Group Title: preparation and properties of vinyl and glycidyl fluoroethers
Title: The Preparation and properties of vinyl and glycidyl fluoroethers
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 Material Information
Title: The Preparation and properties of vinyl and glycidyl fluoroethers
Physical Description: 101 leaves ; 28 cm.
Language: English
Creator: Brey, Mary Louise Van Natta, 1926-
Publication Date: 1956
Copyright Date: 1956
Subject: Ethers   ( lcsh )
Fluorine   ( lcsh )
Chemistry thesis Ph. D
Dissertations, Academic -- Chemistry -- UF
Genre: bibliography   ( marcgt )
non-fiction   ( marcgt )
Thesis: Dissertation (Ph.D.) - University of Florida, 1956.
Bibliography: Bibliography: leaves 95-100.
Additional Physical Form: Also available on World Wide Web
General Note: Manuscript copy.
General Note: Biography.
 Record Information
Bibliographic ID: UF00098026
Volume ID: VID00001
Source Institution: University of Florida
Holding Location: University of Florida
Rights Management: All rights reserved by the source institution and holding location.
Resource Identifier: alephbibnum - 000554229
oclc - 13369264
notis - ACX9063


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June, 1956


Th writer vishse to express her sincere appreciation
to the director of this research, D~r.~ Paul Tarrant, for
his guidance and enthusiastic interest. Tfhe assistance
given by Dr. 6. B. Butler and Dr. A. EI. Gropp in the
intiation of the study is alsoa grtefully acknowledged.
The writer ise graeful to the Gener'al Chemical
Division, Allie~ themaical eand Dyr Corporation, fior a grant-
fn-aid foar the lbast year of study.
The assistance of Ries Miargaret Dixon with th organic

preparations and Mbr. L. E. Money with theinfrrare spectra
aided greajltly t the comrpletion et the probles.
Finally, the work would neve have been finished

without the understanding, enoonragemesnt, and assistanoe
of th writer'a hnaband.,


MATJERIALS .. . .. .. .. ,,,. .


OXIDRN ... .. ... .. .. ~




sUxxAR'Y ,.....................

BIBLIOGRAPHYY * ., ********

BIOGRAPHICAL ITEM~ ... .. . ... . .




















ACKOWLEDGMENT . .. *.. ....

LISTOFT~'ABLS .,. .. ..,. .


. . .

. . .







TSabe Page
I Compounds Prepared fromr the Reaction of

Ethy~lene 617001 with IFluoroiletins .. .. 14
IIr Comrpounds Prepared from~ theReaction of

Phuororalohole writh Epiohlorohydria . . 29

IIIS Compounds Prepared E~o the Rsaction of

Flucroalcohole with Ethglene Oxide . .. .. 30

IV Ohloroethers Having Flluorine in the Alpha
Position and Eater Derivativees o the Ethser 1)2

V Chloroethere Having Fluorine in the Beta

Position . . . . . . . . . 4)3

VI Uneaturated Foloroethers .. *. * ** ** 55

VII Oc== Stttttttttttttttttttetchn wave Lang~ths .. .. 84

VIII $~street o Temperature on the 0==0 Abeerp~ltioan

of vinyl 2-Ethylhexyl EtSher . .. . 87

IK -0 Stretching Wave Lengths .. ... 89

X Bands Characteristier of Epczy Gtroup ......9


Figure Page
1. Spectmrm of CH2==CHOf59g (solution) . . .. 67
2. Spectran of C22= CHOCH2CHR(C285)ogapS solutiono) 68
3. Spectruma of C22-=0OC20@22 (solution) . .. 69
4, pecatrum of OR2==HOCH2ZCZPS (solution) . .. To
5* Sp*otrum or ex,==aOnoo20 @7 (solution) .. .. 71
6. Spectrum of CB ==CHOCF2ZCHIP01 (solution) . ... 72
7. Spectrum of CH2==0(CIf4)0CH2CF (solution) .. 73
8. Spectnrum of O~F CH20CH==0HOZCH20CH2 (solution) 74
9. SpectrumI of OR =CHCH20CH2 slto)****7
10. Spectrum of CE92==0HOGR2H;Z(Ca 5)C0489 . . .. 76
11. Effoot, of Temperature ona Absorp'tion Wear Six
Microns of CH2==HOCB20H(02f)0489 .. .. 77
12. Spectrum of CqHPORCH2002HS; .. .. "'''

1=). Spectrumr of 0 pCH~SOO20CH20 (solution) . ... 79

14.C Spectrumr of CH CHCH20CH20F .. .. . .. 80

15 pectrum or ca own ocap~li ...5. '"**

16. Spectrum of CH CHOH20CH2,CP 82
0 jl



Th infrared spectra of +Inyl alkryl ethers havre
unsa charac~teristics whichi hael not been completely
explained. Th oarbon-oarbon double bond stretching ab
sorption near six microns is split into two bands, and the
oarbon-oxyrgen stretch to at a nmuch lower wave length (8.3
alerons) thaln in raturated unsubstituted others (about 9.0
micons). The purpose of his workL ras been to account ;for
these peculiarities in a qualitative way in terms of the
structure, of rinyl others.
in a study of the Ramagn spectra of vinyl alkyl ethers,
Batuev gt g), (3) observed a similar split in the douible
boat stretching frequency. They attrbuted th dloublet to
rotational isorerism, the restricted rotation enhanced by a
resonrance effoeott

Bowever, they did not attemt to prove their thery
In the present study, two methods for testing the
existence of the proposed resonance effect and resultin
isonerisa vere undertaken. in order to demonsrtrateo the

presence of rotational isomers, a study of the effect of a
change in tempera~ture4 on the intensities of the two double
bond bands was msade. Moreo~ver, the presence of an electro-

negative substituent in the alky1l group would be expected
to0 decrrease or perhaps prevent entirely suoh an electron
shift. Since fluorine is the mrost electronegative element,
the preparation of +inyl fluoroethers' and a studyr of their
infrared absorption was an important phase of this work.

TheLw preparation of the vinyl fluoroethers was carried
out by a three-ste procedures (1) synthesis of the cor-
responding e-bydroxyethyl ether, (2) substitution of the
hydroxyl group by chlorinel and (3) dehydrochlrorination to
the vinyl ether.
In addition, a series of glyoridyl fluoroethers vae
prepared. Byr the reaction of ah fluoroalcohol with epi
chlorohydrin in th preseance of exess base, the gly~oidyl
fluorcether was obtained in one stept

CryCH20H + Q 0508201~c + r08 --C 08200829 9 2z + EC1 + ae2.

~the ethylene oxide ring is opened by a wide variety of
reagents, and the glycidtyl fluoroethers can thus be made
the basia for many furt her reactions.
*The term-r Vnylfloroether" is used in this diseertation
to designate an ether having the vinyl, group anaubstituted
and the alty group substituted with one or more fluorine


Thes fluorochemicale used on this project are of

speoial interest because they have been commercially
avarilable for a relartively short t~ime. h11-i
fluoro81efrine, ch~lorotrithoroe thylene, unsyame trical di-
chlorodifuoroet~hylene, and 9inylidene fluorider were far-
nished by General Chemical Division, Allied Chem~ial3 and

~Dye Corporationf. The trifluoroethyl2 alcohol was a product
of Penneylvania Sal Manufacturin~g Com~panyI, and the d K*
b1aethyrl-(3, B,-trifluoroethyL alcohol wasI surpplied by
Peninsular Cheareseearch. The perfluoroprop~ianic and per-
fluorobutyrie acids8 were commercial products of Minnesota
Mining and Manufacturing C~ompany.
Th reagent grde obemicals which vere used were
potassina hydroxide and sedinas hydroxide pellets, obtained
from FPisher Scienifiei Company; sulfurio acidl a Bakecr
Analyzed Reagent; an phosphorne pentachloride ad nah~y.
drous sodium sultate, from General Chemnical Division, Allied
Chemical and Dye Corporation.
TetrathuoroethyUlene and perfluororopopylene were pre-

pared by pyrolgrsis of the sodina1 salt a o perfluoropro-
pionio and perfluorobutyrie raside, respectively, according

to the proedure ofl Hals and co-vrorkers (pj).
Th ex crlodibydro~perfluoropropyl and a4-dlilhydro-
perfluorobuty1 aloahole were prepared from Perfluoropro-
pionic and perfluorebutyrio acid, respectivelyg, by the
preparation of the ac~id chlotride and it~s reduction with
Plthina aluminusn hydride, according to the method of Henne

83 (26).



A. Introdua~tion

The base~-caalyrzed addition of ran alcohol te s 1,1-41.I
thoobro8sin is a convenient metho~d for the preparation of
6K cldithuoroe thers. the reaction vae first reported in
11946 in a patent by Hanford and Rigby (24). TheBy created
various aloohole with teatrafluoroethylene, ahlorotrifluoro*

ethylene, rad chlorodifluoroe thylenel (GPZ-==0BC1) in the
presence of the corresponding sodian a~lko~xide in a pree-
ur~ e ese~l. Independent~lje Milr and co-vorkers (4)2)
added methyl alcohol tos te trathuoroethylene, chloratri-
thuoroethylene, and unayame tricajl dishlorodi thoroe thylene
in the presence of sodinaP methozide. The tebtrafluoro-
ethylenea reaction vae carried out under pressure, while the
other were reacted at a~tmospthertor praesure. Parkg: gg
(46) found that potassiuml hydroxide~ was also an attractive
aatalyst for such realctrions. Knuny~ants and co-vorkers (31)
showed that alcohols add to perfluorpoproylene in an analo-

gous mranner to~ fors cthers of the typel, CF CHFCF2 *
Ethylene glyselI has been added to chilorotrifluoro-
ethylene (34, 44) and to tetrannuorearthylene (24$).

both oasees 10u -hydroxyethyl ether wsasbtained, but.vithb
tetrazfluoroethylene some of the diether,

ORF'2CFI20CH2CH20CF2 2fP was also formed.
Young and Tarrant (65j) showed that s,#-difluoroethere
are easily hydrolyze~d to the corresponding enters by treat-
ment with concentratedi sulturio acid. This property pro-
Vided ai convenient method f~or the preparation of fluoro-
acids and for the determination of the structure of the

B, Exneriabnntal

21 Disoaseion of ornaordur

In this work ethere were prepared by addition of

~t~hy~lene glycol to the following olefinst chlorotrifltooro
ethylene, unsymme tricalrr diahlorodi fluasorotlene, and per-
ftluoropropyle ne. No reaction occurred when ethylene 51ycol
was treated with ~tertrafriluorloethylener and trinyl idene f'luor-

ide. All racrtione were carried out in a pressure Vessel,
with the exception of that employingiE tetrafluoroethyleneI
which was bubboled through the reaction mixture at atmoa-

pherict pressure.
REydrolysis of th g-hydroxyethyl there to esters by
thec use of concentrated sulfurio acLid proved unsuccessful.

Higher boiling materials were formed which were believed to

be ethere of diethylene glycoal For example:

2 CRFP0C1020CH2CN20 R --*(CHNlC~'~f20CH20H220 +- 820.
The0-choroethyrl there were hydrolyzed without difliculty.
The dehydration of the O-hydroxyethyl ethere to the
corresponding rinyrl ethere was tried, using both phosphorus

pentoxide and borio acid (10D) as dehydrating agents; how-
ever, only higher boiling materials were formled.
Th addition of ethylene chlorohydrin to chlaortri-
fluoroethylelrne, in the presence of potassium hydroxide,
vae also attempted, but only a smrall amount of the desired
*Cohloroethyl other vae obtained. nanulta

a. Addition of CB20HC~H20H to CF2==0F01
A solution of 94 g. (1.7 maoles) oft potassina hydroxide

in J00 mal. of erthylene glycol was prepared Bad allowed to
cool. It was than placed in an autoolave (capacity about

1300 al.) which was chilled in a Dr Ice-acetone bath.
Thre hundred grams.(2.6It mnoles) of chlorotri fluoroethylene
was collected in a Drry lee trap, and added to the contents
of the bomb, which was then sealed and rocked overnight at
room temperature. The vessel vae opened, and the reaction
mixture vaa poured into ice water in order to separate the
product fro the potassina hydrcoxide and unreacted ethylene
glgcool. Th organic layer was separated fromp the lighter

at~er layer and va~chedi several times with water. It was
dried over an3hydrous sodium sulfate and distilled at re-
duced pressure through a 65-em.~ column packed with Berf
saddles. There w~as~obtained 25 eg. (1.4 mote1s, a 544k

yield) of the etherl CR20HnCH20CF2 *CI1Q T b.;p 114-180/100
9am n21 1*37952, Layson (34) reported the followring
constantel n ~5 1.3800, ag~ 1.45~6; vbile Park ean co-wolk-
ers (441) reported b1p. 40 /1am
ilo other traction was obtained and very little resir-
due was left in the distilling 1ask.

b. Adi~tion of 0\0808705O to 092==0012
Uneymmretrical dichlorodiFluoroethylener (300 go, 2.25
maolme) we as racted with ethylener glyol by the procedure
described above. Fractionation of the dried prodnot re-
sal~ted InI 131 g1, (0.67 mnole, a 300g yield) of 1sthe~thers

CH20R~IZCR20CF2HC12, boiling in the range 71)~X B(4 as 74 c/3
ama A center traction had the fo'llowing properties bsp.
62.5 63.00/2.2 am., n25 1.6265, 625 1*4905, IIRoale.
33*We M1found 33.42. Agg1. Cal. or 04B401gdg02 01,
LA11 temtperatures are given inr degrees Centigrade.
2Refractive indlices were measured with the D line of

3The rmolar refra~ction Values (MRfound) were calculated
from experimental data using the Lcorens-lorents equation;
theoretical values were determained from the additive values

36*36. Found 01, 36.0r4 .
Six~ty-five [grme of a material boiling at 82-60/2 ma.
wae alo obtained. This matZerianl was later shown to be the

d~iether of ethylene glyool, CHC120F20OHCH20'CH20C2H12 (0.20
rsoles an 18$ yield).r An anayt~ical sample had the fo~llrow-
ing constantsa b.;p. 900/2.2 mas, n25 1.435194, aii5 15786,
M~oalo, 52.661 ~M~round 52*50* 4842,. cale. ror
06 60q13920 8 0, 21.97; H, 1.84.h Founds 0, 22.33)
H, 2.08.
Proof~ of structure of the dietfher
(1) Ryldrolysis to the ester
Trea~rty-two gramre (0.067 mole) of

CHC12CF20OCH2CH20CF20R01r2 was placed in a 200 al,1 three-
necked flask equipped with mech3anical stirrer, reflux con-
denser, and thermometer. Three al. of concentrated @ut
rurio acid was added, and ~the mixture vaer heated cautione-
ly, with stirring. 1A vigorous reacteion occurred, with evo,
lution of~ hydrogn fluoride and heat. After the initial
reaction had subsrided, the reaction mixture was heated with
for elements and bindings gi~ven in Langtes Handhadk pf
ChemistrY. 8th rd a~ 1952.
4This analysis was performed by the wrriter; however, with
-two other exceptions which wil be noted, the analyersee
were performed byr the Clar Microanalytical Laboratory,~
Urbana, Illinois.

stirring for an hour. it vae then allowed to cool an

poured over cracked 10*, The organic layer was separated,
washed with w~aters and dried over anhydrous sodium sub~
fate. Distillation through a 15*om., column packed with
Ber1 saddles resulted in aLpproximately 6 g. (0,021 aole, a

310~ yield) of the Iester, CHC12COCt2H 20aH200812, b.p. 148-
O 0

50Q/3 am., n251 1.4840, d 5 1*5386, MRoale.52.68, M~found
52.79. Agg), Cale. for 048401l4048 01, 49*95. Founds
01, 48.319. Th infrared .spectrum exhibited a doublet for
the carbonyl, stretching wave length at 5.62 and 9.70

(2) Eateritisation of ethylene g~lyrol
with dichloroacetic acid
Since no reference was found in th literature con-

cornin this eater, synthesis by reaction of ethylene gly-
col with the ap~pro~priarte acid vae carried out.

Eight grams (0.13l mole) of ethylene glycol, 42 g.
(0.C32 mlole) of dichloroacetic raicid, And 2 ml. of concen-
trated sulturie said were mixed well in a 200 al., round-
bottom flask. A distilling head was attached to the

fLasli and the mixture was refluxed gently for two houre.
About 3*5 g. or water was collected during the reaction.
Th crude eater was distilled from the rkeaction flaskt at;
reduced pre ssure. The dist~illate vae washed with sodium

oarbonat esolution, then water, and dried ovear anhydrous
sodium sultate. Distillation~ through Ude 15-0.. column
resulted lin; 16 g. (0.036E mole, a 4c3r yield) of th est~erl,
b~p. 139-490/)3 aml. A center traction had the constantet
brp. 14.64703 IgP~l n25 1489, dZ5 i*5337. Its intirared
spectrum was identical with that of thes hydlrolysis product
of the Malither.

e. Addition of CH20H~CH20HI to CF2==CFCF3
Perfluoropropylene (304) g., 2c03 molesI) Was reated
with ethylene gl~yool b~y the sam procedure to formi 106 g.

(O*So moales 25 yield) of the ether, CH20HCH20CP20HFF~Cq,
boiling in the range 91-75e/39 mep. An analytical sample
had the consrtante t b.p.,72-74of40 am., n25 1.3192,
a 5 1.5227, MQoale.28.4s, MIFo~und 27.57.~ eagg Cale. fo
a5 gF 028C, 281.31; R2.85. Founds 0,28.27 8, 29 .80
Attempts were mrade to dehydrofluorinate this ether bp
treatment with both aqueous and alcoholic potassisma hydror-
id.However, in each easer onlyr starting; material was re-
Hydrogen fluoride wras evolved during the distillas-
tion, probably from hydrolysisr of the ether to the erser.
Seventeen grame of higher-boiling marter~ial was obtained;
+This anaslysis wa performed by the aioroanalytical labor-
atory of Dr. G. Weiler an Dr. F. B. Strauss, Oxford,


it was collected over the range 630/2*5 mer.-85o/3 s**
Slixty-five g~rams of very higlh boiling material remained in
the distilling flashr* Refractionation of the higher boil-

ing~materal resulted in 6 g. of a compound, btp. 84-870/10
mn., which appeared to the the ester, CH20RCH20 C ICHP3q it

bnd the constantal n25 1*3545, (i1*514895, M1oale.28).46,

Mound 271.78. A strong Iinrared absorption band at gi60
micron indicated the pr~esnce+ of a carbonyl group in the
compound. rNowvere, its analysis was not in close agree-
ment with the ~theoretical valuesr

d. Attempted addition of~ CN20HCH20H to C3P==082
The low boiling point of vinylidenre fluoride (-820)
made it necessary to introduce it into the 1300 al auto-
elave in the gaseous state. It vae addel to a reaction
mixture of 94 ig. of potassium hydroxide dissolved in Soo
81. of ethylene glyool to n pressure of 500 lb./rsq. in.
Rooking overnight aat rools temperature resulted ine only a
slight decrease in pressure. The reatction mixture was
then heated to 1000 and rooked two hours, after which the
pressure dropped to 75 Xb./aq. in. The bomb was rocked
overnight at 1100, brut there was no further change ig pree-
sure. It was then ooled in ice, the unreacted gas was
allowed to escape, and th contents were poured into about
one liter of ice water. There was no separation of layers;

but hydrogen fluoride was evolved, as aborn by etching of
thre glase container. 0 -Hydroxyeathyl seaetate, which vould

be formed by hy~drolysis of the ether, CH20HCH~20CFp2C@, is
soluble in water. Separation of the, deter fromt the aqueous
mixture was not deemed6 WOrth hile,

e. Attemspted addition of CB20HCH20H to Q20122
Tetrathuoroethylene boils at *F6g ~t~hus it lis not con-
densed by .kry loe cooling. It someetimes polymrerises esx-
plosilvely when under pressure. For these reasons th prep-
aration of~ the ecther wras attempted by bubbling the olsfin
through an etfhylene glycol-potassium h2ydroxide solution at;
atmaospherto prsesure.
A- solution of 170 eg. of potassin~a hydroxide in 900 all.
lof ethylene glycol was placed in a one liter, three-nacked
flaskl equipped with sleehanical stirrer and inlet and outlet
tubes. Tfhe olefin vae generated by th cautious heating
of j02 g;. (2.13 malers)~ of sodina ;perfiluorobutyrate. As
the clefin formed, it was passed through soda lia tube to
remove th carbon dioxibde which is formed simultaneously,
and then through the cethyflne glycol solution wIpt~h Vtig~or
one stirring. After~ al th letln had been babble
through the solution, the reaction mixture was poured into
icre water, but no organic layer formed.


CommanMds Preasradl from the ]Renotiorn
of Ethrlene Glrool with Fluoro81efins


1.4840 O

(1) CH20HOlH20CF2CRFC1'

(2) c~a20BZOR2CF20B0Q12
(3) (c0a012072 2" 2

(4) (08012 OCOB..2

(5) c~l~glaon~caorgearer3



25% g

Asks. .
114-18+/100 8

a30/2.2 me a
900/2. 2 m. r
146**$0/3 m.



72,,4*/40 me 8*3192

933.5 33*42
52.66 52*~50
52.68 52*"79
28.45 27*57

Cah e..
%S. 81E S91
* 9iQ.36
21.97 1.84 -
- 49*95
28*31 2*85 -
ibA r6E 591
2.33 2.08




1 48*39

compound ni 1.3808,
(44,) reportedly B~p. Moof

*Lawvson (34) reported f~or thris
ajl 1*456; Park and co-vorhers

to Attempted addition of 08I20108208 to 074Z==0?01
Ethylene chlorohydrin (220 g., 2.7 molesr) was placed
in an autoclave haing a capacity of 30t0 al. and cooled in
a Dr leee-acetone bath. Twentyr-eight gr~amsn of potasebam
hydrcoxide and 100 g;. (0. 86 molel) of chlorotrifluoroe thyl-
ene, which was collected in a Dry Ice trap, were added.
The vaessel vae sealed with a rupture 41skt attached and
rocked at room temperature overnight.
When the contents of ~theo bomb vere poured into water,
a smal amount of organic layer formed. This was sepa-
rated, washed, and dried ovrer anhydrous sodium lultiate.
There was obttained 4*5; g. or matal~eria, the infrared speo-
trum of which was identical with that of CH20C10H20CPCf20RFO1
(The preparations of this compound is described In Chapterr
The reaction was also run at 50oand 1060 under prea-
sure and at -300 at atmlospherie prerssre. Hoevers, the
best BIeUl vae only 10 g. (ati *}OO). Considerable amounts
of ethlene oxide and potaesina chlorides were formed in
the reaction.,

In all the base~ratalyzed additions of alcohols to
fluoro81efinr which have been reported, only one of the two
possible isomers, the g(,lediflooroether, has been formed.

Theb attacking reagent is ~the anoleophilio alkoxide long
therefore the double bond of the clefin mus be polarised

inr such a manner that the =1MP2 end is the more positive
part oft ~the~ molecule. Miller and cowork~ers (42) have ex*
plained this as the result of the tendency of the fluorinezc
atom! to form a double bond and thus enter into resonance

with the olerinto double bond. Thesy have postulated the
followrsing mechanismr for the additionD

80" +0 =0rater RO ~O-C .

808 +R 6- _l~ RO 04~G

+. RO .

Because the reaction PI one -which to well-eatablished, it
wae not considered necessary to prove the structurtes cd the
ad~duate beyond the usual saolari refractions, analyses, and
inftrared spectra.
Thel addition of ethylene glycol to f~luoro61efi~asr t

complicated by the f~ormaation, in adcditifon to the 03-hyrdroxyr-
ebthy ether, of the diether of ~t~hylene g~yeol. The dI-
ether was isolated only in the case of the unsy~mmetrical
di chlorodi fluoroe thylene ; hydrtolys is to the e t er by
treatment with concentrated rsuUlfat acid occurred readily.
The ester was also syntheesied by esterifloationr of othycl-
ener glycol waith~ dichloroacetios acid. The two eaters had
identical infrared espctra; thus a proof of structure of

the Alther was obtained.
Th lack of reaction of tetrafluoroettttttttthylenet~t at atmos-

pherie pressure, rePOrted bJ Park gggg g,3 (43)1 was con-
timned in this wor~k.
None of the adducot of ethylene glycol and rinylidene
fluoride was isolated, although there was evidence of reno-
tion.t The probable ease of h~ydrolysis of the expected a~d-

duct) CH CF200H20H20HB, t~o the heater, (3-hydroxyethyl see-r
tate, would maElb isola1tiong of the other unlikely. Young_
(614) was unable to isolate tbe corresponding othyl other,

CH OF20RCB2CH, nd obtained ony the hydrlysia product,
er~thl acetate.
Th infrared spectra of all comepounds were obtaind
froP fresrhly distillead samples. Aill vere consistent, as
fcar as could be determined, with the assigned structures.
The 6-hydroxythyl there exrhibited th broad 0-8E stretokfh
at; 3.00 microne, and this band was absent in the rspetxrum
of the diesther of ethylene glyool. Strong carbonyl ab
sorption at 9.62 and 5.7~0 mpicrons was present in the speo-
tnrm of 080120008~2082000012
0 0



Aa,._ .Inlrednahkion

Th addition of aloohole and phenols to the ebthylene,
oxide ring has long been a subject of study. In 1859
Rloithner (52) observed the addition of phe~nol~ tio othylenr,
oxide to form~ (-p~henoxyethyl alcohol by heartingy the two
spaterialsa in a sealed tub at 15oo forF ten hours. In0 1860
Rebboul (49) reported the reatcjtion of ethyl alcohol with
epiohlorohydrin wrhidf occurred when he heated them in a
closed container at 1800 For ten hours. he obtained the

aiaple adduct, 028 OCH2CHOHCH201, as well as two other
compounds, 08201080808201 and C2HSOCH2ZCROHWR20CZa5' Ef
isolated the first compound by treating the mixture wai~th
potaeolum hydroxide solution, thus ftormaing the lower boil-

ing ethyl glyoidy1 ether, C2 Soca cyca .

Repeated experiments (5, so, 2;1, 29) have srhow that
alcohol add to the ethylene aside ring when a. catalytic
amount of acid, such as suiltur~ia acid, is present. The
addition of phenols to the ethylene oxide ring, however,
is not aided appreciably by acids but la effectively oat-
aljysedb by organic or inorganic base (7, 9, 59)* Bowever,

boron triflooride~ (3J) and stanni chloride (39) to serve
as clatalysts f~or the rebaction.of phenols with gpichlora-
hydrin. Regardless oft catalysts the direction of addition
of hYdroxy~ comppounds to eplohlorohydrin is the same, re-
sulting in a seondary alcoholt

ROB + Q CHCR201 ---RQCH20HlORCH201.

The opening of ~the ethylene oxide ring takes~ place by
the attack: of a nucleo~phlio reeagent on earchrbon (17). In
basic solution the attackinu~g raent is the alkoxide tent
0 O' 08

In the presence ofr an acid catalyst, the coanjugateb acid of
ethylene oxide is attacked by the alcohols


ini 1891 Linrdean~n (36) reported ~the preparation of
glyoidy1 there in one step by the addition of a phenol to
opichlorohydrin in th presence of excess sodfium hydroxide.
Tfhe mlixture vae allocwecd to stand for ten to twelve hours
with freque nt shakring. A considerable amount of the rlprp
aetrical3 Aliphenyl glyoeryl other vae also formed, by the
fuLrther reactionl of the glycidyl ~t~her with phenolt;

p -05 + 080 080820 + nca0B -- cp-0CH2HpH2s + Na01 + 820

(*oH +C t HCH20 4 Mast 9-00IH2CRORCH2 9 *

IfC the gclyslidyl other is the desrelad product, it cans
be obtained In higher yields- by using only a catalytic
amount of base. The, chlorohydria is formed and separated
and Is then converted to the glyoidy1 ether byj treatment
with an equivalent amount of basket

'9 -08 +e CqCH C#C2C1 b ase s 9-0082080808201

*0~CH2CHOHCH2C1+t Na0H (P C).00R2 Z Wa9 2 + a1 20.

1. Discur.anaso of procedure

SIn this research the addition of fluoroalobhols to
ethylene oxide and opichloroh~fydrin was attempted Iln an
effort to obtain (3hydroxyethyl fluoroethere and glyoidyl,
fluoroethers, reacotions which are analogous to those 3ust
described for unsubstituted alcohols and phenole.
TPhe fluoroalcohole which were ~avai~lab were tri-
fluoroe thy, alrcoholi) o4p -dihydrope rfluoropropyf l salhol;
M/o-~dihy droperfluorobuty1 Ralohol; sand dLF-dimethyl1-(a, AzG-
trifluoroethyL alcohol.

it should be noted that the esthers which ma be pre-k
pared bSI this reaction will all have fluorine blta to the
ether oxyrgen. Thereorer the vinylr others which could poe-
siblly be made treap them will be tinlV (h-fluoroethers.
All attempts to add trifluoroethyl alcohoa~l to epi-
ohlorohydrrin usilng concentrated sulfAric acid resulted in

only ercy small gyiel1a of the adduct, CF3CH20CB20HOHCHI2C1.
Bowever, in the preseence of base, trithuoroethyl aliooholi
added to epichlorohydrian and to erthyrlene oxide in good

2. Procedlures and R~eults

a. Addition of CF 08208 to epichlorohydrin
(1t) With a arstalytirr amount of eulturio acid
One hundred grame (1t.0 mole) of trifluoroethl rralbooo
and 46 gr. (0*S mole) of: eplohlorohyldrin were placed in a
~500 al. flask equipped with a refin condenser. ITwro al
of concentrated Iralfurts acrid was added dropwise to the
mixture t~hrog the condenser while the flask was gently
shakenr. The ixture was refluxed twenty hours. Barina
carlbonate vae added to the cooled solution, which was then
distilled through the 65-om, ooluman. A small amount of the

ad1~not, OF CH2Wi00H2HOEC201, B*p* 73-5*/17 mas.r wasr ob.

(2) With a catalytie amorunt of pyridine
One hundred grama (1.0 mole) of trifluoroeth~l. alco-
hol, 185 s* (2.0 moles) of epichlorohydring and 2 al. of
pyTridine wrere placedb in at 500 mi., flash equi~p~pe withr
mechanical stirrer, reflux coiondenerl and thermometer. Trhe
mixture vae0 heated to 80-900 for 12 hours. Fractional Als-
. tillation of the reaction mixture throg the 65-em. column
resulted in 39 g. of unreacted trifluoroethyl aloohol,
b~p. 74o, excess epichlorohydring, and 95*5 g. (0.go mole,

a 500~ yield) ofC the ether, CF CR200B20HOHOII2C1, collected
over the range 61ogy7 me,. 7 0/14 apm. A senter fraction
hald the constantes b.p. 85-60/19 am.,, nz5 1*3951.
6 5 1.3716, Manoalo.39'3.33 MRtound 33.67* kaage cale. ror

0589017302! 01, 18.41. Found 01, 18.91.
Sir grame of unidentified material boiling at 80-20/
4) mam, ae also obtained.
(3) Use of exeses sodium7 hydroxide with' refluxing
Flifty grams (0*5 mole) of1 tlifluoroethyl alcohol, 46
g. (0.5 mole) of epishlorohydrin, and a solution of 25 g*
(0.62 moles) of" sodium hydroxide in 300 a~l. of water wrere
placed in a one liter flask anrd refluxed eight hours. The
oily layer wsas separated, and the aqueous layer vae ex-
tracted with o~ther. The, organio layer and other extracts
were comibined and dried over anhydirous sodium sultate.
Fractionation through a So-em. columnn packsed with glass

helices resulted in 18 gg. (0.07 aole, 28P yield) oft the
glyoeryl diether of trith~oroethyll alcohol,
CF CH20CH2CHOHC~~oH20CH2C b.p. 860/16 rm., 925 1*3528,
a & 1*3690, Realo.39.34, MIRtound 39.97*. .4881,aL Calo. for

07Efigkr6 3 On32*823 B1 3*93. Found Os 31**Fi flr 3*53*
(4) User oft excees sodina hydroxide without heating
tlifluoroethyl alcohol (50 g., 6)*50 mole) and orpi-
shlorahydrin ll6(46go 0.001 mole) were added to a cooled
solution of 23 g;. (0.62 mo~ile of sodium! hydroxide in 300
al. of water. The reactants were sized thoroughly, and the
mixture was allowed to stand at roomr temperature overnight.
Th organic player as then separated, dried over anhydirous
.eothus sultatesr and distilled through the So**am. column.
There was obtained 24 g. (0.15 8olel a 31P 2ield) of g~3y-

01471 t~ifluloroethy. etherl 98 CIRaCH20H2Cr, b~p. 82-50/

120 am. (13P-50/*5.. prees.), 925 1*356o, a 5j 1.2666,
MQ~eale.26.62, Miound 26.93. Bggg, Cala. for Cyry@02:~s
a, 38*473 Re.4*52. Found C, 38.98; &r 4*51 *
In addition, 12 g.e (0.047 moler, a 19$ yield) of the
1Ther atoiia c refrction ralue used for 'epoxy" oxygen was
1.890, determined by. floree-Gallardo and Pollard (20).
2Thise analyala was performed by the ailoroanalytical labora-
tory of Dr. G., Weliler and Dr. F. B. Strause, Oxf~ord,


glyceryl diether, CP C'3H20CH2CHONCH20~HCH2CF was also o~b-

(5) nseaction or or~3(10ago with Or30H20ZCH2CHOHCH2C1
Forty-six grams (0.24 'mole) of CF CH20CHi2GHOHCH201 vas
placed in a 500 mrl., round-bottoma flask equipped with re*1
flux condenser. To this was added 2f; g. (0.25 mole) of
tri~fluoroethyl alcohol and 12 g. 10.30 mole) of sodium
hydroxide disseolved inlj 150 al. or water. The mixture wasl
refluxed for one hour and allowed to st~and overnight. Thes
organic layer vae separated, and the aqlueous layer wajs ex-
tracted with ether. Frational distillation of the ctom*
bined organic layer and ether extracts resulted in 11 5*
of CHaCHaCH20CH2C,, identified by its linrCared spectrum,

and about 23 g. (0.09 mBole, 37P yield) of the glyceryl di-

ther, CF CR20OCH2CHORCII20CB20fP, b.p. 99-1010/23 am. The
infrared spectrum! of the latter wtas identical wi~thi that of
the high boiling fraction obtained fCrom the tr~iluoroethyl*
alcohol-eplohlorohydria reaction.,

(b) Reaction of OF 0H200tI2CB082 with B01

Glycidty1 trithuoroethyl ether (t)j g., 0.29 mole) and
40 al. ofa chloroform were mixed in a 250 mi. rrask and
cooled in ice water. Fift arl. (aibut; 0.6 mole) of con
centrated hydirochlorio acid was added gradually, with
stirring and cooling of the mature. After all t~he acid

wae added, the organio layer vae separated, washed with'
water, and dried over anh~ydrorus sodina sultate* Fratione-
tion through a 1) sulted in 30 g. (0.16 moler a $4$ yield) of
OF 082008202080)1201, b41p. 8~5./1~9 mne. Its intzrare8 speo-
trm vae identical with tht of the product obtAined _ia
(2) above

b. Addition of C28828 5co topichlorohydiri
Forty-two grams (0.28 mole) of CZ'5aonZO, 29 g. (o*31
moler) lof eplohlorohydria, and a crooletrQ solution of 16 g.,
(0.4 mrole) ofr sodium hydlroxide in 190 al. of waterr were
sized in a 500 al. 1lask and allowed to stand overnight.
.She procedure described for trifluoroethyl- alcohol was fl.a
lowed. fPrnational distillation resulted in 5 g. or s a ix-
ture oft the alohol, vater, and probably same ofl the gly-
laJ~y1 ether; and a second fraction of 11 g. (0.05t3 mole,
19P yield) of the ether, rCH2J10HCRB2CH2Cz'5* * 780/p6 se,

Soo3/2o am. A center traction of this material had the con-
stants: brp. 810/86 ma. *1 790/64 am.,, n25 1.3419r

445 1.3534. M(Roale.31.24, MRtonnd 32.08., bpgg, Calow for
cgLF06" yosc 34.96; Re, 3.42. founds 4, 3S.155 Re 3.36.
eaur grams of mlaterial boiling: in the range 84ogg1
mm., 101C0/12 am. Was also obtained. It vae believed to be
chliely the diether, Cl9HOfGn20CH2HCHZOR2CH202'5*

e. Addition of 0 PyfR20H to epichlorohydrin
~Twenty-seven graS]1 (0.139g mole) of at,O(-dihydropel-
fluorobtutano1, 12*5 8. (Q.135 olae) or epichlorohyarin, and
6*5 g. (0.16 mole) of sodiumn hyaroxide dissolves in 24) al.f~
of waster were mixed and allowed to stand overnightl at r~oom~
temperature. Fra~ctionation of the dtrid prodmot: resulted
in 8 g. (0.031 moles, a 23# yield) of the glysidy1 ether,

qpcRocag~c3r ** 79"/49 rmO., n25 1*3350, a 5 1.4429,
.cle36.96, MIRtoune 36.71. Aprg;. ,Ceal. 2or 07Ryryogs
or 32.823 R, 2.76. Found C, 32.10Q, ER, 2.81.
In addition, there was obtained P*S g, (0.016 maole,
a 21ck yield) of the glygceryl diether,
(3$Cf CH200P2CHO RCH20CH 20:B~ ?, b.p. 112-1fjo/rf ara,,
.25 1.3338. 6 5 1*5569r M~ale.5?*81. IWrouna 6o.4o.
Ag ,Calo. for Gyg22024#10 8 0, 28.96; R, 2.21. Found:
CI, 28.81; 8, 1.91.

6. Attempted addition of CF C(CEI)208 to eplohlorohiydria
Attempts to ad this tertiary alohol to epichloro*
hydrinr using an excess of sodium hydrovide, as in the
above procedure, and with a catalytic amount of pyridine,
vere unsucceessfl. In both cas~esonly sartmring material
vae recovered,

~Addiction of CF 3CH20R to ethylene oxide
F~iver grams of potassium hydroxider was dissolveld in

150 g. (1.5 mole) of trifluoroethy~l alcohol. The cooled
solution was placed in ithe small autoolave, which was
cooled in a Dry loe-acetone bath. For~ty-f~our grams (1.0
mole) of 6UthyleneM oxide was collected in a Br lee tra
and added to the contents o f the autoolave. The latter was
sealed and rocked at 706 for 4 hours. It; was cooled to
room temperature, opened, and the reaact~i mixture was dis-
tilled through the 65-om. fractionation column. Forty-
three gras of excess trifrluorsethyl alcohol was recovered,
and 197*$ QS. (o*75~ mole, a yes vieta) or the other,
OF 02200820208,2 was collected over the range 820/85 a..
680/90 ma.l A center traction had the constantes b~p.
8 /80 am., n25 1*3502, & 5 1.2902, M1oalo.23.84,
M9tound 24.04. ~adL Gale. for a4& F 02D be 33*343
8, 4.90. Found C, 33.10; BI 4.86.

ir A~dditon o Of Q2P0820B to ethylene ozide
Four gramas of powdered8 potassinra hydroxide, 105 s*
(0.70 mole) of 0r2lSCagon, andr 29*5 s. (0.67 mole) or
ethylene oxide were reacted in theb usual manner. Thlree
grams of the alcohol was recovered, an 42 go (0.22 mole,
320 2ield) of t~he ether, C22'SCR020C2C20H, b.p. 85-950;
87 am., vae otained. A center traction had the proper-
tiest b.p. 870184 rg, n25 1.3370r d2f 5 13806,

NRoale.28.46, MRfound 22924. &aag] Calo. for O0xp50152r
o.rrt 3094 3*63. FPoundr Q, 30.66;l rs 3.77*

gr Addition of C @CR22H8 toethylene Oxide
Three gramsa of powdered potassinra hydroxide, 125 g*
(0,62 mlole) of @fC20H20, and 13*S s. (o*31 maole) or eat-i~t
ene oxide were reacted byV the sam procedure. Distilla-
tioan through the $$*oa.~ column resulted in 44 g. of the
alcohol and 47 g. (0.19 molre, a 62P yield) of
0320CH020C2C20H, collected over the range, 83.940/5t, are*
A senter out had the consltantar 'br~p. 912o/4-m~. (159o/
ata. press.), n28 1.3300, 4f4 1.4695ir MWoalo.33.os,
Mifound 33.90. ngag[. Calec. for CgHyF702t Q, 29*51t
8, 2.89. Found Q, 29.34)t P, 2.87.

b. Additionl of OF Q(Cf3)20R to ethylee oxide
Four gramsa of powdered potassium hydroxide, 77 g.
(0.60 mole) of CF3C(CfI3)20H inl aseatropic solution with
about 191 g. ofl-ethyl alcohol, and 22 g. (O*So0 mole) or
erthyene exide were treated in the usual manner. CAs a re*
ault of distillation through the 65r-ea. column, So g. or
unreacted alcohol and 30 g. (0.174 mole, ra s3305 yieltd) of
the desired other, OF 0(CRI~ )2002202202, sollected over a
boilingZ point range of 906f80 glam. r4of33 ma.,, were ob--
tained. A center tracttion of the lattfer materialf had the
constalnter b.p. 920/77 III**l 822 7, 3749r d 21.1931r
9oal.33*08,~ MRfOUnd 33.02. ~Agal. Cale, for OglyfI~02'
Q, 41.86; R, 6.4~4. Found C, 42.Q05 W, 4*81.


of Ph~armales~alls with Enia.arshlrehrnrin

Table II

s Prepared from the Ren n





(1) or3CRB20CH2CHOHC~201
(2) CH CHCBg00H20f

(3) (cF3CH20Car-)gCRON

(4) 089080820082 2'5

(5) cO CHCH20CH2Cy@

(6) (C ~770870082")20808


B& ~L
85-6~o/1 a*,
82-50/120 Iam.,
860/16 ***
sago(6 met*-
79 /84 amr.
79*/9P am.

154 am.



1.3394~ 1.4429

1*3338 1*55i69


.Qates Esnt
33.33 33.67
26.62 26.93
39*34 39*97
31.24 32.o8
36.96 36*,71
$7.Y1 60.40

&a4 &~a &
- 18.41
&ll M it





38*47 1*52
32.82 3.93
34.9p6 3.42
32.82 2.76
28.,96 2.21

-38*98 4*51
-31.82p 3.15?
-35*15 3*36Q
-32.10 2.81
-28.81, 1.91

Coampounde Prec ared fromp th Reaction
of Phuarnablcohols. with Ethyrlana Czide

'Pable. III





(1) aF3CH20CH2CH20H
(2) 0I2 S'rcaO20CH2H20H
(3) C3J7o20ongCH20B

(4) CF C(CH )20CBCR2CgoH

5ic4 84+/80) rrr
320 870/8aG am.
621ic 9128/94 am*,
35% 92+/7c7 me. r

33.34r 1.90
30.94 3.63
29*51i 2.89
4~. 86 6.44

F.9.s oA
& &15
3r3.10 4.,86
30.66 5.7"r
29.24 .8
42.05 6.81


g~al .
23.84 r



Th ability of fluorine to alter the properties of a
raoleole~ is again exhibited in the rebaction oi fluoroaloo-
hole with epoxy comapoundra. Unsubstituted alcohols add
readily to the ethylene oxide ring it a catalytic amount of
sulturio acid Is present. however this work ha~s shown
that thuoroalcohole require a basic catalyst for an eff~i-
cient reraaction. On a slight amount of adduct was ob.
tained when sulturio acrid was the catalyst employed, but
yields of about 20-600 were obtained when sodium hydroaxide
or pyridine wats used. In this respect the fluoroalcohols
resem~ble the~ phenols; this isr probably due to theirr simi-

larity in acidity Ea perfluorosloohola 10-12 (27)1

a, phenorl ;4-10,
The lack of reactivityr of the flruoroalcohols and

phenole in acid solution is probably due to the low con-
centration of elec'trone on the hydroxyl oxygen available
for' nucleophilia attacks on the carbon of the sirigr Likre-
vise, the fact tht unluorinated alcohols do, notreact as
readily in basic solution as the phenols e spro~bably due to
the low concentration of alkoaxide lon, the attacking reat-
gent in basie, sout~ion. However, Soyd and Mparle (8) found
that th rate of addition of substituted phenoxides to
eth~ylene oxide dimitnished with an increase In the noridity
of the phenol. Theyg attributed this fact to the incrueaed

stability lof the phenoxide ion with greater acidity of the
phenol. The two effects~ appear to contradict each others
the more acidio the alcohol or phenol, the greater is the
concentration of alkoxide or phenoxide ion, but it is als~o
the more stable or less reactive. Probably both effects
are important, and optimum conditions may be attained by a
compound of intermediate acidity.
B~y the addition of ftluoroalcohole to opichlorohydria
in the presence of at least an equivalent amount of base,
the glycit~y1 ether is obtained in the one operation in
yields of about 20-30). However, the latter reacts with
some ofC the fluoroaloohol to form the glcesryl diether,
thus decreasing the yield of glyoidyl ether. Heating the
reaction mixture results int complete conversion of the

glycidy1 ether to the glyceryl diether. Supporting evi,
dence for the stnructre of the diethe1sr was obtained by
Isynth~esis by the base-catalys~ed reaction of tr~ifluoro-
ethanol vith OF~C~H20CH2CHOHCH201. TPhe latter compound was
obtained both from the pyridine-oatalyzed reaction of trL*~
fluoroethano1 with eplohlorohydrin and by treatment ofT
trithouroethyl glyecidyr other wi~th9 hydrochlorio Pacid.
TPhe addition of fluoroaledho~le to ethylene oxide,
catalyzed by a smral amount of potassina hydroxide, was
uncomplicaterd byr major aide reactions. Yieltds~ of about

30-6Q$ of the adduct, a(3-hydroxyethyl ether, were obtained.


The terti~ry flucroaloahol, OF C(0@3)208, dliffred
fraom the primaary fluoroaloohols in its lacok of reactivity
with epidhlorohrydring hawveer, it added toEthy~alene oxide,
resulting in a 350 yriel3d of the ether.
The infrared spectra of ~the compounds deeoribed in
this chbapter were obtained and were consistent with ~the
.assigned structures. Thsespectra of the glyoidyl ethere
and a disonssion of their crharaclteristics are given lar
Chapter VII.



A., Introduction

~PZa terceplac~ement of the hydroxyl grou vith chlorine 'by
treatment with phosphorue pentachloride~ la a well-'known and
useful organio reaction. A~ppliations opf thte reaction to
others ofZ th tyrpe prepared in this wo k have been re-

ported. Park and co-wor~kers (41~4) prepared

CH2C10R20CF20RF$1 byr heating the 4-hydroxyethyl other with
phosphorus pentachloride and phosphorus oxycahloride. Boyd

(6) treated g~lyseryrl dipihenyl ether, (P-=DGH2CHOECH20-q ,
with phosphorne pentachloride and thereby obtained the
ch~lore decriative.

Pardk and co-workers (44t) and Aypp 8$ Bgg, (48) haer

prepared dyt-diflooroethere by the addition of aloahole to
fluoro61erine and have studied the eff~ect of treatment

with elemlental chlorine. Both groups repoorted that the
chlorinated ethers were Ve~ ry tablb8e chemitcallyr; hydrolysis
to the aeters aourred with difficulty or not; at all,

depending on the degree ofl chlorine substitution.

B. Elxornerintal

la. .Mrisaaana prandaurs

Sy the methods described in chapters III and IV,
B-hydroxyethyl there of two types were prepared!

(1) cH20RCB20CgRe and (2) CR20HC11200B2Ry. The ethers of
type (1) were succeaefully treated with phosphorus penta-
chlorid by the method of Park and co-workers (44), in the

presence of phosaphorus oxychloride. However, it wras later
found that the absence of phosphonru oxychloride did not
decrease the field of chloro~t~her. The ethers of typ (2)
were diluted with chloroformr before treatment with phos-
phorue pentachloride, an much better yields of the
**Bhlorsethyl there were obtained.' The glyceryl diether,

CF CETC20CRI!H I20HOCHg0CH2CP, was also treated ~i~t~h phosphorus
pentachloride, and the corresponding chloroether wasr
obtained, wi~th the chlorine in the 150ML position with~
respect to both of th sethe oxygens.
The use of 'thionyl chloride as a chlorinating agent
gave none) oft the desired r6-chloroothYl ether,
Hydrolysis of two of th chlorinated there having
fluorine in the alph gposition wasa attempted, and the
corresponding eaters were obtained.

2. Procedur~es and ranults

as CR201CoH20Q~Cf20H1
(1) Preparation
The a-hydlroxyethryl ether, CH20EIOH20CF~208F0Y 1 (59 g
0.33 mole) was placed in a Soo al., three-necked flrark
equipped with a mechanical stirrer and reflux condenser,
Seventy-three g~ram (0*35 mole) of phosphore~s pentachloride
was added graduallyr, while th mixture w astr~red Vigor
ously. EFach addition of phosphorus pentachloride resulted
in immediate reaction, cas shown by ~th evolution of hrydtro*
gean chloride and heating of th mixture, until about two-
thirds of the chlorinating agent was added. Then the
reaction subsided. AfterL~ addition vrae complete, the roeas-
tion mixture was renamed twenty m~inutee; it was then
cooled and poured intor ice water. The organic material
settled to th bottom and was~ sepaRatebd fro the water.
It wares washed writh sodium~ bicarbonate solution until nenc
tral to litmus, then tried ove anhydrous sodium 9altae.
PFnaplly, it was distilled -thrn a 15-0.. tractionating
column packed with Berl eaddles. Others was obtained 17*5

g. (0.089 mole, a 27P yrield or CH2010H20ZCPZCHOFC1, b.p.
830/100 nme. 970/9g MR** from which a center frctionr had
the oonetalnts1: bcp. 8~5c/1oo me.~ n25 1*3883. d(5~ I,447X I

Iaa~aol32.o5, IQ~rouna 32.14. Park a~nd co-workera (44i) re-l
ported, for this compound, b.,p. 800/100 sam., nio 1.3929..

In addition, a higher boiling fraction wasr obtained
whidnh had the followineS propertiset b~p. 9j50/29 nr. .
940/27 ma.r n25i 1.3703, ag53 1*538~5. An intrare~d spectrrm
of this material exibied no ORI stretching frequency or
carbonyl band. It was probably chiefly the dietther oft
diethylene glycol, (08CI10F20CB2CH2"~ 20.O
(2) HYpdrolysis
Forty grama (0.20 mole) of aHClH20H2CF20HF01 wasr
placed in a 500 al. ftlask equipped with a mechanical
stirrer, ref~ltux condenser, and thermometer. Ten grams ofC
concentrated sulturio acid was added, and the mixture was
heated cautionely, with stirring. When th temperature of
the liquid reached 820s, a Vigoollne reaction began, with
evolution 'of hydrogen floride and heat. After an hour ofl
continued heating and stirring, the temperature had rsten
to 980. The mixture vae then allowed to cool and poured
over cracked ice. The oily layer was aeparated, washed
W~ih water, and dried over anhydrous sodiumr suliate. D~ir-
tillation through the 15-om, column rersrulted in about 12 g.

(0.069 ole, a 34) rield) of the ester, CH2C1r20C60HFCI1,

b.p. 1060/47 am. 1050/45 am., n23 1.4r3691 a 5 1.4256,

MP~eala.32.06, MLRiound 32.20. Abgg;. Gaole. for C4s~cl2FWgs
01, bo*Sa. Found 0lt1, b.op.

b. CH2010H20CF2gdH012
(1) Prepalration
Treatment of 45 g. (o.23.alole) of 0920HCH200F2C0HC2
with 60 g. (0.29 mol~e) of phosphromru pentachloride by the
procedure6 described above ressulted in 13.3 g. (0.063 mtole,
a 27$ yield) of CEI2C10H200F2~CHCO12* boiling in the range
86-80/33 ma.rr A center tr~action haudl the conatantes b.p.
870/33 an., n25 1.4270, a 5 1.4833, un~cale.36.92, MRiound
36.95. dead, carle. for 0485 e3P20s 01, 49*83. Founal

(2) Hydrolysis
The, ether, C~H2010H20CF20RrC1 (12.5 g., 0.o58 mole),
was treated with three al. f coancentrated aulturic acid by
the hydrolysris procedure just described f~or CH201CH20CF2*,
CHFC1. Four grmams (0.021 laole, at 364C yield) of the ester,
CH200B2 0812,was obtained. Its constants were t p

207-1l/810 prs. 25 1.4719, a 5f 1*4544.~ 11Roale.36.93r
MdRfound 36.85. The coanstants given in the literature (15i)
are! b.p. 209-12076 13.,dl 1.200e. Anal, Calc. for
*This density is believed to be in error. By comparing the
vrales: CH a000C2H5* do 0.0 20100002H55 62o 1*159,
and CBC12400002x' dZo 1.2821,one would expect an addi-
tional chlorine atomr to raise the density at least 0.1
unit above that; of 080120800285.S (These values were ob-
ta~ined from the Handbook of Chemistry and Phrains. J0th

0 8501302t 01" 5$*56. Founill 01. 54*85. This deriva-
tive serves as proof of structure of the ether,

e. Preparation of CHZC10H200P2CHFCq3
Treatment of 84 g. (0.40 mole) of CH20HCH20CF20HFClg
with 88 g. (0.42 mole) of phosphorue pentachloride, by the
usual procedure resulted in 2$ g. (0.11 meole~, a 1727 Yield)
of CH2C10R120CFr2CHFCP3, collected over the range 45?0/45 ma.-
$4*35 a.An analytical erasple had the constantat b~p.
~60/37 ma. ,n25 1.3349, 4 1.4749,, Maroud
32.33. Bgage Calo. for05 5017605o 01, 1.38. IFound:

Twenty-nine grams of a material boiling at 700/30 man.*
760/27 lam. vae also loolated. Its infrared ppectrum showed
the 'absjence of hydro~xyl and carbonyl groups and was very
similar to that of the 9-chloroethyrl ether. It was be-
lieved to be th diether of diethylene glycol,
(C CI3)frF~CI20CB2 2"20, and it had the constant t
n28 1.32831, 28 1*5452, MQloale.533.31 M0~ound 5335. How-
everl analysts' did not confirm the proposed structures.

A. Preparation of CF CZOH20CH20H~C1020CR20@
Fifty grams (0.19 mole) of CF 3CH20a2H~CH2aCHORCH2CHC in
100 al. of chlo~rofr was treated with 44 g. (0.21 mole) of
Ed,, Chem~ical ERubber Publishing Co., Cleveland, Ohio

phosphorus pentachloride by thle sname procedures as in the
precedingh reaction. Dietllastion resulted in 28 g. (0.1~0
mole, a ~54, yield.) of Cr~3CH20C20~HC10H200H20f, b*p* 59 /
6 ram. 630/7 Iam., n26 1*3587r <(6 1*3933, Mloalc.42.68(
Paround 43?35* An41, Cale. for a7Hg01P6 21 01, 12.91.
Found: 01, 13.92.

e. Preparation of CP CH20CH2CH20I1
The other, OF CH20CB2R20H20 (101 g., 0.70 mole) in 350
ail, of chiloroform was treated wpith 167 g. (0.80 mole) of
phosphorue pentachloride by the procedure just described.
Prationat~ion of the dried retaction mixture reslulted in

60 g., (0.37 mole, a 53P yield) of Br3CH20CH2ZCH2C1, b.p.
114-15e/atm. press., n27 1.3590, ag? 1.3034, W~ealo.27.18,
#Riound 27.46. d~lagg Gale. for Cq48401P Os Q, 29i56;
R. 3.72; 01, 21.81L. Found: 0, 29.412; f8, 3.68; 01, 22.08.

f* Preparatio2n of OgFS~CEI20CH2CB2C1
Thirty-nine gramne (0.20 mole) of CzP5CH200HCH20WZH io
100 aml. of chloroform! was ~trzeated with 52 g. (0.25 mole)
of ,,hosphorus pentachloride by the customary procedure.
Fracotionatrion of the dried p2rodiuct resulted in 21. g. of
02 5020CH208201 (0.099 mole, a 4~95 yield), b~p. 640/118
mpa. 640/96 ma. An analytical sample had the constanter
b.p. 680/113 am. (120-lOf~ata. premse), n26 1.3448,
dZ6 1*3792r MIRggy, 31.80, MI~tound 3e*72* 4082-.. CalQ. for

05%P560150 Q, 28,251 ae 2.83. Found C, 27.61); R,

g.r Preparation of C @CH120CH120H201
Forty-four grama (0.18 m~ole) of~ 03~?7IGH20CH2082H in
100 arl. of chlorof~ona was treated with 46B g. (022 mole) of
phosphorus pentachloride by the usual procedure. There was
obtained 31.j g, (0.12 mrole, a 67d yield1) of
OF CH8200R2CH201 collected in the range 750/91) I~ar 7o/
70 m~at, A center traction had the properties b*ps 7587/
80 ame.t n24 1*3381, 62 1.4c673, MIRoalo.36.42, MQfoubd 3713a
Aggg, Cale or C6 01" gg170r 01, 13*50. Found: 01, 13.04.

he Preparation of CF 30(Of)2I00H2CH201
Eventyp-four grams (0.14 mlole) of CF Ca(C~3)20CHCR2N20
in 65i al. of chloroform wras treated with 31 g. (0.15 mole)
of phosphorus pentachloride. There was obtained 12! g.
(0.063 mole, a 45P rield) of 073 (O3 C20CR2201, b~p.
71 /92 am.P 69q/75 xam. A center traction had the con-
stante a b~p. 690h/75 an*. (1350/ata. prees.), n2 1.3784,
62 1.2102, MRoalo36.412 1 MRfound 96.*M* 41* Cal9. for
C806 to30s as 37*81t He $*29* Found: Ct 37.74;i st 5.02.

C. ~Dirennasin of Raeults

Th procedure whlich vae adopted for replacing the

T~a4~ IV

'Chlore therst~~~~ttttt~~~~tttt Hairnvina. 11xri ne ~n the Alaha .Position

and...Ea8tar.. Darivativese~ of..the..Ethsera

( 23o)



(1) CH201052 20RP0RBQ 14

(2) M~CH201CBHg0H1

(3) C~zolag am,

(4) CH2010H 08012 a~

(5) CiclHgc10H2 2 a3



850/10o m.
1060/7 m.* ~
1050/ 4~5 m. 3
86-7*/33 xma.
11607 Ja

1,33~9 1.~749


,C...lQo s


40.52 j
49. 83
5il 5*56



*Prepared br Park ands co-vaorkers (44), wh~o reported b~p.
800/100 mle., nDo 1*3929.

Table if

_Chloroe~thers EiavinaP Phorine i~n the Beta Poinit~io

(27 )

1 326 8


1.30 4

(27 )


(1) (CF CH200R2")2CB01

(2) OF 08"2008I220121

(3) 02 SCHI20CB20H201

(Ip) 0 P7C70200I205201
(5) cr30(ca~3 )20CB2ongol


Ilagg B.II:P,

490P 618 1 mm
67i% 75*/80 am.
454 690/30 p5aM.,

i9lals.. Iound
42.68 43*35
27.18 27.46
31.80 32.72 r
36.42 37.32
36.42 36.34

2;9.36 3.72
28.2~5 2.85

29.41 3.58
27*61 2*93

37.74Q 5*02

201 9
21.81 ~



camonna ut

37.8l1 5*29 -

hydroxyl, group of the q~Y dif'luoroetherse with chlorine was
the gradual addition of phosphorus pentachloride to the
either, followed by refluxingi for twenty mrinutes. Yields
of 24-7ff of the chloroethyl ethers were obtained. TPhe lowt
yields were believed to be, due to further otherification of
the hydroxyethere, ass evidencedl by higher boiling mate-
rfalr which vere not positively identified. Addlitional
refinxing of the reaction mixture resulted in lower yields
of the chloroether and more of the high boiling material.
Thde cxhlorination of the I-fluoroethers, formed froms
the addition of fluoroalohols to ethylene oxide, was ears-
ried out with chloroform cas diluent. Yields of 45 67$a
were obtained, and very little higher boiling material was

Twro of the chloroethyl Yolt,a-ifluoroethere vere hygdro-
lyzed with no difficulty by heating with concentrated sul-
furpio racid Yields of 34 and 36Sd of the esters were ob-
tained. One of the eaters thus formed, C1-chloroethyl di-
chloroacetac~te, vae a known compound and thus served as

proof of structure of-the ether, CE201DHW20CF2HC12* from
which it was prepared.
The infrared spectra of the compounds described in
this chapter wrere also obtained. Of especial interest was
the carbonyl stretching absorption of the esters. AL.
though t~he spec~tra of rtelativesly few -haloesters have

been published, it is known that the oarbonyl stretch is
shifted to shorter vave lengths fromr that which occurs in
unsubstituted esters. Ethyl trichloroacetate absorbs at
5.65 microns (4), and the setersr of perfluoroacids have an
average value of 5.60 mnicrons for the C==0 st~retdh (25)*
Saturated, unsubstituted eesers exhibit the carbony~l
etretchilng abslorption at 5*71 5.76 microns (4).
TIhe esters prepared on this project had the following
carbonyl absorptiont 082010820 CBFC1. 5.6o mic~rons

CH2(101COR20CC12. 5.671 microns; ~an anal2 OCH2C20CB1 CH12

5.62z and 5.70 microns. Thus these eaters also display a
shift in e~ar~bonyl, absorption to lover vave lengthen from
that of th unsubstit~uted esteks.



A. I ntrr~o~no tion

Like the glyoidy1 ethere, vinyl, others have been known
fior mpany years. In 1878 Vlslioenus (4i3) prepared tinyl
ethyl ether by heating chlorsoaetal with sbdina at 130-~00
Itsa synthesis fromr acreta by heating with phosphorus pent-
oxide and quinoline was reported in 1898 by Clarise (13)*
VinLZ al~kyl others re oammonly prepared by the
reaction of alcohols w~ith seeQtylenil at about 120-80 0
strongly alkaline medium, a procedure which was patented
by Reppe (5l), Shoesakorskit and Gracheva (156) have pre-
pared a-methylvinyl. albyi there by the analogous reaction
of primary alcohols with mrethylanetylene.
Several unconventionalS methods for? the preparation of~
oinyl alkyl others hae been reported. Adelmn (1)
described the reaction of primary arlphatic aloaohole wi~th
Vinylr acetate in the presence of mercuric sultate at; low
~temperatures to for the vinyl other and acetio said.
Shostakoventi gi~a_,(57) roundl that br heating unsymmertri-
eel acetals to 14o-50 I, Geoomposition to a tinyl ether and
an alcohol ocourred. REtppe (So) reported the reaction or

viny~l chloride with sodium~ alkoxides in Ialohol solution to
form the corresponding vinylT eth~e when heated to 1000,tor
about twelve hours.
TPhe dehydrohalogenat ion of a- and whaloe thyl others
has been reported by~U many workers. ol-Chloroethyl ethers
are rather unstable andC formr the corresponding; vinyl ethers
when they are heated with pyridine (d8). The synthesis oft
the Oc-ohloroethyl; there is accomplished by the reaction of
acetaldehyde with th appropriate alcohol and hydrogen

05O~ 080 +D 8+ n08 -- Cs~H iCHC + 820
9-Haloethere are in general lstable compounds and require
anchr more drastic treatment in order to omn the vinyl
others. Chalmers (312) found that it vae necessary to heat
9-chloroethyl there with powdered sodinaP hydroxide. He
obtained much lower yields of vinyl ethers fro the (3*
bromoalkry1 ethers, a result which he attributed to the
formatilon of dialty2 others of; diethylene glycol. Lawoon

(34) prepared CR I=CHOOP20HFIC1 by cheating the @*iodocthyl
ether with a mlixtur of powdered actinuas hydroxide and soda
lime~, a,-Uneaturated there of the type RCH=0(0R")R,*
have been prepared by a four-step procedure, of which the
final reaction was dehydrobroaination of the Q-bromoether

by heating with finely powdred potansinra hydroxide (33).
A study of the aneathettie properties of vinyl tri-

fluoroethyl, ether and oiinyl pentafluoropropyl ether

(CRZC=OO0082 2'S) has been made, and some phreiol'alom>-
stants~ of the former vinyl. ether are reported (32r38).
However, no description of the preparation of these vinyl
fluoroallkyl ethers aas found.

g... ..5;xperimensnal

1. Disoueston of procedure

The finalrX step in the proposed synthesis of winyl
fluoroalkyl e the re, thae dehydro chlorinati on of ~the B *
chloroethyl ethers, was the most difficulty part of the
procedures. Some of the desired vinyl ethers were prepared
by reaction of the chloroethyl. ethers with3 alcoholic?
potassina hydroxide, but the yields were low. Treatment
of~ the chloroethyl ethers with powdered sodi~um or potassium
hydroxide wasr ineffective as a means of obtaining the
vinyl there.
Because of the limited success in dehydrochlorinating
-ohltoroethyl fluoroalkry1 ethers, several other methods of

preparing vinyl others, using fluoroalcoholas, *
attempted. The reaction of alfoohold wr~ith acetylene was not
used because of lack of proper safety equipment; however,
the-leess hazardous methy~lanetylene was reacted with the
fluoroethyl alcohol, and a small amount of Ameathylving

trifl~uoroethySl ether vae obtained. The reaction o~F a
alcohol with Vrinyl, acetate bty the procedure of Adelman (1)
was unsuoossesful, as vae Reppe'sr (SoC) vinyl chloride
reaction. preparation of the B*chloroethyl ether of tried
fluoroethqyl alcohol by reaction of the alcohol with acet-
aldehyde and hydrogen chloride was also attempted without

The preparation of ally trifluoroethyl3 either wras
earried out; in order that a comp~arison of its spectruansith
that of tinyl trinuoroethyl1 ether could be made.

2.ProceduesB aL resultss

a. Del)hydrothlorination of CR3201CH20CF20WC1~C
Fhirty~-eight gram~e (0.19'mole~) of CH2010H20CF20EF01
wasr placed in a Soo-ma, three-necked flaes equipped with
mechanical stirrerl addition funnel, and distilling head.
A solution of 18 g. (0.32 mole) of potaessumo hydroxide in
120 al. ofJ 8-propyl alcohol wras added dropwise to the
ether, with heating and vigorous stirring. Salt formtion
began immediately. AI distillate ooneisting of a mixture
of vinyl ether and alcohol was collected over the arpproxi-
maBte) range 65-70o. it was poured into ice water, and the
organic layer was separated, washed seve~tra t~ime w~it
wastertr and dried over anhydrous sodiumn sulatate F~raction-
ation throg the 1$**m column resulted in 16 g. (0.10

mole, 520 yield) of the vinyl ethers CR~LH =P0HOF2CHC1 b~p.
71-30, n25 143531, d 5 1.2408, Mwoalo.26.72, MRfoun 28.06.
La~rson (34) reported for this compound a boiling point of
Treatment of the PNehloroethyl ether with aqueous
potassium hydroxide and with tri-gytbuty1 amaine was ineffee-
tive as a means of preparing the vinyl other.

b. Attempted dahydrochlorination of CH2010H20CF20CHC12
STher dehy drochlo rinat ion of th is ether was att emp ted by
the procedure described above, neing gebutyl and gn-amqy1
alcohols, but none of" the vinyl other was isolated. Con-
siderable salZt formation occurred during the reaction, and
a yellow-brown solid material, believed to be a polymer of~
the desired vinyl1 ether, remained in the reaction flask.
A mixture of powdered sodiuma hydroxide and soda lime vae
also used with no- suooess.

c. Attempted dehydrochlorination of CH2010H20CF2CHFCFj
Solutions of potassium hydroxide in ethyl alcohol sa
g-propyl alohol, and powdered potassium hydroxide, were
all tried ase dahydrochlorieinatn agents for C~gIZCH OODPg*
CNFCFP3 However, in no case was the vinyl ether isolated.

d. Dehydrochlorination of CH2C1CH20OHCH20
Twenty-five grams (0.115 mole) or aor3CH20CH2CHI201 was,

treated with a solution of 17 g. (0,5 motle) of po~tassian
hydroxide inl~ I~ m of absoalute ethyl alcohol by the
procedturel described in go for CH~2CICH20CF20HFCY1. Fraction-
ation ofi the dried orgaenio layer resulted in 6 g. (0.048
mole, a 32 yieldd* of the vinlyl ether boilingS over the
range 42-55"r iA low6 boiling traction was collected which
had the constantat b.p. 42-80, nl 1.3180, 427 1.18,
MRoalc.21.85, MRfoun E22.24, The oonetants repported
for CH2=CHOCH203 are as folloval b.p. 42.370, 25 1.13
C32, 38).
A sample furnished by Air, Reduction Companyl Inc., had
the constants n27 1.3168, dq 1.118, when measured with the
esae equipment as the ether prepared abover. Its infrared
spectrum was almost; identical with that of the prepared
oinyl there

se. ebydrochlorination of C2 J~CH[20CCH2CH21
Seventeen grams (0.080 mole) of QZF~0oca ollHC was
treated with a solutionl of 11 g. (0.20 mrole) of potassrium
hydroxide in 70 alT. of absolute ethyl aaloohol by the uesulr
procedure. Fractionation of the dried product resulted in
about three grams (0.017 role, 2UZ yield) of the vinyl
ether, OE2==CHOCH12Cz'5, boiling in the range 52-760c of
which a center traction had the conesantal b~p. $4-600,
n27 1.Uf 1a .227, MlRoale.26,47r MIRfund 27.92.

Agal.~ Cale, for 05 5 508 0, 34.10; R, 2.86. Found:
C, 34*513 5. 3*22.

f. Debydrochlorination of O@P7CI200H20H201
The chloroether, OgP CH20CIH20H201 (25*S g., o.opy
moa~le),as treated with a solution of 11 g. (0.20 molOel) of
potassium htydroxide in 70 al. of absolute~bethyl ablcohol.
There vae obtained four grams (0.0318 ~mole, an 100~ yield) of

CHTy==~CHOC20 7 collected In the range 77 95e. Froma
this an anzalytical samp~le had the constanta$t b~p. 78 -
82, .26 131 66 .U oale.325.f6 Icfound 31.08.
Agg~bb Calc. for ag 85~ 70s o 1.87t H, 2.23. Foundt
C, 32.01t Rt, 2.49.

g. Attempted dehydrochlorination of C~jC(CH3)20CH20H2C
Nine grams (0.047 mole) of OF C(CR 3)20CH20E201 vas
treated with 5*S g. (0.098 maole) of potassium hydroxide in
35 al. of absolute othyl alcohol. Howeverl only starting
maateriarl was recovered.

hr Dehydrochlorinrt~ion of Cy3 OB20CH2ZCBC10Z~H20CH2
Thilrty-six gramls (0.13 mole) of the chloroether was
placed in a 200 al., three-necked flask equipped with
mechanical stirrer, reflux condenser, and addition funnel.
Fourteen grame (0.25 m~ole) of potassium hydroxide wase dis-
solved in 30O al. of mnethyl alcohol and added dropvise to
the other with stirring. A preolpitate f1orme, and the

reaction mixture became war. it was heated and stirred
for an hour after the addition of the alcoholic potaeesha
hydroxide. it was: then filtered, and two laygersr became
apparent. The~ lower layer vae separated, dried over ashy*~
drous sodium sultate, and distilled. From it was obtained

19 g.c of the originlld chloroether only.- The upper or alco-
hol layer vas distilled at reduced pressure, and a Itrao~-
tiona boiling at 29 -520/28 am.1 vas obtained. TPhis was
vashed with water and dried over anhydrous sodium surlflate.
Frectionation through the 15.a column r~esulted in two

gr~ame (0.oo84 moale,6 a 6tS% Jield) or the unea~trated other,

CF3H20r=-CH OR0ZoBCH2 )*by.. 86 900/34 am1., n24 1*3536,
6A4 1.3533, YMicule.3?*35r around 38*21. Absaorption of the
C-0 stretch vaea apparent in the infrared spectrum. How-

ever, th analyses were somwa different from th theo-
retical values, probably indicating; the presence of i1**

to~ Reaction of frifluoroethyl alcohol with methylaaneylene
A solution of 9 g. of potassium hydroxide in 100 Cf.
(1 mole) of trifluoroethyl alooho'l was placed in the small
autoolaves, which vae cooled in a Dry lee-aoetone bath.
Fitfty-two grams (1.$ males) of meathylacetylene was collectal
la a Dr leetas .and added to the. contents of the bomb,
which was then sealed and rooked at 2250 for 318 hours. It
vae coolred to room temperature, the excess methylanetylene

was allowed to escape, and the contents were poured into
lice water. Twenty Igr~ams of an oranyaio layer formed and
was separated, vached, and dried over anhydrous sodium sul-
fate. Distillation resultedl in 4; g. (0.04 arole, 40 yield)
of material boiling over the range j0 67+,~9 which was 'be-

lievred to be CH2=0(0Ry)00H12Cf,, with the constantat
n26 1.3322, dE 1.107. MRoale*24.73, MRfound 25*98 Mine
gramspl of unidentified higher boiling material was also ob.
Although the (X-methylvinyl ether was probably impatre,
as evidened by unsatisfactory~ analyses, the compound is of
interest for its infrared absorption in the double bond
region. ~Impurities are likely~ to be poltymersr or hydriolysis
products, which probably would not interfere in this

j. Reaction of trifluoroe~thyl alcohol with ally ohloride
Twenty-five grams (0.49 mole) of potassium hydiroxide
vae diseolved in 115 8* 4.15 mole) or triuluoroethyl
alcohol, and the solution was placed in a 500 al., three-~
necked flash equipped with mechanical stirrer, reflux
condenser, and addition Funnel. Thir~tiy-tur grams (0.L44
mole) of ally chloride wasz added dropwiser to the refluxing
mixture, wsith stirring. A large amount of white preci~pi-
tate was formed. The mixture was refluzed one hour after

EJnantruurated .Xlnarnat~hen~


@..2,.. a
71-3* 15331
42-8a 1.31800


.J*57*8o 1*3360



(1) ong==ono~Crgoural
(2) CZIZ==0OCH2 3 ~j

(3) ca2==CHOCE202'S

(4) CH2=CHOCH2 3 7

(5)l CHg==0HocHg00BCF



240 74


& & ~
3410, 2.86
31.87 2*23
42.86 5.04

&hi id9
34.51I 3.22
32,01 2.49
42*4~j5 $*A




1At atmospheric pgresu~re
2Lawsron (34) prepared this ether, b~p. 71.4*,
3Air Reduction Com~panye In ** reports the constantat
b.p. 42.7a/753 me., ago 1L.3193t trants asag, B (32) report a
specific gravity of 1.13 at 25*,

the addition of all ~the aeltly1 chloride. It vae then
cooled, filtered, and distilled through the 65-em. column
at atmospherto pressure. The frollowing fractions were ob-
Fraction 1 -- b~p.. 43-6o -9g
reaction 2 ** b~p 61-700 ** 26 g3. (flat 660)
Fraction 3 -- bP 73-60 -- 58 2*
Residue -* about 5 g*
Fraction 1 was probably unreacted ~lyly chloride, and
3 was chiefrly trcifluoroethyl alcohol. Fraction 2 was
washed with1 cold wratetr, dried over anhyd;rous sodium sul-
fate, and distilled through thr~ern 15*.olumn. Thirteen
grama (0.093 mrole, a 22P yield) of ally triftluoroethyl
other boiling In thie range 6;1 750 Wars obtained. From2 a
center traction of this a~n anaytical s~ample had the con-
atantat b*p* 74*5 ?#*So, a 1*360, of 1.092, Manalo.
26.47, MIRtoUnd 26.6?* BD81* ,Calo. for OS 7 30s C, 42.86;
61, 5.04. FDound: C, 42*45; B, 5.15*

21. Dianatllsion. at REbanit;

The results obtained from the dehydrochlorination of
the B-chlooroethylJ ethere indicated that this is not a
satisfatory method for the preparation of vinyrl fluoro-
ethere. Only2 one vinyl other having fluorine in the alnhas

position was isolated as ~cRIO~pHP0B0F2HF This compound

had been prepared earlier by Levaron (34). Some vinyl
there having fluorine in the Bdgga8 position were prepared

but; in low yields.r These were CH2f==COCWH20f3,

CH2==HOCH202'S* and Of=I=CHfOC~H2C F and an imlpure sample
of CF CH20CH~=-0HCH200H2C1P was obtained.
However, the others which vere bpreparled were sifi--
oient for the determination of the effoot of fluorine sub-
stitution in th alkyl group of vinyl alkyl ethers on
their infrared absorption spectra.
Inability to prepare vinyl there fro two of the
chloroethers having fluorine in the af~r>B position vae
probably due to the reactivity of both the chlore deriva-
tive and the corresponding vinyl ether.
Thes low Jfields of vinyl 8-flooroalkyl ethers were
probably the result of the reacetivity of the vinyl ethers,
for there was evidence of both polysrFization aan hydroly-
sis. Considerable salt formation indicated that dehydro-
chlorinhatn had ceurred.
The lack of anacess with the other methods of pre-
paring vinyl there may be due, at least in part, to the
unusual acidic properties of the fluoroalcohols. Vinyl

othyl ether, for example, wacs prepared in fair yield by the
reaction of acetaldehyde, ethyl alcohol, and hydrogen
chloride to fore ethyl d:-cxhloroethyl ether, followed by
dehydlrochlolrination with pyridine. However, when the same

reaction was attempted with trfluoroethyl alcohol, only a
trac of hea vinyl ether was obtained, as shown by th
infrared absorption of the distillate.,
The bas4e-catalyzed addition of tfifluoroethylr aloohol
to methylaietyglene resulted in a very 1p yield of PImp1;re~d
d-methylvinyl trifluorcethyl other.
Ally1l trifluoroethyl other was prepared by the esso-
tion of ally1 chloride with trifluoroethyl alcohol and
potassium hydlroxide.



A. Introduetzfiran

This work on vilnyl ethers grew ou t o an infrared

spectral study by O). B. Butler (11) of the selective
polymerization of monomere possessing both Vrinyolozy andli
allylie substituents, such~aasc~w 08040==08
H20==02 ,

Polymaerization wrasr carried out art low temperature with
boron trifluoideb ase catalystl a procedure which was be-
lieved to affect only the vinylaoxy group, leaving the

Zlrl1 double bond unchanged. Th monompers exhibited two
banda in the regionn of carbon-carbon double bond stretching
absorption, one at 6S.18 micron which disappeared entirely
in the polymer and a second at 6.08 microns which was much

weaker in the polymers the portion of this band remaining
in the polymer could be attributed to the ally double
bond. The strongest band In the spectrum of the monomer,
at 8.32 microns, was also completely missing In the polysrer
spectrum. Because these three bands diminished In inten-

atfty or disappeared entirely when the Viinyloxy group was
lost in the polyserization process, they were believed to
be associated with this gSroup.



Recently, Htase and Simon (221 obtained analogone re-
sulta in a study of the acid-catalyze$ polymerization of

iJ-vinyloryethyl methaerylate,. CH12==0(Of)00~CnZH0H20CH=C2*

Infrared bands whichtk they reported present in the monomer

and dPiminished or mPiessgin romp th'e spectrum of the polymer
were: 6.10, 6.17. 7.58, 8.30, and 10.2 alorons. They
found similar changes in the spectra. of vinyl butyl ether
and its polymer.
The 6.08 and 6.18S micron bands can be assigned immons
diately to the carbon-carbon double bond stretching vibra-

tion; however, the very strong 8.32 micron band cannot be
accounted for as easily. Saturated. unsubst~ituted ethere
are known to ebhibt strong absorption near 9.,00 micron
which is believed to be due to a vibration involving the
carbon-oxygen bond (21 61). Esters and aromatic etthere
have this band rat a lower vave length, in the region of
8.00-83.30 microns (2). T~homepson and Torkington (6j0) found
a strong band near 8.00 microns in esters which they
attributed to a vibrtion primarily controlled by a carbon-

oxygon Lond. Techamler and Leutner (61) reported that com-r
pounds having: t~he structure ==-J-0)-O, such as eaters, acids,
lacton~e, and mixed alliphatie aromatic ethers always have
two intense bands, 7.87-8.70 and 8.92-9.70 microns. Thus
the 8.32 band, present in the rinylogty monomer and missing
in the polymer spectrum, is probably the result of a


vribrationr associated with the carbon-crygen bond of the

vitylexy~ group.
The substitution of electronegativ e atoms, such as
chlorine or fluorine s ShdML to an ethr oxygen has been
shown by E. W.iB Moliason (40) to shift the characteristic
Co-0- band near 9.00 micron to Zlower v ave lengths. Bands
at 8.2-8.4~ microner in the spectrar of M.,d-difluoroethers
were believed to be analogone to the 9.00 micron band of
saturated, unsubstituted others.
Bsveral studies have been ald~ of the vibration

specotra of vinyl ethers, D~avison and Bates (14)1 studied
the inf~rared arbsorption due to earbon-carbon doubler bond
stretch and olefinto earbon-hydrogen deformation vibra-
tions of five vinyl alky etherst othy1, buty1, isobutyhl
2-ethythexy1, and 2-chloroethy1. Kirrmann and Chanoel (30)

compared the infrared and Rmaman spectra of the first three
ulinyl ethers listed and of vinyl ally ether. Both groups
of investigators reported doubling of the carbon-carbon
double bond stratehing frequency and attributed it to
rotational isomeries. The latter group listed t~he 8.30
msicron band as present in the infrared spectra of all four

oinylrl ethers; but it vae absent in their Raman spectra.
They made no assignment of this band. Batuer, Prileashaev,
and Shosrtakovakii (3) had earlier made a systematic study
of th Ramoan spectra of eight trinyl etherasr methyl, e~thyle~~~~ttt~~3


propyl, isopropy1, butyle isobu~tyJ1, isoamy1, and iso~oty1.
They found the very sharp and characteristic carbon-
carbon doule bond stretching Vibratn to be a tripets
6.06, 6.10, 6.254 microns. This they believed to be due
to rotational isomeriesa whieh reutsBtt in the doublet 6.OF,
6.25, along; with lFermi-resonanoe splitting of the 6.07
(1645 a band at 12.2 microns (820 em. l).
To explain the existence of rotatioal isomerse, Batuer (3) postulated a resonance structure for vinyl
others. CR-Hg-CH=-R, for whidh rotation of the a~lky1 group
about the carbon-ozyygen bond would be hindered, r~esulting
in the isomeras

CH2- a08 and 082~ \O .

In addition to th infrared and Ram~~IIII~~~an spectra of rinlyl
there, a number of independent lines of evidence lend
support to the proposed resonance. For instance, th heratl
of hydrogenation (16i) of. ethyl rinyl ether to 26.,7 BQJ1.
per mole+, while that of the corresponding hydrocarbon,
butene*,2, to 30.3 knal. per mole~, indicating a resonance
energy of about 3.6 1*81. per mole. Ally1 alcohol, on th
other hand, shove a slight lexatartion of the heat of
hyd~rogenation, wit~h a value of 31.6 keal. per mole. It is
interesting that the heat of hydrogenation of divingr other

is on'ly 7. heal. lar~ dilating the same resonance energy as
in ethyl Vriay1 ether. Wheland (62) ha explained th is act
as due to the imrpossibiitiy of maintaining without strain

the plcaneti moaleoule which would e re quized i;~T re onance
with both tohi bonds. coeuzrred.

Shos~rrtaosii .(54) originally proposed the resonan
structure foir vinyl ethers in order to, explain their
unnenal chealeial reactivity. Met only do anaero~us reagents

add toI the double bond, knoinding alcohol, ocarboltli
aciars, halogens, and hydrogen halides, bu~t to addition
vinyl there are readily hydrollrzed lit a trace of acPIA to

present and they are easily polyearized with acid estalysts
(53, 55). In contrast, ally there are not readily
hydrolyzed, and more drastic conditions are reqpired for
thei polymperization.
Novever, noa direct proof of the extetence of rota-
tional, isomerism~ in vinyl there has been reported.
Hisuschima g)[gg, (43)i deonstraited the prssenes of rota-
tional isomers of chloraoaetone by observirng th effect of

temp~eratures changes on the intensities of infrared bands
which wesre dujte to the isompers. A1 rise in temperature la
areases the intensity of the band resulting fro the

higher-energ~y form and decreases that of th lower-energy
isomaer. In the present verk a similar proaethlre has been

applied to the carbon-carbon doubble bond stretehing bands

of a rinyl alkylr ether.
The infrared absorpt~ion spectra of ey~excomspounds
hav recently been the sUbJect of considerable study, and
characteristic bfandts for the ethylene oxide ring have been

reported. field .efughi (19P) definitely identified a band
atk 7.94, 8.07 alerons as characteristio of the eyspry

g~roup. Shreve and co-vorkrers (58) sals noted the presence
of the 8.0 micron band, but suggested that a pair of bands
near 11, and 12 microns was mrore usefJul in identifying the

ePoxyT structure. Patterson (47) atUdied a series of epoxy
comlpounds, including glyeidyl ~bat e~thettttt~~~~~~ttttr, whioh had eands
at 10.90 and 91195; microns, and glyortif~ phonel oe~r, wi~th
corresponding absorption at 10.94 and 11.841 microns. A
band at 1L3.2 microns waos also observed WhCich may be char-
saterietto of the epoxy group.

B. Eprmna

1. Discusrion_ of pI~roced~ure

a. Material

The vinyl, and glyidy1 fluoroethers were prepared by
the procedures described in the preceding chapters, and the
freshlyr distilled analytical samles were need in detrer

dining their infrared rspectra and other phyeleal pro~perties.
In addition, a sample of tinyl trifluorceth~yl ether was

geneu~ronly supplied by Air1 Reduction Ctompany, Inc They
reported it tob be the purest they have been able to makle,
having the constantly b~p. 42.70/753 ma., ago 1*3193.
Although it contained 0.014L phenyl d-amphtlhylai as a
stabilizerg this was too little to interf~ere with ther
infrared absorption at; concentration uesed
Th vinyl 'buty1 ether vae a product ofr Delta Chemnical
Works. it wasp tiractionated through-a 15-er*aolumn packLed
with Be~r1 saddles, and a portion boiling at; 93.30 wa
The vinyl 2-ethjUhezyLeather was obtained fro Carbide
and Carbon Chealoals Co. It was also distilled, sad a cen-
ter traction having th following~ properties vas useds

b~p. 1770/ata. pree.., n2) 1.4266r & 3 0.8055*
01701471r ethyl ether vae prepared by the acid-cata.
lysed addition of othyl alaoohol to epichlorohydriai, fol-
loved b~y dehydorohlorinration with aqueons sodium hydroxide.
Its constants were s b.p. 1280, rr2fi .4070, i45 o*9377r

compared with b.p. 124-601 n251.4o06, 445 0.94, reported by
Fairbournearrgt Pag (18).,

b.Determaination of spectra
The Iinfraredb spectra vere determined wit~h a Perkin-
Elae~i~r Model 21 double-beams infrared recording spectro~phom
tomneter equipped with sodium chloride optics. The region
3*75-5*75 microns was omitted from the figures because at


the absence of any significant absorption of,the ethers in
this ra~nge. The aspectra vere recorded at a speed of

approximately 0.3 micron per minutes. A alit achedule,of
927 was used, response of 1,I and gain of 6.
Moast of the vinyl ethers were too volatile to allowP
th determination of their infrared absorption as liquids
in a demount~able Csell. The spectrrum of liquid vinyl 2.

ethylhery1l ether is included, however, for comparison withn
its solution spectrum. Approxim~atelyr 0.2 gLa solutions of
the vinyl there in Erastmanu S~pectro Grade carbon totr~aa
crhloride were prepared and placed In a sell at 0.1 ppam.
thickness, with comapnenating cell of about the sene thieck-
ness containing carbon tetrachloride only.
The study of the effooat of temperature on the inten-

sity of the carbon-carlbon double bond stretehing bands vael
performed with a demountable cell which could be heated
with less danger of serione damage to0 the cell. Vilnyl, 2-
ethythelryl ether was need because of its relatively high
boiling point.~ The cell vae heated by wrapping with
heating tape. Attempts to obtain lovP-temperatur e pectra
vere useucceessful because of interfering absorption fromo
maiasture which immediately condeneed on th cold cell when
it was exposed to the air.P

The glylcidy1 ether% were lese volatile than the vibyl
there, and spectra of the 11quida are given. The solution


3 I




';, i






F s 1
C Ha=- CH 0 Cq Ct H
S4tUrTON (N CC ty

Fr c 2

Cz H,
SeaLu-rON In CCs..

8 8 to

i 1
"i-, ~



j I

i i

r i

i i

_ __ __ _


d ci



ri i








F s 3
CHa = CH OC H,C F,
So~usron \N C C<.4

t 7

B MCit~ IS ~


i 'i;11


Ilo 4.
CH.= CHOCH Ca f:,
Sokutlost 14 CCLs

8 7 8I 9 I

r 2

I -




F s 5
Sos~utron \nsCCs..

I s a s s a 1 r

F s a. 6
CecHotC H OCHiC~ FC r.

SIlC RO t3

1 I 5 """""'
t r

, a




'' i


i '1

i j

i Ir



I :

I if `

i i
I i


F r 6. 7

SokUTIONu \81 CCL4

-i~i ii H-





F s e 8
3 oLTO 1.. noCC L4




p 5 4 7 8 8 to


F s e. S
Sos.urson in CCi.4





- CD 'c




lls rI
Cto O.5

lll I
to 45






F a. 11
of C H,*CH OCHa. H CcHs

-C_-- ..









o o


I li I -l
8 9 14


I l 1

C t

i i




IFeac 13

Se aU rson t CC s.

7 -




(-- ~----c--~------~'















tO Ir

--U a. o


" to

rpect~ru of~ glyoiCyl trifluoroethyl ether is also included
for comparison with that ofr th liquid.

G. _Dianausion of Results

la....itazl therC

6-I streteh

The~ elefidea carbon-hydlrogen s~tretching rribrations
near 3.25 and 3.30 P~eatron (4) appear only as weak shoul-
ders in the srpectra of tphe vinyl there. Strong alkyl
oarbon-lhydrogen stretching absorption is present in the

spectra of1 the bputyl and 2t-ethy~haxy1 ethers at ~S~P. 3.40 -
and 3.150 atorons. The4 thoroethers have much weaker
absorption La this region, as at result of the relatively
smaaller nouber of rLalky hydrogen artomas present.

C==C! atretahI

in TPable VI are shown th wave lengths in saioron a o
the bands asseociated writ the oar~bon-carbon double bond

stretching vibration. F~or vinyl there, this vibration has
been reported by Davison and Bates (14) and Unirrann and
Chanoel (90) to appqear? in the Infared as the doublet
6C.12, 41.20 alarons, of which the latter band is always more
intense. Bakuev agggy (3) found that In the Raman spectra
et viny~l ethere having a secondary arlkyl group the 6.21I
band was nt as intense as the 6.0,og 6.10 pair, which they

reported present La all the Vinyl others. This they
attributed to ditterent relative anolunts of rotational
isometrs present,

0==0~ Stratahing..Wars. LenPths (Micons.)

CR2==0 RIOC4Rp*------6.05 shoulder, 4.610 aeairum, 6. 19 atr~ong
OR2= =H0CB2CRf(C2HS)C4B9--6.06 weakL, 6.09, weak, 6.20 strong;
082==0800820@-----------6.08 mediump 6.15 medina
CBI2==CHOCH2C2JP******----$.OE medium 613 aedbium
CH2==0EOCH20 PT-----;-----.6 raedina, 6.13 medina
CB2== OfrCF2CN1------------6.0)~ me7PldiumP
022==0(c308 10cr2W-----599 medium, 6.07 weakl 6.16 medina
OF CH200H==0HOCR20CR20F3------5*9 shoulder, 6.02 mediuum
CH2= 0CH20ZCIHI2(0j--------*----~6.06 yeakr

Perhaps the vinyl fluoroet~here present an analogous
srituation. The intensity of the lower vave length band~b
(6.06-6.08 micirons) relative to that oft the second band
(6.1c3-6.15 mricrons) or the C==0 oules is lowes in

CH2==0ROCB20f,~g inreasees In 082==080E1082f5 2 is still
greater in CH ==HOCR2C Py, s o that inP the last the bands
are nearly equal in intensity. Thse terio hindrance of~

the perfluore groups may stabilize the isomner correspondilng
to the 6.06*6.08 maicron band. These bands are at a sliht
lyr lower watve length than in nonhriiurnated vinyl ethera.
The spectmrru of vinyl buty1 ether) exhibits the typical
doublet at 6.210 6.19 microne. The shoullder at 6.05
maicron rsy anyorrsepond to the 6.05 3ine ofl the triplet
6.0)i, b.10, 6.21 reported byr Batuevo ggg(.a(3) feor the
Ramaln e~pectrum of this ether. Mea~kins (41) has reported a
shoulder in the Iirnfred spectrum of thNi ether at 6.06
microns, but it to not mentioned for any of the rinyl
there in the other infrared studies (14~, 30). The solu-
tion spectrum of vinyl 2l-ethqphazy1 ether exhibits a stal.
la shoulder at 6.06 micronsl which Becomes a distinct band
inJ the liquid s~pectrum, i addition to the 6.09, 6.20
doublet. Davison and Ba~tes (14) reported only two bands,
at 6.13 and 6.,23C abr~ons, for this compound.
'he Asdedil~uorother, CH2==ROCF2CEFC1, has a single
0==0 stretching band, at 6.o51 microns. Thus the strong
inductive erreot ofr two fluorine atom subsltituted in the

altyl group aggfigg to the oxygen ates prevents conjugation
of thejxgen electfrons with the double bond. The single
bond charaocer of the carbon-oxygen bond to restored, so
that rotation is sufidtiently tree to prevent the existence
of stable isom~ers. Th indbnative effoot of fluorine in the

Ibgga position, insulated from th oxygen atom~ b a


methylene groupr is not suffiient to ovrcame the r~eso-
nance, as evidenced by the doublet at 6.06-6.08, 6.13-6.15
microns in the spectra of the Tinyr 6*flluorcethers.

The ar-methylvinyl flooroether, ~CM2==(O iC~3 )0ICH2 3,
possesses three bands in thi regionF: 5*99. 6.07, an 6.16
microns. The internal. rfnJl~e t~her,

OFC~l~H200CH==0HH20CH2 3, exhibits a shoulder at 5*99
microns and a band at 6.02 microns.

The spectrum of ally trifluoroethylv ether is shown
for contrast; with that of vinyl trifluoroethyl other. The
ally ether has onl a sin1el weak band aet 6.06 micron.
In Taler VIII are shown the; results of th study of
the effect of topperature upon the intensities of th
three banda in the enfb~n-car~bon stretching absorption of
vinyl 2-ethy~lhexyll other as a liquid. It may be seen from
this table that the ratio of band I (6.06 microns) to band

III (6.210 microns) remains constant, within the exapert*h
mental. error of the easuererment. The ratio of band II

(6.09 microns) to band III (6.20D micronsl)i however, La-
oreasee noticeably with increasing temperature. Beads r
and SIII mst therefore be due to one+ isom-te th more
stable form, and band S2 isc then due to the hnigher-energyr
isomaer. rI these bands correspond to the triples, 6.o51

6.10, 6.20 microns, reported by Batake pag al, (3! for vinyl
alkyl ethers, then their explanation of the 6.091 6.10 pair

Table VfII

Effect at..7.emps.traintaon the C==C AbsorPthsn
of Vinsll 1-]Et~h~rbexrll Eher


Microns rbM 50
256 *0.143 *o.147
0.188 0.198
0.179 0.181

Rat( l





0.462 r

0.30) g

_tq Sand IIIE

o.482 1;

o*506 1
0.477 1
0.488 1


Ave rage


*0.10O1 *0.111

o*153 e.172
0.161z 0.173

0.341 .





so.11 *o.14 *02S7
0*131 0.149 0.260

Ave rage

*Th first values shw at eadrh tepr~sta sf ar hose of the
bands in Figat 11, page 7?. The others a~re aditional
measurements for which the spectra are not givenr.


resulting from spliettng of a 6.081 band and thus arising
from the same isomeria form is unlikely.

048 deformation

A series of lines from 6.7 to 7.,7 micron present in
the Raman spectra of vinyl ethere was attributed by Batuev

k4,irh (3) tao arbon-hydrogen def~ormation ViLbrations. A
band at about 7.60 microns which apears in all the srpectrar
of the vinl ethers of this study and la not present in
the substituted vinyl ethere or the ally ether appears to
be characteristic of the vinylozy group. It is one of the
bands reported by Hans and Simon ([22) to disappear in the

spectrum of the polymaerized vinyl ethr.
Davieson and Batse (14~) have reported 10.40 and 10.62

micron as average values for the out-of-~plane elethioi
earbon-hydrogen deformation bands in the infrared spectra
of vinyl there. Although vinyl 2-ethy~hexyl other is the

only ether for which the spectrum is here shown in the

region beyond 10 microns, it was found that all the vinyl
there studied exhbited the two bands in this region.

e-7 atretoh

Moleoules possessing several fluorine atome eXhibit

very intense absorption in th region 7.15 too microns
(I). Vinyl triflooroethyl and ally trpifluoroethyl ether
both have bands at 7.00E and 8.60~ microns which seem to be


reported by Tsohamlder an Leutner (61) for the =O-0I-


sharacteristie of the C;PS group. Sallar bands are also
present in the rspetra of 082 =0(0133)008201 and
CP CH20CH= =CRICE200B20P .3
Very strong bands in the spectra of the etherre,

082==08008HZ2 2 and CBI2==CHOCH20 P also probably dlue to
the carbon-fl~loorn stretch, occur in the 8-9 micron

0-0 stretch
In TableC ii are shown th wave lengthsr of a band
which is characteristic of the inCfrared absorp~tion ofC
viylC ethers and appears to be associated with the carbono-
oxygen s tretching vibrat ion. This band-ta la the region

0.0 Btratehing Unva


082===0800820 q
082==30a002 w

8.3,1 micronsr
81,32 aplorona
8.331 mairone
strong 0.7
strong EBF
*.3, *40 microns (t)

group. In the onee of the thoroethaer earbon-fluorine
absorption mpakes such an assignment more difficult. Hiov-
ever, vinylr trifluoroethyl ether does exhibit a band at
8.31. microns which is not present iJn the spectrum of the
corresponding ally ether.

Weak absorption near 3.27 and 3.3~3 microns, which is
present in the spectra of atll. the glycidyl there in this
studyt, can be attributed to the carbon-hydrogen stretching
vibrations of the epozy group (37). The altyl1 carbon-
hydrogen stretching vibrations are similaw to those of the
rinyl te~re. Moset of the absorption in the 6.70 7.50
micron region is probably due to earbon-hydrogen defousaw
tion vibrations.
in the specrtum~ of glyaody1, trifluoroethyl other,
bands at 7.70 and 8.60 microns which were attributed to the

OF3 group in the vinyl there arle again present. In the

region of 8-9 mi~crons the spectrum of qR pHCHf~20C2025

resembles that of th corresponding orinyJL ether; the same

simlarity Is present for q$b 980200R20 77 and Its cor*

re spending orinyl other.
From Table I it may be seen that the infrared absorp-
tionb of the glycidy1. ethers near 8.00 microns and near 11

and 18 microne is consistent wit~h thec previousr studies
which' reported these bands as characteristic of t~he epoxy


Bankwtr Charlacterletiae..9;r .. _Epgg_clsrap.

pf17Mli.L. Elther

oza s~
073 B2
Of C~s~E**
CS'?%" a~

7.97 to*95 11.70
*.9 *08 11.78
7*95p 11*10 11*74

daalhs bg 11.o 1.7

The strong band ati 9.00 micronsr in thse pectmrm of
glycidyl ethyl either is due to acarbon~-oxygen sretc~hin
Vibration. However, strong e~narbn floin absorption
probably maska this band lin th e spetra of the glyoidy1


Vinyl fluoro~ethers were prepared by a three-step
proceduret (1) synthesis of a P-hydroxlrethy. fluoro-
ether, (2) resplacem~ent of the hydroxyl group wi~tht chlorine
through use of phosphorus pentachloride, and (3) Ashyrom
chilor~ination of the **hbloroethylZ ether byI treatment with
alcoholic potassina hydroxide.
Two types ofr B-hydroxysthyl, fluoroethers were pre-a
pareds those having fluorine present La the slpha position
of ~the alkyl group, by the base-catalyzed addition oft
ethylene g~lyroo to 1,1 difluoro$1efins;~ and those with
fluorine substituted in the bggs position, by the addition,
In basie medium, of~ fluoroalcohole to ethylene oxide. The
new ethers prepared byT the firstr method were

CR20H1CH20CF2CHC1l2 sad CR20E~HZCH20CF2CHFCF. The new
4 thoroethers which werep synthesised we~re CB2M2080R20CR20q

0812080820CR 2027j C20HCH20CH2 3 7, not. CHI20CH20WC(CBJ)2 3.
Treatment of the a~bove there with phosphours pen~ta-
chlorite resulted in formation of the corresponding
PLohloroethyl there in yields of about 20-504.
By meane of the dehydrochlorinat iqn reaction,

CH2==CHOCH20q, CB ==CHOCH202 3, and CEg==0HOCH2 3 7 were
prepared in low fields. Only the larst-nmed vinyl ether
is a new com~pound; however the physical constants ofl only

CH2==CHOCH2 F3 are present in the literature; no method of

preparation of~ these vinyl 8-fluoroethers has been reported,
nor have their infrared spectra been avaiable
Attempts to prepare vinyl. others from th chloroethere
having fliuorine present Jin the algh position,

CH2C10H20CF2CHC12 and CH2C10H20CF20IHFr~3 were unsuo0eae-
ful. Houverer, a known vinyrl ether, CH2==X00OO2CHFC1, was
prepared bgy this procedure.
A method of preparing glryoidyr f~luoroethers in one
step by the reactlion of c and,*41hydroperfluoroaloohol
withk epiohlorohydrin and an eqpivtalent amount of base wasr
developed. Th reaction is analogous to the raddtion ofli
phenol to eplohlorohydif~n. The effectiveness of a basio
estalyst was attributed to the relative acidity of' the
fluoroaloohols e os copared with unrsubstituted Aalohols.
YildsL of) glyoidyl others were rather low when prepared by
this procedure because of their further reaction with
alohol to form dithers. Three new glyeidy1 others were

prepardt (1) 9 gCB~HCH2C~gP (2) F~oCRCH20tR2C2 u

(3) Cf5H 0HCH2CH20 Fp Diethers of (1) and (3) eren

isolated. Theb tertiary fluorololohol, CF C(CR )208, gave
none of the gljeity1 ether when stretd wjithb eplohloro
hydrin by the same procedure.
The infrared spectra of vinyl and glyoidyl ;floro*
ethers are presented, and assignmrents of bands character-

intic of the functional groups arJe discussed.
Two lines of confirmatory evidence are given for the
existence of VBinyl orthers in two isomerior formal

"C==Q and == s Rotation of the alty1v

group about the carbon-oxygen bond is hindered as a result
of th contribution of the resonance structure,
CH --CH==0-R. The oatbon-carbon doubler bond absorption,
always presenting at least two bands near~ 6.1~0, 6.20
micron in the spetra of unsubstituted linyl alky1 ethere,
is replaced by a single band at 6.o5 microns in the

aspectum of CH2==CHOOF20WC1.Z Thus the strong inductive
effect of thel rdsfa fluorine itatoms prevent s any conJugation
of the unshared pair of oxygen electrons with th double
bond. Fluorine substitution in the bggs position, as in

CH2==CHOCH20P does not prevent conJugation, for the usual
doublet occurs, shifted to slightly lower wav lengths, in
vnl others of this type. The lrelative intensities of the
double bond bands were found to be dependent upon tempera-
ture; thi can only ber explained by the exisltene of
rotational isomsers. The 6,30 micron band is attributed
to th lower energy form and the 4.10 micron ban to the
isomer of higher energy,

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