (at 25 C.)------1.270 Molecular Weight (calc.) ------533 Density (grams/cc. at 27 C.)------1764 Wiscosity (centipoises at 20° C.).------106 O Eacample 13 Eacample, 10 185 grams of diethylbenzylamine, Using diethyl-n-butylamine as the starting (C3H5)2NCH2C6Hs compound in the electrochemical proceSS there was obtained a liquid fraction which was identi 5 was dissolved in 2000 grams of Commercial anhy fied as relatively pure normal (C2F5)2N (C4F9), drous liquid hydrogen fluoride and electrolyzed di - pentafluoroethyl - n - nonafluorobutylamine, in the manner of the preceding examples. The electrolysis was continued for 93 hours with addi which was found to have the following proper tions of the amine as needed to maintain con ties: 20 centration. The liquid product collected from Boiling point (at 743 mm.).------° C 13 the bottom of the cell was washed and fraction Refractive index (at 26 C.) ------1.275 ally distilled to yield a fraction which was identi Density (grams/cc. at 27°C.)------1792 fied as relatively pure (C2F5)2NCF2C6F11, di-penta Molecular weight (found)------469 fluoroethyl-tridecafluorocyclohexylmethylamine, Molecular Weight (calc.) ------4. 25 a Saturated trifluorocarbon amine compound hav ing a fluorocyclohexyl ring, resulting from COm Eacample 11 plete fluorine Substitution of the hydrogens, and A laboratory cell was charged with 809 grams addition to the benzene ring, in the aromatic of anhydrous liquid hydrogen fluoride and 48 amine starting compound. grams of dimethylaniline, (CH3)2NC6H5. The 30 This fraction had the following properties: latter was a redistilled Sample, B. P. 190-195° C., n20 1558. The applied D. C. potential was Boiling point (at 742 mm.).------C- 163-165 maintained in the range of 5.0 to 6.0 volts Refractive index (at 26 C.).------304 throughout the run, during which additional Density (grams/cC. at 27°C.)------1892 dimethylaniline was added to make a total of 71.7 Molecular Weight (found).------568 grams. The duration of electrolysis was 186 Molecular Weight (calc.)------583 hours, during which time 17.8 faradays of current Eacample 14 had passed. The total cell residue, apart from hydrogen fluoride, weighed 135 grams, from 40 grams of N,N,N',N'-tetraethylethylenedi which 73.7 grains of fluorocarbon-like liquid WaS 40 amine, (C2H5)2N-CH2CH2-N (C2H5)2, was dis obtained. This was washed with base and Was Solved in 2000 grams of commercial anhydrous fractionally distilled to yield a liquid fraction hydrogen fluoride and electrolyzed in the manner which was identified as relatively pure A. previously described. The run was continued for 69 hours, additional amine being added to main (CF3) NC6F11 45 tain the organic concentration at about 2%, di-trifluoromethyl-undecafluorocyclohexylamine, resulting in the producing of 264 grams of cell having the following properties: drainings, which were washed with aqueous potassium hydroxide and distilled to yield a liquid Boiling point.------C 110-111 Refractive index (at 20° C.).------286 50 main fraction which was identified as relatively Density (grams/cc. at 20° C.).------1835 ra - pentafluoroethyl - tetrafluoroethylenedi Molecular Weight (found).------428 anine, which was found to have the following Molecular Weight (calc.) ------433 properties: This compound is the first member of the Series 55 Boiling range (at 736 mm.) ------C - 153-157 having the general formula RR'NC6F11, where R. and R.' represent Saturated aliphatic fluorocar Refractive index (at 27° C.) ------1.291 bon groups, which may be the same or different, Density (grams/cc. at 26° C.) ------1858 and C6F11 is a fluorocyclohexyl ring. Illustrative Molecular weight (found) ------61.2 higher compounds are (CF3) (C2F5)NC6F11, deriv 60 Molecular Weight (calc.).------604 able from methylethylaniline; (C2F5)2NC6F11, Eacample 15 derivable from diethylaniline; (CaF) 2NCs11, derivable from dipropylaniline; and Using N,N,N',N'-n-tetrabutylethylenediamine as the Starting compound in the electrochemical 65 proceSS there was obtained a liquid fraction which derivable from dibutylaniline. These compounds Was identified as relatively pure normal can also be derived from the corresponding satu rated dialkylcyclohexylamine starting compounds (CF9) 2N-CFCF-N(CFs) 2 as shown in the next example, N,N',N',N'-tetra-n-nonafluorobutyl - tetrafluoro 70 ethylenediamine which was found to have the Eacample 12 following properties: Using diethylcyclohexylamine as the starting Boiling range (at 751 mm.).------C - 242-248 compound in the electrochemical process there Refractive index (at 25° C.) ------308 was obtained a liquid fraction which was identi 75 Density (grams/cc. at 25° C.) ------1902 2,616,927 13 14 Eacample 16 two are constituents of -CF2- groups, there Using 2,4,6-tri(dimethylaminomethyl)phenol, being from One to three acyclic nitrogen atoms having the structural formula: and from three to twenty-four carbon atoms per molecule. O 5 2. Compounds according to claim 1 wherein (CH3)NH,CA YCHN(CH3)2 each nitrogen atom is directly bonded to three -CF2- groups. 3. Compounds according to claim 1 wherein CHN (CHs), the compounds are high-boiling fluorocarbon O monoamines wherein the molecule contains a as the starting compound in the electrochemical Single nitrogen atom and at least eight carbon process there was obtained a liquid fraction atoms. which was identified as relatively pure 1,3,5- 4. Saturated aliphatic fluorocarbon tertiary (CF3)2NCF23Cs'9, wherein C6F9 is a saturated amines, wherein the molecules contain only car fluorocyclohexyl ring. This fully fluorinated 5 bon, fluorine and nitrogen atoms and each ni triamine product compound resulted from Sat trogen atom is directly bonded to three carbon uration of the aromatic ring by fluorine addition atoms of which at least two are constituents of and from replacement of the hydroxyl group and -CF2- groups, there being from one to three all of the hydrogens by fluorine atoms. This com nitrogen atoms and from three to twenty-four pound was found to have a boiling range (at 20 Carbon atoms per molecule. about 740 mm.) of 221-245 C. 5. Saturated aliphatic fluorocarbon tertiary. Eacomple 17 monoamines, wherein the molecules contain only 40 grams of N-methylpiperidine was dissolved carbon, fluorine and nitrogen atoms and the single in 2000 grams of commercial anhydrous liquid nitrogen atom of each molecule is directly bonded hydrogen fluoride and electrolyzed in the man 25 to three carbon atoms. ner of the preceding examples. During the 50 6. Saturated aliphatic fluorocarbon tertiary di hour run additional amounts of the organic Com anines having the formula: pound (totalling 110 grams) were added in Order to maintain the concentration. The liquid cell drainings (216 grams) were washed with aqueous 30 Where the primed R's represent saturated ali base and fractionally distilled to yield a 197 gram phatic terminal fluorocarbon groups and R rep fraction of relatively pure C5F10NCF3, N-trifluoro resents a nitrogen-linking saturated aliphatic methyldecafluoropiperidine, having the following fluorocarbon group. properties: 7. Saturated fluorocarbon tertiary monoamines 35 containing an N-bonded cyclohexyl ring, which Boiling point (at 730 mm.) ----- C. 65.0-65.5 have the formula: Refractive index (at 24 C.) ------1275 Density (grams/cc. at 24 C.) ------1.760 Where R and R' represent saturated aliphatic Molecular Weight (found) ------336 fluorocarbon groups. Molecular Weight (calc.) ------333 40 8. Saturated aliphatic trifluorocarbon mono The identification of most of the foregoing fully amines having the formula: fluorinated product compounds Was further Sub stantiated by the infra-red absorption spectra, Which in each case establish the absence of un Where the R's represent saturated aliphatic fluo saturation and the absence of hydrogen (either 45 rocarbon groups. - as carbon-hydrogen or as nitrogen-hydrogen). 9. High-boiling saturated aliphatic trifluoro The fluorinated N-alkylpiperidine compounds carbon monoamines, wherein the molecules con are claimed in our divisional application Ser. No. tain only one nitrogen atom and it is directly 290,316, filed on May 21, 1952. bonded to three Saturated aliphatic fluorocarbon Having described various embodiments of the 50 groups each of which contains from one to eight invention, for purposes of illustration rather than carbon atoms, the total number of carbon atoms limitation, what we claim is as follows: per molecule being from eight to twenty-four. 1. As new and useful compositions of matter, 10. The Saturated trifluorocarbon amine com Saturated fluorocarbon tertiary amines of the pound having the formula (CF).N. class consisting of fully fluorinated alkyl and 55 cyclohexyl tertiary amines wherein the mole EDWARD A. KAUCK. cules Contain only carbon, fluorine and acyclic JOSEPH. H. SIMONS. nitrogen atOnS and each nitrogen atom is directly bonded to three carbon atoms of which at least No references cited.