Preparation of compounds of the type CF₃CH₂CHYZ frompolyhalomethanes and acrylonitrile or vinyl acetate

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Authors Wang, Tze-Seng, 1919-

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•raEPARA'EIOH: OF GOMPOUNDS OF THE TYPE GF. GH.CHYZ. .:Yy . \ ■:/ ■'2-'jOMETHAWES AND. AG1 QE FINYL ACETATE

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A Thesis Submitted to the.Faculty of the ' 1 DEPARTMENT OF CHEMISTRY ' , .

In Partial Fulfillment of-the Requirements ■ For the' Degree of" ■: : AG -::'T ;

, V ; MASTER OF SCI.E1GEIn the Graduate College

' ; ■ ■ University of Arizona

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: ABSTRACT .. ' .' PREPARATION OF COMPOUNBS OF THE TYPE CF^CHgCHYZ

FROM. POLYHALOMETHANES AND ACRILONITRILE OR VINYL ACETATE■ . by■ ' ; ’

. Wang Tg@=s@ng •' The preparaticm of C^ClgCHgBrj'CfjOH2CRBi?C02H and

r@Lat.ei . eompwHds. .is .'b'edioHS’-'aBd.' expeMslve. by the.-.wmal flnorinatioH and bromination reaetionso Yields are 'generally very low, A proposed alternative route to Gompotmds of- this type is the condensation of carbon tetrachloride or ; other polyhalomethanes with; aerylonitri-le • or vinyl'-acetate 8 either by peroxide, or-light catalyzed additiono The termi-

1 nal CÎ gremp is then convertible to/a triflimr©methyl group, by standard procedures0 .

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STATEMENT BY AUTHOR

This thesis has been submitted in partial fulfillment of requirements for an advanced degree at the University of Arizona and is deposited in the University Library to be made available to borrowers under rules of the Library.

out special permission, provided that accurate acknowledgment of source is made. Requests for permission for extended quotation from or reproduction of this manuscript in whole or in part may be granted by the head of the major department or the Dean of the Graduate College when in their judgment the proposed use of the material is in the interests of scholarship. In all other instances, however, permission must be obtained from the author.

APPROVAL BY THESIS DIRECTOR

This thesis has been approved on the date shown below:

Brief quotations from this thesis are allowable with-

SIGNED:

ALEC E. KELLEY Assistant Professor of Chemistry

/ Date

The writer' wishes to express his heartfelt thanks to Dro Alee E0 Kelley for his advices encoumgement 9 aad guidance during this entire research^

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INTRODUCTION

The chemistry of flourine eompounds has been studied for some- time 0 However8 the : most frmitful methods; for. the . preparation of organic fluoro compounds: .were di scovered only within the last thirty years o' Organ! e . f luoro compounds have now. become an .important": item":amon-g.v.commereial -ehemieals0 For instance j,. dichlorodiflmoromethame :1s used widely, as. a re» frigerant; the polymerization of tetrafluoroethylene gives a product of extreme- chemical..inertness'o

Among: the . several - ways: - (l̂ 2,3), to. prepare organic fluoro compounds are direct , fluorination"addition:.of hydro® gen fluoride to olefins, replacemant'. of halogen, and electro® lytic fluorination of aliphatic carboxylie acids0 In direct fluorinatioms rearrangement ,:: d:egradatl.on-,... polymerization, . and substitution take plaee0 In the addition of hydrogen fluoride to . carbon®carbon, double bonds, the mode of addition follows Markowiikowss rule;, but .the.- position, of" equilibrium is unfavorable at ordinary temperature for the simple olefins0 The 41ectrulytie (proeess ■:C4) is useful primarily for.per® fluoro compound So , The most- widely applicable method is the exchange reaction taking place, between an organic, halide and various inorganie fluorides» However, the replaeepent reaction generally stops when two fluorine atoms have .beem.introduced at a single.carbon atom0 In order to introduce three

flcmrine atoms on a single carbon atom? the halogens'attached to a single carbon atom should be activated by a double bond (1'). o This requirement leads'.-to a. proposed alternative:' route y to prepare compounds of the type GF^CHgCHYZ by using aery= lonitrile or vinyl acetate.as starting material^ since both : acrylonitrile or vinyl acetate have a double bond which is possibly, attacked readily by polyhalomethanes when catalyzed by; free*. radicals*;; \ ■ V , .

• CH2»CHGN CX3GH2CHXCN.

OH3C0OCHfCH2 » CX^-^>CX^GHaCHX-Q-,g=Cl̂

If these. reactions.,are1 possible.' a. GX^ group is thus obtain^ able. These two addition products might- give rise to a dou= ble bond in the following ways:

; VM ' CH3COOGHZGH2GX3_^mat_^ GH3 GOOH : ̂ ,C%^OH=QHX

'Substitution by three: fludrine atoms of three halogen atoms : In: the allylic posit ion, to a double bond is easy to carry out as mentioned above s . ':: : . v ;

V ClgCHsCHX-Ih&g:..,gf3CHICHI. tiZ . ', ^GFgGHgCHXZ %:

The addition of polyhalomethanes to unsaturated compounds containing terminal double bond was. given much attention during recent years (%6),o' The following reactions are' -

3

; '. '' RCHsCHp * OGl^- >- RGHClSH2CCl3 ' : . ' : : :■■■:>

' ‘ RGHoDHg ̂. GBr^— ' RGHBrGHgBSf̂ .'1 ■RGH§GH2, . f CHC1|---- ^ RGH2CH2CGl3

' : RGHsOHg A OBrGlg— .— > RGHBrGH2eg013 V . r ; ̂ '

These reactions are initiated either .by peroxide or by light of the appropriate wave; length = However9 whether :■ the reactions will take place as its ted: abore $ or yield products containing more equivalents of. unsaturated compounds to one equivalent of ha1ogenated methane is determined by the R group, in the unsaturated compoundss the lability o f . 1 the' most reactive halogen atom in -the halide. and" the molar ■; 1; ratio,of the two reactantso Our .choice of acrylonitrile and vinyl aeetate as starting materials has been considered:rather unfavorable, for the addition reactions3 since the nitrile and ester.substituents are negative groups which deactivate the double bond* v:- : ; ygv V;v i- i/.:..,'/ .' But the advantage of acrylonitrile, if it is.success*:: f ul"r in. ; the ' d ondensat ion fi .is that th e nit rile can b e convert ed easily to other functional groups such as or =,Gl2HH2§while the ester group in vinyl acetate might be eliminated.in a variety of ways to. provide;useful terminal substituents0 I

.:,v. Bi3C¥3siQi :

A preeedtire fdr the' prepa#at;iom. of egmpamids of the type CF GHgGHYE has been proposed;, where Y stands for a functional group such as halogen or nitrile, and Z is either a similar group or hydrogen = First9 CX^GH=GHY would he pre« pared; second^ GX^GHsCHY would be conirerted to CF^GHsGHYj then to GF^GH^CHYZc In order to introduce a GẐ group into an unsaturated compound, free radical reactions were considered 0 In the mechanism of free-radical addition reactionsso far presented, it is assumed that the chain is initiatedby the hemolytic scission of carbon=halogen bonds using perox;$de.■as catalyst-'i’ 1^}' ':■ ■ 'v:■' — ',' ‘

^GOB)^— 0-GQQô GO2^»: ;■ 0,(or ^-eoo^Bi^— '» .cx3 ■

Or by using light of apprpprlate 'waire lengths - . '1. .. GX, ■ x-L̂ uo — -x'.CY. » X 0 .1- ' . , :

The oCXg radica1 generated by either of thes e . proeessee adds'•■■■ . ' V ̂ .’V ' .. ; ■ \ - ■ : ■ . ' ' •' 'to the olefin:

fGliy: RCHsCH — — > CX_-GH^.CHR .J ■ ' ■•■■■ ■ ; '• .V*'. ' . • C i ■ * ; :The new free radical, GX̂ GHg'GHR, will undergo both chain transfer with another, polyhalomethane, or chain propagation with another molecule of unsaturated compound (?)»

Chain: transfersC X 3 C H 2 - C H R ^ C X ^ — — — ^ C X ^ G H g C H I R ^ C ^ o ; ; .;v ■ ■ V ■; ■ ■ ; ;

Chain propagation s . ' ■ , ; ' v' ■;i:. G23CH2CHR^RCHSCH2- ^CI.CHgCHE.CH^CHR : .

The react 1 on .sf’ ■ ehaln transfer gives monomer ̂ ioe-0, one mole; of polyhalomethane adding to one mole of unsaturated com- pound; whereas chain propagation yields teMmerss .i»e>̂ ■ pr®̂ . ducts containing more than one molecule of unsaturated compound per mole of Thus 5, ; : ■ ■

Our purpose is to get as high a yield of mohdmer.as ; ' possible| telomers are not desired0 Therefore s;excess of the polyhalomethane should be used. Also, the yields of one-to- one addition .product might be .favored by using either a very reactive halide and/or an unsaturated compound which will pro= duce a reactive Intermediate radical RCMCB2C%3 that undergoes chain transfer in preferetiee to chain propagation6: Among the- polyhalomethanes, carbon tetrabromide and bromotrichlorome- thane are more reactive, since the homolytic scission of a C=Br bond requires less energy: of activation than the similar scission, of a C-Cl bond. Table I.shows the bond energies. •

1 ' , Val-Ws ,f0r- single bond energies (6) \ -Bond ■ . ' Bond energy (Kcalo/mole)

r; • ' '/O-’H v ... y'v:'‘V ■ V $7

: ' . : Ta&l# II ■ ; ' ' . ' : ' '' Ea3i3_tl3PĴ E of Polyhalomeiihaa#& In Mdltlom ReactionsPoljhalometkane Unsaturated Gompdo. Weight % of 1:1

; ' ;v ■■ prodmht .

BrCGl3 . CH^CHGI none ,: : :B r G C l » V ; - G H ^ s C H ^ O ^ e i e H . / V

■ x . ' : g. 3 :CC14 GH2sCHGI' ' nonecci^ • : :;/:gh2sgh»o m̂ i 3 : - 25,6

- . ; • ; 0 ■ ■ , ' :CHGi^ GHgSGHGEf ; none

GHG1_ / OBLsOH=o=G=GHg ■' none' ■ . ' ’ 0

Prom these experimental data listed in fable XI,..it is1 apparent that the yields of one =to-=one products, and - polymers are not entirely determined by the. lability of the most \reactive halogen in the polyhalomethames, but that the B group in the-unsaturated compound'also; plays an important roleo Kharaseh pointed out (6). that the effect of R is exerted in activation or deactivation of the.tihsaturatei.double bondo When R is a positive group such.as GH^, the carbon- carbon . double bond''is r activated. toward free radio al addition 0 . This relationship may; be explained by hyperconjugations . C H 2" C H - C H 3< — - - - ^ i ? H 2~ C H s C ?3

A 0 G%3 radical is deficient by one electron and reacts at a point of maximum electron density

prepjlea© 'readily: Whereas3 if R is' a negative- grotip$ such as -ON, the resonance has withdrawn, electrons from the double bonds 9CHos0H0l GH0=CHsG“N tThe electron deficient 0 C3L-. group will .not. add to acryloni- triie as readily as to propyleneo ,

:V .;;Although vinyl.acetate .has : a negative group f QHLOOO= :y which has an electron withdrawing.::effeGt due to inductance: •

its resonance effect. is similar to that of the methyl grouprrather than the nit rile i < ^

■' CH-qCH-O-G-CH^— — ^:CHg=GH=Q-g=OH_ ̂ 00 0 ■ ' / ': ;v2 - ' 3

S©s: oGẐ .radical will add.. readily to vinyl acetate o The orderof reactivity of these three unsaturated compounds is

is true s

> CHosOH~0~G~CH~ > CHosCH=0M

The e%p@fimentali.results postulate;

; . - : .i■ ̂ a >̂̂ le : ■ //iReactivity of unsaturated compoundsCompound • ,, Halide ■ Weight % of 1:1 product

:ry,'-GI^GHG^ y: ' : BrGCl^ -eE2eGH^0=eOGS3 BrCCl3 \ p/'VjV.;,,:

■OBGigiGKGf':i ■ ;/' ' . i .- /BrGG^ ; home-':' ; ,i':y":'i ' • ' Actually^ acrylomitriles. free, of inhibit.or an.d in the -

presence of peroxide.3 is .one of. the fastest .polymerizing, of

* This figure is taken, from data given.in reference 6,

:;: -;. , - - r' ̂':, -: ̂.: r. ̂'.■;. . •■,./ :/; :-.;V . /'::;: --;:;.# . ;the vinyl type monomers. (9)» Conditions favorable for a one=■to^eho addition reaction of acrylonitrile with polyhalome®thanes have yet to be discovered0 ;■ ■ " \

V;:'';'iJhe;;reh1hlîs- of addition ef several polyhalomethanesto ;yinyl-adetate:'are>listed -in' :fablei:I¥0:V'

• X'' ̂ ■■ : ; / x ' ': , Mditibn of halides, to vinyl acetate . ;X.

Halide.. (moles) . Vinyl acetate (moles) Weight % yield- ©f';' .■ . - /; v- ■ ' ' ' -' - - ; 111-pyodmet \ .

V-eBr4 -'r//- \ °”5 .:X ■ '1 'X H ' ' - ;;:i'' • BrCCl.; .Qti53' :: - 0oav v:-'-;. - 44.3

X'X X :x'x;:;x;;';' . 0o50 ' ;; ;x:;x.;-:,X;"':'17>5x;x::;: x;-;' x

CHCl^ 1«5# 0o30- none(polymer)In; the addition: reaction with vinyl acetate9 carbon tetra= X chloride is preferred to bromotriehloromethane and-;carbon X,.Xx tetrabromide because of its lower costj the lower -molecular weight -of its, products, andv. the ease of recovery of excess ;reagent;: and .preferable to '/.ehlorofora/for its yield of one- to-one/producto X'; ;

X yfhe product :©f:theXadditlon:rreaetio.n;of, .carbon, tetrad X chloride .is. a -saturated.: ester9 1 $'3X 3X, 3-tetrachloropropyl ./■ X 'acetate! ;. :;x:-: : -x'..■: i:;X-''.v "V’x'x■■ - v - - ' v / ’Xy

. :: ' ■ - CH^CH-O-C-CH^CCl,-— — ̂GGl,GHo=GH=0-C=CH, '; I'-2; :: t? 3 : b- 3 2 t : « . -, 3 -;

Besides; the one-to-one addition : product s . s®.m© high - molecular weight subBtaBees'. are' a'ls©■:obtained . The ratio of one^to^one.produet t© higher boiling substances are listedin Table V<

Table fProducts.of addition reaction

/Weight of .. Weight % of Telomers moles Crude- Produet 1:1 Product

1 .5 0 .5 146.0 17.-5 : : 82.5

5 .0 1 .0 1 . . ' 1& 5 .5 25 .0 - / 75.0

10.0 2.0 39045-. ' 25.6 74.2 .After removal of unreaeted earbon-. tetrachloride by

distillation9 the crude products/were 'di'stilled '.under, .reduced pressure to obtain one-to-one components. The residue (telomere ) was a brown and very sticky material.. If the tempera- ture was raisedy the telomers-. deepmposed. • : ■

The addition products 1 s3;,3g3=tefraehloropropyl acetate (CH^GOOCHGiCH^CCl^)9 is readily hydrolysed by dilute sulfuric acid or by dilute potassium-hydroxide. When dilute - sulfuric acid is used as catalystg the reaction proceeds in the following ways ; - ’

ci3G00CHCicH2eci 1> ê cooi.5. ̂ ei3eH2cidio|:3CH2CHCl0|j— — -- -$>eCl3CH2CHO^HCl

The aldehyde- produced is- unstable, and. loses ...another: molecule of hydrogen chloride - spontaneously:

CC130H2CHO , ̂GClggCHCHQoHCl

The flmal ppedmot iŝ ^ When dilute' pbtassitim h^rdxfie ■ was us ed as 'catalyst3 a tarry product was obtaiaed, probably by;arising -from aldol condensations and othe r. side reactions of the aldehyde * Khar as eh report= ed (6) allattempts to hydrolyze the addition products I- ■■ bromo«=3 ̂ 3 9 3”triehloropropyl acetate (CH^COOCBOHgCCl^) f re=; , . suited in simultaneous hydrolysis and dehydrochlorinationj, s© that ^ “diehloroaerolein was :obtained| he was unable to isolate 3V3 3 3~trichlor©propionaldehydes Gpl^CH^OH0o

' ; -.Upon decomposing the addition esters 193s,3 »3“tetra=> chloropropyl aeetate^ with concentrated sulfuric acid: or with OpiEcentrated hydroipdie • acid> the final product was still

proeess lor the decomposition 01 an ...; ■ acetate ester to:.produce' an:\'0.1̂ ; pyrolysis ;at a high ’ ;temperature

under mild renditions should, lead to the desired product;, 15,15, l=tri'fluoro-3-chloropropaneo . . •

' \ / ' EIPERIMEMTAL ; . ; ; '

Apparatus'o The experiments in -which a polyhalomethane was added to an ©lefin were earried out in a. three=neck round . bottdm flask ;with groundglass joints equipped with a Teflon stirrer« a therimometer, and a reflux condenser on which a dropping funnel was mounted, and the outlet of which' was con— neoted to a trap. The flask was heated hj means of a heating mantle. For the reactions initiated.by light a mercury vapor ultraviolet lamp ; was used as the f light source o Reaction of carbon tetrahromide..with:aerylonitrile, ; initiatedby benzoyl peroxidep Ninety, grams (0o2y mole} of carbon tetra bromide dissolved in 1®0 ml0 of acetonitrile was placed in the three-neck flask, and lo5 g» of benzoyl peroxide was added The mixture was heated •slowly from room: temperature to 60®e With continuous stirring; 5P3 go (00l mole) of aerylonitrile was added drop by drop through the dropping funnelo The reae= .tipn was continued for. five' hours'.after the addition of aery-;: lohitrile was completeo The reaction mixture turned deep orange color

The tar-like substance only slightly dissolved in ; • petroleum etherj benzene, or ethanolo Distillation at Id mm0 . pressure yielded; no . one-to-one addi tion product .e : •

This experiment showed that under the described conditions the reaction,did not stop at the one-to-one stage, but continued to form t e l b m e r s y . ;Reaction of carbon tetrabromide with acrylonit rile„ initiated .by ultraviolet light 0 Using the same quantities of react- . ants and apparatus as described in the previous experiments but with ultraviolet .light employed as the initiator instead . of' bensoyl peroxide, a-similar reaction • was,, carried out for P four hours, then the reaction mixture distilled direetlyo Acetonitrile distilled over at atmospheric■pressure = When the pressure was reduced to lo: mm0 excess carbon tetrabromide • distilled overo There remaimed in the flask a gummy substance .which was insoluble in llgroin, but soluble in acetone., Row-; ever; in this experiment, still no one-to-one product Was ob- tainedo ' . i ' ;. ■ ,Reaction of bromotr1ehloromethane with acryionltrile/initiat-

by benzoyl peroxide. One mole (197 g.) of bromotriehloro- methane was -placed in the; apparatus, and heated to 65°, whereupon (D.3 mole (16 g.) of acrylonltrile containing 4.5 g=» of benzoyl peroxide was added drop by drop. After three hours

' reaction time the mixture had turned yellow, and Was ;di stilled' at 6? mm. pressure. There.was. recovered 132 g. (6? ml.) of

bromotrieliloromethane» The residue was. a yellow jelly-like material which dried quickly to a white amorphous powdero This powder could not be dissolved in any of .the ordinary ' solvents® : ;A . Alt hough hr omo t r i chlo r ome tha ne is a . reactive .chemicalin this type of reaction and was used in large excessg it 1 still did 'not .add to acrylonitrile to produce a one-to-one - addition compound under the described conditions Q. . •Reaction-, of: bromotr 1 ehloromethane; • with acrylpnitrlle 9 i inlti^ ■ ■ ated by ultraviolet lights The quantities of reactants and apparatus employed were the--same -as- described ■ preyiousiy* ex- cept that' Ultraviolet light was used instead of benzoyl perox- : ide as the . initiatoro The reaction mixture did not change to ' a deep color9 but did. become .turbid0 The mixture distilled under atmospheric pressure at to: give a recovery of 152 gc(76 mlo) of unreacted hromotriehloromethaneo : The residue . -■turned a deep red color^ and . a brittle black solid was ob-= taimed. , .. ' ' ■ - ; '

, Several other trials with different ratios of these : two reactants gave almost the -same results. If the temperature was raised over 8Ge a deep red gelatinous material resulted./'I.;. These results showedthat the nit rile grbup hassueh a

strong effect on the double bond that, the reaction does not .■ follow.', its usual. course to-give .primariiy a one-to-one addition product.- Instead, r extensive. polymer 1 zatioh: predominates.;;

■' 16 •B@ae.tion of carbon tetrabramide mth vinyl acetate catalyzed by benzoyl peroxideg One hundred, grams (603 mole) ©f earbon tetrabromide was plaesd in the apparatus = Twenty-six grams (Oo3 mole) of yinyi acetate.containing 1=5 go of benzoyl peroxide was added to tbe.carbon tetrabromideo The mixtmre Was heated t© 60° and refluxed'for.- six hours mth stirring0 A slightly red colored liquid was.obtained0. The reaction mixtnre was'distilled under 6 mmo pressure3 15 go of color- V less liquid (n^lo5929) was obtained at 80°0 Another 25 go of very slightly yellow liquid Cn^l0585l) was collected at 100°e A third fraction of .2.8 g0. of an orange colored liquid was .collected at 100 0 In the dry ice trap there was 15 mlo of a brown mobile liquid which had a very irritating odor0 . Beaction. - of chloroform:'with Vinyl acetat e 9 ’initi at ed by ' ■ benzoyl peroxideo In the usual apparatus 180 gc (lo5 moles) of ehlorofom: was heated to 60°o There was added drop by drop 43 go (0o5 mole) of vinyl acetate containing 3 go of benzoyl peroxide p The reaction was continued for four hours0 The reaction mixture was distilled under 175 mme pressure at 40°.to remove the excess chloroform leaving a yellow, very sticky gelatinous material as residuei

. This experiment showed no one-to-one product was. foraedo •Beaction of bromotrichloromethane with vinyl acetate9 initiated by benzoyl peroxide o' A 106. go- (0»53 mole) portion of

bromotrictilorometihane was placed in the. apparatus and heated to 60° withstirrlngo A 23o5 go (0.27 mole) poptlonof.vinyl aeetate containing 10 5 go of benzoyl peroxide was -added drop- wise o: After four hours ©f react ion. time. .'73' mlo . (128o5 go) of..a very cle’ar yellox̂ lsh'. liqnid wasrobtainedo ' .The reaotion -mix- ture was distilled under atmospheric pressures After excess / brometrichlorometharm .was: ;removed.s :r,the:vpressure was. reduced to 5 . ™° ? and 34°̂ go of a. colorless oil ..was collected at . 74° bo;:S5°fn̂ :;:i:o4W 7.) \ ;:4: iReaction of carbon: tetrachloride with vinyl acetate. imitl.= acted "by benzoyl peroxideo . .'.Fire. moles . C:770 go ) : of carbon - v ; ■ - - tetraehloride placed , in. the-usual: apparatus was ■ heated to 60 ®. One mole |S6 g0) of vinyl acetate containing 6 go of benzoyl per oxide was introduced .'drop by drop . into .the . apparattis» jl The temperaturs. of.the .mixture .rose .slowly to 75°o'. ■■ This tempera^ ture : remained constant for: 6© minutes , . then dropped to . 60 0 r The reaction was - continued for one: more -hour after: the tempera-? ture drop; The total reaction time was. four hours* - -

;v The- reaction, mixture. was distilled:under reduced, pressure (by aspirator suction)* There was recovered.$92 go of carbon tetrachloride' at 60° * The residue .was: a colorless oily liquid, which.-welghedtlAg'bŷ . g'* Mstillatlorr-of the .'residue under. 8. mm0 pressure . at 60° t o y i e l d e d 6© ,g*(42 o$ ml*} of h.vcdldrless:. oii:;(.n̂^̂^̂ ̂ 0 v- . . :V :

4 Sbreral other, experiments .umder the same conditions *

■ . . 1& with- diff@rent:v,'qraHMl5:ies'.v:0:£ .reacilrants were. carried, out ®.The.-resttlts were'::iisted;:.iS':ifahi.@ri:o. -Idenfcif ieatioa., of carbon,t etraehlor ide.̂ l̂nyl aeetat e - addition prodact.(1,3•» 3 % 3=tetraohlor0propyl acetate)■ o- . Fifty five - grams: of addit ion' prodaet. .was. hydrolyged by 5 50 ml 6 of 5% sulfarie. aeido,. The'mixture was distilled with st eairu Twenty nine grams of a. colorless oil was . ‘recovered s': This oil was redistilled under 3# •mm.'o " pressmrey . 14 go of./liquid being. .col® leeted at 87°o This liquid gave strong fmehsln^aldehyde reactions, and bromine /was • very/:readily/decolorizedo. These facts indicated, that the hydrolysed compound,was an unsatur~ ated aldehydeo•

This hydrolysed eoiiipoiaB'd "formed: a 29 4adinitr©phenyl" hydrazone melting at 1620®163®s, cons istent with ^^-diehlero® acrolein which was found by Kharaseh (6)0

A 12o5 go portion of the hydrolyzed product: was. dis= solved in 53 g°. of carbon tetrachlorideo .. Bromine was added to the solution drop by drop at room temperature until, .the red color persisted 0 . distillation Of" the /brominated. solution' at IS mm0 yielded. 14o5 go.of colorless .liquid.at 100°o■Becomposition.',@f.;. carbon::tetrachlorl de°vlnyl, acetate addition, product by ..concent-rated... sulfurie'.acido A portion of 80o5 ge of the addition' produet was treated' with concentrated sulfuric ae id e At the beginning// of treatment- the - reaction:':tppk.: plaee very vigorously * and gas and. heat evolved =, The gas gave a

white precipitate with aqneons silver nitrateo Sulfurie acid Was added centinuously until no more gas came off,/ A deep, red solution was obtained. This colored solution would hot

\ ̂; s e per et ©' ■ int o: ■ two la ye r s. Distillation of the colored solu=: tion under reduced pressure gave no distillate, but a polymerized tarry substance. remained ih the flask, ' lii another experiment the deep, red solution: was poured, into cold water; the final product still ^^-dichloroacrolein tests.Decomposition of carbon tetrachloride°vInyl acetate addition product by eoncentrated hydrolodle acid, A portion of 8 g, of addition product was placed in a test tube, Five grams of colorless concentrated hydroiodie/acid was added, , The mixture was heated in a water bath for five minutes, a deep red solution resulting. This: solution: did not separate into two layers on standing. When cold water was added to it, a black oily layer (3 , 5 g,} appeared at the bottom of the separa»

Upon distillation of the black oil under $ mm, pressure, iodine vapor appeared' at 35^ ,1 and a red oil was collected at SO0, This red oil gave the ̂ ^dichloroaeroleih

- tests,; ' ■ i: V/.V' ■Decomposition of carbon tetrachiorids-vinyl acetate addition product by high temperature, A glass tube (600 mm,x 18 mm,) filled with glass beads was mounted vertically in the center

- of . a : cylindrical electrie furnaeeo- The lower end of the tube

was connected with a one-hole rubber stopper through whiehaa smaller glass tube led.to a receiving flask (containing 1 ge ef hydroguinone) o:' This flask was immersed in ice water0 From the flask a rubber tube led to a dry ice trap, the outlet of which was vented to a ho©do. The upper end of the - glass tube was equipped with a two-hole rubber stopper» In one hole w s mounted a simdl dropping'fihnneli the other was connected to a carbon dioxide generator>, The electric furnace was turned on and the temperature raised to 400® to 420® while carboti dioxide was passed through continuouslyo Eighty grams of the addition product was added drop by drop to the heated glass tubeo When the decomposition procedure was completes, a light yellow mobile liquid was obtained. This pro- ' duct was washed with water» then with sodium bicarbonate $ and dried with magnesium sulfate. dRedlstillation of the Washed product (with 5 grams of hydroquinone added) under S , mm. pressure yielded 40 g. of colorless oily liquid at &3® to 04®= The prodaot did not show, a fuchsin-aldehyde reactions, but bromine was decolorized very readily at room temperature.

■ The decomposition was tried at' Other temperatures8 . but at 500° the decomposition gaye a thrry. substance.1dentifloat1on of the nvrolvsls product of the addition ester. Infrared spectra showed a strong :-absorption peak' in the region of a GC1- stretching band.(13 to 14 microns). Another band (©to 6.25 microns) showed the existence of a carbon-carbon

: tmeon jugated .double bond:- (10) 0 .FromsEeh inf ormafcionp .alQBg ■'

the deeomposition: produe,t .is', itidieated to be 1, 3 , 3,3«tetra= ‘ chloropropene, CC1̂ CH®GHC1«,

Three grams' ■ of ■ the: decomposit ion, prodmct was aided : to ':S©;.ml ®:;■ of;■ ‘

' phesaef1!' ©xalie;:ae£S^ ; ; ’ 1 "'/'Addition'' ::%he ^'eee^ . gave.

'Aa slightly, yellowish .liquid, which boile d..at95° ■ td' • 96'0 ̂ under --' .8 mmo pr6s's®re»' ■: : ̂. : %" /

. ;Pp##amtimmr of .,. 1-chlor® f 3v3,3 -trif luoro propene 'fr©# /' 1 •tetgachlcg® propeme by r'eplaeemeaty method 0 A dry. 5© ml a flask .' was equipped with a reflux' condenser, cooled with water at 30 ? topped with a distilling head which.was-j in turn, connected with a declining, ice water ,eondens erv A receiring" flask was cenmect ed wit h the declining condens er v.whi eh . ..had . a : vent lead= ing to a dry ice trap, then to a hood0 A 11 = 5 go (0o064 mole) portion of 1,3,3,3-tetrachlorepropene- dried • thoroughly.with" , magnesium sulfate was placed ln-.th'e"flask, . and.23ge .(Ool3 mole) of antimony trifluoride was- added0 ...The flask was heated by a heating mantle o At a flask temperature of 78° the reae=

. tion began, and gas .bubbles w©re erolredv. When the temperature rose to 100° „ a black foam formed, and. no more.vapor was erolr= ed0 A tarry residue resulted0 The.liquid product collected in the receiring 'flask weighed:' 3 • g», and boiled at 23° to. 24° (lito (14)- bop6. of-CH3CH-aHCi9.;21°)o

The fluorinated product was . oxidized, at 15 ■ by potassium permanganate , in. alkaline solution, but no trifluomaeetie acid.:could .be ,isol.atedo ;:'>V '"i

SUMMARY

Acrylonitrile has ' a strong negative gromp 9 whichdeactivates the double bond.to the extent•that polyhalome= thanes s, • even: the most act ive : bromotrichioromethane, will not - readily add to it o The domfeie- :bond-in vinyl acetate acts in a diff erent - wayo Polyhalomethanes /such’ as- carbon:' tetrabromide ? bromotriehloromethane5 and earben. tetrachloride ?•but not chloroform^ add readily to vinyl acetateo . Generally, the yield of one-to-one product is not higho Decompositions of the carbon tetraehloride-vinyl acetate addition product to yield a substituted propene can be accomplished by pyrolysise However^ as in most pyrolyses-the • side reactions could, not be avoided so that considerable, charring, ocemrred*.. Thus the. yield of product was- rather low, ; Exchange of, fluorine for chlorine in the; t r 1 e hi or ome t hy 1. group gave only a low yield, of l-ehloro=

. , ' ,.,' .: ': : " / BIBLIOGRAPHY '' v : : :

t. lo ■ Ov- Ito Holler, t?Chemistry of Organic - Gompounis,?a W,,: B0. v\ : \: Saunders Company; Philadelphia ̂_ . PAo , ̂ 195Sy- P® o79o

;■ : :; 2>; ' Aa' L» Henna, nAliphatie-Flnhridestw ;in H, Gilman,: :: ̂ ^- ganie Ghemlstry;11 Yol> 1, 2nd red ®lohn. illey & Sons,

: ; - Hem - York, :' Ho.:Y . \p& ■ x V ;’ 3 i..; Aa' I»> Henna , ^The Preparation of Aliphatic Fluorine. Com—

pounds,!f .in Ro Adams, nOrganie Reactions,11 ¥ole II, John : V;',...■. .Wiley Ac Sons, Hew York, H 0 1947, ;P® 49» : . : : [ S:::•' 4®: Wo Ho Pearlson in Jo Ho- SimonS g' -̂ Pluorine: Ohemistry;1? '' ■v , - Vole Academic : Press, Inci , Hew Yorlc, Ho Yo, 195:08 p®. ' ; 479; J® .H®. Simonavand ■H?-e::,d0.;Brlee.-, lhlde

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'/vv..