Document KReYvq0KwYjd2a91nQRNz0o7o
PPaatteenntteedd AAuugs.. 2244,, 11994488
29,4.407,17177
UNITED STATES PATENT OFFICE
FLUORINATION OaF OuRGnANIC COMPOUNDS FLUORINATION OF ORGANIC COMPOUNDS
SoI ptmepns Site Calle, a. ene to Joseph H. Sfmons, State College, Pa., ~dsnor to Hinioia Ming & MansiscirisCompass, Minnesota Mining & Manuh~cturing ~a~mp~ny, SUF lan, corporoafDteoiroarnt St. Paul, Minn., a eorpol~tion of Deh~ware
No Drawing. ApplicationDecember, 146, No Drawinz. AppliestI0n ]Dec,ember ~, 1948, Sell No. ThE Serial No. 714,918
' Cit. (CL 380-530) 2 S ~]ahus,
1
`This appicaton 4 a contnuation-in-pat of whi maybe cvoed the Borinaptroiceossn, This applieztion is a contlnuation-in-par~ o! coment applcaton Ser. Na. SFL, fad whbout the evelbeingrendered Acie owing eopending application Ser. No. 562,5~0, ~d
which may be evolved in the fluorination process, without the vehicle being rendered acidic, owing
Sonemb6e Fis nowabendonad. Tothebasicmutual pring. thasbehound November ~, 1944, now abandoned. This velo wie 8 methodafdircly havariageous 10 mala Das Vehi35c2l0eh This ~nven~on rela~es to a method of ~rec~]y
to the basic nature of pyridine. It has been found advantageous tv maintain a basic -~ehicle as such
urinating Gree Compounds byTackion WHA Vehicke 3 re Tavera tothe ested Bio ~uo~natl~ organic com~s by reaction nian rints Had sown ila, Faden resto in anycha Eyrdin io 36 el~menta~ fluorine in a liq~d solvent diluent.
5 vehicle ls more favorable to the desired fluorination reaction In many cases, Pyridine is an
The furoif ooraectompiounnd In un celnt ove. a arse umberofSEAR Com The fluorination of orga~c compo~ds in an
excellent solvent, a large number of organic com-
inc law hele by eke oF Geen) pobeung nFIERdYTosle her. inert liquid v~hicle by means of e]ementa~
l~unds being highly soluble therein.
rinehas prvionsybers Drop. Bee the Fasidine san Fei wih fuori o form & fluorine h~ ~rcviouslY been ~ropesed. Sec the
PYridine can react with fluorine to form a
SClolrps n"d,Benwnhiincgh PmabtoeinotnNsasSn1hy3d0h;o sHbiedd 10 o(rhneartne pyridine, ach 3a Tuoropyndne Calco~ and Bcnn~ng Patent No. ~,013.030,
10 fluorinated pyrldlne, such as fluoropyridine
a Aarne Aa reps POATORED Se~t. 3, 1935, w~[ch mentions anhydrous ]i~uld
(wherein a fluorine atom replaces a hydrogen
Rosin corde, Moriah Ac, and Soo. stomand dec bonded carbon mom by hydrogen fluoride, fluorsulfonic acid, and fluo~
atom and is directly bonded to a carbon atom by
inetd hydrocarbons 5. fultate. Thise Be & coven hn Sa Gninguished rom theac rinated hydrocarbons as suitable. ~ese are
a covalent bond), as distinguished from the
Tepresntative of acc dod Heal law, dive complex prvlowy tioned. However. r~pre~enta~ive of acidic and neutral liq~ds.
di~ive complex previously mentioned. However,
vithaavee 4f0ou5ndTetxhsaotnapblienceoe,, WhhaichmariskeTdaadd: 1tIhSeBHuobrnlaeteadnpdyrsidtineestohins sproldeucnetdismataesrtia I have found that p~idine, which is readily 15 the fluorinated pyridine thus produced ls itself a
available at a reasonable cost, h~ marked
highly stable and insert solvent diluent material.
Tantagesove the age and metreLauds re. TheSuorinatedpyidne 8 bal, forms addon vantages owr ~he acidic and n~ut~l liquids
The fluorinated pyridtne is basic, forms addition
Vis proposed. `rrain + ate Complete wih Raine. 10d actions Amiacy ~o~ly proposed. ~ridine is basic.
complexes with fluorine, and functions similarly
Semen oon the mist chemicals to pyrine. Hence theeect of forosof Elementa~ fluo~ne ~ the most chemically
to pyrldine. Hence the effect of fluorination of
civ iment own. Formatstsimoanck the dine Savend ook 50. derease the ~ctive element known. ~uorinatlon Is somewhat Snirtooniboa 5n ShSionse Te. 2 TASWERARret of th tert ort srsstering sIml]ar to oxi~tlon, but is an even stronger acon: Piorine Teale vialenily mith Toes Joan relative to the gaa soe beng uo. ~ction. ~uorlne reacts ~olentl~ with most Crrani compoundsSveaWi duced ATRL ALKA Dub reyto consume some. of he organic compounds, even a~ reduced temperafire envi deirctive Gecomporiion or Maorne, making Nuria for formation tures, causing a dest~ctive decomposRion or
20 the pyrldine solvent is not to decrease the molecular ratio of the inert fluorine-transferring solvent relative to the organic solute being fluorinated, but merely to consume some of the fluorine, making it unavailable for fluorination
Geprinion wee the Tacion 15 SATION. gg of the STE Ste degradation, ~less the reaction is controlled. 25 of the organic solute.
Givin Tuk cana bewed 3s adst 20 A reduced emperbliowu0rC,ethsera,te Obviously a ~i~uid cannot be used as a diluent
At reduced temperatures, below 0 C., the rate
vehi heh th onpnle Comind tp pa of Muorbation of ihe pyridine. soest. Clbmt vehicle, tn which the orga~c compound to be
of fluorination of the pyridine solvent diluent
Torinated 1s toned, 1 he `vehi 3 fell ployed in sh proceasuls sow, 1 tht for fluo~nated is disgolved, if the vehicle is itself
employed in the process is quite slow, so that for
Unfavcraily eueie to the clemeatary fuorine, price purposes th dent remains cst unfavorably reactive to the clemently fluoEne.
practical purPoses the diluent remains essentially
I ia marily be sippesca they ving 90 prcine cventa an berecovered85 ich I~ would natur~ly be supposed that p~ldine 30 a pyridlne solvent and can be recovered as such
Toul rescind wi Sure, 5a does WH ibe as wo~d reac~ v~o]cntl~ wi~h fluorine, as d~es Tennene "Tren a: Meher temperature, th rateof fio benzene.
The discovered, con0etxpecetatinon, thar ination of the pyridine wi be sow when the ~ have discovered, contm~ to execration, that icin has ieFRc to fuornt a tem. Sohn. sonaine4 oreue Sompmind. eile pyrid~e has ~It~le reactlvi~y to fluo~ne at temPersie bom 0 C. 43dhasotherpropecis 33 Whichfn sadly fuorinted. Insoc cashee peratures below 0~ C. and h~ other prope~ies ch uke 1 eh sulle for es 2 3 fe endency for te forin toms to riots ~ch mak~ i~ ~gh]y suitable f~r use as ~ fluo-
with little loss. Even at higher temperatures, the rake of fluo-
rination of the pyridln~ will be slow when the
solvent contains an organic compound solute 35 which is readily fluorinated. In such case the
tendency is for the fluorine atoms to fluorinate
Fomtion aaat 5 Soe 2 aan rian the PTE: rination 'diluent.
the solute as against fluorinating the pyridine.
iin cemesiaryfocrine 1s introduced into See Hucroatedprime bs cttnetetive ~en elementa~ fluc~ne [s in~uced into
Since fluorinated pyridine is itself an effective
ovine a Tehed temperatures, a moecins inet seve diva, 1 oan be rsovered and pyr~Inc a~ r~duced tom,futures, a molecular
Inert solvent diluent, it can be recovered and
Compsiy formed, whiz Suri Wmsary 4 ed aihe luen Inperforming hePORES c0mpl~ is fo~ed, wherein fluorine atoms are 40 used as the diluent in performing the process.
Soca ha by he Borin moles: and ths bon ibs occasions. The vention amore loosely held ~ the ~y~dine molecules, and this
upon other occasions. The invention embraces
Complex can act 45 8 Fustnating gon. The ihe eof Suorioaied ridin 1 on mrtsven complex can act ~ a fluo~ating agent. ~e
the use of fluorinated pyridine asan inert solvent
Compl rnstersBin 10 theorganscom, Ghosh, and soneSse 1 ayboGece 5 complex tra~fers fluorine to the orga~c com-
diluent, and in some cases it may be desired to
pound ote10 0to aiseRaornattiheornes| cmpayJt cxcwhhoivTAeLSlwe,of pound solute ~o ~ to ca~e fluo~na~on th~eo1
employ it exclusively, without making use cf
a: modemie snd controled fashion which 45 pyridine in a moderate an~ controlled fashion w~ch 45 pyrldine.
vos he vile 4nd Gesirucive or dgradutve Tous he Invenio 1+ nok restrict to the use ~voids the ~olen~ and dest~ctive or degrad~tive
Thus the invention is not restricted to the use
Sion charset of rchSuormaion. The of sul Teiinnud,es porn ria: action characteristic of direct fluo~tion. ~e Secs ie,iretfrom(0 reuing when tives which keviseform.addin. complexes effec~ Is ~ different from tha~ resulting whcn Sorin i diva 4 aSiTple SOMUGE nh WAR SorinDuar eaves Ce una: fluorine is dissolved as a simple solution In an
of stmpl~ pyridine, but includes pyridine derivatives which likewise form addition complexes with fluorine but are relatively insert to fluorina-
nr cent vehicle whichdotsao:for the 50lon (1 6. yee bandingofSucre) when iccnoomemp~plelexsxo..lveMMnotorerveoeovhveiercrl,,e ttwhheehicpphyryidd~oienese naaobb~ssoofrorb~rsmrreellaa-- 50 eteimmopnplloo(yyiee. dde. aussvatsleoonllvvceeennttboddnildlluuineegnnttssofffoofrrluofAlruuionoreril)nnaatwtaohbbellnee
ily mich Jerse Gumi of Sucre hando oven compound souks Afetecoample a tivel~ much larger quantities of fluorine t~n do
organic compound solutes. A further example
hea WhichGo ho Tor uch aCOMIC. A Tio) price Othercompounds emialing solvents w~ch do not form such a complex. A
methyl pyrldine. Other compounds COnt~tnin~
Fiberaavintage ofDine In(ha 1scpable hebrineringmaybecoped asequivalents f~ther adv~tage of p~ i~ that it ~ capable
the pyridine ring may be employed as equlvalentz,
ofShirin al amounts of bydrosenBaeride 85 Sh os GUOIREr aB4 oir ado rng com of a~rbi~e small ~o~ts of hy~ogen
55 such as quinoline; and other _~dne ring ccm~
-- Ex1h0i0b5it || Cnorteno.reucse.
11000055..00000011
STATE 07524645 STATE 07524645
aver 33 sms gen gm usd, sme: pounds containing more than one nitrogen atom
44
black slurry was ether-extracted.
The ether so-
BE g E S EE Cs sTte in the nucleus, such as diazines. r The reaction vessel may be of copper or silver
lution was separated, washed with water, dried over solid NaOH, and fractionated through a
B Ea E ey ET LI construction to render it corrosion-~esistant, pro*
small five-plate column. Cuts boiling from 80-
RoE. vlded with a cooling Jacket for temperature con-
86 C., t~talling 23 grams, were refraction~ted
SE a Corel Oo 1B.5 Til 8pm oyibis trol, and with mechanical stirring means. The
through a small metal-packed column having an
BREaESSEhEE | nd pe RS fluorine gas stream preferably enters into the
estimated 30 theoretical plates. Decailn was
CE SRI SE SEe S SIehba E a vessel below the liqUid surface and in the form
u~ed to back the distillation. The follow~ng frac-
of small well-dispersed bubbles. Inlet and out-
tions were obtained:
let ports may be provided for continuous opera- lO
ESy a ei t nis wr y tion. Where the reaction product is removable
25 avapor,further additionsof the organie re- ou By| ee)| Mr as a vapor, further additions of the organic re-
Brn ee actant may be made from time to time, or con-
Cut
B.P.
(co.)
Weight Refractive Inde~
Ee tinuously, without further addition of solvent
................................. 68-79
ent" res conmdeiyebenprosvideed 15 rr) HEBE MHees diluent. A reflux condenser may be provided.
15
2 ......... : ....................... l
3 .................................
79-800 l
1.~
The fluorine gas may" be diluted with an inert
13. 80-820
Pr ee LR gas, such as nitrogen, in order to retard the re-
!.49~0 I. 49~1 1.4921 1.4753
Sora action and permit of better control of heat in the
Bens Te reaction vessel.
Cut 5 had a molecular weight (Dumas gas den-
c E auh smo a tr, t uo BalleWS I A catalyst may be employed but, in general, 20 sity method) of 95.6. It was separated by low
there is no need for catalytic assistance in view of
temperature filtration through a slntored glass
BELATED the fluorination activity.
disk, the lower melting fluorobenzene (M. P.
ey i DLT Ei WE ~'he reaction of pyridine and fluorine is flinsi deye re 05) aete Hat trated by an experiment in which pyridine d~s-
--42 C.) being thus sevarated from the l~gher melting benzene (M. P. 50 C.). In order to ob-
P ERE E S IRT Lwm u Hh Vl da in 8 solved in 2-fluoropyridlne was treated at 0 C. for 25 tain a pure sample of fluorobenzene, only a 0.2
four hours with fluorine gas diluted with nitro-
gram sample was collected in the first fraction.
Ee Sr Oh SEAT Shp le Re dey gen, resulting in the conversion of 40% of the
This sample had a melting range of --46 to --42
Bin Ee TaaE SE en SR ~yridine into fluoropyridlne. In this case the EE eT TS EET EE Euoropyridine served a~ an inert solvent diluent. EE EE The absence of a different fluorinatable organic ELnLEP Sk on ER i solute to preferentially react with fluorine exCe plains why the pyridtne was fluorinated to this a extent. When such a fluorinatab]e organic so-
C.; a refractive index of 1.4698; and a fluorine content of 18.6% as determined by Parr bomb fu-
30 sion and titration of the resultant fluoride ion content with standard thorium nitrate. The theoretical value for fluorobenzene (C~H~F) is 19.7 %; and the reported refractive index value is
Er: lute is ~resent, the rate of fluorination of pyridine
1.4684.
FERC ITTE S riu ta anr reeys is made much slower, so that it is possible for the 3~ The residues from the first fractionatlon were
pyridine to behave ~s a highly inert (non-rea~-
distilled in a simple distilling flask, and the fol-
Tmner ren: Ee tire) diluent. The following examples further serve to illus-
lowing, cuts were obtained:
FE aT o = reo [=i trate the invention. All parts are by weight,
ccpt as noted. Brample 1
pet vs ernet Em | 1 A reaction vessel was charged with 19 parts of hmmm aRuEn o Emeno ee] BHEE)] toluene dissolved in 79 parts of l~ridine. Fluo-
Toe} mel 3
rine gas diluted with nitrogen (1:25 ratio) was
`passedthrough thesolution,th temperature be- avy residueremained a5 . passed through the solution, the temperature be-
A black heavy residue remained as a pot residue.
EOMTR CIEE Aenseis ing about m20 C. After purfflcation and distil-
lI ation ofttheerreessaullltiinnggrereaaccttiioonnmmixixttuurree,, twvoo 8fl0u:- oorriIinnnaatttheeddispyperyxirpiddeiirnnimeewewanastsoffnoolryrmmaeedds,m,ddaee!mlmoaomnnsostturnarttainotgfitftnlhhugee-
o110r0i0n0-1a-1t1e0d1C0tCo.".haiatetneaasppwrreerseseuorbestaooifsnf1e1ud39.-00rmrOiaemmn.e.,,dwwi~aatssimllmeodorareet go Pprreeffeerreennttiiaallffulouroirninataitioonnoofftthhee benbeznezennee..
dense than water, and contained by analysis
Exampl~ ~
REECDEEGREE | ie rSemees isnn 46.4% fluorine. The other bored at 93-103" C. at
Atmreo ssurc eandpconth ainee d19-r 90%A l ofsie wera selsand 180sar ofSo Tn atmospheric pressure and contained 18-20% flu-
oy w EE ooHrin:e;
A glass reaction vessel was filled with 65 grams
ottlifoongnlaaattceeiddalppayyrcrieiddtiilcnneea..cidAAanddrdryy,,16oo9xxyygggreaenmn--fsfrreoeefe,,drffylluuoforrraiincnee-
iy ie ar and nitrogen mixture (1:10 ratio) was introduced
J IR rn] ~luorlne diluted with nitrogen was
through a copper tube at the rate of 0.1 reel of
ZEIT LE through a solution of 30 parts acetophenone in 79
fluorine per hour, for a total of 11.5 hours. The
NIE parts pyrldine at a temperature of --25 to --40~ C.,
reaction vessel was kept at --10 to --25 C. The
es: Spun ay 08 3 resulting In fluorination of the acotophenone and
reaction proceeded smoothly, with the evolution
EEiRi E o, FTne cs sto, we the production of difluoroacetophenone.
of white fumes. Products containing combined fluorine were
prag ed I RErT INT A solution of 90 co. of dry, refractionated benAss ganrt, pa zene (B. P. 80 C.) in 160 co. of dry, refractionated Eo pyridine (B. P. 115-116 C.), was treated with
obtained. It appears probable that some fluoroacetic acid was produced.
Example 5
tat IT eee 05 i 0.75 reel of fluorine, which was diluted wi~h nitroEE EnEInT ns gen in a l:10 ratio. The nitrogen had been EE Crs nas treated with alkaline pyrogailol to remove any
Fluorine gas was passed into a 10% solution of benzene in. 2-fluoropyrldine, at a temperature of 0 C. A solid reaction product was obtained
BmaEnT rE o~Tgen and then dried with phosphorous penter ES IRR |, DiSe Re oxide. The reaction temperature was --15" C. FOR Sele RoE ST The reaction proceeded smoothly. White fumes
which, after removal of fluoropyrldine, wa~ found to contain aly~roximately 20% fluorine by weight.
ET ars . were evolved and the solution became dark and
mms TR somewhat viscous.
A10% solution of butyric acid in 2-fluoropyrl-
EE wr rm ei, | SI pnd Se The reaction products were poured onto iceFE mmr - SREIEERTTS cold dilute hydrochloric acid and the resUlting
dine was treated with fluorine ate ~. Products containing combined fluorine were obtained, and
11000055..00000022
stare rsziess STATE 07524646
surmr 5 66 9,447,717
1:appears potable ha someSurobutarcsd subnsetfao thne trienbutlforyms3 i~ appears PrObable that some fluorobutyric acid
substantially inert to the fluorine but form~ a
Efe mali copieUren ai4nB.r: was produced.
molecular complex therewith acting as a fluori-
come 7 Toi agent To to cand srl spn nating agent for the dissolved organic compound
neticc xcoi mdaiinntiIennd2crZcpuoirinavaes was; R I PEOCIOS Lorati0ontCerooelBnt S' oBuoarnaanned Acetic acid dissolved in 2-fluoropy1di~e was
to I)roduce fluorination thereof in a ~nooth non-
Eas mona, wnat i The pros. | PERofaUd crane compoune. treated with ~luor~ne at 0 C. The reaction pro- 5 violent manner, and recovering a fluorinated
product of said organic compound.
Sade maa,wit io proces of produitorn Surne ceeded smoothly, without explosion. The prod-
8. In a process of producing organic fluorine
Hating Ghote cmbdinots of he SOUS ring Veneer; Trine io ucts were not analyzed.
compounds, introducing elementary fluorine into
plait deli wl cabinents of 3 mitareseal smpong Boor Having described various embodiments of the
a liquid mixture essentially comprising fluoropyri-
into, whe an bs os: 10 dns and up added orgie compound solute invention, for purposes of ~]ustratlon rat~er 10 dine and an added organic compound solute
ln aproc of roduin cpa urine RBA 5 hl scheto ori the Stary than limitation, what I claim is as follows:
which is highly reactive to fluorine, the mixture
composaouSnchcChompe racing cg mainlinedat 3 tempera sue tht 1. In a process of producing organic fluorine
being maintained at a temperature such that
somone oe seswhichComrierRCUDE aSurapyain sere bs Baud sevendi compounds, the steps which comprise reacting
the fluoropyridine serves as a liquid solvent dilu-
Oe aml ns Ba even i, 2 ih 1s baal ar to th rice fluorine with a fluorlnatable organic compound
ent which is substantially inert to the fluorine
solute in a substantially inert liquid solvent dilu-
SeE ta eine e itroeofionteao,aBdevioeand , |18 218fonrm1yaolgeacaglearncofmo paesdtohevreewidthoswnge ent of the class consisting of pyridine and fluori- 1~ basutafoflrumosrinaamtinoglecaugleanrtcfoomr pthleex dthisesroelwveidthoargcatinnigc
acne sd Brad pts pros ri Sent 3 nated py~ldine, and recovering a fluorinated compound to produce fluorination thereof in a
Sueto gat . one pane aTeovring3 product of said solute.
smooth non-violent manner, and recovering a
reedemai SAIS htstring HLA Brckoad organscompen. 2. A method according to claim 1, wherein a fluorinated product oi said organic compound.
reducedtemperature l~ maintained not exceeding
Suro e Sosen 1. sneons. about 0 C.
JOSEPH H. SIMONS.
eTri amectahmopdiancacse8inEoircoton1, whereinsud `BEPERENCES CITED & A method according to claim 1, wherein said
organic compoUnd is a hydrocarbon.
armmee n dsendiAnh ioSmineSNheYdAd mo rtowoing oming reteeunecosf rdrr112 the 4. A method according to claim 1. wherein said organic compound is an aromatic hydrocarbon. 5. A method according to claim 1, wherein said
REFERI~NCES CITED
The following references are of record in file of thls patent:
eating sam herald 2 1151 57 organic compound is an acid. medoor 13 cit 1,wheressid "NITEDSTATES PATENTS 6. A method according to claim 1, wherein said
T~NX'J.',~J STATES PATENTS
orga compo se Ac. om organic compound is acetic acid. pTTi& paces of pratcing rene suai 32,0"S"BSSBE cucucsa oonSt0, 38 7. Tn a process o~ producing organic fluorine
compounds, introducing elementa~j fluorine into
br ed a liquid mixture ea~entially compr~ing pyridine
Number 2,013,030 2,013,035
Name
Date
Calcott et al ......... Sept. 3~ 1935
Daudt et al.......... Sept. 3, ~935
Sada Sais ores compara te and an added organic compound solute which uyracine ie ore he cheene ReAECH Rs ~s highly reactive to fluorine, the mixture being
FOREIGN PATENTS
mained se reve su TatthPy gp Namber _ Couatry Dae maintained at a temperature such that the pyri-
Number
Country
Date
actres 08 Badsoe lien whEh 5% TOO Pras eer Tn,108 dine sc~ves as a liquid solvent diluent which is
786,12~ France ............. JUne 3~ 1955
11000055..00000033
STATE 0752647 STATE 07524647
