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Some reactions of fluorocarbon nitriles : syntheses of amidines, thioamides and triazines

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Title:
Some reactions of fluorocarbon nitriles : syntheses of amidines, thioamides and triazines
Creator:
Reilly, William Leo, 1926-
Publication Date:
Language:
English
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57 leaves. : ; 28 cm.

Subjects

Subjects / Keywords:
Amides ( jstor )
Amidines ( jstor )
Amines ( jstor )
Ammonia ( jstor )
Boiling ( jstor )
Flasks ( jstor )
Fluorocarbons ( jstor )
Hydrogen ( jstor )
Liquids ( jstor )
Nitriles ( jstor )
Chemistry thesis Ph. D
Dissertations, Academic -- Chemistry -- UF
Fluorocarbons ( lcsh )
Genre:
bibliography ( marcgt )
non-fiction ( marcgt )

Notes

Thesis:
Dissertation (Ph.D.) -- University of Florida, 1955.
Bibliography:
Bibliography: leaves 54-56.
General Note:
Manuscript copy.
General Note:
Vita.

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University of Florida
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13304237 ( OCLC )

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SOME REACTIONS OF FLUOROCARBON NITRILES: SYNTHESES OF AMIDINES,

THIOAMIDES AND TRIAZINES







By

WILLIAM LEO REILLY


A DISSERTATION PRESENTED TO THE GRADUATE COUNCIL OF
THE UNIVERSITY OF FLORIDA
IN PARTIAL FULFILMENT OF THE REQUIREMENTS FOR THE
DEGREE OF DOCTOR OF PHILOSOPHY












UNIVERSITY OF FLORIDA
AUGUST, 1955












TABLE OF CONTETS


Page

LIST OFTABM , . . o . . . . . . o . . . iv

LIST OF IML1TRATI * , * . * . . * * � , * v


IJN�ROU�TION . � . . , . . � . 1

HistoVY . � . . . . . . . . . � . . 7
Reactions of Fluorocarbon Nitri e � � � * 9

"MDIENTAL P)CIMUF . . � � � . � . . . � . 10

eneral Coideratins * . . . ]A ) � * 10
Aoetforonitrile U � . . . . . . � .
A ines * a o � * * . . . . * * * * 33
Fluorocarbon alidines**** 23 1-methyl and K# 1-dimetbyl Alkfory aidnes * 114 metal **its of the alkforyl sidins a * . 16
Attszutd preparation of the alkali neta
salts of the alkforyl aidian . * 0 18 Acid alta of the alkforyl amidini . . . 21 AcylaUd alkforyl amidines . o. * . * o 22 The butforamidine with sodium hypobromite * * 25
Fluorocarbon Thioaides # . * � * . * * * 25 2,1406 tria(alkforyl) 1,3,5 a-Triazines . * 27 Infrared Spectra of Alkforyl Triaoines . . . * 29
DMCUISSICN o # * # # * * # * e * * 34 �� l

AlkforylAmidines . . . * * . * . . , 34 N-substituted and N, N-disubstituted midas . 39 AmidiniumSalts. . * � � . � * . . 140 Aclated Alkforyl. idi * . . . . . . * 141 Reaction of Butforaudine vith Sodium Hypobroidte 44 Fnuorocarbon Thiomides � � * * . 45 * , 1 Alkforyl.'.- sne * . . . . . . . . 46
Infrared Absorption Spectra of Alkforyl s-Trl a 49














BIBLIO o o 9 o � 2 ��4��� B IOl W 0 0 � � S � 0 � S 0 0 * 0 0 BICQ HIOAL NM 0 0 0 0 0 0 0 S 58


11�

















LZBT OF TAVIJ5


Table Pago

I Alkforyl A e . , . . o o o . . . 1

II N.-sustitut4 Alkfoylamid s . .

iii 9-8ilverAJkforylkudtnos . . . . , . 19 IV N-ercury Alkforyl d . . . . . o . ,* , 20 V Acid Derivative of Alkforyl Audines . * . . * 23 VI Alkforyl Thioamides * .9. *... 28 VII Alkforyl.hraie. . . . . . . ,. . . . 30

VII pKb Vauefor Certan Ais * 37

IX Otiaum conditions for Alkforyl NIt ile Trlmviatie, 49 I Comrative Tields of Alkforyl smTriaslaw # * 10















LIST OF nlITRATI(


beamd Sptr'a of 2,I4,6 talia(netfou-l) L,3*5 0-triIfa * 31 Infrard Spectra of 2#14#6 tris(propforyl) 1#3#5 Os-tins1 * 32 bnfar4 Spectr'a of 2#14#6 tra(buztfoy1) 1,3,5 swt 1s v 33
















PFRLIKART IUJZA


All theatre reported In this dismrtatm w in the cntigrae scale and umorreoted.

Rafractive indices were dbtrinsd vith a Abe* at 29,

Molar refractm were calculated by the Jam*amts


Equati, o


The value for the atomic refrations vtre ta-n t4 Lage' 5n.k, Highth Edition. A value of 1.100 was uied for flacrm.

Dnsities wvre determined at 25 with a Ponmter calibrated with utter 02 b .

Mlecular wi ,hts were determined by, the metod of Vapor Density ow.loyinv the method of victor Nayer.


















The 414osver that fluorine could be opined vith carbon to pro w. a new series of amouns fuarnihed the beginning for the devlepmnt of a branch of hmist.y kDOW - fluorocarbm
*mltrY. The impetue for the rapid devlopmet of t i field ws provided by the fast that the copoud formd of the union of fluoine and o pdu sam of the moet chemilly inert trials ko to a The latter day &Yaeolmest of the field hoivr, is dmo to the discovery of the m reactive auroarban derivatLves and their emplaust in chemical, syotheia. The sew* and usefulness of the cmoum so ro ham ad, the field of fluorocarban AhemStry me of the mt intenively studied branches of chemistry today.
MW research that has follod the discovery of tham ,

- has that the reatios of fuarosarbsa eriva*tvs Are not identical vith Snalog0oam orgaoi reactions but extend from sedifted organic reactions to Sam reactions not fiad in organic, Ohemistry, This variation in reactivitw fron ooWttimial argan" raOt4*n ha provided the omist with my uique and Interesting


On the basis of our present day knowledge of carbon


IMODUCTMN









2

f rine omowr and their du~vaeaveterev e -eld apear t aiasst joy hyr~ocarbwmsopon stucur O& be prdodin the

flaiwoe.bieSMU and amw bOt f.u~ in orgaei abmstry. Me

the me. Obe thU has been iedte replaceet of the Iudpocarbon structure in the solocU~l by the fluorocarbe utrate hs been fon to Produce CORVOmds 14"e Propertisso reactivity sm to a greet extent altered or eve copplt y ..mgo The, at step thni to emlo thee. 100l0CUl in cemial sythesis.

one Wa of the field of fluorocarbon Cheistry vieh sb pns. of being of great iq retan is that Of nitren ootainiM f r the field of orgi Chemistry, the nitrogen drivatives of hydrocarbon osepouds, occupy a position siVnifisent In imprtance end devlpnwt,. The field of the nitrogen contain,, ing flf oderivatis sho promise hut has been invve ttgated only to a very limited extent,

w specif i area of the field of nitrogen deivativee

*1b should produce soma interesting reaction and cn s Is that of the aitrilee or cyanides. The nitril. groups, being of an unsaturated character, is highly reactive. This wautinof the carbon to nitrogen bond coined with the stroM electronegative effect of the fluorocarbon radical should show enhaned roetivity or reactivity of a nature sufficiently different to produce a significant change in the final producta of the reati,

It has been noted that manny of the ractions of nitriles require aid catalysta to initiate the reaction and In may oas









3

the initiating acid is necessary to stabiliue the products. Thus'. the euionolysis4 of organic cyanide occurs genrally in the pre.sence of the hydrochloride of the anine. lcoho1vyss35 and reactions ith merpw tans36 involve an activated nitrile nucleus, and product stability is only accomplished through salt formation. rt has been noted by Kindler and TreA while study the Influence of subtitwts on aromatic nitrles, that the more electron inducing the attached g , the greater s the reactivity of the nitril. toward ydroge sulfide additi Polriation studies of nitril17es indicate that once again acid neowsary to Initiate the pol -aeristion4, indicating that a mre restive canter Van that presented by Vie free or-ani@ nitrile Is nseasary for reactivity.

The reactive nitrilo structure may be presented as# 4k -U
R-C4=

CA Partial charge


The fact that acid oatalysis is so effective in addition reactions end polysWiSetiN is pr 1ably duo to th fact that t proton stabilises and enhanes the reactive carbon it* so that under ai catalysis the, reactive nolecule now apears





Ibis strnetiae provides a atimaoid site very suitable f r reation. The alkfo atrilee would have an additional advantage in that the in. dictive effect of the very elestronagative fluorosbm radical w il









14

activate the molecale to such an exigent that any acid catalysis would be





+4 0



This contention va fou t De true in that what vo-ld be codn~ed aormal reaction s amog drocarbon cop u e ound to be quite nor a. reactions for alkforylaitri1w.

This can show by considering swom reacio s ot erganio

chemistry and caring thea with what might occur in the fluorocarb= nitrileso

Cley, Partridge "n Short*k have show in the reaction of

anine, with eyanide. to form idines, that an quilibrius mixtre is stalisheds, and through the hoice of suitable conditions, midinee ould easily be produae4 Since azidines are usually stronger barn than the amines or amia from which t. are produced carinf out the reaction in the presee of an *oniumlt produces an Saidiniva salt* Provided the temeratuwe - below the dissociation teratne for the ltj, the e uilihriu would be disturbed and the conversion of the eysnide into the amidine vould be promted. The retim apea t4 be controlled by a nmber of factors The presence of a m strongly aninoid nitrogen atom in the base would facilitate addition to the cyanid, the increase in strength of the base would decrease the prp tion of the amidine converted to salt with a corresponding e0alW dioslewit of the equilibriu between the cyanide, bow and Midines,











The use of aldori jntriles in these experiments g'uld e.flinate both of these ooiVMoatiorns, The endanced reactivitv. of the cyAnide gvor diw to the inductive effect of the fluorocarbon radical to ich it is attached# would cause th base to be attracted to the cationoid site more easily. c the amtinea are forud, even though the finorco carbon ridical would tend to dre its basicity, the idie would not be affectd by y equilibwima or coetition with the base for the available acid to satabilise itself. This stability hould be an Ino harent proprty of thei molecule itself. Therefore, &lfoaylitriles should have at least tw advarilvages over orga.-ic nitriles in wro lysls. The first is a more readily available re tion site aad tLe second is the !act that no imorted stimaul is nacsauy to stabilize the vleoiale, )ne it is formed.

Another pbe of the reaction of nitriles that would appear to be of interest is that of polyrization of these In the field of organic hendstry nitrile. are know to tri _wize to form the oywnuio ringi


R

C
I N
3R1
R -C C OR



Benocitrile was found by 01cm17 to condense =der the influmo ot sulfuric acid to form oyaphnin. Ther are m additional referecms to the poijusrization of individual nitrites,19. 48 1h~e, firce and Bolt"0 polywrised trichloroacatmxitrile under the Inflice of hydroge








6

hlorid. and pressure to produce the 2# 4# 6 tris (trichblaM thl) I, 3# 5 triaim s Vhi te y t n fluorinated to giv the alkfoyl derive tire along ith eigt other fdluorine c tining omo ad.. The substance a fud to be very resistant to acid ad exhibited no basic prpertis at all4

Use effect of the fluorcao gru in these Polymerizatimn reetism w ldppear to be interesting and rtby of stuy he expected activation of the nitril should occu and pd1$wrixUa n should then be of an uncatalybed natmrso

Ormu~mann ,- isiseo and Sqeide18 hate proposed an interesting inhwnisa for triasine for'ution in an said cataysed state. The

*primfty product* U a substituted linn chloride of the type#


LaO 1 aiC" 41C


C + C R 01 IR/
L

It is a salt like structure %hih on decos~ition with vater yields the sacorutary amid.. Thq propose the next step to he a dies synthesis typ reaction in uih the primary product* Is the diezse and the third mote, of nit wile In the dimnophile.

R-C C-RR-P /*, C- R- Ca



/ "' \/ G
' Rl Il
101









7
Tte product then Imes hydrogen chloride and aromatizs, to form the triasinae, er thing could happen with the activated alkfwryl ,,trilo vleoule to give a siallsr dism arrangeet followed by coWLng to give the triasias.

These, then se so, of the interesting possibilities that pre sntd themselves whe the wrk va undrtaken* The intent of th* wk va to study the effect of the adjacent fluorocarbon radical an a r-etUW nitrile site with expectation of chemically estsblishbW e preconceived ides as to the nature of the reaction of alkforylaitrlla in addition reactions. The ork was further extended to u the alkforylidias produced as a synthetic tool in preparing other fluorocabon derivativs.



?he history, a fluorocabon compounds and their 4erivativs met date back to the diseovery of fluorine by Nism in 886.29 Prp'ess was "ry slow at the start, due partlj to the experimental diffiCulty in preparing fluorine and the extraiordinary reactivitir of the elents easing it to rest explosively with most orgamni W , Probably the first furabnproduced, a mthfre as prepa-ed, by Lsbeas and Damens in 192626 It was prepared by the action ot fluorine es, charcoal fff4O followd up this work and fully characterized the cOoumwd nethfres along with saws observations on higher haomhgs, possibly ethforane and propfores, aso produced in the reation, Later, Six" and BjojC#44 empoying mercury salts 0 an explosion in. hibiter# reported a direct fluorination of carbon and isolated a nuwhw









8
of fluorocarbons. It the elucidation of the pica properties and the chemical inertness of these comounids uhich occurred asan hmlogous series aalogoua to hydrocarbons, it was se that thes compouds might wll s as a basis for a an chemistry founded on fbaorocawbm rather than hydrocarbons.
The interest in these new compoud son provided new w" of preparing fluoroearbona. These oonaisted of (1) controlled reaction between elementary fl rine and liqaid hydrocarbons, copper neab being empled to provide effective yeometrX for reac s,p,28,14 silver plating of the copper gauze to provide catalytic surface as as beneficial geomitryj15 (2) powerful fluo inAg agents suah as eobatia fluoride whichwe prepared 6, 38 and used in the repisomut of ohl. rime by fluorine to prodaft a fluorooarbon.0, 12 and (3) probably the sest Vrsatlle and meet eorsially applicable process was the electraOhaIcal press as reported by SiMosj5 This last proess involved the pro tn of fluorocarbons and fl derivatives from eaetam cOntain1ng materials by the passage of an electric current of low voltage through a mixture of hydrogen fluoride and the carbon training Compound* A great nuer of materials could be emloyed such as khydr.-m carbons, -arbWie aside, esters, alcohols, aid Chlorides, et-ers, maims, sulfide., ete., iving the chemist a wide varI* of starting materials with hich to wrk. It me tese latter day developin+,O whiCh paved the v for the twrendou volume of synthetic endeavor n" being d0e In this new and rapidly expanding field of chemdI research*.













A.ev 'oitrile* -e first prepard by svert*k? In 1922. It

vs ps'epwe* by the debydation of the acetforadde through the aotim of phosphorus pentcade Sims that time the other m rs of the iseii hav, boeen prepared in exactly the sam fasMhom. The fluore. nutow aitriles rge a of the reaotioi found aw the ogani nitile., The ftooabnnitrils, ~~~s readjinL base to fws' th. acid salt and the rmnia. Hydrogeaation over platinum oxides yields gfod oonversicin to the auIneA and they undergo reaction with OiUnard reagent to form alkfasIL substituted tohm 027k fluoorbon nitrilse have also ben wsed with the GrIcuard r.agmnt to prod a series of alkforyl keto...31

The mast striking differsat displayd by the fluorovarbon

derivativ when contrasted with their organic analqs is in the boilU9 point* of the tw Aterials The acetforomtrli. boils about lit9 boiew that of tie byr&ao s analog.it6
The fluorooarb nitrjlea ae gernl&y prepared f*rm the

=Ae# which in readily prepared frost the aster or the WWyI halide by inmoURlsI- and can be slmt quanttatively 4s44Me to the nitrlJ through the action of phosphorus psuntexidegit? Thy am also he propared by the setwrochsuSial pros, using the hyd~resarbonm alogs as stati- mtrials FluorOeco nitrles are produced although there Is me decoepitim tsF


mso nomnlature ued though the twit is that proposed by No, SiMs, The reader is referred to che.. f. No 26p 131? (19 84) for a more coxplst. treatment of the subject.
















EXPEDUNAL REKM


Gneral Considrtions

fth reatimn and prepwatioin which follow a1 hawe a Comm chemlaal source,, nomly thes loroawbou nitrilee It Would, tbmrefw b* of oom �Intrt to list som goeral, cosideration of tho eam te usoed and the methods of preparation for the starting eeterials wsed.


Mtfewilc Acid Pucpfwric Aid DKUtcr A414 Ambldreas Ammnia Ank~dous Nothyl Amift A*lYdmUs Dithyl WAxiG haIW*au Wdroren Sulfide


Purchased from Wiineta ining and Nutawn Compz,

Purchased from Missoeta Mning sd IlarufAoturing Oaqx.

Purchased from YfAiseta Xining and Manufacturing Go .w

Purohuia" from the E. I. Wsant de IMeurs and Gou,jo Ines

Purchased frc. The Wathese Covaqrp Inc*

Purchased frow The Matheson C*WaW, In..

Purchased from The Mathesn CoMW, Inc*


Mwe fluooarbon nitrilee vw prop""s as described In the literature with OV4l slight 1 oiloaia In the prosde,'"4 T"0 flIuorocarmn nitril s as prepared wre found after a cis plate distillso tm to be of sufficient purity to we in the. ew rimenta. All =Jr 10










purification wir aco~1ished with the easily diulable eter or the eqiaelyr oauy recrystallisable amide since both of these products wre quitia stabl, and .mvemt to handle*

The operation of the nitrilo *an be schematically reprsented by the following set of cheiial equationss


;' RgCOOR + H20
Et20
RfCOC- + H 0 fC0W2 +1Q11 RfGOW * P205 RP0 * H39% X-. CUrs C275a-, 0Fr

The experlital thod for the ac"fo iaitril. will be -scrift bed Thoother eber of the series wre preared by an analogous series of reaction,

Aotforaitrile

Kthrl acetfor too- Into a 500 c round bottom flasks fitted with a reflu condenser an protected from atpheric moisture by a drying tube placed 1l4 g. (1.0 mole) of acetforie ad To this a added an ice cold mixture of 96 C. (2,0 sole) of ethyl achql and 75 g. (0.8 mole) of omcentrated sulfuric asid Ihs Wxt was aflowad to stand at rem temperature for two hours nd than refluxed for a additional two hor. On cooling, the ref lux con er is ramoe and the flask fitted with a dovawad condener, The crude product was obtaind by stopping the reaction mixture of all liqid boiling below 700. This crude eater was washed twios with saturated sodium carbonate solution and dried Oeaq









12
eahydrou calcium sulfate. Th. crude aster s fraotionated in a dist~flation coIuu packed with glass hel.cs of approiatel y nine theoretical plates. The yield of pure ester boiling at W-62 , as W g. Tield 92%, based o aa.nt of sod used.
A-etfard&. A three nooed, 500 cc roand bottm flaskp

Iimwd in a Dry Ie-acetwe mixtre, ws fitted with a delivy tab* and a cthrou ubih moist air was excluded by a .41u q*KIA drying tube. Into the flask was placed 158 g. (1*O mole) of eth.l acetforate along vith I00 ac of ethyl ether. Into this s-tu was caondsed a lagex s of anhydrous ami. The reaction mixtvr vas then allowed to wsu to room toertare and the wm s inia allowed t ditill off, to solvent vas then stopped from th reactlom ixture, leaving a %hite solid which cud be reorystaULed frn ethyl etbormptroleu ether to yield pure acetforamide (s.p. 75). The solid 1i091bed M g,, 91% of theeretloal yield, based on the original aunt of ester.
AcefornitileowA mixture of 113 gm (1.O vole) of acatfar'. a de ad X50 g*. (1.1 =oI*) of phopwrus peontalAo was planed in a romd bottom flask fitted with a reflux onadenser which in trn was sonnected by a rubber tube to a glass trap isema--d in Dry Ico-Wetan viXtuMr. The solid alltureg wte heated to 10 and held at this trature for three hours, evolved acetforoutrile which was collected in the traw. Distillatio, to a new tra-p qu 76 C. af eaetforonitrile. Yield 68% of theoretical bagd on tba aside used.














Fluorocarbon Arildins
,- A reaction vessel conistinv of an 80 RL cylindrisal glas flask fitted with a deivery tube and co eted to a Dr7 lcs-acetone reflu on s was plaeed in a Dry Ice-acetone bath* Into the flask w distilled 11,2 go (0.40 ,,O) of ao0tforoitril. A large exess of anhydrou amiWa was then allowed to cndense into the reaction vessel containing the oodnsmed nitril., The Dry Ice'.acetono bath asremoved and the mixture allowed to ref lu undr the Dry Ice'aeetone condenser for one hour. It w noted that the mixtu" did not react at Dry lceeceton. teoperature# but at slightly dove this tewerature a violent reaction ensued. The ces wnia vs allowed to distill off and the reaction mIxture allowed to oe to re te m rate The resulting pro uct was th fractionated through a col Packed with glass belice. under reduced pressure to free it of any dissolved amia. The final product as a colorless liquid, b*P* 35-360 01 uian n2

1.3801 eS 1.4940., . . Analysis Calculated for C2F3N2H~t No 25.00% Founds N, 214*84s%

The succeeding memers of the series we low mlting solids

which resulted whan the excess amnia wa allowed to distill off from the reaction mixture, These were recrystallised from ethyl ether-, petolem ether In tie cold to remove any dissolved asmia and iie. dried they were not found to be hydr.eepio, A *=nary of properties










follow In Table I.*

AnalyIsU KJeldahl's Methods &aopl. retbmed with aoeinw
trat d smLfurie woid and Selenium mtal ste distilled into an ess of standard smid and back titrated ith base to mstW1 rod and point,

ProprtiLes - The midlues are slightly baslc oopuns soluble SU ether, alehol =4 motm but insoluble in wao, Thoy ,rl,,, 4n & inorgni� acid to form the ao-ium salt of th. inorgani seld and fluorocarbon acid, They 4dolyze lin aqumm~ or aleoholie to fo the fluo onide or acid and inla. The amidine ge not found to be hroeopi if prorl freed of amnia.

Weasthyl and N, WN-dimtkhy AWkfryl Asidins

N-nsytv Afttfor aiM. A reaction vessel moniting of an 80 Al cylindrical glass flank fitted with a delivery tube and oonected to a Mry le-acetone reflux condemr wag piced j a Dry I mot=* bathe Into tUs reaction vessel was, condensed 11.2 g. (0.1 inle) of aIetOrOmtrile. To the cfndsnse nitrilo a add a moderate meas

6.2 g. (0.2 **le), of arthyl amine. The Dry Iee-ecetwo bath vrs as ve and the mixture allowd to reflux under the Dry -c sastoan ondena~r for 010 h*r, At the end of this tins the exoess ad newa alloud to dis. till off, leaving behind a high boiling liquid* The liquid van


*It ham been called to the attention of the athor that these Ounde have bean orted in a patentY by a modifioation of the abOv presedur after the work had trM sopletod in this laboratory,










TABUE I

AlKfty' Aaldinew


RjG(MH)NB2
Rf





CFr


C3r


B.P*
0 c


350'-36*


- 144

- 5


25 -25 S -13801 1.9 ~-53 -


N.R.
Ca ltd Found


17.58 17.50


Qalculated Found

25.00 2.84 17.21 16.93 13.22 13.21


% 11*1


90 95 75








16

distilled under reduced pressure to yield i14 g. of pure R-thyl perfluoromtamidine, b.P. 35-36 *1 -, n245 1.3801, d25 2.I4AiO. Anaiji Calculated for C311 N, 22.200 &*R. 17.5O. Found. i,121085o M.,. 17.59.
The other mbers of the series w- prepared In tly the

sam wi sr. They were found to be wore heat stable and did not reuire vwuum distillation* The distillation was throuh a nine plate oouln packed with glass hellees, The analyses were an described for the an* substituted auldinss,
A list of the phyuisal prqrties, of the substituted amidins Prepared appears in Table II*
Metal Salts of Altrylamidines

Silver Salt of ADafrmzidine.- TO 5 ell (0.0"L 10010) of ast.
Sdissolved In 15 ce ot anhydrous ethyl ether w added portion ie 4i. o (0.020 mole) f silver =diM.A atediato evolution of heat was noted almi with the frmation of a wite solid. Th. uixtme us vigorouly stirred ad s~ lumps, of silver owid, noted were brohm mp. After all the bl* silver =id was consumsd the white solid was filtered, vmshed a number of time with etbl ether and then air dried The material was found to be the silver drivative of the smidine The salt decoosed an heating at about 20040, Analysis Calo.ated for C2FJN Age No 1271P Ae, 48.7B Founde No


The remainine mers of the series were prepared in exacty the 0,2s IM . The silver salts we" all found to be white solids, dsCOMgsIng without mlting at temratures of 2000 or abm .






TABLE nI


&-substituted AlkforyiZ&in.

B*P** d2 25 %N No Re oc, C Found Obs. Found

- 47-�48 1.2909 1.3919 22.20 21.85 23.59 24.10 CF3C(N I)IN R 2 1,
R
4 -f 920 1.1795 .3812 20.01 19.72 29.10 27.40


R-H R 126.50 1.4258 1.3664 15.91 15.63 28.79 28.10 CF3CF20 (IM)N%.
fl-4 R4'% 1100 1.2969 1.3678 24-.75 114.43 33,79 33.20

f-H flMe 137 1.5Wo 1.3561 12.37 1 2 02 33.40 32.50 , R


1,#f


LW42 U3%8


.6 n.41 38.38 36,70










The properties of silver salts of akforylsids ere given In Table In.
%Arew salts of the Butforamidlase In a test tube immersed In O ol bath Was p1004d an InUtm e MiXture of LO g- (O. Ml) of buto formIdine and 5 g. (0o03 nole) of meracri o . Th. mixtuv mr s heated to llO to melt the asidlas and vas vigorously stirred. Tom formation of the ibito wowy salt could be noted and was es emtially ospist. in two hours. The malt was allowed to cool and um ted andimwas leached out of the solid by continuous extraction of the solio ifled malt ith et q ether, The areoated narsuia oxile cud be rewved by euatrifugati using ett(l ether as the solvent. The haswer mercuric mules settled fIrst and the uer layers were found to be sentiil the aidi" insrc1 welt. After a mnuber of aetrfuatows the pure salt as obtained as a white solid that dsomsed at 178�, aalysis Calculated for C6F OAEI # 9I* %00, !g, 32.31. fmdt No 8#1a2# Ag, 32*60,
Tim mrcury salt of the acetformidine could not be pmpered
sine this addiwe decopsed wry easily vhon heated. The propferm-. dim muted In eotly the same fahion as the batforaidins to ive a merury dorivativ
The properties of the mercury salts of the alkfo*17 midlns Sw saUnUrsd In Table IV.

Attempted Preparation of the Alkai 1ital Salts of the Alkforyl Amidines Potassiu AA and ButforamIdin. in-juid Amoni Potassim, md.s Prepared by dissolving potssaiu metal in liquid ia Ving









TABLE III

N411lver jlfyl Amidins


ZC (NH) NHA9
Rf


C?,..


200 (dec.)


240 (doc.)


CF


% Ag
Calculated Foud

4~8,78 4~8.40


40.38


CalcuatedFound

12.71 12.28 1.36 10.27


277(dc.)3360 32.80 8.74 8.50


277 (dec,, 33*60











TABIZ IV
e GrZyI Azid1m


M. P., (doe.) 159 (dec.)


%to9
Calculated Found


38.38 38.20


Calculated Found


10.65 10.22


1" (dft.)


32.31 32.60


atCN )N ) N


C2F!


Cr










Irm as eata1dyt.
Ila a flask onsaitniz 5 go. (0.10 mole) at potml aS.& d 17 go (1.0 %a).) of liquid ammia ves added n1g. (0.10 ma)) at btow'

ter~im..The mixture ws allowed to ref = under a Dry Zsems.ton omdwr for we hour, Ca removal of the es mon&IA a viseou cramg syr remained ?e viscous syru *eared to be ad an distillatiom was found to decopse.

Potsium amd and the butfqrl n4.tris ja U. !Ld 40T a fIak OotaiW 5 e. (0.10 MOle) of pOt,, O, Was COndugind 1905 g. (0.10 mole) Of butforyl nitrile, A large "s"of amia was o dw in with tbo uxe and the amtents of th. flask wr allowed to reflux under a Dry Ioe-ac condenser for oe her The solution grsdua13ly darkened to a 4W brown* The wamse ammonia ma l d to distAll off leaving a brl S7Vj trm w ich aotbiug could be distiled or extracted.
Petaslun t~rde and butforaidin in y S lchol.- I a flask containing a solutios of 5 g. (0.10 mole) of pot~aim kydrId dissolved in 25 %l of smahao4 gms added 21 go (0.10 mals) of buWW~o dinso, The ullte was allowed to stand o uwr, The alcohol was removed leaving a heai MyrV from which only butforemide ouldA be distilled. The rest of the mterial resisted both exWetimm and distillationAcid Salts of Alkfbyl Amidines
The acelforic acid salt of bu ramidine, IX a round bottom

fskcontining 15 cc OC acetoi. acid was dissolved %.3 go (0-025 MUg)








22

of butfeniftne* The clear solution whioh formed v allowed to stand fore hour. The em sd w remved under reduced pressure leaving a residue coniatikg of a whiite soli4. The solid residue cou3A be purified by sublimation and vwa found to be the .tforiO acid salt of the butforaidinso

Analysis Calculated for G6%,721 IV N, 8.59, I.., 326. md, I8.I42 N*E., 321&.
The a kforyl mridinenwre found to forn salts with Urganio organic and fluorocarbn acid. The pr'ooedurev ur the sa flor a& the salts except in the case of the formation of the alkfewl midine yFormation of the midine tydrochloridAe neossitated dissolving the auldine ini ainhydrous ethyl ether and bubbling awkyd4roi bkqgen chloride through the solution from *lch the fluorocarbon idne hydrochloride separated4 Som ropresmtative acid mats on given in TblIe v.

Acylted alkforyl Auldines

IBncl butforMiAM.- A solution of 11s.6 g. (0.17.4 male) of bmsoyl chlwids was placed in a round bottm flak fitted with a drappingv funnel, condenser and protected from atinar u miture by eyirn tubes, The fk v- i cooled in an ioe bath until the cotents mre at oc A solution of 3? g. (O.T m.) of butta'idite in 5 a* of dx7r ethl ethw I sloly adfd to the flmk. An idiate evun. tion of hydroe chloride vsnoted along with a 1mite precipitate of the butfouamidine hydrochloride* After the addition ms coilet, the flask 11s allowed to ur- up to room te erature and to stnd f







TABLK V
Acid Derivativs of Alkfeo rl Amidine

Repo, 0 . Eo % N
0
. CalcUted Found 2alculted Found


CFCO(NH)H.cI > -360 14.9 U3 C0Fc(NH)NH2CHCOGH Sub3.. 172 174 16.29 159.4 C073(M)NHU.C G COOH Sub'* 326 323 8.58 8.80 C3770(NH)Mff2.IU 130 2w 2141 -M C97C()NH2,oCH3CON Subl. 272 277 10.20 1,0,26 037(NR)NH2*C397C0W Subi. 1426 1420 6.58 6.143











hour at this temerater.. The aixtw was filtered free of the nbite amine hydrohloride and the ethereal solution car'efully stoppered to preserve it from the atmosphere, The ethereal solution ie found an dilution vith petirolem ether and cooling to precipitate a solid melting at 6163%. Rerystallizatioi from thyl ethpror trolem ether gave a white soli4 n, 630(. AnawiT Calalated for GU yH7tNZr xO 8.861 Founds, v r58

The actyl derivative wes prepared in the * mnner ando s fod to be a liquid boiling at 152. The great septibility of Uh derivative to hydrolysis m account for the poor nitrogen amnly. Anlysis Calculated for C 6V.F1i INO & S 11.06) Foundi 1s 10.37 Sapoifiation equiva1litm Calaulateds 254&; Foud 255%

Sutforyl chloride was found to react with the buttarsudAix to give a variety of proute# ine of which could positively be identified athe desired acylated derivative, The reaction im carried cut aractty described for provion properatioms, the following products beink- Isolated and idietfiod in tUe retion m~ixue

1. bUtforamidine hydrochloride

2# liquid fraction boiling at 73*# 64 mw me, neutralX

Oquivalont indicatine,. it wv butforic amid

3. liquid fraction boiling at 115-1160 a 64 m whichh

kqyrolised qaite rapidly an standing, to give only

butforamide,











Mb. htfersaidim with Sodiu Hypdargwts

A eM " "=d httom three asked flask 6oatni 36 g.

(0.90 nol) of softit hyMLde d-so ved in 100 *O of water was fitted with a stirrer, droplng funnl ad condmesero Tb. ondsner UM cnaeted by a elivery tlbe to a trap cooled in Dry Io-aoetone i_=t Tm rsation vessel -- s cooled to 0*, 28.8 s. (0.18 ole) of b m
- a4&d acp*U W sad oolg and stirri~ continue until thw red color of brom disappeared ma only a light yellow color rwImsd* To th s ol-ati was added 32 g. (o.150 sole) of hitferamidias along with an additional 50 cc of water. The imine slow.ly dissolved In the solution. Tb. reaction mixe was left for on hour in the Ice baft allowed to come to rw teqrature and rerflue for two and on hal hours at 1000C. The Dry Ico-wetou. trap yielded after distillati through a peak eolum 2,6 g. of material boiLing at 17-18* with molecular usijit of 253, which could be identified as the propforyL brasds., The contents of the flask on acidification yielded large mm~ts of the buttoruaide.

Fluorocarbon Thioemidey

Thiabutforamide from butforouitrl.- Into a, heavy walled pyro glass tube of approximtely 60 mL capacity, previously constricted for sealine end evacate4 we allowed to condense 6.8 g, (0.35 sale) of butf oroitrile and 3.4 g. (0.10 moes) of -ydrqen sulfide. Th tube was sealed off ad allowed to warm up to room temprture and left at this temerature ovemrnit. The tube was opened and the volatile material, c isting entirely of hydrogen sulfide, we allowed to








26
distill off into a vacu system leaving behind 8 g, of a pale yellm solid The solid m~e reoystallised from other-petrolso ether, yielding 6.3 g. of pure thiobutforawmde, mp. 490 And1751 Calculted ftor % S Ng 6.12 s 13.9 Found No 50851 S, 13.81.
The tbiqwopfcaside ould be prepared in the w sa wr the reactim proeeding at room twq atuwe.

The tbio...tforsmi~e vans not successfully prepared under these conditiona a conesifrle aunt of eharring taking plazo in the reaotn veeleo It ias found that if the reactim ws ept at 0 for eigo ohoure satsfac7tor yields of the thioeoetforamA. vm Obtained The reaction could also be mderated throg the use of a sovent such as eOrl other, but reaction t s wre extremsiy lgm, (0125 brs.).
Thioutfr~ide frem butforsai4Izeo. I* a round bottom flask fitted vith a two hole rubber stpper arrling a delivery tube and a ding tUcbe iUs placed I5 go (0.071 moles) of butforasidine dissolved in 250 Of e4thl eth. Into this solution was bubbled an exces of hydrogen sulfide until the solution was oWlIetQy satwat*4 The solutiont WI them a&IUW4d to stand one hour. The ether use removed ~mder reduced pressure and a high boiling liquidin left in the flask. The liquid somatims orytallised = standing to yield the orude ti. aid.s Usually the liquid v distilled under x'dused, pressure to prodwea liquid. hich imediato.y crystallised on coolin The pre*t recrystallised, from ether-petrolem ether Vas found to be yellow zeedlas melting at 4i7-4~8,










Analysis Wclulated for C47H2NI 1, 6.121 Sp M397, Funs li, 6.011 8t 13,90.
This ethod, was found to be quite suitable for the prOp arai of the other moeows of the series, yields being in most oe04 1IOt


The propert es of the fluorocarbon thioaxides ar lrlsed In TAble M


2U&..6tri(a2kfow1) .35 i.2,k6.tii~t~tor~) A~%. -trss~w raupp.r~trila..

Throurh the use of a maum system 54 go (0.3? mUa) of propforwsitiil

- condesed into a stainless teel autoclave. The atoolve i Wad at 30* for 120 houws after which the vwsel im eflwed to eeei The volatile material (27 GO) i allowed to distill out of the vessel before it va opened, The vessel found to cntan 16.8 g. of high boiling materialo The high boiling material wa subjected to distluation through a aime plate colum giving 6.3 g. of olorless liquid boiling at W2-122.. 05 1.3131. dP 1.6506. Analysis Calculated for CgiIa I, 9.601 MWW 43;5.3 a1a35. ftund* So S.991 (.WL., I431; 5.F,44W2.
The othe fluorocarbon nitriles ere found to act quite

IMuiarW to the pforoitrile with 300o as the optima teerature for reaction. The butfuritrI le however, gav better yields at the slightly higher t toreof 3 0.











TABLE VI


RfC(S)NN B2po
I Rfl O45




cPrCr2(s)S)% 6&
@ 23.

CF3072C72C(S)W2 69
0 21am


0 G
0.-


%S
Calculated

21.78 17.88 23.97


Found 25.23 18.18 13.90


% N
Calulat d

10.82 7*82 6,12


Found 10.85 7,53 6.01












ZaUe a round bottom flank fitted vith a refv lim 0uiawer v" pissed 5 go (0*34 woles) of propfaraumidne. The flask was ploood In an oil bath and boated at 125 fer three hoe, the wrlutioa of ammona being 0otedo At the ma of this tift the resulting liquidva amed and tktm subjectemi to distillation through a se1m pake with glass beliess oAM esleulated at aime thsorotisal plates. The distilate mwa cslorlwe liquiA boiling at woo U25 1.31U5, d25 1604.

The wetforamdine sesid not be used in this prep.ratior sins an heating* it PrOdu4 a Volids a Portion of iaih could be, identified AS. thettOranid.. T2he butforanidine appear to be, a Ten' suitab). Megeot in t"IS rstIcs rivins- excellent yieldsn of the battosyl substituted triasines,

The Pr~~rties of the 2,Is,6,tris(&WkOaYl) 1.3.5 s-U-laixae ar" sowised in Table VIZ.

X.Owared- SWIMtr gEf Alkforl a-r
A Perklns aA Zlmsr model 21 double boom infrared ,pe~trwbOt metw er eO1sye in the pisaratics of te spetroramn of the alktory #triSIaes A dmutable soll, misting of tee saltplates proesed wwe the liquid ism uje4 The sel tbickwooeas .pvt

0.027 -eo
The infrared spectrogre for the alkoryj e.tins. prep"r


follow.















R ..C ... (R)..(R)N.






CF2

CF3O?2C72


0 l



95-96*

121-122 1610


25
n



1.3161 1.3131 1.3095


TABLE VIZ





Calod. Found


1.5930 285 288 1.6506 435 31 158 0 am


So'.
CaleM. Found


w


435 576


Galod. Found


9.60 7.18


6m

8.99 6.96









100





o0










cr3- c c-cF
II I
NiN








0 I
3 5


7 /1/3/


13 /5










joo

















N.N.



C .'r-C C-CS
,,,,-c

Icz'











SIj 3 5


7 9 II /3


13 /S









100






























0


357 9/3/


jN,
C C-C3F7, c N

I
C3F


13 15
















DZCrUSIW


Use aSWON71L sadines M. prepared by the intiaa Of SI

Sinmian os tumoarm uitvlle without the inflmes of &44 eatovt.. U* sosdtL maw hia the a&ktyl asidines gurn prpa Indicatie that the fmtim of those co~o=4o and4 the ehii by vii*h this restim ocaur an quite differet &Mo thorn fon in organic chatry. "M. fact tbat the flummwbn nIU4r2M tows gteb fr.. mAiJam byv the addition of isoas to nittules is esificant In that these s.eo1 m he thirt easily preare and stabl examle of eampeof of this type. Ttha. bees reode two irwtmeoes of inidi..e haVing beem, paed~ U by the additlon of midnes or SIMiA tO nitrilss ,Athout acid OxataIste Uwyet1 in Ons inataaes the isolatIOD Of the free ai$ine vasn alai d but other lnvftltU~OrG O.44 not obtain the eouna xoept bw fowutios of a piez'ate "Ilt. In the other oft* the etezigl isolated4e very wisteble and had to be kept at very los to" ewaturus uder doeSosation or" else deoqitIou occure4o In both these turtoose the soleoual to whi&ab mnt was added was of me ehaned oatinic type* the, eapud being triohlrmthyl Cyanide d ethyl

oraotrtrnae.The enhanced creativity of these 00O' t IS PnbeblY due to the indutive effect of the substitamte of the Soecul. In this rapet$ these oeipud *ho a similarityr to the fluoreenrbaa fitri)As











-' probably reacted in a *sir faho

The erganlo madinsa hare boom prep"r. by a n~b.r of ditferm eat mothods, but there awe only three of suffliieit Iq~tame to De mtioned here (1) the conversion of the ame, ester to the Smldlas through the us. of amona53 (2) the reaction of alkali mtal avMe vW nitrils$ end (3) the reactIom of the *ac uult of the asm or

smoma with the aitrilow. TUs l.t inthod is probably thi smost widely used preparation for the amdln The inthods of prqpaati a m be

e~,aridby the following ehemLeal equAtiina

()RC* #RM RC(MHIOR*H~l


(3) R4 W *HCI~ RCQICuk 'C




(3) nyu + uC7 Rc(NH)w32HIl

It am be so from the description of the preparation of the aMUdiS that the reaoti~os As bmsial oo of sad imid ogent (iu.o) seeking a oatinod s9te In the nitrIl.. The orguia nitrilo stros~re as -e ar construct it from OW Woledgs of its rsotlions is cos In whish there adt pprtial ngative a" positive charges is the raluls This dipo awl si in thbe molecles became of differeusas in .Ictre. nogativityr betwean the cocstitatont atem,61 The ergarni Arniil m be Pitured ant


S* partial charge











It ha been suggested that the formation of the naidin In the prosoe of inidi. catalysts occurs according to the follown mchamis






R H w alkyl grow







The 1 terdiat (r) is ui nstt I in tUm prs.
of hoam iu in ndprbalythroughI b4woen banding is moe

bth mmulIn to give the aldinium s&at fthe acid. This

behoisiaftu ts, that them re to conditions essar for lidife f'matiop smne organuic nitrilee. The nitril. mt be, I* a activated state having a suitable reactim site ava-1iabl and th muidinoe m faimod aet be m basic UJm the an from 1hich it e preparA If the wand eesd&tion vu not e, the aNia salt wMsl p*f.ref tiall1Y remain and the q ilibrium wU shift to the *A& Nmvein

mismAN Salt and not the Midliiumsat forMtali A sarch of the litef'twe on the basieity of ortnis, axidins reveal thkat the v&ax for 402Y a slAV). substance is available, Umly setesde.2 The va as gives u pib 1.59. Coring-! this value wi the p b valU for certain wsss, it cma be readily sem that the smin s a" =e burie than the amma cmuds (wow jbich they WOe faum4 It bas ben couded by saw investigators" that in gal, aIUtiLOg









37

fwbatUo 1A wen eolote with salts atf wek bow*e TABUA VMI





CH 3N 3036






It has boon netiod In the study of s~oetttd hmii

that adi' formtion Is usaly pramte4 by grow M4.b t a .leeave olif (p*h2Brp R, I) sAd In retardd by, those *ich st -# oleran soms (1.0, C),01 The in&O~ve gr Will 4a in the fwtiO of themlexI by inenmiz the polsritq' of the a).ml, but thw also decrease the baiityV of the auldins, am* it Js fmv4 ftU wil retard iaddW= "It formatin by UVspmsiW the oquUjJW= mW from mUld"n formation.

The Canditiam =dr vhioh the s&kfOy inidiaes form Asat that weither of these. tue IdMee PostUAe for rgMIa eIdIno forMati 10 of IWrm In the synthesis of slkfaryl midine, Shins the path to formation #VGW to be quite dliffetsat Since no ivwt.4 stimls
-w WeION7 for akW7 auidine famution or stability, the differ-6
-m betumus orgaul nitz-ia a" the �lmmrbomniaitrtlno+ mt lfti the grmtez' Inductive offet of thefooim 11W po 4jsmt to the nitail. stmutur, fte oloot'.. witbdrawing tws of the Mlkfryl









38

Cm is m a evidmsd in stuies In coanotIm vith the *3.6tropilli. addition to doubl bomb found &adjasmt to an &ary%


date hum in general ben those of waganl nitalles wn he ant show a aoalate so clear picture of the possibilties at thee flarom' bm oupombo he value of the alktorrl redies3. adJament to anu waturso ted sit. besm weerdi1 aparnt in the reati.on of the flurocarb nitriles to fors amiAlus.

The fluarocarba nitrile strw&ture might be pictutred ss

F


F


The in tive effet of th a1kfor grou a one side of the resotve carbon site A the elootronegative nitaroen atom co the other esi iP n effect to this carbon center wieh rener it re-tive y pesUitiw This cationoid site Is present in the moue without ea ontaido stisials. The somaia molocele beint nslejiilUlse in chwg ter is attracted to this poiive s.it.. The pssible raactiGA mumAM MWthe be illustrated -,I

.I,.I

Ni


N +'N3 " I"RAICIt











It had been noted that when the reactiop to fowm the aidina 10 ooMucted. in the presnce of aniwt ohlorie no idiuni chloride va foWi# This would Indicate that the alkoryl amidins formed was a weak base than the anamia from ihich it w prepared* Th postulate of an equilibriva betwen a tpothetical nitr.i interu' dlat. and the uamniu salt is not valid for the fonmtm of the alkforyl widine since the ammo salt could be isolated modhil free the reaction =Lxtue Although the alkforyl aidi w pres red in this reaction no amidinius salt was foun. This miditio& ilA havo ben iqoesib1. if a ehanis involvin aidatalysi was


The mchism then postulated for mi ine for at-o from the fluorocarbon nitriles Is the addition of anmoia to the free nitrile alog with a proton shift to give the stable midin.

!!a1bstitod s-ad- -N Nisubstituted 44LMtiw

The substituted amidines ca be oked upon as forming In the ses mner as the unsubetituted am ines, the o L'fefrme belng that the basicity of the amin sppears to be very Imertt for formstion of the substituted amidine, The umnosubstituted "WIy sine reacte quite readily as did the dlsiibstituted a&WI ad"ne in both e00e the reaction w s fast and as complete as vith OM Iso It ill be noted from Table VTII that the basicitv of both of these -Inns eds that of amia The fact that the phenyl substituted =inops such as Aniline wold not react with the aitrile even after heating, GulM possibly be eplaiad by the fact that the basicity of the amine








40

toa impiortant nasw dwation in the rea t on. * Anilin is a orsida w ably weker base then either wviami or a&kDWI siUbtted mines and hoe would yield a poor nionoid nitroen to tke part In the restiom 4,itional study an Vo formtion of e aidines wth espet to the staoo gth of the bas. AUl be seessary befere a on e 4oflito e vms1 siaw am be reasedol



The salts of the m dine show soe ver7 tntresting properties with respect to the influeme of the alkforyl radical on their waId base strwogth. the organic smidims have bee .41.4 by sum Invustigators.U carboxylic acids beaoie of their acid like character in eSlutimc of akndrof onmias It has been possible to prodn.. intsfli salts of the organic amidine, uixlng ehydros amonia as a solvent#13 The orpanio amidine in solvents such as ether or water has been found to be too weak an acid for suceesful preparation of ntaflij derive ives. The fluorocarbwa S jine, haver, exhibits sufficient mid properties in organic solvents to forn these mtalli slts, Thia again idicatoo the electron iunducing affect of the f1.uorooaobon fro* on the overall basicity of the ddino meoule. The silve ad MMo OWr salts of the amidie von. prepared in NO~drovs ether adw fOnd to be Mtalline material which domosed on heating. The salts which forims4 inoato that the alkfavyl ani~lne are swbasoi asiA.. AlthOugh three replaceable hydrego atoM are aVaJIable9 Only am ,Jdrogan was reploed by the moallic These structures be repreftted by goeral fomlsel










The alkali nMt salts resort all atts4 at isolation snd ould not be prepared. A possibl reason for this is the fact that san the reaction wa, rm In aqueau or alcholie 1a, b Irolpis owaved, When the alkforyl amidine vutreated with alkali ustal in an s smmPna svent decompsition ocured, The dsqmositim of Mlurine Containing iopo n likquid appia containIng alkali wtals bm been noted by )I.D. and has been used as a Uiod of efor analpis. The product of the reaction w a sy o vieh resisted mrytsllisatmLon extraction or distillation. Sinoe nothing that apeared to be of interest at the time mid be Isolated, the ex oint ium discontinued*

The alkorrl smdineep besids being acid enough to form metal sal4., exhibit basic properties in the sa solvents *it am suffi. ient to bring about the formation of scid sale. A nuNber of the s4ts vere pre using inorgP-nic organic A fluorocabo naci, Odlr -w acid molecule reacted with one emidine mlecule to formt an OdAti salt* The structure of tese cmoatfrost anales ad neutral equivalents ears to be

H


BrCIItrHA



The alkfrYl AIMes are quite easily ylated to form the

N-substitut Sl dArIvat&,ea. The ourse of the reaction leading to the N-aoyl alkowy-l SMIdise could yIeld two taUtinmris OlAted










pw&O4t


(I)








(n)

The tue isomericefares should have distinctly different charNP actaoriatic, 8trtwtm (1) should be acidic in nature du to the tie adjacnt electron finding grua uhila (nI) should be a neutral no~cule or at ant a very weak ac1 The hydrolysis of (1) should produe the mixed seordw amide (MI) while hydrolys of (11) would proue the pl.am&7 mids (IV).
H
,;(o)?L�o)I R (o)uu

(In (iv)


The N-banWq derivative o4' te buttwidine fo un to be
a otral coqpod since it w not soluble in aueous sodium hydrU%,. The acetyl derivative was hydrlyzed by squw base to fom ostamd and tb butfwmds. The Kubuttowyl derivative vhich could not be obtained in a state sufficiently pure eough to Oharactorise tp kp*oLSd exlsively t the butfw__de.
The ,Uulhoosi acid derivative. of the organic smidines have beow shown to display a similar reatin29 32 Tu., Barber cing








1.34

su lfar derivatiws (R-8or) concluded that thre possbly ,,ls two isinrs of the" oommnde the stable fora bein of a structa* siisilar to (1) an a uwstable form siniliar to struetwo (nI) which coul be Convuted to (1). Northae vas ab e to isola.te only,- mafanlyrl &rat (Y C14 - ulu esicpal f m g the so&=i salt aMA om 4*oIois gave amides of type (IV). Th author coml-ded that a structure similar to (II) was n 5fl on the bais of the date Obtained.
A oxpariasm of the two structures of the ecylatedamid will show that the exJljst of the two differeat eouds am be ,accli~shed wiami a electron inducing subetituent is adjacent to the dine funatiosal grotV. This electron inducing wop can then am to ible the twdrsaom an d prevent Prototom





Nz R
RrC I



This tYPe of tautomeriin would occor but for the electronl Injdwing effect of the alkfery radical which stabilises the ii nitrores so that the rapid ehang* of proton Is laenod or ntirely halted.

A .OnsAWationU of the )id*.lysis prodiwts ad tboae rxt,

neutrality of the ylated alkfryl amidines would Iead to the samclgo sim that the ayl derivatives of the alkfWyl mirre probably eist a strwture (.),













Threa.tic of the butfwmidine In tin pre of s hypohalito v t4 to produc th pvopfoayl brmi i the bwttIt has, bown show by Mastedl and SohbasitP that tie *1kfwyl amides give unexpected result* in the Hoffann 1"abrandto Reati on the butforam e farming Profoyl broaide Instead of the expected prW4*oyl amine. This am product was obtained with the butforamidla. The remti. as aplied to -thm butfaramide ie giveas s

* IaWO A RgO(O)Er

Rfe (0) NI]r - Ov.. " * *0 X3


Doe U-br.. subistituted amide beine an isolatable eamoun4,

Tha reactioa nehanisu for convesio of butforaidine to

proforyl broA ln loestas that the sm1ine va first hydrolyzed to the andA. a that the latter than rated with sodU_ hbpohallte to give the isolated popforyl bromsid.
All attempt to prepre an Sebromo, substiuW midine ws

without success the reation being t ied Lu a nuer f solvents mude a variety of conditions. Ti indicates that a noral conditi ns of formation of 5.brow derivatives of the amljane the a3Moryl amLdinee do not react to give these compouns,~ The silver salts of the alkor~l aidiaes were also used without m~y succses The eohanisa thn propoed for the formation of the propfrjyjl bromide fro, the but. foeruadine, since the butframids a isolated in the reutim SAitwes











is for the frmation of the butforaitie by hydrolyals and then broad.nation followed by eUination wMI



The luoocabonthioamilM wre prepared by two different

the. The ation of hydcen sulf as fowr to eyert bth the florocarbon nitrles and the fluorocarbon adllaes to tbo flroseas thiornidos at ron taq tre.

fte floroabmn nitril. iaen soa"e in a glass tube with hj droge sulfide vw fomwd to react at remn toqpewatare to pr.AiS tUs f]lvon thioa ide, The reotm was folad to be very rids ad In the case ot ectteromitrile so v~gorou that charring of the rea-. tats or products occurred,
The organic aitr ils have been found to add hy'ogen sulfide uder the inflee of heat and pressue?. 5 the reaction being eat luid by &kal hydreoeulfls, It vas shoui that electron inducing croae aid in the adiiona of hydrogen sulf ide to armtic DitrilesD the ti for ration decre ag vith the ae el ctrgativsa subtituewt an the ring.23 The rWd reaction of the fluorocabon ritriles sho al n the great eletrn at ranity of the alkforyl radical, since these coiodft form almot quantitative y-i.ls of the fbaorooazbma thcWWe byT hy~ogms sulfide addition at room t~eratre
The fluorocarbon midines react with h-droien sulfide n a solvent of ethyl ether at a tomeatwe to form the thioemido The ration requiros a large ess of hydrogen sulflde to convert the fluorocarbon adlias to the fl thieridep.










The fluoerocarbon thiornid.., prepare in this mnner more found to be anbst-tia .y pure eins In mwt m s ov before distilation tbey soidlfled The fluoroearbon thiomd.. as Prepared, wre fod to be low m*Ing# pale yellow solids with the meption of the first m et hi ot i w emw a p.e yelow lIqu. The thioemA appeared to be quite o.t1e and ould be stored for a awdw of week In sea"e vial without =W apparent decompositiono



The praperatom of the 2,ta,6trio(alkfor3.) 1,3v5 trisoame -e sosempisbed by two dif ferent mthods. The tinvt involved the ti' rosaim of te alkforyl nitrile undr pr ours, The scond comeenmd the colUng of three ses of alkferyl amdIne with the reoultant Je of emsia to fora the trinslas

TrinSrsatiep of the fluorocarbon ntrle ir asSm.- Z* f c nitril. ws foud to trimerlse wder the Inflnuoe of Pressure to form the triasins, no sold oatalysis being necessary, fthee M 00 dfMiite set Of esditisft for triaersatiAs f0und, but tiM pressure rane fmnd moat Satisfetory between 70-900 posoi Thm, OPtNUIR tepestoeaers to be been 300-35e od Us, reaction time moy very botwm 3D-20 bovro, the criteria being &a sutfiCienti great pssre decrease*
The f nitraes show a striking difference in pol.uertsaton whM compared with their organic anae1p# in that no activating Influme was necessary to effect this rae&tin The mechmaim proposed for the formation of a triasine under the inflm










of acIA has been a dieas type synthesis in which tw mles of the nitrile condense to f~a the dios and the third sere of the nitile then acts as the dimephile. The mohenisa . sows to be appliemble to the synthesis of the trazi fr the alkforyl itrile. Te reaction sequence Js listed belw.



. ,C4! I -f





dis disuophilo

A possible mehanism which is proposed is that twu moles of the wm active fluorocara could onda nse to form a diane tpe structure followd by onnation with a third mole to form the triasliw.
The reaction ears to require ririd rales for the sie of the molecule involved fer$ a the sise of the alkforyl rascal in-* ereeped the YUil Of the triasine W noted to define. The effects of pVsUre w noticed to have an effat upon the synthesis. At the lU~w Pr"ese of 300-4WQ p~s#i., reactionl did not take p1MFs but at presures Over 600 p.s.1. effective trisrisa on s saspligh .

Condensation of the alkforl amidines,- The alkforyl emidines Vhe heated in the atmosphere above their melting points trisrise to form the alkforyl s-triae in goed yield. Te exeptlon is the acetfcwmdine which was found to hydrolise in atmosphere on hating to ftu the carrespmiding side. The reaction appears to be a co- liUg










of three moles of the amidiio with splitting out of tmia to form the triazine. It was found that when butforamidine was heated Jimt slightly Is th the theoretical amount of inani wms evolved fto the coupling ad ecribed below.





iJ. --MC _c

IR


The alkfoyal tains ere found to be a netral substance V=R7 resistant to ai attaak. The 2.4.6gtri (paropfol) 1.3,5, s.tai - in w stable to , esta'ated sulrcl.e aid even aTter 72 hours *at 300Q. triazies wr f-ound to be very susceptib to Aan hydrolysis givi% the sodium salt of the flumroeatan aid an treatment with squs alkali and the estrified a cid an alkaline alcoholic b*oeI--,.

Th. following carts are inserted for cering the tw methois devised for preparing the alkforyl s-triaines. 3h Table no the value. for the teperatre and the tim are shom as th Idloh ga the best yild of the alkferyl jstiasi in thaewe erimats, rhe pressure is am antogenum pressur and depends Wm th quanttr of starting m aerial WWlo 4 hOwvW, presres Above 600 p.s., mW messary7 foar trlawistin
Table X give, the coaarative yield of the tm thDs for the preparatl of the alkforyl a-t.riainess













optlu Conditions for Alrml
Nt41. Tr!d!ini


R R
I k

I


0"


300 300


Tim.
M&

28 110


700 810


Teblel

EgMILntvo U.1ld of kWMkt J) =!isUiwS


AR


Alk.=Iy Nitrile


c2Fr OFr~


AIVMIw Amile


17%


Infr.d Aborption 8pectma
4owot .~~WLr .fr,
Th. lta rod speo.t of the alkforyl O-t slass show a VWY characteristic strong bad in tb* re~gin 256% Ole (6J4,). The ba" v" foud at the sam loatio In al three mere of the ser'ie m4 Is b.1eve to be c-eroteriwti for the O in conjugated celi


09r


17o0 170


oFr.








0

Stuie -w3.vlag the oo.iugated syclic str.trtw the

me bsorptis hae bwu assigned as being within the rwne 3660.. 'o 1lo A strog absorption at or ne 810 " (12,4,q) h bew attributed to the ring structure of pyrimidin in stuie of these wwm.3The taine ring str'ucture wt being very differnt, show characteristic ahomption, at this point too*
















SIMARX


The mthods of pepaatim and sare ptWleal and .*umieul

properti.. of six distincot classe of nitr'ogen containing flunorocarbo derivatives awe prootd Thoso compounds w the result of an investigation of a varietq of reactions of te fluorocarto nitril and detonstratep by ther fomatm, om of the unique plieot e of thi dorivative.
UL A swl of alkforyl saidines were prepared and aim of their p sical and chiocal properties dstermine4 ?tse counts are believed to have the following structure


I



The specifla omounds In *lh Rft oqas C3 rs a-nd Germ prepared and cbaraoteriasd. Tbaee moud rep snt the first instance of an unsta3Uod, addition of inumia to a nita-il to yield a fme amdic.. A possible reaction mechanism Is proposed in an attempt to explain, the apparent difference, in amidias formation between the fluorocarbon and the organic nltriles.
2. A series of INustb-ll ad N N,-m tkql .kubgtitut" alkforyl auidis woe prepared and sam of their physical properties deteied,











These cooumb are believed to have the foloving structure#


t.R



Rau Rm

The sp cific ooads fo Rt equals, CF-, CYg., and C r was

- and charecteriude

3. A series of mtallic salts of allcoryl midines wrs,

prepared. The salts prepared ouprae the N14eilver alkf r7l widnes and the X--curio &Wzrl amidi . The metall c salts show the spparent aoidity of the al yl midlaes li mutral olyvent. Vhe nslysis of these cooands Indicate that the alkfryl amidines aot as naeabsioe sids
ii A sese of sold *alt* of the olkfor7l idu.es wre

Prepared ad chacterised. These derivatives ue. foed with the inorganic, the organic ad the flumrocarbon acids and Indicate the #pparmt basicity of the alkforyl smidines under the condition of the reastiom,

S* Acylatioa of the *Wkoryl ales produced the N-syLoed derivatives of the alkforyl amidines These oaounds, whch lydrolpe to the priesry amid. ad appear to be nmtral s stances, indicate that the inino nitrogen is the site of sylatin, As such$ Vhy represent a departure in stracturs from st slated organic idinee, Thes cqwounds m believed to have the following str-wutes lr045C(0) Rfg









53

6. A reactioB shoWing the r g of t toml vadw the influence of sodium lp$ponite to the p rpfuryl bruie Is presented. A possible path of the rearrangment i proposed*

7. A series of o de re preaed and oeme of their properties d.temlnd. The peparation of theise o9 nds wae acomplisbed by tw ethods eploying in the me case the alforyl aidine and in the ether ae* the alkfor l nitrileo The oox ans believed to have the stotures

a


The c onsIn ~ioh "f eq"Uml C"3-, r-2?, wAi C9r' " prepared and oharesteirsed.
8. The ,3,5, tru(o oryl) 2,,6, o-ulminee wre

prepared and ohotertsd These coapouds wre prepared by toe
t synRthe using in the me case the mkoryl asmine and In the other ease the abforyl nitarUs. The 'prepared arWe believed to have the strutu.e


I,
N N




The compond prepared and cheamterimed we"e foritfI equals, r, c2F" and C3r These cOWOunds represent a OPArtwO fro the Snventio l reaction of organia chamstry in that the trimizsa-tio of the alkforyl nitrile we accoplihe4 without the use of a atalyst., The Infraesd speetra for theoe coppol is aUo presented.















BIBLIOGRAPII


1.A34rs S. 1wP es of IMIc Org&UtO ItatOMs' Nev Iawkw John Wey "n SCIA IM.,s 1950.


3# Bllow* Los *The Infrared Sperea of Colex NolOaulee, N lor k Jo z "107 and $On Inc* ,195 o( )


S. Bernu a , A., A n. 292 (1877)
6. Cd, , 4, GOroee, sav , A# B arber, . 4os, 1 ss Lo.o).
and Sb.1K., Z. Dt,, Ind* eo.COho. 1&r 290( 17). 17. 0o5h As., Cogt. rend . 239 (1848).
8. Coi nol, Us J hs, , ,m. Soo. , , 331) (1928)o
9. Crt s , . nd iiwll Lo, J. Aso Chnom Soo* go 88T (19)3) 100Da ys A, 011str'oi Mehanisms of (rganio Reatioros'
New Tats American Book Coo, 1950o
no. Dichlar, lo, GArm Patent 671,785 (Februr 14, 1939)o


1336 Franklin, E., "The Rita'ogen System of Compounds$
Now borks, Reinhold Nubliphing Coo, 1935.
11. Fred.nhageno K., and Cadenbacho 0,, Bler. 10 928 (193k)o X50 Fukubara, No, and Bigelow, Lt Jo As, Ohem, Sc. f, 2792 (1941)o




lie. Ornu, C., Weime 0*, andI SeIAs S.# Ann# M 77 (1952). 19. JItawrt Rot J. prakt. Chse (2) 1& 283 (1889)o









55
20. kst*4 16's an Khlbam, V., J. Ax*G.. Sha o . cc* 16.1 1% 21. Mte, D., U* S. Patent 2,676,965 (April, 1 ). 22. Jm, .s no , J, an Ohe. Soo. P, 143 (1948). 23.6 Mds1rLA, U.~ 187 (1923), 24, Xinllrj L Ann ). p 1 (1926)o 2%. L~es A.,Ha&,o of Chemistry*. �1ghth Ed,# Sandusky#
Ohioo Hw.*eok Publishers, 1952,


27* illr,4 U7ts I., and HeBe, L , Anal. Chem,

28. 1illr, W. T., Calfee J. D, and Bipelow, 4 ,# Am. Chou*
Soc. 2, 198 (193750


30. M.beas , Pierc, 0,, and Bolt, Rot Ind. W Chg ob).
(1947).
31. Mcee,9 E.0 Pierce, 0.*$ and JNsyors,,P., 4a Am* Chn* So%
Z. 7 (195),
32. Nor". yp E,, Pierce* A. ad Kurtess, D., .1, An* Chms
Soc. 6, 2763 (1942).
33. KI, .,a and Short, W.,J. Chw So,. p 147. YUi Oxe ~ Partridge, me and Short, F., J0 Chem* Soo. 35. Plner, A* and KIlein, ?., Bw. Vj 1889 (1887). 36. Pinners A. and Ulias F,, Bar. Us 1V25 (1868).o 37. Roberts J. ', ebb H and EhiU, Los J. A . Cheu.
Soo .. 1,I~89%O

38. Ruff, o., Z, sagw. Chem I 738 (1928). 39. Ruff, 0, a.d Aser, 4# 4o anorg, algem Chem. __b
In9 (1929).
4o, Ruff,.an Kelm,, &, 4* asorg, allg... Oh.m ,















43. Short, L, ua Thaqpsons Mop Jo Chem. oc. =2 1680 44. simov, J. H. iaw Blok, to P., J.* Ax* cbeu.. soo. 61-. 145o Sims, J. Hp, st slop bins Bectrocem Soc. 21 46,j Simon.,j4 H., 'Fluoz'a chmistry', vol. r, Mew ?ork
Academic Press, Inc,,*%O

47 w rt pF Bull* C)*,*t aci. Acad. roy. B*ig,* .8 34~3

( FIIMa ius
2*. o. 1 h 176 h (15)o .
















AGKNODEMENZI

The author wishe to thank Dr. Henry CGl Brown II for

his guidancoe, assistant and interest during the course of the work*

He also wishes to thank Dr� Joseph f. Simons for his

Interest and wi helpful suggestions, and Dr. T, M. Reed and Nr. D. ftlipovioh, for their help and encouragemnt during the course of the investigation.
















BIOGRAPHICAL NOE


Villain Lo Reilly w born In BayonneV6w Jere Jul1y 19, 1926k

He attned 1st Virginia ,iuleyan Gofle fro 8eptembr L47 matIl June L950# reoeiving the degree of Bechlor of 6cienc. He mtered Duquesne University in Septber, 1950 and received the bgre of ter of Science in Aueust, 1952. He then enter4d the Univeaity of FlidA in Septmberw, 952 and has been in attenenoe simne that date.

the author Delongs to Gama Sigma Epsilon and AI4ua CUi Signs fraternities,
















COMMITTEE REPOT


This dissertation was prepared under the direction of the
candidate's supervisory committee and has been approved by all awners of the oaltte. It was submitted to the Dea of the College of Arts and Science WA to the Graduate Council and was approved as partial fulfillment of the requirements for the degree of Doctor of Philoeqby.


Aupst 13, 1955




Dean# Gollege of Arts and Science



Meant Graduate School

Supervisor Committee#




Full Text

PAGE 1

SOME REACTIONS OF FLUOROCARBON NITRILES: SYNTHESES OF AMIDINES, THIOAMIDES AND TRIAZINES By WILLIAM LEO REILLY A Dissertation Presented to the Graduate Council of The University of Florida In Partial Fulfilment of the Requirements for the Degree of Doctor of Philosophy UNIVERSITY OF FLORIDA AUGUST, 1955

PAGE 2

TABLE OF CONTENTS Page LET OF TABLES .......... ±y LIST OF ILLUSTRATIONS ............ y PRELIMINARY REMARKS ............. vl INTRODUCTION ............... 1 History 7 Reactions of Fluorocarbon Nitriles • • . . . 9 EXPERIMENTAL PROCEDURES 10 General Considerations .»••••••. 10 Acetforonitrile ........... U Amidines •••.•••,.*,... 13 Fluorocarbon amidines ••••••••. 13 N-methyl and N, N-dimethyl alkforyl amidines , lU Metal salts of the alkforyl amidines .... 16 Attempted preparation of the alkali metal salts of the alkforyl amidines ..... 18 Acid salts of the alkforyl amidines .... 21 Acylated alkforyl amidines ••••••. 22 The butforamidine with sodium hypobromite • • 25 Fluorocarbon Thioamides ......... 25 2 t k,6 tris( alkforyl) 1,3*5 s-Triazines .... 27 Infrared Spectra of Alkforyl Triazines .... 29 v * « DECUBSION •»), Alkforyl Amidines N-substituted and N, N-disubstituted Amidines . . Amidiniura Salts Acylated Alkforyl Amidines ........ Reaction of Butforamidine with Sodium hypobromite Fluorocarbon Thioamides ....... Alkforyl s-Triazines •••••*.,** Infrared Absorption Spectra of Alkforyl s-Triazines 3U 39 Uo Ul Wi U5 U6 U9 * ii

PAGE 3

P«c« SUMMARY 51 BIBLIOGRAPHY • »•••••#•••••••• 5U ACKH«a«DGFMESTS ••«•••••••••••• 57 BIOGRAPHICAL NOTE * * * 58 ill

PAGE 4

LIST OF TABLES Table Page 1 Alkforyl Amidines IS U N-sufcstituted Alkforylaraidines •••»*»«» 17 m N-S liver Alkforyl Araidinos '»«•«•»•»• 19 IV N-Mercury Alkforyl Amldlnes • «••••«•• 20 V Acid Derivatives of Alkforyl Ami dines •••••• 23 VI Alkforyl Thioamidee • »•••••••••« 28 VII Alkforyl s-Triaainee • ••••••••«•• 30 Tin pKb Values for Certain Amines • •••••••» 37 H Optimum Conditions for Alkforyl Nitrile Trimeriaation • U9 X Comparative Tields of Alkforyl s-Triaaines • • • • 1*9 iv

PAGE 5

LIST OF ILLUSTRATIONS Page Infrared Spectra of 2,U,6 tria(methforyl) 1,3,5 8-triaxine . . 31 Infrared Spectra of 2,U,6 tria(propforyl) 1,3,5 s-tria*ine • • 32 Infrared Spectra of 2,U,6 tria(butforyl) 1,3,5 e-trlaaine , , 33

PAGE 6

PRELIMINARY REMARKS All temperatures reported in this dissertation are in the centigrade scale and uncarrected* • . Refractive indices were detemined with a Abbe* Refrac tome ter at 25°. . » Molar refractions were calculated by the Lorens-Lorenta Equation. n 2 -l u ra ‘ D ' * * The value for the atomic refractions were taken from Lange's Handbook, Eighth Edition. A value of 1.100 was used for fluorine. Densities were determined at 25° with a pycnometer calibrated with water ® 25°. Molecular weights were determined by the method of Vapor Density employing the method of Victor Meyer.

PAGE 7

INTRODUCTION « The discovery that fluorine could be c cabined with carbon to produce a new scries of compounds furnished the beginning for the development of a branch of chemistry known as fluorocarbon chemistry. The impetus for the rapid development of this field was provided by the fact that the compounds formed of the union of fluorine and carbon produced some of the most chemically inert materials known to man. The latter day development of the field however, is due to the discovery of the more reactive fluorocarbon derivatives and their employment in chemical synthesis. The scope and usefulness of the compounds so produced have made the field of fluorocarbon chemistry ante of the most intensively studied branches of chemistry today. The research that has followed the discovery of these com* pounds has shown that the reactions of fluorocarbon derivatives are not identical with analogous organic reactions but extend from modified organic reactions to some reactions not found in organic chemistry. This variation in reactivity from conventional organic reactions has provided the chemist with many unique and interesting compounds. On the basis of our present day knowledge of carbon

PAGE 8

2 fluorine compounds and their derivatives , it would appear that almost any hydrocarbon canpound structure can be produced in the fluorocarbon series and some not found in organic chemistry. In the cases where this has been accomplished, the replacement of the hydrocarbon structure in the molecule by the fluorocarbon structure has been found to produce compounds whose properties and reactivity are to a great extent altered or even completely changed. The next step then is to employ these molecules in chemical synthesis. One area of the field of fluorocarbon chemistry which shot® promise of being of great importance is that of nitrogen containing fluorocarbons. In the field of organic chemistry, the nitrogen derivatives of hydrocarbon compounds occupy a position significant in importance and development. The field of the nitrogen containing fluorocarbon derivatives shows much promise but has been investigated only to a very limited extent. One specific area of the field of nitrogen derivatives which should produce some interesting reactions and compounds is that of the nitriles or cyanides. The nitrile group, being of an unsaturated character, is highly reactive. This unsaturation of the carbon to nitrogen bond combined with the strong electronegative effect of the fluorocarbon radical should show enhanced reactivity or reactivity of a nature sufficiently different to produce a significant change in the final products of the reactions. It has been noted that many of the reactions of nitriles require acid catalysts to initiate the reaction and in many cases

PAGE 9

3 the acid la necessary to stabilize the products. Thus, the ammonolysis^ of organic cyanides occurs generally in the presence of the hydrochloride of the amine. Alcoholysis# and reactions with nercaptans# involve an activated nitrile nucleus, and product stability is oily accomplished through salt formation. It has been noted by Kindler and Treu 2 ^ while studying the influence of substituents on aromatic nitriles, that the more electron inducing the attached group, the greater was the reactivity of the nitrile toward hydrogen sulfide addition. Polymerization studies of nitriles^ indicate that once again acid was necessary to initiate the polymerization, indicating that a more reactive center than that presented by the free organic nitrile is necessary for reactivity. The reactive nitrile structure may he presented ast -$> R— C5H S • partial charge The fact that acid catalysis is so effective in addition reactions and polymerisations la probably due to the fact that the proton stabilises and enhances the reactive carbon site so that under acid catalysis the reactive molecule now appears asi* R-C-NI1 This structure now provides a cationoid site very suitable for reaction. The alkforylnitriles would have an additional advantage in that the inductive effect of the very electronegative fluorocarbon radical will

PAGE 10

u activate the molecule to such an extent that ary acid catalysis would be unnecessary, f F F^-C C=N * * * This contention was found to be true in that shat would be considered abnormal reactions among hydrocarbon compounds were found to be quite normal reactions for alkforylnitriles. This can be show by considering some reactions of organic chemistry and comparing them with what might occur in the fluorocarbon nitriles. Oxley, Partridge and Sho:-t& have shown in the reaction of amines with cyanides to form amidines , that an equilibrium mixture is t j established, and through the choice of suitable conditions, amidines could easily be produced. Since amidines are usually stronger bases than the amines or ammonia from which tnqy are produced, carrying out the reaction in the presence of an stramonium salt produces an aaldiniua salt. Provided the temperature was below the dissociation temperature for the salt, the equilibrium would be disturbed and the conversion of tiie cyanide into the ami dine would be promoted* The reaction appears to be controlled by a number of factors. The presence of a sore strongly anionoid nitrogen atom in the base would facilitate addition • to the cyanide, the increase in strength of the base would decrease the proportion of the amidine converted to salt with a corresponding smaller displacement of the equilibrium between the cyanide, base and amidines.

PAGE 11

The use of alkfaxylnitriles In those experiments should eliminate both of these complications* The enhanced reactivity of the cyanide group due to the inductive effect of the fluorocarbon radical to which it ia attached, would cause the base to be attracted to the cationoid «* ^ site more easily. Once the asddiaes are formed, even though the fluorocarbon radical would tend to decrease its basicity, the ami dine would not be affected by ary equilibrium or competition with the base for the available acid to a tab ilia e itself. This stability should be an inherent property of the molecule itself. Therefore, alkforylnitriles should have at least two advantages over organic nitriles in anaonolysis. The first is a more readily available reaction site and the second Is the fact that no imported stimulus is necessary to stabilise the molecule, once it is formed. Another phase of the reaction of nitriles that would appear to be of interest is that of polymerisation of these compounds. In the field of organic chemistry, nitriles are known to triraerise to form the cyanuric ring* Benzoni trile was found by Gloes^-7 to condense under the influence of sulfuric acid to form cyaphenin. There are many additional references to the polymerisation of individual nitriles. 19 * 1*8 pi* rc * ^ Bolt^° polymerised trichloroacetonitrile under the influence of hydrogen

PAGE 12

6 chloride and pressure to produce the 2, 6 trie (trichloronethyl) 1 # 3, 5 triasine, which they then fluorinated to give the alkforyl derivative along with eight other fluorine containing compounds* The substance was found to be very resistant to acid and exhibited no basic properties at all* The effect of the fluorocarbon group in these polymerisation reactions would appear to be interesting and worthy of study* The expected activation of the nitrile should occur and polymerisation should then be of an uncatalysed nature* Crundaann, eisae, and Seide 1 ® have proposed an interesting mechanism for triasine formation in an acid catalysed state* The "primary product" is a substituted indno chloride of the types NH R-C* l 8 U c R'' S C1 NH R-C* \ H II c-*I R m R-C \ » W Hal* It is a salt like structure which on decomposition with water yields the secondary amide* They propose the next step to be a diene synthesis type reaction in which the "primary product" is the diene and the third mole of nitrile is the dienophile* R-C » H JST *7 RS r' n ci C-R H \ A R-C C-R I II M N / N R Cl .N R-C * C-S l II 8 N / C I R

PAGE 13

7 The product then loses hydrogen chloride and aromatizes to form tine triaaine. The same thing could happen with the activated alkf aryl nitrile molecule to give a similar diene arrangement followed by coupling to give the triazine. These then were some of the interesting possibilities that presented themselves when the work was undertaken. The intent of the work was to study the effect of the adjacent fluorocarbon radical on a reacting nitrile site with expectation of chemically establishing some preconceived ideas as to the nature of the reaction of alkf cry Ini tr ilea in addition reactions. The work was further extended to use the alkf ary lami dines produced as a synthetic tool in preparing other fluorocarbon derivatives. History The history of fluorocarbon compounds and their derivatives must date back to the discovery of fluorine by Moissan in 1886. 2 ^ Progress was very slow at the start, due partly to the experimental difficulty in preparing fluorine and the extraordinary reactivity of the element, causing it to react explosively with most organic compounds. K Probably the first fluorocarbon produced was methforane as prepared by Lebeau and Damiens in 1926. 2 ^ It was prepared by the action of fluorine on charcoal. Ruff^ followed up this work and fully characterized the compound methforane, along with some observations on higher homologs, possibly ethforane and propforane, also produced in the reaction. Later, Simons and Block, ^ employing mercury salts as an explosion inhibitor, reported a direct fluorination of carbon and isolated a number

PAGE 14

a of fluorocarbons* ' 1 th ths elucidation of the physical properties and the chemical inertness of these compounds which occurred as an homologous aerie 8 analogous to hydrocarbons, it was seen that these compounds might veil serve as a basis for a new chemistry founded on fluorocarbons rather than hydrocarbons* The interest in these new compounds soon provided new ways of preparing fluorocarbons* These consisted of (1) controlled reaction between elementary fluorine and liquid hydrocarbons, copper mesh being employed to provide effective geometry for reaction,^ 1 * lh,29,U? 8 ii TOr plating of the copper gauze to provide catalytic surface as veil as beneficial geometry;*^ ( 2 ) powerful fluorinating agents such as cobaltic fluoride which were prepared 38 and used in the replacement of chlorine by fluorine to produce a fluorocarbon, kO, 12 and ( 3 ) probably ths most versatile and most commercially applicable process was the electrochemical process as reported by Simons.^ This last process involved + the production of fluorocarbons and fluorocarbon derivatives from carbon containing materials by the passage of an electric current of low voltage through a mixture of hydrogen fluoride and the carbon containing 4 compound* A great number of materials could be employed such as hydrocarbons, carboxylic acids, esters, alcohols, acid chlorides, ethers, amines, sulfides, etc., giving too chemist a wide variety of starting * materials with which to wark* It was these latter day developments f . which paved toe way for toe tremendous volume of synthetic endeavor now * being done in this new and rapidly expanding field of chemical research.

PAGE 15

9 Reactions of Fluorocarbon Nitrile* Acetforonitrile* was first prepared by Swarts^7 in 1922 * It was prepared by the dehydration of the ace tf or amide through the action of phosphorus pentoxide, Since that tine the other raeabers of the series hare been prepared in exactly the sane fashion. The fluorocarbon nitriles undergo many of the reactions found among, the organic nitriles. The fluorocarbon nitriles hydrolyse readily in base to form the acid salt and the ammonia. Hydrogenation over platinum oxide yields good conversion to the araine^ and they undergo reaction with Grignard reagents to form alkforyl substituted acetophenones, 22 The fluorocarbon nitriles have also been used with the Grignard reagent to produce a series of alkforyl ketones,^ The most striking difference displayed by the fluorocarbon derivatives when contrasted with their organic analogs is in the boiling points of the two materials. The acetforonitrile boils about 1U5° below that of the hydrocarbon analog,^ The fluorocarbon nitriles are generally prepared from the amide, which is readily prepared from the ester or the acyl halide by ammonolysis and can be almost quantitatively dehydrated to the nitrile through the action of phosphorus pentoodde,^ They can also be prepared by the electrochemical process, using the hydrocarbon analogs as starting materials. Fluorocarbon nitriles are produced although there is soma decomposition to HF^« *The nomenclature used throughout the text is that proposed by Dr, J. H, Simons, lb* reader is referred to Chora, Bag, News 26, 1317 (19U8), for a more complete treatment of the subject.

PAGE 16

EXPERIMENTAL PROCEDURES '' r-ncral Consider a lions The reactions and preparations which follow all hare a common chemical source, namely the fluorocarbon nitrile. It would therefore be of ease interest to list some general considerations of the reagents used and the methods of preparation for the starting materials used. Reapents t Aeetforic Acid Propforic Acid Butforic Acid Anhydrous Ammonia Anhydrous Methyl Amine Purchased from Minnesota Mining and Manufacturing Company, Purchased from Minnesota Mining and Manufacturing Company, Purchased from Minnesota Mining and Manufacturing Company, Purchased from the E* X, duPont de Nemours and Company, , Inc, Purchased from The Matheson Company. Inc, Anhydrous Dimethyl Amine Purchased from The Matheson Company, Inc. Anhydrous Hydrogen Sulfide Purchased from The Matheson Company, Inc, The fluorocarbon nitriles were prepared as described in the literature with only slight modifications in the procedure. k? the fluorocarbon nitriles as prepared were found after a one plate distillation to be of sufficient purity to use in these experiments, AH major 10

PAGE 17

11 purification was accomplished with the easily distillable ester or the equally easy recrystallisable amide since both of these products are quite stable and convenient to handle. The preparation of the nitrile can be schematically represented » by the following set of chemical equations! RfCooa ROH . H2SC|^ RjpCQGS HjjO RfCOQR Et20 RfCONife ROH RfCONH 4 p 2°5 > RjCN h 3 po u R— CFy», CgFtj-j CjF-pThe experimental method for the acetforonitrile will be described. The other members of the series were prepared by an analogous series of reactions. Acetforonitrile Ethyl acotforate. ** Into a 500 cc round bottom flask, fitted with a reflux condenser and protected from atmospheric moisture by a drying tube, was placed 11U g. (1*0 mole) of acetforic acid. To this was added an ice cold mixture of 96 g. (2.0 mole) of ethyl alcohol and 75 g« (0.8 mole) of concentrated sulfuric acid. The mixture was allowed to stand at room temperature for two hours and then refluxed for an additional two hours. On cooling, the reflux condenser was removed and the flask fitted with a downward condenser. The crude product was obtained by stripping the reaction mixture of all liquid boiling below 70°. This crude ester was washed twice with saturated sodium carbonate solution and dried over

PAGE 18

12 anhydrous calcium sulfate. The crude ester was fractionated in a distillation column packed with glass helices of approximately nine theore• tical plates. The yield of pure ester boiling at 60-62° mas lU5 g. field 92$, based on amount of acid used. Acetf or amide. A three necked 500 cc round bottom flask, immersed in a Dry Ice-acetone mixture, was fitted with a delivery tube and a condenser through which moist air was excluded by • calcium chloride drying tube. Into the flask was placed 158 g. (1.0 mole) of ethyl acetf orate along with IDO ec of ethyl ether. Into this mixture was condensed a large excess of anhydrous ammonia. The reaction mixture was then allowed to warm up to room temperature and the excess ammonia allowed to distill off. The solvent was than stripped from the reaction *. mixture, leaving a white solid which could be recrystallised from ethyl ether-petroleum ether to yield pure acetf or amide (*.p. 75°). The solid weighed 102 g., 91$ of theoretical yield, based on the original amount of ester. Acetf oronitrile. A mixture of 113 g. (1*0 mole) of acetforaraide and 150 g. (1.1 mole) of phosphorus pentaxide was placed in a round bottom flask fitted with a reflux condenser which in turn was connected by a rubber tube to a glass trap immersed In Dry Ice-acetone mixture. The solid mixture, when heated to 150° and held at this temperature for three hours, evolved acetf oronitrile which was collected in the trap. Distillation to a new trap produced 76 g. of acetforonitrile. Yield 68$ of theoretical based on the amide used.

PAGE 19

13 Amidinea Fluorocarbon Aaddines Ace tf oramidine * A reaction vessel consisting of an 80 ml. cylindrical glass flask, fitted with a delivery tube and connected to a Dry Ice-acetone reflux condenser, was placed in a Dry Ice-acetone bath. ** Into the flask was distilled 11*2 g. (0.10 mole) of aeetforonitrile. A large excess of anhydrous ammonia was then allowed to condense into the a reaction vessel containing the condensed nitrile. Tlie Dry Ice-acetone bath was removed and the mixture allowed to reflux under the Dry Iceacetone condenser for one hour. It was noted that the mixture did not » react at Dry Ice-acetone temperature, but at slightly above this temperat turc a violent reaction ensued. The excess ammonia was allowed to distill off and the reaction mixture allowed to come to room temperature. The resulting product was then fractionated through a column packed with glass helices under reduced pressure to free it of any dissolved ammonia. The final product was a colorless liquid, b.p. 35-36° • 11 mm* 1.3801, d 2 ^ l.ii?U 0 . Analysis Calculated for C 2 F 3 N 2 H 3 * 9, 25.00$ Found* 9, 2h.8U$ The succeeding members of the series were low melting solids which resulted when the excess ammonia was allowed to distill off from the reaction mixture. These were recrystallised from ethyl etherpetroleum ether in the cold to remove any dissolved asxnonia and when dried they were not found to be hydroscopic. A summary of properties

PAGE 20

1U follows in Table I,* * Analysis Kjeldahl's Method* Sample refluxed with concentrated sulfuric acid and Selenium metal} steam distilled into an excess of standard acid and back titrated with base to methyl red end point* Properties The amidines are slightly basic compounds , soluble in ether, alcohol and acetone, but insoluble in water* they hydrolyse in aqueous inorganic acid to form the ammonium salt of the inorganic acid and fluorocarbon acid* They hydrolyse in aqueous or alcoholic base to form the fluorocarbon amide or acid and ammonia* The amidines were not found to be hydroscopic if properly freed of ammonia* N-nethyl and N, h -dimethyl Alkforyl And din ee N-methyl Ace tforaml dine* A reaction vessel consisting of an 80 ml* cylindrical glass flask fitted with a delivery tube and connected to a Dry lee-acetone refits condenser was placed in a Dry Iceacetone bath* Into the reaction vessel was condensed 11*2 g* (0*1 mole) of acetforonitrlle* To the condensed nitrile was added a moderate excess 6*2 g* (0*2 mole), of methyl amine* The Dry Ice-acetone bath was removed and the mixture allowed to reflux under the Dry— Ice acetone condenser for one hour. At the end of this time the excess amine was allowed to distill off, leaving behind a high boiling liquid* The liquid was • *It has been called to the attention of the author that these compounds have bean reported in a patent 1 ? by a modification of the above procedure after the work had been completed in this laboratory*

PAGE 21

15 a 5 8 K £ O Pu 5? 3 R CM as 8 v\ CM H CM • e*r CM CM 3 3 05 £ o UN « P*T co UN -5f UN V 0 1 • • 0.0 •o as UN co -=r «n f CM UN •t • • ft O •© w % n i * £ i t\ .A b & o~ 4* CN O

PAGE 22

16 distilled under reduced pressure to yield Hi g. of pure N-metbyl perfluoroacetamidine b.p. 35-36° 3 11 mm, 1.3301, d*5 1.U&0. Analysis Calculated for C3F3H5N2 N, 22.20, M.R. 17.50. Found. H, 2 1.85, M.R. 17.59. The other members of the series were prepared in exactly the same manner. They were found to be more heat stable and did not require vacuum distillation. The distillation was through a nine plate column packed with glass helices. The analyses were as described for the un4 substituted a -ai dines. A list of the physical properties of the substituted amidines prepared appears in Table II. Metal Salts of Alkforylamidines Silver Salt of Acetforaraidine .To 5 g. (O.OkU mole) of aoetforamidine dissolved in 15 co of anhydrous ethyl ether was added portionwise 4.60 g. (0.020 mole) of silver oxide. An immediate evolution of heat was noted along with the formation of a white solid. The mixture was vigorously stirred and any lumps of silver oxide noted were broken up. After all the black silver oxide was consumed, the white solid was filtered, washed a number of times with ethyl ether and then air dried. The material was found to be toe silver derivative of the ami dine. The salt decomposed on heating at about 200°C* Analysis Calculated for (^FjN^Agi S, 12.71, Ag, U8.78. Found* N, 12.28, Ag, U8.U0. The remaining members of the series were prepared in exactly toe same manner. The silver salts were all found to be white solids, decomposing without melting at tenperatures of 200° or above.

PAGE 23

N-subetituted Alkforylamidlnes 17 I vS* 4 •I col S\ (2 SB VA % XA % * • • AJO • o CD a 4 Os VA • m CM £ co • r-l CM o CM SI 2 ^ Os CM H *1 3 3 r— CM Os CM f£ Os 8 o CM a CO «A rl H 4 o & .f -! I « « s X SB 33 SB O «A pt« O CO CM Os r*• CO CM «A SO Si a CA 4 co VA 3 rl f NO 3 03 £ O CM •
PAGE 24

18 The properties of silver salts of alkforylanidines are given in Table III* Mercury Salts of the Butforartidlne. * In a test tube immersed in an oil bath was placed an intimate mixture of 10 g* (O.OU6 mole) of but* foraaidine and 5 g* (0*023 mole) of mercuric oxide* The mixture was heated to 110° to melt the ami dine and was vigorously stirred* The formation of the white mercury salt could be noted and was essentially complete in two hours* The melt was allowed to cool and unreacted aaddine was leached out of the solid by continuous extraction of the solid* ified melt with ethyl ether* The unreacted mercuric oxide could be removed by centrifugation using ethyl ether as the solvent* The heavier mercuric oxide settled first and the upper layers were found to be essentially the amidine mercury salt* After a number of centri fugations , the pure salt was obtained as a white solid that decomposed at 178°, Analysis Calculated for G 6 F li, K U H U H £* N » 9 , 00 , Hg f 32.31* Pound* N, 8.U2, Hg, 32.60. The mercury salt of the acetforamidine could not be prepared since this amidine decomposed very easily when heated* The propfor amidine reacted in exactly the same fashion as the butfor ami dine to give a mercury derivative* The properties of the mercury salts of the alkforyl amidinee are summarised in Table 17* Attempted Preparation of the Alkali Metal Salts of the Alkforyl Aid. dines ' obassiiaa Amid e and B utfor;au.dino in Liquid Arr-onia ,Potassium amide was prepared by dissolving potassium metal in liquid ammonia using

PAGE 25

19 Sr 3 CO * 3 £ eo ss 3 3 oo t*• CO • * 0,-0 s° 8 CM R 8 3 » 8 8 • • <2 £ •4 n CM i

PAGE 26

TABLE IV 20 3 CO 8 Os *

PAGE 27

21 Iron as a catalyst* In a flask containing 5 g. (0*10 mole) of potassium aside and 17 g* (1*0 sole) of liquid ammonia was added 21 g* (0*10 sole) of butfor aid. dine. The mixture was allowed to reflux under a Dry Ice-acetone t • * condenser for one hour. On removal of the excess ammonia a viscous orange syrup remained. The viscous syrup appeared to be hydroscopic and on distillation was found to decompose. Potassiua amide and the butforyl nitrile in liquid ammonia. To a flask containing 5 g. (0.10 mole) of potassium amide was condensed 19*5 g. (0.10 mole) of butforyl nitrile. A large excess of ammonia was condensed in with the mixture and the contents of the flask were allowed to reflux under a Dry Ice-acetone condenser for one hour. The solution gradually darkened to a deep brown. The excess ammonia was allowed to distill off leaving a brown syrup from which nothing could be distilled or extracted. Potassium hydroxide and outforamldioe in methyl alcohol .In a flask containing a solution of 5 g* (0.10 mole) of potassium hydroxide dissolved in 25 ml of methanol was added 21 g. (0*10 mole) of butyraaddine. The mixture was allowed to stand one hour* The alcohol was removed leaving a heavy Syrup from which only butforamide could be distilled* The rest of tl» material resisted both extraction and distillation* Acid Salts of Alkforyl Ami dines The acetforic acid salt of butyr ami dine. In a round bottom flask containing 15 ec of acetforic acid was dissolved 5*3 g, (0*025 mole)

PAGE 28

22 of butforaraldine, The clear solution which formed was allowed to stand for one hour* The excess acid was removed under reduced pressure leaving a residue consisting of a white solid* The solid residue could be purified by sublimation and was found to be the acetforic acid salt of the butforamidine. Analysis Calculated for ® , 8*59$ N#F.* , 326* Founds !,o*UU, K»£*$ 32U* The aUcforyl amidine 8 were found to fora salts with inorganic, organic and fluorocarbon acid* The procedures were the same for all the salts except in the case of the formation of the alkforyl amidine Hydrochloride* Formation of the amidine Hydrochloride necessitated dissolving the onidine In anhydrous ethyl ether and bubbling anhydrous hydrogen chloride through the solution from which the fluorocarbon amidine Hydrochloride separated* Some representative acid salts are given in Table 7* Acylated Allcforyl Amidines a «i ~Fengo -1 butforamidine, A solution of 2U*6 g* (0.17U mole) of *•: f bensoyl chloride was placed in a round bottom flask fitted with a dropping funnel, condenser and protected from atmospheric moisture by drying tubes. The flask was cooled in an ice bath until the content* were at 0°, A solution of 37 g* (0*17U mole) of butforamidine in 50 cc f of dry ethyl ether was slowly added to the flask* An Immediate evolution of hydrogen chloride was noted along with a white precipitate of the butforamidine hydrochloride. After the addition was complete, the flask was allowed to warm up to room temperature and to stand for one

PAGE 29

Acid Derivatives of Alkforyl Amldlnec 23

PAGE 30

2k hoar at this temperature. The mixture was filtered free of the white amidine hydrochloride and the ethereal solution carefully stoppered to preserve it from the atmosphere. The ethereal solution vas found on dilution with petroleum ether and cooling to precipitate a solid melting at 6l-63°C. Recrystallisation from ethyl e ther-petroleua ether gave a white solid, rap. 63°C. Analysis Calculated for K, 8.86) Founds N, 8.58 The acetyl derivative vas prepared in the same manner and was found to be a liquid boiling at 152°. The great susceptibility of the derivative to hydrolysis may account for the poor nitrogen analysis. Analysis Calculated far CgF^NgO s H, 11.06) Founds K, 10.37 Saponification equivalent* Calculated* 25U) Found* 255 Sutforyl chloride was found to react with the butfor ami dine to give a variety of products, none of which could positively be identified as the desired acyl at ed derivative. The reaction was carried out exactly as described for previous preparations, the following products being Isolated and identified in the reaction mixtures 1. outf or amidine hydrochloride 2. liquid fraction boiling at 73° ® 61* ran gave neutral equivalent indicating it was butforic acid 3. liquid fraction boiling at 115-116° tf 6U m which hydrolised quite rapidly on standing, to give only butforaaide.

PAGE 31

25 The Butforamidine with Sodium Hypobroadte A 500 cc round bottom three necked flask containing 36 g. (0,90 mole) of sodium hydroxide dissolved in 100 cc of water was fitted with a stirrer, dropping funnel and condenser. The condenser vae connected by a delivery tube to a trap cooled In Dry Ice-acetone mixture. The reaction vessel was cooled to 0°, 28,8 g, (0,18 mole) of bromine was added dropwise and cooling and stirring continued until the red color of bromine disappeared and only a light yellow color remained. To this solution was added 32 g, (0,150 mole) of butfor ami dine along with an additional 50 oo of water. The anticline slowly dissolved in the solution. The reaction mixture was left for one hour in the ice bath, allowed to come to room temperature and refluxed for two and one half hours at 100°C, The Dry I co-ace tone trap yielded after distillation through a packed column 2,6 g, of material boiling at 17-18° with molecular weight of 253, whioh could be identified as the propforyl > • * . bromide. The contents of the flask on acidification yielded large amounts of the butforanide, Klaorocarbon Thloa-nxdes Tliiobutf or amide from butforonitrlle, Into a heavy vailed pyrex glass tube of approximately 60 ml, capacity, previously constricted for sealing and evacuated, was allowed to condense 6,8 g, (0*35 moles) of butforonitrlle and 3,U g, (0,10 moles) of hydrogen sulfide. The tube was sealed off and allowed to warm up to room temperature and left at this temperature overnight. The tube was opened and the volatile material, consisting entirely of hydrogen sulfide, was allowed to

PAGE 32

26 t distill off into a vacuum system leaving behind 8 g. of a pale yellow solid. The solid was recrystallised from ether-petroleum ether, yielding 6.3 g, of pure thiobutforamide, m.p. U9°» Analysis Calculated for C^F^NSt N, 6.12j S, 13,97 Founds H, 5,85} S, 13.81, The thiopropforamide could be prepared in the saw manner, the v reaction proceeding at roan temperature. The thioacetf or amide was not successfully prepared under these conditions, a considerable amount of charring taking place in the reaction vessel. It was found that if the reaction was kept at 0° for eighteen hours, satisfactory yields of the thioacetf or amide were obtained. The reaction could also be moderated through the use of s solvent such as ethyl ether, but reaction times were extremely long, (100-125 hrs,). Thiobutforaraide from butforamldine ,In a round bottom flask fitted with a two hole rubber stopper carrying a delivery tube and a drying tube, was placed 15 g« (0,071 moles) of butforamldine dissolved in 25cc of ethyl ether. Into tills solution was bubbled an excess of hydrogen sulfide until the solution was completely saturated. The solution was then allowed to stand one hour. The ether was removed under reduced pressure and a high boiling liquid ws left in the flask. The liquid sometimes crystallised on standing to yield the crude thioamide. Usually the liquid was distilled under reduced pressure to produce a liquid which immediately crystallised on cooling. The product recrystallised from ether-petroleum ether was found to be yellow needles melting at U7-U8®,

PAGE 33

2 ? Analysis Calculated for Cj^lfeNH* H, 6.12; S, 13.97. Found* li, 6.0lj S, 13.90. This method was found to be quite suitable for the preparation of the other members of the series, yields being in most cases almost quantitative. The properties of the fluorocarbon thioamides are suisaarised . in Table VI. 2.U.6.tris(alkforyl) l,3»St s-triasinae 2.U.6,trls(ethforyl) 1.3.5. s-triazine from propforonltrile. Through the use of a vacuum system 5U g. (0.37 moles) of propforonitrile was condensed into a stainless steel autoclave. The autoclave was heated at 300° for 120 hours, after which the vessel was allowed to cool. The volatile material (27 g.) was allowed to distill out of the vessel before it was opened. The vessel was found to contain 16.6 g. of high boiling material. The high boiling material was subjected to distillation through a nine plate column giving 6.3 g. of colorless liquid boiling at 122-122.5°. n?5 1.3131. & 1.6506. Analysis Calculated for S, 9.60) M.W. U35| S.E. U35. Pound* M, 8.99J H.W. U31| S.E. UU2. The other fluorocarbon nitriles were found to act quite similarly to the propforonitrile with 300° as the optimum temperature for reaction. The butforonitrile however, gave better yields at the slightly higher temperature of 350°.

PAGE 34

TABLE VI 28

PAGE 35

29 2.1i.6,tris(ethforyl) 1.3,5 s-trl aslne from propforamidine.Into ft round bottom flask fittod with a reflux condenser was placed 55 g. (0.3U moles) of propforanldine. The flask was placed in an oil bath and heated at 125° for three hours, the evolution of aamonia being noted* At the end of this time the resulting liquid was cooled and then subjected to distillation through a column packed with glass helices and calculated at nine theoretical plates. The distillate was a colorless liquid boiling at 122°. n 2 * 1.3135, d 2 * 1.650b. The ace tf or ami dine could not be used in this preparation since on heating, it produced a solid, a portion of which could be identified as the acetforand.de. The butforamidine appeared to be a very suitable reagent in this reaction giving excellent yields of the butforyl substituted triasines. The properties of the 2,U,6,tris(aikforyl) 1,3,5 s-triasines are summarised in Table VII. Infrared Spectra of Alkforyl s Triasines A Perkins and Elmer Model 21 double beast infrared spectrophotometer was employed in toe preparation of the spectrograms of the alkforyl s-triasines. A demountable cell consisting of two salt plates pressed over the liquid was used. The cell thickness was approximately 0.027 ran. The infrared spectrograms for the alkforyl e-triasines prepared follow.

PAGE 36

TABLE VII 30

PAGE 37

DISCUSSION Alkforyl Amidlnes The alkforyl amidlnes were prepared by the action of anhydrous ammonia on fluorocarbon nitriles without the influence of acid catalysts* The conditions under which the alkforyl amidlnes were prepared indicate that the formation of these confounds and tive mechanism by which this reaction occurs are quite different from those found in organic chemistry, The fact that the fluorocarbon nitriles form stable free asddinee by the addition of ammonia to nitriles is significant in that these molecules are the first easily prepared and stable examples of congxjundb of this type. There have been recorded two instances of amidlnes having been prepared^* ^ by the addition of amines or ammonia to nitriles without acid catalysts. However, in one instance the isolation of the free amidine was claimed, but other investigators^ could not obtain the compound except by formation of a pierate salt* In the other case, the material isolated was very unstable and had to be kept at very low temperatures under desiccation or else decomposition occurred* In both these instances the molecule to which ammonia was added was of an enhanced cationic type, the compounds being trichloromethyl cyanide and ethyl oyanotartronate* The enhanced reactivity of these compounds was probably due to the inductive effect of the substituents of the molecule. In this respect, these confxjunds show a similarity to the fluorocarbon nitriles

PAGE 38

3 $ and probably reacted in a similar fashion* The organic aaidines have been prepared by a number of different methods, but there are only three of sufficient is^ortanca to be mentioned here) (1) the conversion of the iaino ester to the amidine through the use of ammonia,^ ( 2 ) the reaction of alkali metal amides with nitriles® and (3) the reaction of the acid salt of the amine or ammonia with the nitrile*® The last method is probably the most widely used preparation for the and dine. The methods of preparation can be sumarised by the following chemical equations t HC1 (1) RCH ROH RC(HH)0R»HC1 RC(NH)0R«HC1 B&CffiOHHg'HCl ROH NH* HC1 (2) RGN KK% RC(HH)HHK RC(ilH)NH2«HCl (3) RCH NH^Cl iiSl » RC(HH)NH2*HC1 It can be seen from the description of the preparation of the amidine that the reaction is basically one of an anionoid agent (amine) seeking a cationoid site in the nitrile* The organic nitrile structure as we can construct it from our knowledge of its reactions is one in which there exist partial negative and positive charges in the molecule* This dipole arises in the molecules because of differences in electronegativity between the cons titu tent atom* 1 The organic nitrile may be pictured as t * IhC • I 6 partial (harts

PAGE 39

36 It has been suggested^ that the formation of the aaidine in the presence of acidic catalysts occurs according to the following mechanism R-C H R* JcSjCl * m r-c • i r \ ci B • H or alkyl group R-C • It V Cl . (I) J R-C NH2 NHR R-G-NHg \\ NHR* cr The hypothetical intermediate (I) is unstable in the presence of the ammonium ion and probably through hydrogen bonding is decomposed by the ammonium ion to give the awidinium salt of the acid* This mechanism suggests that there are two conditions necessary for amidine formation among organic nitriles* The nitrile must be in an activated state having a suitable reaction site available and the amidine once formed must be more basic than the amine from which it was prepared* If the second condition was not met, the ammonia salt would preferentially remain and the equilibrium would shift to the side favoring ammonium salt and not the amidinium salt formation* A search of the literature on the basicity of organic antidines reveals that the value for only a single substance is available, namely ace tami dine. ^ The value as given was pKb 1*59* Comparing this value with the pKb values for certain amines, it can be readily seen that the amidines are more basic than the ammonia compounds from which they are formed* It has been concluded by some investigators^ that in general, amifHn*

PAGE 40

37 formation la oora complete with salts of weak bases* TABUS vni pKb 2 * (CH 3 ) 2 IIH 3.2? cnyiHg 3.36 NB, .. U.7U W«2 9.U1 It has been noticed in the study of substituted benzonitrile . that amidine formation la usually promoted by groups which act as electron sinks (pMeSOg, Br, NOj) and is retarded by those which act as electron sources (MeO, OH)*^ The inductive groups will aid in the formation of the complex by increasing the polarity of the molecule, but they also decrease the basicity of the amidine once it is foamed* This will retard amidinium salt formation by displacing the equilibrium L away from amidine formation. The conditions under which the alkforyl amidine s form, indicate that neither of these two ideas postulated for organic amidine formation £ is of importance in the synthesis of alkforyl amldinee, sines the path to formation appears to be quite different* Since no imported stimulus x was necessary for alkforyl amidine formation or stability, ths differ* ence between organic nitriles and tbs fluorocarbon nitriles must lie in the greater inductive effect of the fluorocarbon group adjacent to the nitrile structure. The electron withdrawing nature of the alkforyl

PAGE 41

38 group la known, as evidenced In studies in connection with the electrophillic addition to double bonds found adjacent to an alkforyl substituent,^ The reactions of the fluorocarbon nitriles studied to date have in general been those of organic nitriles and have not shorn a complete and clear picture of the possibilities of these fluorocarbon compounds. The value of the alkforyl radical adjacent to an unaaturated site becomes readily apparent in the reaction of the fluorocarbon nitriles to form amldines. The fluorocarbon nitrile structure might be pictured ast *f * r \ c-c * s* * r The inductive effect of the alkforyl group on one side of the reactive carbon site and the electronegative nitrogen atom on the other side Impart an effect to this carbon center v lch renders it relatively positive, Ihis cationoid site is present in the molecule without any outside stimulus. The ammonia molecule beinj nucleophillic in character is attracted to this positive site. The possible reaction mechanism may then be illustrated asi a m -y r f-osi Rf-C • H *NH, * * + RfC * s1 / H-N'-H R RfC m m \ »% R f -C-HH 2 II NH

PAGE 42

39 It had been noted that when the reaction to fora the aaidine was conducted in the presence of ammonium chloride, no aaidinium chloride was formed* This would indicate that the alkforyl a mi dl ne formed was a weaker base than the ammonia from which it was prepared* The poetulate of an equilibrium between a hypothetical nitrile intermediate and the ammonium salt is not valid for the formation of the alkforyl araidine since the ammonium salt could be isolated readily ^ f is ii ' Ci * from the reaction mixture* Although the alkforyl amidlne was prepared in this reaction, no amidinium salt was found* This condition would have been impossible if a mechanism involving acid catalysis was operating. The mechanism then postulated for amidlne formation from the fluorocarbon nitriles is the addition of ammonia to the free nitrile along with a proton shift to give the stable amidlne* N-suba tituted and HN-di3uostituted Asaidines The substituted ami dines can be looked upon as forming in the same manner as the unsubstituted amidines, the oni* difference being that the basicity of the amine appears to be very important for formation of the substituted amidlne* The monos ubs tituted alkyl amine t reacted quite readily as did the die ubs tituted alkyl amine) in both cases the reaction was as fast and as complete as with ammonia* It will be noted from Table VIII that the basicity of both of these amines exceeds that of ammonia* The fact that the phenyl substituted amines, such as aniline, would not react with the nitrile even after heating, i could possibly be explained by the fact that the basicity of the amine

PAGE 43

Uo is an important consideration In toe reaction. * Aniline is a considerably weaker base than either ammonia or alkyl substituted amines and hence would yield a poor anionoid nitrogen to take part in the reaction. Additional study on toe formation of amidines with respect to the strength of the base will be necessary before any more definite conclusions can be reached. Amldiniua Salts The salts of toe amidine show some very interesting properties with respect to toe influence of the alkforyl radical on their acidbase strength. The organic amidines have been called by some investigators^ carbazylic acids because of their acid like character in solution of anhydrous ammonia. It has been possible to produce metallic salts of toe organic amidine using anhydrous aataonia as a solvent. *3 The organic amidine in solvents such as ether or water has been found to be too weak an acid for successful preparation of metallic derivatives. The fluorocarbon amidine, however, exhibits sufficient acid properties in organic solvents to fora these metallic salts. This again Indicates the electron inducing effect of toe fluorocarbon group on toe overall basicity of the amidine molecule, toe silver and mercury salts of the amidines were prepared in anhydrous ether and were found to be crystalline materials which deconqxaed on heating. The salts which formed indicate that toe alkforyl amidines are monobasic acids. Although three replaceable hydrogen atom are available, only one hydrogen was replaced by the metallic ion. These structures may be represented by general formulae i (RfCOmjNH)^

PAGE 44

UI The alkali metal salts resisted all attempts at isolation and oould not be prepared* A possible reason for this is the fact that when the reaction was run in aqueous or alcoholic media, hydrolysis occurred* When the alkforyl amidine was treated with alkali natal in an anhydrous ammonia solvent decomposition occurred* The decomposition of fluorine containing compounds in liquid ammonia containing alkali metals has been noted by McBee 27 and has been used as a method of decomposition for analysis* The product of the reaction was a syrup which resisted crystallization, extraction or distillation* Since nothing that appeared to be of interest at the time could be isolated, the experiments were discontinued* The alkforyl ami dines , besides being acid enough to fora metal salts, exhibit basic properties in the same solvents which are sufficient to bring about the formation of acid salts* A number of these salts were prepared using inorganic, organic and fluorocarbon acids* Ctaly one acid molecule reacted with one amidine molecule to form an V ataidinium salt* The structure of these compounds from analyses and neutral equivalents appears to bet R I A R f -C-NH 2 *HA •.cyiaU J. A: n. dines The alkforyl anddines are quite easily aeylated to form the N-eubstituted acyl derivatives. The course of the reaction to the N-acyl alkforyl anddines could yield two tautomeric aeylated

PAGE 45

H2 products • H r^R^C(NH)^C(0)R^ ECl (I) R f C(NH)N^ R^COCl ^R^G • N-C(0)R f HCl I (II) The two isomeric forms should have distinctly different character is tics* Structure (I) should be acidic in nature due to the two adjacent electron inducing groups, while (II) should be a neutral molecule or at most a very weak acid* The hydrolysis of (I) should produce the mixed secondary amide (III) while hydrolysis of (II) would produce the primary amide (IV), The N -benzoyl derivative of the butforamidine was found to be a neutral compound since it was not soluble in aqueous sodium hydroxide. The acetyl derivative was hydrolyzed by aqueous base to form acetamide and the butforand.de. The N-butforyl derivative which could not be obtained in a state sufficiently pure enough to characterise it, hydrolysed exclusively to the butforaod.de. The sulphonie acid derivatives of the organic ami dines have been shown to display a similar reaction, 2 * 32 Thus, Barber using H R f C(0)H-C(0)R f (III) (W)

PAGE 46

U3 sulfcnyl derivatives (R-SOg-) concluded that there possibly exists two isomers of these compounds, the stable form being of a structure similar to (I) and an unstable form similar to structure (II) which could be converted to (I). Horthey 2 was able to isolate only one sulfanilyl derivative (H^N -C^-S ) which was incapable of forming the sodium salt and on hydrolysis gave amides of type (IV). The author concluded that a structure similar to (33) was more correct on the basis of the data obtained* A comparison of the two structures of the acylated amidinee will show that the existence of the two different compounds can be accomplished when an electron inducing substituent is adjacent to the ami dine functional group. This electron inducing group can than serve to immobilise the hydrogen atom and prevent prototoropy. Bf-CJ H N H H This type of tautoaerisra would occur but for the electron In* ducing effect of the alkforyl radical which stabilizes tbs imino nitrogen so that the rapid exchange of protest is lessened or entirely halted. A consideration of the hydrolysis products and the appar en t neutrality of the acylated alkforyl amidinee would lead to the conclusion that the acyl derivatives of the alkforyl aaidines probably exist structure (II).

PAGE 47

hcac -ion of But.toramid.lae with Sodium lypobromite The reaction of the butforamidine In the presence of sodium hypohalite was found to produce the propforyl bromide and the butfesranide. It has been shown by Busted and Kohlhase 20 that the alkforyl amides give unexpected results in the Hoffmann Hypobromite Reaction, the but for amide forming propforyl bromide instead of the expected propforyl amine. This same product was obtained with the butforamidine The reaction as applied to the butfor amide was given ass The H-brorao substituted amide being an isolatable compound. The reaction mechanism for conversion of butforamidine to propforyl bromide indicates that the amldine was first hydrolysed to the amide and that the latter then reacted with sodium hypohalite to give the isolated propforyl bromide. All attempts to prepare an N-bromo substituted ami dine were without success, the reaction being tried in a number of solvents under a variety of conditions. This indicates that under normal conditions of formation of 8-brono derivatives of the amidines the alkforyl anddinea do not react to give these compounds. The silver salts of the alkforyl ami dines were also used without any success. The mec nanism then proposed for the formation of the propforyl bromide from the but* foramidine, since the butforaaide was isolated in the reaction mixture.

PAGE 48

liS la for the formation of the butforamide by hydrolysis and then broadnation followed by elimination and rearrangement. i-lnorocarbon Thioamides The fluorocarbon thioamides were prepared by two different methods • The action of hydrogen sulfide was found to convert both the fluorocarbon nitriles and the fluorocarbon amidines to the fluorocarbon thioamides at room temperature. The fluorocarbon nitrile when sealed in a glass tube with hydrogen sulfide was found to react at room temperature to produce the fluorocarbon thioamide. The reaction was found to be very rapid, and in the case of acetforonitrlle so vigorous that charring of the reaci tacts or products occurred* The organic nitriles have been found to add hydrogen sulfide under the influence of heat and pressure?* 5 the reaction being catalysed by alkali hydrosulfides. It was shown that electron inducing groups aid in the addition of hydrogen sulfide to aromatic nitriles, the tine for reaction decreasing with the more electronegative a substituent on the ring.^3 The rapid reaction of the fluorocarbon nitriles shows again the great electron affinity of the alkforyl radical, since these compounds form almost quantitative yields of the fluorocarbon thioamides by hydrogen sulfide addition at room temperature. The fluorocarbon amidines react vdth hydrogen sulfide in a solvent of ethyl ether at room temperature to form the fluorocarbon thioamides. The reaction requires a large excess of hydrogen sulfide to convert the fluorocarbon amidines to the fluorocarbon thioamides.

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1*6 The fluorocarbon thioanides prepared in this manner were found to be substantially pure since in most cases even before distillation they solidified. The fluorocarbon thioanides as prepared were found to be low melting, pale yellow solids with the exception of the first aeifcer thioacetf or amide which was a pals yellow liquid. The thloamidee appeared to be quite stable and could be stored for a number of weeks in sealed vials without any apparent decomposition. Alkforyl Triaaines The preparation of the 2, U,6tris (alkforyl) 1,3,5 triasine was accomplished by two different methods. The first involved the trlmerization of the alkforyl nitrile under pressure. The second concerned the coupling of three moles of alkforyl ami dine with the resultant loss of ammonia to form the triasine. Vrirngrisation of the .fluorocarbon nitriles under pressure. The fluorocarbon nitrile was found to triserixe under the influence of pressure to form the triasine, no acid catalysis being necessary. There was no definite set of conditions for trimerization found, but the pressure range found most satisfactory was between 700-900 p.s.i. The optimum temperature appears to be between 300-350° and the reaction time may vary between 30-120 hours, the criteria being a sufficiently great pressure decrease. The fluorocarbon nitriles show a striking difference in polymerization when compared with their organic analogs, in that no activating Influence was necessary to effect this reaction. The mechanism proposed for the formation of a triasine under the influence

PAGE 50

U7 of acid has been a diene type synthesis in which two moles of the nitrile condense to form the diene and the third mole of the nitrile then acts as the dienophile. The mechanism appears to be applicable to the synthesis of the triasine f ram the alkforyl nitrile. The reaction sequence is listed below. Rj O 8~ A R--C* \ *7 h* ‘r*f * ,ltt N N ii V * / C l »f s* Rf diene dienophile A possible mechanism which is proposed is that two moles of the more active fluorocarbon could condense to form a diene type structure followed by condensation with a third mole to form the triasine. The reaction appears to require rigid rules for the size of the molecule involved, for, as the sise of the alkforyl radical increased, the yield of the triasine was noted to decrease. The effects of pressure was noticed to have an effect upon the synthesis. At the lower pressures of 300-1*00 p.s.i., reaction did not take place, but at pressures over 600 p.s.i., effective trimerisation was accomplished. Condensation o f the alkforyl amidinea. The alkforyl smidines when heated in the atmosphere above their melting points trimerize to form the alkforyl s— triasine in good yield. The exception is the ace tf*o r ami dine which was found to hydrolise in atmosphere on heating to form the corresponding amide. The reaction appears to be a coupling

PAGE 51

of three moles of the ami dine with splitting out of ammonia to form the triaxine. It was^ found that when butforaaidine was heated, just slightly less than the theoretical amount of ancnania was evolved for the coupling as described below* The alkforyl trlasinee were found to be a neutral substance very resistant to acid attack* The 2,l*,6,trie(propforyl) 1,3,5, s-triazine was stable to concentrated sulfuric acid even after 72 hours* at 300°C* Ths triazlnes ware found to be very susceptible to alkaline hydrolysis giving the sodium salt of the fluorocarbon acid on treatment with aqueous alkali and the este rifled fluorocarbon acid on alkaline alcoholic hydrolysis* The following charts are inserted for comparing the two methods devised for preparing the alkforyl s-triasines. In Table XX, the values for the temperature and ths time are shown as those which gave the best yield of the alkforyl s-triasine in these experiments. The pressure is an autogenous pressure and depends upon the quantity of starting material employed} however, pressures above 600 p.s.i., were necessary for triaerisation. Table X gives the comparative yield of the two methods for the 3nh 3 preparation of the alkforyl e-triasinesi

PAGE 52

U 9 Table ZZ Optimal Conditions for Alkforyl Hitrile rriaerlzation & R i \ R*c-r^-c»iJ-oa 1 l R reap* •c. Time hr a. Pressure Held CFy 300 26 1000 51.0 Vr 300 110 700 U 1.0 Vr 350 U5 810 17.0 Table X Com>arative Yields of Alkforyl s-Triazinos R R R C-N-OB-ON i t R Alkforyl Hitrile Alkforyl Amidine c*y 51 * °2V 10* 35* C 3 F 717 * 6 U* Infrared Absorption Spectra of Alkforyl a-Triazinea The infra red spectra of the alkforyl s-triasines show a very characteristic strong band in the region 1565 cra**^ (6.h^)* The band was found at the sane location in all three members of the series and is believed to be characteristic for the -ONin conjugated cyclic confounds*

PAGE 53

So Studies involving the conjugated cyclic structure, the -ON* absorptions have been assigned as being within the range 1660lii80 cm“^.^ A strong absorptitm at or near 810 car*(12.U0^) has been attributed to the ring structure of pyrimidine in studies of these compounds,^ The triaaine ring structure not being very different, shows characteristic absorption at this point too.

PAGE 54

SUWSARI The aethods of preparation and some physical and chemical properties of six distinct classes of nitrogen containing fluorocarbon derivatives are presented. These compounds are the result of an investigation of a variety of reactions of the fluorocarbon nitriles and demonstrate, by their formation, some of the unique applications of this fluorocarbon derivative. 1. A series of alkforyl amidines sere prepared and some of their physical and chemical properties determined. These compounds are believed to have the following structure! H I II Rj-C-WKHj The specific compounds in which Rj equals! CFj-, CgF^-, and C^F-p were prepared and characterized. These compounds represent the first instance of an uncatalyzed addition of ammonia to a nitrile to yield a free ami dine. A possible reaction mechanism is proposed in an attempt to explain the apparent difference in aaidine formation between the fluorocarbon and the organic nitriles. 2. A series of N-tnethyl and M, K -dimethyl substituted alkforyl amidines were prepared and some of their physical properties determined. 51

PAGE 55

52 These compounds are believed to have the following; structure* H S .« Me R-H Mb The specific confounds for equals* CF^-, and C 3 F 7 were prepared and characterised* 3* A series of metallic salts of alkforyl amidines were prepared* The salts prepared comprise the N-s liver alkforyl amidines and the N-aercuric alkforyl amidines* The metallic salts show the apparent acidity of the alkforyl amidines in neutral solvents* The analysis of these conpounds indicate that the alkforyl amidines act as monobasic acids* U* A series of acid salts of the alkforyl amidines were prepared and characterised* These derivatives were formed with the inorganic, the organic and the fluorocarbon acids and indicate the apparent basicity of the alkforyl amidines under the condition of the reaction* 5* Acylation of the alkforyl amidines produced the N-acylated derivatives of the alkforyl amidines* These compounds, which hydrolyse to the primary amide and appear to be neutral substances, indicate that the imino nitrogen is the site of acylation. As such, they represent a departure in structure from most acylated organic amidines* These compounds are believed to have the following structure* Rf-OIWKO) RfNHg

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$3 6. A reaction showing the rearrangement of the butforaaidine under the influence of sodium hypobromite to the propforyl bromide is presented* A possible path of the rearrangement is proposed. 7* A series of thioalkf or amides were prepared and some of their properties determined. The preparation of these compounds was accomplished by two methods employing in the cane case the alkforyl amidine and in the other case, the alkforyl nitrile. The compounds are believed to have the structures S n Sf-C-fiBg The compounds In which equals t CF^-, C^F^-, and Gjfjm, were prepared and characterised* 8* The 1,3,5, tris (alkforyl) 2,U,6, s-triazines were prepared and characterised* These ccnapounds were prepared by two independent syntheses using in the one case the alkforyl amidine and in the other case, the alkforyl nitrile* The compounds as prepared are believed to have the structures A VC C-R* * H | 1 K H V" l R f The compounds prepared and characterised were for Rf equals* CF^-, c 2 f 5 **» and These compounds represent a departure from the conventional reactions of organic chemistry in that the trizserlsation of alkforyl nitrile was accomplished without toe use of a catalyst* The infrared spectra for these compounds is also presented*

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BIBLIOGRAPHY 1. Alexander, E., "Principles of Ionic Organic Reactions", New York* John Wiley and Son Inc., 1950. 2. Baker, H., J. Chen. Soc. 19U3. 101. 3. Bellamy, L., "The Infrared Spectra of Complex Molecules”, New York i John Mley and Son Inc*, 195U. U, Bernthsen, A., Ber. £, U29 (1876). 5. Bernthsen, A., Ann. 18U. 292 (1877)* 6. Cody, G. H., Crosse, A. V., Barber, £. J., Burgess. L. L. and Sheldon, 2. D., Ind. Eng. Chen. 3£, 290 (19u7). 7. Cahours, A., Coopt. raid. 2j ^ 239 (18U8). 8. Cornell, £., J. An. Chen. Soc. go, 3311 (1928). 9. Curtis, E. and SJickell, L., J. An. Chen. Soc. g, 887 (1913). 10. Day, A., "Electronic Mechanisms of Organic Reactions", New Yorkt American Book Co*, 1950. 11. Dauchler, K., German Patent 671,785 (February Hi, 1939). 12. Fowler, P., et-al., Ind. Bhg. Chen. 39, 292 (19U7). 13. Franklin, E., "The Nitrogen System of Confounds" , New York i Reinhold Publishing Co., 1935* 1U. Fredinhagon, K., and Cadenbach, G„ Ber. 6£, 928 (193U). 15. Fukuhara, N., and Bigelow, L., J. Am. Chen. Soc. 6£, 2792 (19i»l). 16. Oilman, H., and Jonos, R. C., J. Am. Chen. Soc. 6£, 1U58 (19U3). 17. Gloss, S., Ann. 115, 27 (I860). 18. Grundmann, C., Weisse, 0., and Seide, S., Ann. 577. 77 (1952). 19. Holtswart, R„ J. prakt. Chen. (2) 283 (1889). SU

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55 20. Hue ted, D., and Kohlhase, V,, J, Am. Chem. Soc, 76, 5ll*l (1951*). 21. Hus ted, D., U. S. Patent 2,676,905 (April, 195U). 22. Jones, R. G., J. Am. Chem. Soe. JO, 11*3 (191*8). 23. Kindler, K., Ann. Igl, 187 (1923). 2U. Kindler, K., Ann. 850, 1 (1926). 25. Lange, A*, "Handbook of Chemistry* 1 . Eighth Ed., S&ndueky, Ohio* Handbook Publishers, 1952. *» . . < 26. Lebeau, P*, Damiens, H., Corap t, rend. 182. 13l*0 (1926). 27. Hiller, J.i t'nt , H., and McBee, E., Anal. Chem. 19* 11*8 (1947). 28. Hiller, W. T., Calfee, J. D., and Bigelow, L., J. Am. Chen. Soc. 22, W (1937). 29. Moissan, II., Corapt* rend. 102. 15U3 (1886). 30. McBee, E«, Pierce, 0 ., and Bolt, R., Ind. Eng. Chem. 29, 391 (1947). 31. McDee, E., Pierce, 0., and Meyer, D«, J. Am. Chen. Soc. 917 (1955). 32. Nor they, E., Pierce, A. and Surtesa, D., J. Am. Chem. Soc. 6U, 2763 (191*2). 33. Oxley, P,, and Short, V., J. Chem. Soc. 1946. 11*7. 34. Oxley, P., Partridge, M« and Short, F., J. Chem. Soc. 1948. 303. 35. Pinner, A* and Klein, F., Ber. 1£, 1889 (1887). 36. Pinner, A. and Klein, F., Ber. U, 1825 (1088). 37. Roberto, J., ebb, R., fluid McElhill, J. Am. Chem. Soc. 72, U08 (1950). 38. Ruff, 0., Z. angev. Chem. 41, 738 (1928). 39. Ruff, 0., and Aacher, E., Z. anorg. allgem, Chem. 183, 197 (1929). 40. Ruff, 0., and Keira, R., Z. anorg. allgem. Chem. 192. 21*9 (1930).

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• 56 * III. Ruff, 0., and Kein, R., Z» anorg. allgem. Che a. 201, 2 US (1931). U2. Schwarz enbach, G., and Lutz, K., Helv. chan, Acta. 23. 1162 (19L0). U3. Short, L. and Thompson, M«, J, Chem* Soc. 1?52, 168. UL. Simms, J. H ., and Block, L. P., J. Am. Chen. Soc. 61, 2962 (1939). U5. Simms, J. H«, at al., Trans. Electrocfaem* Soc. 9 $, h7 (1 9U9). * • * ; « . .. . . t U6, Simons, J, H., "Fluorine Chemistry", Vol. I, Hew York: Academic Press, Inc., 1950. U?. Swarts, P., Bull. Clasee oci. Acad. roy. Belg. 8, 3U3 (1922). I > ' > * 4» U8. Weddige, A., and Komar, M. S., J. prakt. Chen. (2) 176 (1385). I|9* Young, D«, Fukuhara, it, and Bigelow, L», J, Am. Cham. Soc. 62, 1171 (19U8).

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ACKNOWLEDGEMENTS The author wishes to thank Dr. Henry Clay Brown III for his guidance, assistance and interest during the course of the work. He also wishes to thank Dr. Joseph H. Simons for his interest and many helpful suggestions, and Dr. T. M. Reed and Mr. D. Pilipovich, for their help and encouragement during the course of the investigation. 57

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BIOGRAPHICAL NOTE Mlliara Leo Reilly was born la Bayonne, New Jersey, on July 19, 1926. He attended eat Virginia '* 3 ley an College from September, 19U7 until June 1950, receiving the degree of Bachelor of Science* He watered Duquesne University in September, 1950 and received the degree of Master of Science in August, 1952* He then entered the University of Florida in September, 1952 and has been in attendance since that date* the author belongs to Garaaa Sigma Epsilon and Alpha Chi Sigma fraternities. 58

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COMMITTEE REPORT This dissertation was prepaired under the direction of the candidate’s supervisory committee and has been approved by all members of the committee. It was submitted to the Dean of the College of Arts and Science and to the Graduate Council and was approved as partial fulfillment of the requirements for the degree of Doctor of Philosophy. August 13, 19 $$ Dean, College of Arts and Science Supervisory Committee « Dean, Graduate School