Title: Synthesis, polymerization, and properties of certain aliphatic tetraenes
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 Material Information
Title: Synthesis, polymerization, and properties of certain aliphatic tetraenes
Physical Description: vi, 59 l. : illus. ; 28 cm.
Language: English
Creator: Raymond, Maurice Alphonse, 1938-
Publication Date: 1962
Copyright Date: 1962
 Subjects
Subject: Polymers and polymerization   ( lcsh )
Aliphatic compounds   ( lcsh )
Chemistry thesis Ph. D
Dissertations, Academic -- Chemistry -- UF
Genre: bibliography   ( marcgt )
non-fiction   ( marcgt )
 Notes
Thesis: Thesis--University of Florida.
Bibliography: Bibliography: l. 55-58.
Additional Physical Form: Also available on World Wide Web
General Note: Manuscript copy.
General Note: Vita.
 Record Information
Bibliographic ID: UF00097973
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 - 000421845
oclc - 11020408
notis - ACG9843

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SYNTHESIS, POLYMERIZATION,

AND PROPERTIES OF CERTAIN

ALIPHATIC TETRAENES


By
MAURICE ALPHONSE RAYMOND










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











UNIVERSITY OF FLORIDA
December, 1962












ACKWLABDOeTI


The a*tkhr *xpreSis deep oppreelatio to Dr. George

B. Butler, i.e
wre of Ijeetlmable value.

TkLhks are due the members of the supervisory cor-

mittee and to fellow sttdeAts for their 4dvi*e and criticism.

The author expresses a great appreGistion to Mist

Beatty lliett for her dilligea s speed in the typing of

this dissertatin.

The fina nial support of this research by the Ameriea*

Chieical Society Petroleum Research Fuad iS else gratefully

askarwledged.












D5"IC.ATICO


to Imr puotnts











TABLE OF CONTENTS



page

ACKNOWLEDGMENTS .............................. ii

DEDICATION .......... .... *.......*........... iii

LIST OF TABLES .................. .............. vi

LIST OF FIGURES ...................... ......* vi

CHAPTER

I. INTRODUCTION ............................ .. 1

A. Historical ..................... 1

B. The Probability of Cyclopolymer-

ization ........................ 10

C. Statement of the Problem ....... 18

D. Interspatial Interactions in

the Ultraviolet ................ 19

II. A STUDY OF INTERSPATIAL DOUBLE BOND

INTERACTIONS ..... ..................*** 24

A. Selection and Synthelis of

Medel Compounds ................ 24

B. Results and Discussion ......... 27

C. Experimental ................... 38

















111. PMVWRI&4?li LriV &TWILS ...... 48r...L

A, Ro"Its 0" Di"W#480 ......... 48

Ie E 9600*9gooOksagse gO1.........

IVc NIT .."Awy... 0 ,,, 54
SWWYIaRAkAM .... ,..,r..........,... ".*fee 5

1914MAPKICAL SYATCX~ .& .....,.,......,,, 59










LAST CF TAMII


Tkle p




3. P~1ep seeatm ef MN46hir cCDiloefie VWith
Lttal Ai6yl Geotta tr CG4ly4)u .......... 16
14. iAbWPr ea of frdL4e Derieive ......... a
5. Pjpertab lem of Tfrtreslse ................. 50





UST GOF FiMBUU



Figure PrIe
1. Dlibikietia F itL ftr L6rUik eJ
levi Cibme CI. *e ...................... 11
2. UlISwtle*t A*Opelm SpeSI f 1,3,9,11.
Dedef3 ttest e aid W ,3LDepMkMlele- ......... 30
3. WUitraeleot Ab pbi* &Spwtrl ot 1,3,6,&-
I lASOAM*le MN 1,3r*Memsll ........,.... 31
4. Ulft ilet A*r~Vkl-tt Spee f o ,6-
DlwsUy)th r**Se, lWd 13-otOhylo0e meae 32










CNIKM I


A. PMibtovleal



The pelymism~..m of 1,96dia~n. k&s boon eatried

sw to yield Wables %6%*#tAt4 p~lyxf". WstXt do"e by

04jarCrow44pi. *a VA114 (1) on 411allyl. quarternary



b *a altoofttinj ib~vu41,eet a i1itme.lel mechanism,

V^%4h rwtultkd In a polymer eett&ining rboutting cycllc

WJels to Illuatrated boleiwi


R +


-4


A rigseom ttrwetv*@ etwdy of t* p.elynmt svfltvr d

thO prOPM9d a9eal1.

TIU 4W@1.polysvLStirtom, &A it 6kell bt r*fwred to,

I






va set supext6 in vlow v hypth.lss 4t) that asio

"a-wyabod djew yield frees-inbw A polynerob

Wallis@ (3) kad OWffVd that Gtos'bma'e7's (4) eqvA-
t*s Nt t e1 ptmt oh~ald difto frot thes betrved walsO

fe artala dk*i.6 boesA-9 of the fal.rq to allow for

oessalwal vlelliai In the polymerls4tin of diallyl

ikt"4&t*, &is"*& (5) observed that 43 pere**t of the
mewdor uMte wwe ayclised. Tkis w.i141 re*4lt in forma-

ties of 10- or llemmrod riago. Later wouk on disilyl

Phthal~ts 4 B sw ad (eato (6) ha4 d hv that tia. cycla

tation mry be as kigh to 81 pefeeat.

ltt*4gn (7) has fevuM tbht the polymer of 2-.stkyl-

lL~....heu~di...- was 5O porgat eyelltswd. Spfetroeeopi
exinaii'tetion of the pelymor comfifrod tke fbet that Ow

pClytr it formed by cyeliuatiee of e~. mmemr wait Into

a 2,14.4 iuetleysl~pe&Iae FLOGg JOlS at tke A. sRAd 5-

p.~tems to the rosidual mersma unlV*, uile k erge

the hesvmI vin~yl polyfirsetieft at the. vixyl group.










n


Tho 6trwatore me wtket osedirmad ky asoolyysie,

~14 yie214 boetls wetld &ad a polym'ric scid i.e

ainuti1lo tioa eqsivailat corra4peaded to two units of the











1~d "tAh by ZU09100 PS4 r"4&I't, aM Ai jtra eatlysis

l lbsW@SW W19, a WA-Is polywr wltit p.Ada t dobL*
bos.












1-1vo, by **linic laitla os a polymer was eitalimo

wkith 00%taLMM 1-01 double bwls per womiser unit and,
UP40 GeGAIatleII yi*)elde very little prdruct. This owdoz.es

My be explal by a eysli. polywrisati~e usvairsm:








Mo&l (9) he pepge~d a polyiner fro ll4-.dimetihylexio


In the c*Atn.

field (10) describe* bko ,.lymoertloat *of 2,j-dlpAnyl-

,11"evisLAe" La Shlk ba 104 b@4 able to 466612 Ovalle

pVlyat by All the **'o mIoe*l .d oIf a-Itletk : free

ridleml, anivale, qatloaIe, am L4ot caialybls.

Tbwas an dbbr exasrLoks *sppI in Tbblo 1.






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MA96001001YP UK P044wlsatloa of ollyl ftra~* 9
104 to 14 W maleour oiqkt polymer bwovwe of cegrido.

Sft* @bat tr*^Sfor (31). For ex..p~e,, the po.1mwlu*a.
Us*m &f Illyl alooko1 1.es toa polymer having a Egoe
of paiywo1satim (O)P) of %. 5; the polywetrStiea of

allyl &*state results Is 4 polymer with a DP of g,. 13;
s" illyl bea$+4s yilds a polymer with a DP of 9.

htvef, In the *at* Of OLallyl saimpo i, it Is possible

to get igh, molecular weigbt pelym~rs.
Butler was uable to oIbtain say polymer wrtk the

mo'mm-lyl quartarmay saanos, but ho ob&aeir m polymers

with DP's from 2550 for the diaIlyl quarternary &mines.

Valet osd Yrvel (24) polywerived dImq~th &,d'mdtdmsthylene

pinalate to a oyelle polymer having a 1.usrlar wiS&t. of

200,9000-300,000 Stllo (29) pelymerised 1,6-hapbedivas

to a cyclic polymer hUving a "),eluv weight of 10,000-

aOQQ, using Rolglor catalysts. Crowew an dvtlrt (11)

and ia:v (12) polyatisod arylic anhydride to mleoular

wsjht9 U higq a 95,a 0 00, Mve1 (17) pelymeuisod Zs5-

dim , y1~1,5-h~xrdI~6 to a cyclic polymet, bat could

eRbg get a low moelealar vqIgkt .1 in the polymet1iseti
of 9~4htyl-1.bpoxtond t"i momolef 6InAa.g

Theo* 6ximpl&e Illetrrate tIAt in the oyeiop'lyoor-

isaties of dIa1~ly1 mmot. C a higher Moloula? wdigkt

polymer is obt*and %ban for the moswellylic Am1.g.
MIemIUWova Imd I*LrIk (38) Fend S thlig Uw4petwd

for the *4ymr1Sitio* of dial yly 1mOtWYl1Si)eA. fbW







calculated the total activation energy for the radical

polymerization of this monomer and found it to be ca.

9 kcal. per mole double bond less than that for allyltri-

methylsilane; however, Gibbs (33) showed that this lowering

of the activation energy did not apply to all diallyl

polymerizations. He found that in the case of methacrylic

anhydride versus methacrylic acid, there was essentially

no difference in the total activation energies in the

polymerizations.



B. The Probability of Cyclopolymerization



During the polymerization of an unconjugated diene,

there is a certain probability that the monomer will

cyclize. We may calculate this probability and, along

with it, the percent cyclization that we may expect on a

statistical basis.

Treloar (34) has calculated the distribution function

for the length (r) of a paraffin chain having five links.

The probability that the chain will have a certain length,

r, is not expressed by a single equation, but rather by

a complex series of equations. These were solved graphi-

cally to give the distribution curve in Figure 1.

Consider a 1,6-diene undergoing polymerization: in

order to calculate the probability (P) of intermolecular

versus intramolecular reaction, we must be able to calcu-

late the probability (P,) that x and y (see below) will





11






















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&ppfgugh 4. V~* a dietwwo rm~r, within whiek.i, we Will
"&#me ~064b to tSke PISSO




R -- x





ws e maptb ealealave the probaility (P2) of x *ppe"b
I" vatIAi this dittemwe t%5W other dtbld teud I^ t&b
sy~taa sad qm P & P2
SiJ1l firet arsmol that the five-link eaLaR fIM
w to y My bo treated as a LatufAted paraffin Iahal, I.e.
that t4 djiff4r4*0. in bead 4SQ16 oad bevW length for
the aouble bead portion do not go.bly claaage ths dieu~tam
r. Soem4, we are, oly smeiraed wLt1 the probability
tkat r ll be *qm1 to or let$ thef, Dr. We will maim
Dr to H I-si than 1.3 bead lengths (22).
We MY mm too the flleriag *ppr*Kimtiea for the
Prability "tCie^:
IqmtieL 1. PW m.0,9 (r-o.33) t 0.01
4 DOag D' I bond legth, we W Integrate oquatism 1


P f1 P(P') 4?

0d .3 33 OL
*1 Q .O3 1: i3.6'6~
3 13 fdr a .01f.33 .3 49 @1 f.33 dt
@ .030 t 0-8ft









UI&* iem m O aste to of aq v Ihdt 0"10
1 La tM 60400 by *ISO oaltulati t66 4#bt*6jy of

4m1e b"o. ? IFr. tb mot."Mier W4obt to

%4 S. POW wbg 006 $A doaty Is .714. s. Per me.
Thosafte, the mb of mL ef**t per cabil Asaqts EN)

for per* mw w r 1$2
If M &U6 6., - j. j1 j!

The n r ot doebilk bon" per tobie AwStlrr vqvai 2N.
For "lutI* of i t:



TMe prerbality x epprtbaiaklg withina the elifta, r,





1Y % expug*6 tb efeatW tri~tief *, Ia tI*lo per liter:
Iqualloa 2. PV w %.05*WG3 sC.r

Lkttkft r 1.54 1 (1 bea length)

P, 1.SAlO*4 C
The ratio of *p n*.w*%js to Ime1melcular pre"IpStion
to ba eqrse to Utw b.~s
EqsetL1 a P a 3
pe. 1.klo C

by Sutlt vblmatet9 o lb i*A equation 3 for C, w
*t&4in LM rc*1t4 im Tib1O 2.







TAUTJ 2

MQMAILTY (s cwCizxicw Ix 1,"bM s


T.43 0325
1.00 ajo% 71

.10 2%.00 96

A 1 25 OIO ". (

.001 &W.so@e 1"00,0







J5 M Ow be1b~t~8 IhS stfOO ot Wet wlealation

Of IM 46010 bOW i A O Ift VtIVhtY 1$. 1w*. The

ftly *mhmw~b)e ortdo LtL r t"d **ewe Wkm te mwtyyirw
Stp 64ba.sd to b" t1be bead lips betV It an dI.
In awhibwewLly *bsiag a d*itam eof a" bon lewith

fa PLt, wG a". vottk tM 4ieta~co at IM" tropmustv
two" befteaR U &1v)er lt "lit. It I$ ewftn that

%boat togoq vill Iattpst ltlw'.1mI'r &76 intramlevlar
*W4Wr of a Eebla bl d to x it bhe rAWP wy.

Thi r9*%.1* In Tal d 2 meglbet t~he eyelfbatiam shshh

mW mar. ubol x t4&4* w*Lth the p*dAnt d##re bead of a

prevL..gly oaod4, immywllod meer wait. 51.e tke 6..

mawered rFiR I$ th~e Mt fmorabi* Su, the Povkability

of fwemi nQ it'W V? *&to *111 be nSid ashly 1..

In .al..Iatiag the pre.et sygliestieR for lawrg tIM

(10-12 mmobwo), mwvad (35) .bt&Al d 6 valw of 31 par-

**at .yelilebien. Me thki mde a m Pek calez.atiom to

d10Eutin* ~ thO p?&.oat Oelsaltea would be If the

pemobnllfty of 01' fmis of the larger rim @15.5 uesa

libcl o4% This reoultel In a value of 15 por*oAt cygli-

ke'tkon.

&ia* thd probability of time formatiR d" A*t
a&&"* a* gw"%ly frm am iospq rae Site to tX4 next

Iwo* time si~e 46 It do" in $*INS ftat a 6AMOWO4

rif to T 7. 9&.'mbefed time (too T664 3)j, it is
&A8AW that fIo the pPsHM ,n*I*, the *tWhct of

INKmiiai all th p4b;Ible eyelisa~ies Will set as










TAB3L 3 (3')

PQWISA ATJIC Q M1 OM c6-.DIGUYIMB WITM MTAL ALKYL
COCRD INATION CATALYST$


om)sk*st
poolb 1.
Ring Siam


Estimated
Cyelie taitu
In
soluble Polywor
CW


cramrW1 L)


-s


50-"e

54
20

18

25

27b
25b

38b

17


36b


refsteato 16

O*05M1 iir f*atratiui

GAN Ond~r ~&tttktiqM


(o.nar)


___ _r


___ _________ L __ __ ____







gp oot 04 Is W Nor4f we aw t0s qtM U

Offs Vi1 be 1. W 50 eGa *OW Ay Sy 0i IE, pope


IA th wI 4 0 dballyl tvwfte y bMt

a4&%09 lutist (1) roa v.4 pelyaritastia st a oeaaegro.

tim *nf 1&. 3 94409 PW liter sAd got alm t 1iGO Peroemi

eyetisation. batler OM) 6lo p*4ymvttod lalllyldiw&Uyl-1
411aft *d diallyrdl.kOWlSIlane Ia 1.2 to 1.6 mles per

liter emuaetrativ s" *" iamd slmwat 100 poroent


ewwol and Stills (27) pplyeriked l,6-.haptadion In

eenacctratoLne trng fram, 1.9 to 6.2 solot per liter and

btaid 90-96 pwt.oat syclitatieA. Stills (29) pelyneriaed

lisokopta"nip at a coafnttatl on of 3.1 "let per liter

WW get a po)yatr I1o was ealet4Iy eyclic.

Giblb (22) polyeairsod X,,Xd-i thyleuslwla.x In the

solid state (mop. talf) by Irrs4latlg $=*If$ wAtb a
e**brlt 60 SereW014 MW 411WrW tke p*LY4Wti*9t1@ to Pt*

ot4d at 50-85*. Th4 polymer ebtakmM nwa solublO, and

*hsd a residual va~bu'tisa of ls$-* thn 1 perc4at.

Gibbs prepmod thet "AS keMWAW had V+ergT$OW eycloP.)ymer-

ltatIt In tie solid state.

TftM* PAd etkher exvapid In Table 1 Illustrate that

IswR In bulk pnlywmvisatLos&, eo *to cyeliostio my

takv plaeo, owre thoquh *btItielly it skould be lses

"an 50 p~eet.







C. StCsteme$ .1 toe ft~1mble


L~a "dw to *m-plaia th4* toadowy to eyel~melywoiiaO,

it is pe94C d tdet th*Pe 1I so tort of Imte.atth beM

ta~m v wo ate doWO4 b9#Av j %Mck m stablise

a Vella O--w'm ima In thbe ged *tat0 the 00464w.

Thl8 say b pietue.4 as a hinmsJ~ ativg








Sudh an Intorctimn allot a ap~tod to maife~t

Lt"Af In tbovttevielet SpowUm. of Ibb mo.1, emd a

Stu3y of l,06diemas wa smadrtthoiR to aegeptain the Nirst-

*wm of *a* an inrtflbeti. 5k*6 hWiJVSt34 diseas

abseeb In a re1gio of tke ultzwlelet act oalily acoesisble

for *tvmy a 8491.6 of di-but#AL*Ayl SOmaPOONi Wes PUs*

pred frw albpavielat stey. These eopwowe wove dooigaod

to thet %Mey couad Imiteract 4aa 1a,6-.mterg and beinQ

d4LWvetlwsof ebwal m@.q, bhey mld aboorb In a as senat

rs In WLA abavlei/tt. Rlebhr tkaa saloulato lthe

Uumet&cti rfe wy of 4 m sferbearee (0 max.) feO

tA#$Q emmeesed* bw WbedCtwddid OT) rule,, modol c~eqmmvd*,
v&A&tdb 6wo Um moind mkaw w, were pjr vprd sa

$60640d.








)MIthie psc pW4 5 rlk i







Tka FeROW" two Mow bobw I& t&4jr












k'Wm. (31,31) srisd tho valueSof *Ad A ma.
for .iJmg*%.Od pIlyneas with mo tq few dogh1o be"S:
A a~etved E Aaax. (ma)

1 15,0o00 1
2 21,000 220

3 53,3o. 265

4 64..OW 299-311
It Is e64n Wt.t thre exuiaction Wfflo$Sat (E) lacros,,S
&ad t*h *OP4wiya ftILmm(~ shifts to lower W~WO&

)*afths as tke maert of double bosids (R) LWmV6460S. *m-
demNJ &te4 dom616 bo yt SyhOYs b"* bwn *1*&ol411y
treated as beawim. iadspenadatly of v*s ethtr, $a tAl% a
49aseijuaettd dleme skov~d ak~b st *beat 190 m (*&is@








~1~06r IWO %M& 64 IAMWI *49trtmelt a the dvlo

bea pedw 9 botll 6 M&ACt et 5 me), s*a the mui4W

eaimetina 4tt i~ia abouli b* d..)e tkat of tka =am-

ilfiate( sIJlg.

Very littl. erk ha bI do&@ to stui1y tki speetra

of rinmeJ agatod eefia vetq the double beds may Inteu.

ast with eh, ethir aere$ Spo. Thert has been same

uvk dam on interepatial liatractien of double bhSdt math

e&4rbeoqpL pe"*.

Wimst)ze (40) has rve..ty reported co*mtet l hving

wLthla them the rigid bea ttrwbwst Shin:




0



Am. A C.



The ultraviolet kpoetro of ttw.. t w V as cdqKtd

to tUt wf Ube *tur~ted ketaw showd tkh apperan*

of a mv pej thke Volvo of wieii Is ""m ftsr tit tkytt


So 1V A a C

7,01'. TUa 2" V zm3M
1 3110 272-0 3%O

OU&in1 Xkma. (Su) 214 224.$ 244
I t IS O 1455 253-







TO14A& abtri)buaed "it No P" t.f Ifti4 ePau &o


Iftim)mi (41) wesd 3, p%.aw &APPUedh
rt e)di tint the ** b e armwW ib 0 t (OOW 309 .7DT)
&A t 213*41i 4 (so 30344?I). Ths Iatter psar w at-.
t.tribet It tale djaeo q rptLoa *at qyoj ~b*4A e aebe
*# 6 26 am (1g 11.3987). TI&A # eabl r' rs ..b s a lo
6W e *N Slft of 34. 804 UIhebsurld be due t* a Un
LaisbA? isketastiOR b*b&A thd CiO tam t& darboayl


Go"Is"a (14) *ad *W~Ar a (43) how* recently reportedEEE~~~~EEE~~~EEE
ftemlowe ebdorptlio fat the veempom below:



D. LO

This easpiosa ablerbod at 232 ms wille Woodward'3 rulO
wMId ptectet 4140 om. ehi 8 a. hyposchroie shift has
b~.& attributed to traadasaimir iatweretiea with the
Abrogve ekem.
b3tiett (144) rePwtv a betk hroe Shift of 13.5 ~
god A toaw4old tacrso iiin intensity ift g"S@ frea to I.





I cF.,
0

There have b-rin Sm cosee %&ae ainamle rwpotrs kove
boom reputed fort isuble baW ayot*M







Itwy (4C) bek proper" OMrrrrHI~L~ r~
"Potto Gd valb ff Ass,. AS 2)14 M. Aev~4eein VO

000~0.d11 M tb# .1O1416 = xin~m w tiS sal d

Shomid sew 0t $beat 195 m. Iit to pemible "at this

bob m ia skirt is caused b Int.PaetiOn across $pas
*r tbk. deolO biod,
Wlast*ta (4') reports that bioyelmkop4a4losa *)LwS

a *smiSK ultpo tspoetr witik oberpbtias at 205 i
(KasZ40.9 114 M (Lotjte), WOe (Efm0) WW a sMVld@t

at 230 me (kgO). WiPAtei was able to aelctulte the
tbkorstical aboorption *p..trum for th4s, ea ad In
go 84oommat With the observed %p*etim by sm a a

ground state wker there w" rn- int*Pation betbom the
demble bons *ad an excited state ubere there vas a 0*all

ixteras~tio (0.12 bea arder).

Tbs* it **em thist Ia these rigid *yetsm, %AeU -
eoabo,*g*d doulb bends do iatelftt in a mwwwr wrish

cran be obosvvod I the ultrtvsl.1. Spretra. It Is

esival* that tk* Ops "ha CIa ceapem 4 e~st~alsiag
reaseeonuetod dool* bhoed Syste son intarstt ia a
*tailor GF.

AV9.. 0 7"CA1) bal a O P. oC 224.5 (lei 594-23)
iflk 10 1.5 as Immot tiem Wowmrd's tnt. iry.Id prodiet.
Ales thil .m o a k o5 teuu= (8) to orge ayqloe

pelymIrea4l n esirva stayed.
vew (4,0) kao POOpss*4 @is- &ad,3,S-
am tr14M TWOS at* Jammer Afobs it W14.5 ma (l0s D4431)







avA Uw tres k&o, at ART a (Leg e 3k). IM ?*elted

*O Iv,3aew"O 0 6 A AamA. oE UKam (of 1* .-1).

tUS* *ltOw- tbo** "A O .*4tbly be S 1.4 &"h*VQt1*Q
$a 014 tr943 it *.*4 ast Ma~fefit.t liv ll 494bly 1A

$b. e a. -NMI, pbb tuiews bows a peabo eitlae-

t1*a *wetflelont tim 4". dioe..

the qqvldeae4 fto Iatrsiptial double, bea interrttions

La adrwwnbigowsu. TMe ulttavLo1et sp)eer of wyetrof

*4tr* to Laterattim A& "cr 6~I tiamo Me wrypoe.-

chBrmtc sIhifttv 0"0 t i no t k Ct'ttrmic, &ada ame tin*$

tberv it no shit, bmt a gkhge* La the estimation so-

offiLtse~t sad tks a as* peak **cuts, The se

tgIaf..ir t thhin.g to tbht the spettra are vrually

differer from that of eolwwu* ee.bdi vbre no later-

"t Lo may so~w.


_ ____









cMA MA W


A MUM! V AUIRSOM1I (A3



A. Sei*4A14S arnd Gya-tkMAS of AWO1 C 9



PW Qw pewroo Sf tUi* lO it Was aft"rny to
bate 4O10OMS witkr AdVJveat~d dO~biO bmd 100"O
O*k tkat they &s*ld intseft latetspatralay wit* eon

.a.4"Aat mtima of fiwmoo rim@ seatueitka.

Sl1vas jugWmW"&1 limitatimS ,eov...d the wSo of Siq

isms uo M b at too Short a *S'veleeUi ix tke

ultrur~lolt, It was d*lded to vee defitwtivol of but"
dievam as tk 494 *u. DorirvaCtvs of kntad(.o

jw *aabab at eweley*%ka Imlov tkba 217 amp *ible

plrme inw a "tgimi *sLlly ameltibl with sw in*

etra sd4


.IS1ty *a).q. *n*Ou 1,3..4.n44eercr~ na 31 ,3dl-


%Moo he oo mlpw )r v-' tr~a tA* 80"tra of

41401 st~emol Theew e 0.0
Ad~sme; &a 3%mmWW14wwm46AS- TS WO bwS 0 469i~
of dLbVW41eqZ kpft S 4t Wie of smAlvieg






1AI$a &t 1a Iws M66 Of PfpOMldn Cn She
siev1&Ax, sbteabim "a usewo to ubs *'it's 00) too
aet4tsa atleh $&of S4 ~ft a P464 Pfft to WWu mNA

-Oh. 7 T d" t Uaqt4w 1* botof it a Dt *a
aw %b rel I grm 04bow




A. RCH 0*346 CM CHrSC Li ) 1 P+ + LI1 + C X
1338 13 4 10


3. WCXOJP 3+ R10M -) CO C + 3 PO

at-o thqq $a itJ4 &Sj ?PG I'vectig soqqe if UOslly
whimi at 70* fa s6 period oft 0voral k b lly
*ttft#4 to poopmer thi 4stItM MOae tWA4 StkRi1.


*ad actolisi yloAd no 41tLIlubAo p~dust. vw r.wyin
.trw"U .SIM t6"I (51), It "44 Ifuw that *.tel..tory
yields of totabose osAd be obtaLsed by ad4La@ tka
brP.loin to th yirde (R1lOC0 )at ALA 5.0.
14al WSi toohaqes, yldv for tUw dooessttryaw
a" the xa 14wG~i (Irii tvi,bIre.&.tl.I

10"O LMA brawm4) ~0 7 P"000 I* disthY) ebet An
Il kIt I*a 91glyn. T%6 1w yield* ot clefa gmu
aitf~bv~od to iy lsl of the aoreloln w1i6 tor
UoR of a plymer with poIeet oab..m *?wW. Tbwo
"rhb1 "t bow h"J"&6qd, ape MH 0916 tha
What In Werldiing Md p46 1yn mo ?0rUS Plth thi
y1166.








"m1A Qo m6trueas 1M*Patvg by

WO m~bW OO quilke pae,, ?So Form abserb*d 3.06

M406 *j4t"gA uka hydr~g~emd Ov" a platiin wtlde

96SOAV44 -

ls3-QW mats% e. VON W*Ves by rwmis a Wiltig

peotbm mm&* $ly&l trIvk*ftijw4vbmA.. boiu dsd G r .

slam"*e. I,3mAeWd1ftw vUst "464o *ad oriLftfd sa I

prepm's&ry "C d41wm.

The I.prati .1' 3, e.Iust41eaebe4 lpart7 of

*.rmp1d out by thk fallwtraq tPtLUa 6equemes



i. + 0















3.


Tbe g 1-dL..chd. is te ri-

Swit of a DIlSlbAMO typope retat n b&We*a iOOWae and

0.51W dIe~ids. TWS P~#tImn 16 vrSeble,, e obMt

t tho *A. URyawl I&*" Is brmrasl' by the *M

=W e$ 6" W40 -6 W xm5be fWWlys









so" %r Iva "a f i


Smlho LS& Mae ""4" so" mabd 406pw Smoot




A &&Vo "*boa of %Me 461g l Iwo "* $
ke so$ o *"a two be 0 oS e&4 of

~~~I ~114 OlL-

#"A Jim %ft simvjot"0"" a t "N"N




118 14 64 tloi 4. I t i 4 tIe inam*#A
IO lae inV V I,)lan. 8 2 1,93
desommams sit = on y d as m m4 7 N.6





lbs_ .i~. .~vr -~ 4~L~s ~r 14
4 14*








UI -L ?' 1fl wUI V MP~V t IMS
psalm= ha Mi fp m & ow
a 000 5 i to me 4 awft ---"
60ormmif s 16 et o 444&aI"r0 rwW%6










TMLJ 4
MOWMIT OFI 09ASIA "V NAT 1Y15


7r~ Iir~~--~-7~~



3-D"80I Of' 225. 4.47

1 ,3t~tS*A~n 237.14.51
261.0 3.91

272.1 3'76
266.5 4.44
3,&~1m.$bl19a~stE11*xas.,7 8 4.55

3q24.7 2.05;


a. all maeove"Ats A"*C is 'erbau







*aww $MAW "*se~~c~ct Im 6 0EM6600'sm of oftLo
Ifv so/ 6.aa0 owl. be *0 Gow~~.~ @1 WO~e to.

U_ YI~s ~bs IaN ~S~1l k
knsm"t @e &mm~mu b& ow wofw m


sm"$so t *bad I I) Ia u, e Iwewt estly mp
Vated P6940 bl" 006 &WA may tIne4LI Is a dipes.







TWO hjs.Mrve hGOstlw b4tif th de"1e be&
~.400 PrwL4. 1ww~4~ Ila the q10etevsau esergy level

Of 6*A inoI9e i& %he #VO WM akj hW6Vev,, I&*A iarkie
6"10%m ta the .0t#wes gt&%A r It 1#0f dIP~6240 (or"

b440 M & 41PO1e Ia &RInused i*2 ), oibal i

st.'mW Labe~e'wsflm. The nt result i* s 1grimS *C
tW omri op the 1r .IY* tvaaebtism.
The kkift IS thO UwttV&,t wti *berpt.IR MSMm




04 matiess$t eWll hav th 4esb4* bmdQ fleas *~
(53) to trm..et In tAs k"19004 6Uas. New1wot tk
t*961eO *f Um 0*lvissfmtea shn th4alra&?1istm Ake

tmt LI tlw sycllie 6r"tenltw ion o ewe)y *"Uset-
esily eern4ie.)G thds *Wind inot umee. for tho
kiI~k 84gtes of .yeii*&&hM 4dvl*4 PepMwIpinkm; tOtS.
two,~ we Nol U@Wy~ jutiflo4 La mWL t~o" St4pse




wREMI


4.5 k


- S


I \
/
/ \
i/
/
/'
I




II




(a)
(b) -


220


Fiure 2.


240 260 280
Wavelength (millimicrons)
Ultraviolet Absorptior Spectra of
1,3,9,11-Dodecatetraene (a)
and 1,3-Dodecadiene (b)


4.0 o


Log E


3.5


3.0


2.5 h


200


55











4.5



/ /K \

4.0


Log E


3.5





(a) _____
3.0 -
(b) -------------




2.5
I





200 220 240 260 2b0
Wavelength (millimicrons)
Figure 3. Ultraviolet Absorption Spectra of
1,3,6,8-Nonatetraene (a) and
1,3-Nonadiene (b)




wO


4.0

Log E


3.0





2.5


S0


220 240 260 280
Wavelength (millimicrons)
Figure 4. Ultraviolet Absorption Spectra of
3,6-Dimethyleneoctadiene-1,7 (a)
and 3-Methyleneoctene (b)







t"4 buw 45 w 16qMotI I.n 9 -s *to" d **$I
*4 4. 4* Me wn *t.*Ofs.

T"9) 1..3A&w.OWw The@W 3)t PrOOMAO w -










es"l~)~I wx OW WO F4" U on of664& *ftsnoods OMM
Waf 6ei to a s or I M -m aw too
00 TTr T* "nta*If No bd*a I W60 ",b 5. 5e4. pww
M%6% AS n tin 6o wst tb v d eOom bt tme se y pdo-


&swki betowa the 46V4bond *"tawts







The ~ ~ ~ ~~It4 Mwem&$~ tktVenqsq~ bve~ 06464110
bg'EtpI~lp'le(or d~p.e.I~wnd dip'ail) Inkmeha'w.







Tf seIt *ffeet herb II a gfOM4t 1~1*Q of tb e i tfr
6M 1-7 -/70 ttamAtien Wai In a Oft f of tho ded~tea
6f&4". Thu~ mp- be *zpl.&s 1W evuederinG tke dlv@@t4fa
of the d4poe withineeko 6M bbe traosgs Th* mov1
pe44jpjAtIjv of on a1ky1.4ub9S1%s4* d*ft beui 10 il-
1r~ Cet-ab


4yc d;3







Ig ja"gs we 8 b- b#- b IS IW"
P.IWfSW Ms Md6 M&NW 4i4W*0 t64 IAm"PMlp tL Mw-
&OUM ft MI 4166460Ok~ly *.sahsd "400. N*Mfrg 1A
tse V09 40 UbS we~iDA No 004 bony aw -

w ~ub4 &Owl O p"Ve *#Iged As We, sIt weid
104" t,0nI an the besiv 61t We k %D be t ~&w
WbS L& Ww AdW4Fege 4Sl 64 1w loom WOOSY IAR1A
640* Gt" S"I44 tvgk 44w41em. Th6 igfsebe e~sit
dasudo a fapaa44s eees 1OYS)*0 b rie t4t but&&
La 649 s Vtk the 4S*VI M4I1 4a asb u Ik "-1.


ftft*Uess ha. s wwW1qm gr'p 's'fift th eUm
b*UWIuq' gre. ***Iwo of thASO b*e Il OeWid
be very *10"PULOL to xympeet'j~atia. It may bo GOP-
PEOd ft" thUo V"14 Imt~elves I*d~e~&ttpfetr
la SWO Uf. A glaMM at 0m Ompseblo r-WquMWA
gkvO on 6"&OS of ke WkS 6etive metkyms" jVr*s m



ofset 1!hs E4e Oa I6 I..Rb) i


(tot Irea) Im (4 30,4) I ~ wefle 9*&) lot.

ft*tMM t.iw.1. s** 'pa malaw 4-.3

(0w, Ift br aIII 177 = Oat 264M), ) a


Me 46MMMS 0eA *e SAO fU tArs EAe4
W~ Wo Mo bh 666"4w MbW at 1*I.3 N~g







W" WOt1e0 iNAANWSF ft94to ua t87.1 mm is gsu

O tU14 PSAA-0, ami UIS apnm. 4C of a hLk Ia Sity
b a t ITO WI 13 WOPV~d*m

'hm Othst et i*8 i y b S*060. The otr
(55) of aulyl b4meft it *1"t 4SAL&a1 %* that t

3-4mstowlboom, wt Ibms ae, ekbfts in tmH peethi of
m~M aind MIF 41.40 INSe 1In U4e lMA&AIty of the

abSptiun at shwtor weiveefttf thUa the maxium.
The 00.ttu .t d1IaVILeltALa9 (55) vkoa eomwee

to that O 1,02 dipiayletJhai exhibits the $a fle..
twin, i.e. n* oi'ws *j peittief o ltemaity of Nel-
Skcorptieam, M tkot ig ahi*1U6 in Inteauhtity of

ab4arp4iM on th' eh t umve1.agL $SAO of tbe meLMiH.
OR the b"64of "o, abovI e throo ex"WIdt, It my be
pef*ibi* to *eevrb. the sheakdo on UU swt r VMlath
SiBd of the maixf for mItstruefe to pattrccipaiu .1

UM mAt yteae gr@rL 1R2 thS .0eit4d State.

3,,4)Wm,@thyieiiectm4ihe&-r1,7 (Flgure 4) dos not fill
akeely In 11*4 with the matetraeaa .W tk Ae deae.-
tPO&. It xhibltA a"rpitlem st 22l.8 mm srm rd to

3mhwr1zwwwtiaS at EW.? ma. Th(p reprseat a hype.-
*W phift of 2.9 mat, at an imraMS & if the emaepy few
0*"Vaiai te'oditI of 1.3 keel. POP 401..

LWWL% S- tI+ l of 3Wit 0*V01L tof ft#,
it 16 0o*0 that t"w t" 664~66d 670tow are *eapew of







e~- 4 er Mw- La S-WI 9~1) q~


it Iq@ pambbsbe w %assomm two *se. .1 m~iqe to

sB*414"4 be 4 0"t "Opt bw 14aor"Uab itaomtl
at 4" eafteb"04 the~4 set tie. it the

mmium VSbO U&M soft wo Ottwt. S 1tohW 9If emu"$,
W6 b midl *.so"% fw S" krb bek our%.




At I" me (t% 1* The .WVe W MIefla

abs" 6in ebmwPtI ut 9 aIT (10 am 18a
= (osdw Isu, I@ t13.5). MOMMAGM Is 6sel *=Rgo
Ma OAL tMo teIlo boot* oft fit Laofte I df&IUt gae







?1d iMQ IIe &a I* A&t*t Uw Oevl4 I6"t tl.


so bGO &"me awe SO&A fibs "O ue ft4f M
be 8 am to &v 4&m r# dv of S" sp eow









it tko4 Se O Ie w ft
vp~av66 t*9t~at ibi4*14 hwa meter *3,adopt~go 4o.

SMOSAnt tvk4't %"% of 168 ewVweedL~ 41Mi s All o
W* 69tragol ob *'06*iti~m GofsiIskeats 06age4WOY

gwgeHr tbma tO 4Oigo, ots be% a" 4 Sb gUs$t. Do"

6Sh440f at Ga .0t4a 1tt1cSon. 41 Poto t
~t~abr thsa d.d *6k4.. The *3tistoae aeffied.Leat of

awn notv w Is 11.7 PO*.et gratv tIan tkab s1 of*~

44000. ?]mLRy, Lane- 1,, 7 h&4, an

Oxltbloatl ft obeflWO&I 71 pc~tant greaterr the&a tlht of


L1M*4*trren ObdWS t~ ve boortrtrt 1p eetrion
O"ISiS "0" She 1*"t Ilorei In extipwt*S1 Otffieinnt.
1b4 1Vvtjs *f thd 0mrptlen bissd Is an Iad4q*tl1n of thk

nos of p.041blq oltceeaLe tvantwtme soa tko extla..6

tiOR astffie16at Is Im4.t.ion of t4 o OrbobIltty of
traftitle.. A& tka, mofo of peabbkle Stva*tIa* In.m

m**4 the prsbiqllItW fur y Ivan toanstloa do

owre4S. Name,, nematwt~rean awitk L1 kebed b" ked a

1~ e 4*u&"ti eefTi.6et tkaf t ar dt~*eae 4# 3,6

41 *9yt Oaeead ie6- 1,7 with tI ir mh4tW Ys ah plsia


The psIn.6im data Do e urtri'vl.1*(t SPOOM of bbe
dbim$ wW tokyato Is beko to bo an IndLeatio t bt IR

thAtblr c tkA theS st thS*GV W ldsine IPAL*'&kt *e l &bq01
other. Ga tkA b"Ja at tkit fvjdsO)sj, it egg" )4bqjy







U04t im as inU(B'sats"M 10( df3, the dobi &Mu
oeS vp~d is a smw~f OIt-j*1t fw a~epew4ym4s

t1 by a )w OF ""t4. ilo& al64t betwo1 UK dmbld
bad**
Th4 fb us pYewlioeha "464 imw*s evetto* of on

jMti&ttAC peie~s *a a 1..sCaia Vkk 16 G1r%4.Y iR tX$





R
+t




Thio WMI dP961A the ltt~t tem**y a6t 144AIdO" to




C. Exp.PL insl






Chaaemeaftl Lm* A J.% p.sMef I*Iutwit e( m 't


Ike IBIstillHSI PrVunmin 14W~tfloo div~iM~a of fAesjma

sIsis Gqve EI wu b thS3.4e bW. *a d&"
awsk ela tm* weto. Ike 6eeibliR m ~iseameh


rq d "*" s"', ftf4ehd W" W4& from

GM06"I fre Lavwq4wt4 A+4#ioh Ghsm*ml











AL Uma..M A0 -.ww A- a A- ~
sew" s~ rr~~JUpw `

~-s r 4ri"Ws Un ow &





IeftrJ~ *t Wr)Y ~ i t IA~~l a `b1~ -
&#"&*made owe mbe b&4. wt~bbis S Cemioo 0) h1y
ow m om*46I&dooow0644s"




SIti w iel'oU Wi AS66 A.) *A-bC a Qbimbge 1




1 fS#n4 $44 dOin a*emat~ gaop wa-so witk


0490~ a,.~ b-I of b*. *410?t so#* Wa*U)*



* "44aa V.U) ~6~ MW4~ on 00 me P fe peo I
5 L ~)1 ~ U PI'bL 4b4i


Ir~~r sshi~ &POP.pb


L"W%WASIIP so wPas 'frmu ff1.



inomp amortfm *"On are FrY LW b i










TIm r.4m *&sxty-tbo g. (1.0 '"it) S? trlpkIeALW

kr#4 &a 1f U. (0.5 1) of homemthy'leza dL-
brmade "we Mixed t..IhOv Lna ib b -..ck*4 f lsek

fitted 4U a elrrep~ai a peflt eudeaet.- TNO

tlak wvv fluSghd v tb *Wvila u aa beats iS a9 Oil

bltk to ifo* .m then 61L.,M to See1 Clowly to ro
tomeataft. Wks^ the ta"Orstsfe raeseC d 1140, the

Iiqmwd'q%441Ayy Solidfied.
Tke solid mse rorystallisdr tor meth~al amd

th*v vaeked sevopal times witk beaseae to v .we am

uareactod trtiphomy yi Qpherms. The gilt er thou

dried at 60 S, 4* -0 0o 16 bases* Yield of *alt

me 313 w. (SM), mUp. 300-300 (deemP.)

AlM. Caled. for C442 4Pr 2t C, 65.7; H, 5.14;
o, 8.10; art a-0.8

Famad: C2 Hs9 M 5.271 Psr 7.91;Dr, 22.8


geveSp.4IX AIU elghIbxthAn S. (0.1 molo) S hNexa-

~I4 lomembi i (%k.~)Y~brl~Q I o broLd) &W 700 cc.

of dry dilottq oUp wore, Stivrod Imo a blurry in *

tbhvweehaaed flath .twmq d with a *tirtos, rsflaic ieg.

da*t, tlaerstet, WMa ru*bbot "Ptm. The fla*J

Me thembd ViSA altresm. C- huaalrd forty so. of a
15 p4or*t I-4*Lm of nobe~1 lIthIl in helans (0,22

m1* ot mty1 litA4nm) me. ad&" thtewv th rubber







"im1r by as&" G S 6 aes. tyri*Qo. Tke erd.Ml t v%4
4o &t rea %e2#6#t*4u*"ta roe*tLmas Ike ia-6utj

llbhVO witk tke soft 40400d the eter to wetIa 1,fttly.
?b~v m se tirved t' tbtov bea* at room taloeatoro,

1vt"ln Qie)k ti m issit* floppy bhasai" as gro*-red
$oIutim, r1c1'i jIll h ud e1N..b $114 p""at. Thig w4x

twe va coosle to10 l&a $a let bth, sad 49 *a, (0.6
owl) of Swreleks im lee4 446 of 419"1~ Other V- 6#4dd

Ia 20 mlnetG4. M 6b &A olein was idded, the aol*toin
wo quickly doine.)ue4. Tee g. (Et. 0.3 sole) & 1 u

chloride In 2O so. of inter we$ qvickly added. A solid

mas0 s a formned In the roectlem mixture. Ths wthet loyay

M* reawed and vrWbmd moo witla waor. Then It wet
dried ever mwgawsi6 Sulfate. Th-# other woo rntamod
br dkgttll1Atg W900 a 25 00 Stainles Ste*l PIeeed
solow. The resdi was diStIlled (with hydroquimneu

added) tkreow a 50 em $iplang band esima yieldin@

1-2 9. (T-99) (Yield izi dlslyx 12%)P b.p. 71-73* per
2o 0o
It -m 2 D I 43D4 .-2. When the eempnd was
hjdtogeeted vrJr a platinum emid* catalyst, It abeerbod

3MS nols of hydr.I'a per mole of prodiet.
The ewompeod thb4 the follmiing abaowptiom in

the im tared: 3100 (a), NOQ (a), (7 I ), 1'W (0),


15o (w), t9" (6), 962 (a), 9%0 (m'/, "5 Ma sa 787 ().

UltrIoisiet data are OIvea in TOge A tad Table 4.







"1.6 sul. rev C leis' Co U.8; No 11.1

F90": C a 44-446 No 1103

A *bireed slury Ot 3T38 go (0.1 mos) of allyl.
triee"W~ubmaiu bromidt In I liter of (ethyl etaot

ws4 treoted with 62 ec. (01o moe) owbvtyl litkive LA
UeLwm. Tis wsi stirred 2.5 kours wador a nit,..a at-
m.opkete. The mixture was eoeMd Ift an ioo batk and 14.2
g. (0.4 asic) of noayl aldakydo in 100 cc. ethyl *tker

w*3 dsrld In 30 nisutes. A yellow esler persisted who
all the aldoydo kltd be** added. Amiu. ekluldO
(5.5 g.) Ia 150 ec. of water wee added am the mixture
*titrod alll It warne to room teperatwe. The otlar
lat woo *orperted, we-shId *it* water, driod ever
mar bSfiu a seite, tI ad distilled tkyovepk a 25 eo stain.
less otooi patked el ru. The etoidas was distillMd
thtewg& a 50 an lapinlmg bead coli. Two frsetiea4

wTo. btIatasd 9, b*11iF at 40 6/3 un (2 9.) "kieb
proved to be maesetod a ldehyde; the etMr boiling at
50/1 am (2.5 g.), wkich met thk dieni.
51'wu the tr~stion' *m~alaiss the 416"&1@ alebd
so" aldeb'yd i I. to It me Purified *a a siliegoe pro-

paratwiry o** k b4 UC. Tht y~l~d of put* eeinomWl w~e

2.5 g. (0.0l3 IUI 1%), bp~ 56/1 i -;r 1L9t
20 20
j It .7761 lit. (70) bp. 101!/13 =I 20 1.4612, D% 0.7803.

iiiUMal1t &ata are saksm ift Te14 4 and 71lare 2.







G*I ed. tocN 1 01: C,o .V I, 1133
r1 1'




Ob"M m *d I".10 f. (0.- solo) of 1v)A.LA~bvwm ,0e
ailed Lir a tbkr...a-e ftmA f n* i"r with # tljtrvW
rt411 .esdadser, TWOv ex hastoo **dew MAW Is La s
Slt bka to We *M 411SM& to4001 SI OY t4 PO Wit 1
pet" 6. Tko SoId ow4 at 16. 148*. TU 660i1 .*
WUA W t* hwsaq AM tbe4 dtiod tad di*4*lvt d In ULt
Wer*Prw It %u roproiipitibmd by p*r.lnQ Ile4 SeO
*q1 ve4 cC ofetos.. The oalt *I filtered off aed

4fted 14%q a )0 m Yield #f the **wa
vd~t M @- (40), a-p- 329%,331 ; lit (58) a.- 333-33.'.
to". C610e. fot C 39N 36Pr2 C, 44.4; u, 5.011


vceto2 C, 614.2; I, 5*; P, 8.58; Or, 12.11


Ov.roy.w.- .o0 *I*.tot." g. (1l melt) of tel.
~y*a~i'(tL~e~p~s~.~mbovide) 9" stieed
I& 99Q cq. of dry *MOt eAdr umd'tf 6 &MA~t of nitre-

&**. TbA$ uss al La Isbq ham &VpreP mi ter the
Orm~bI o Sks, dweees*"ive. To W41O *bmry )3* so.
(0.2 06l1) 0f 15 poree 5.t,1 lhteIm (a hMY I
odg.4 at ft* tomporture Tk wa bllPP for two
h~*e, dartls wbekh tke tIe esion of thw o~bqr e.M4
bOmin bright red. This, wse #90494 to 1' (a 6" Ise







both *")J5 as. o f raqia (0.5 saeL) La 100 as. of
GQ~i ebbel WS 44do IR 10 WAA*4teS A so ti1 et o .2
MIS MW d @ id4 in 590 me. of Wtr4 10 qakly ru
Ia. The*tha latt wyas s4 opmsted a dvigi. The othvr
IW O We bF dlvll~atlea tiwuk a 25 ON stalnfteve $tesl
pesa tu ?k pm&4*a w" distillg tred t rug a 50
9*pt1maIg bead ewlol glqvIi a y41*1 o 0.7 so (60), bIp.
5z/I -, a 1.54179 D 0 .7. Quwsltatbw hyrdr....
'420116 '4*
tLam sr a platim saLds obslyst ekhmft Ut th ls ee.'

pw" afteiad 4.01 mwles of ky4r*gQt po p m14 of esop..ms.
Tbe oei*9au be$ the foliwLag "4orptlem In the

lafrswd: 31Q (a), 30Ws 0 (O), 30Q (a), 1940 (a), 10&0
W# 1640 Wx 15" Wo (C) 1430 (S)v IM We~) 1260 (w),p
9%4 (G), .. 9T ), fl93 (m), 8 (Ca), 940 (t), 828 (w), and
780 (W).
Ultravoilet data are givsa la Fglour 3 and Table 4.
kk C4l1d. for C Aa: C, 90.0; n, 10.0

POW co 69,75; go 10.4


Thi go 4 & d1" to t"e pp" Odw o Kra@ SW

b Iau (51). IMfwu 'qra nb,9'mesia.miAs. T1


soat4 product ma rearyIAS111Ad %wise from 95 1"O~at
O5&A and dtl* *4 WW #? W Ykied WS*: .35%,x ..p

fgT6 ee (14t. 7s faf.







*466 shn.Se 414lim I& 4 b IM4168 lot* % %no "4
to 4a 1*9 tbseS 1OW 1 tI'9 a*tee i* doip (@to
oefta ba h. b tb. te a" pooed #at to m I. M- e

fibilk ifa Pogt~d ts I];&* fta, WC&op'$"s -11 w#11.q4o In


Irkls mtOrTI I is b.o $wousd trap IMe" I0 be quite
put-4 *ad lb... e va as "o of belfew diw~da fpm it.
MW Ilafr"bOe U44t1YIS of, this materi-al *Wietmrd thke

14.rwtus..
Obese t"e taeriel doaemplS quite retdily,, It IM
Sed irltowst fwt&'er flevtbe. The yield of Input

Pledwt yi" 8S pyt (fee the Wfolysl$ step).
Ths g m O lSM follow s *beoplea In th

ar evWd: 309W (W), AWO (W), ia W ((a), 1.ro C.). i30
(6), 144) (an), 111 (W)o 13 0 (an), s13 ("), 0t10 (6),
112 (w), 103 (0), W (a), 910 (o, 890 eW), 790 (W)o
750 (W), avid 7"4 (a)


Tikas *ad fi?"tce&M @- (0-15 imels) of we"0fiw
(ftVsbiy peOSM VWV UMCr), WAe 20 M. Of MIkyl *b
"Fe 464Al to a tbodo""Mod 1l~ 'b~i q.1 with StIrv.6r
rofla 00*me~f, and ee*Uwt pvtobtO ImditfoR fW061.

The f1&k t t)U1se w'1UA 24SP"eg. A-bowe 30 ec. OC A
voiut m of 39#7 gs (10*1 2040) .t b r4byt t 4I
it 34W *a. alsy1 64bMt wa sd"4 *Nd tka mixlure hatted
to toflaN are 15 alwat4*4 Thea "a ret of SAO $sLe4IS

Va g dded ~ 0.t *.% b Potted as r too twowtis.







The **A.r Vofluv*d *satiy 4vrieg It iv. it wo $*~Lf'd
&a *l tjein half h Thuru were a ue lquid l4uea.

The fIl 962 ld (am Us, S 7 v- (01,5 ms) Of000103w
Ivo g && #e. of tet vs* i slly. This

was atlyrad 30 m*a9ee, s6 *ad a Umtlaer 1&yW aes
epartf*bd, o vwal with eater, OW dried ow" moke4iu


The qUwf layer wa divtIlled thrtgo a 25 ea s $%*.i

los e, e i ~ 'eI d veoum jeeheod cesimm. 7M. rvsidva
was diS11lLed tbusq) a 50 amspimala bmW eeshm y#9i..

in@ 8.8 66 (5'0/), g22 /; m 1.19&E-7#
Imtrared data h d tka following aborptLems

311Q W# 2*9 OR (rv 171K (a), 1630 (a), 15"0 (s), 14U~
Wo 144k40 W.,r 1429 W2) 1390 Wa. 1390 Wo) 13230 (Wcrp
sad 12" (W).
Ultrowle~lt data are fod In Flgu@s 4. mad Table 4.

-N Ctied. fo C 10 b: C, 81.51 H, 10.5
Pved: C, 89.-T, 89.27; N, I.0j3, 10.58


Yeour sadi vi-tenU gA (0.19 wle) of agmeSimo, a
m1 voyetba of tedina, Md 20 &e. of otayl *obet r*
played in a t&*eomea~d fuR equipped with *tierer, r..

flu* emdemr ro wo a ce a ebwut. mre additum fm me1.
The fC 1Sewm fle ril with mAtPtogo. Tom ee. of a Wsin-
ti, W ?74 9. (@.Pit M016) 6c in-utyl IWM44. it 180 .s.

&Ib~l $%Jer vs a~dde am tka rotation 5tet~d 6"Ly.

tUG tst "S Oddd ~e a Poid of 30 a'obe9 at F







%awwVatwe. Then 14.8 v. (Q. I ms) of b W1
be'dim in 30 oe. .tr eWW1 otlor m4 "4e4 skewl
WMLI4 thd flask S" 4"104 Is 104 wsl,. T,'m.atke
Maio *f emaI aftept I* 1%P *a. of OV~i m A In
vlwy fltle the. flg t v 1Mll .1 ej-o1. The othc layer
vas -ab wli* wabr &M 4vi4 ewer zws~atimi ,vulfte.
Tho Ot36er we 4t464t~d ot" thtsvh & 0 *a StSlaS

-*Joe lsksd oelums *0 tho Vatldu 0 *4 itll1" tbeorgh
*rwnsla boad ..1m yied&rq 4.6 g. (37%), b.p. 60Q/38 m
Tke 1nfria*d SPs.#Fm Sksw teI f.1IFwIma abeeep-


f (s), 1470 (a), 13@0 ( x), 1810 (w), 1110 (w),

1030 (W), 990 (0)9493 (),o T40 (W), Wnd 730 (W).
UI*PWf*Iat "tb are rtrad in FIisui 4 and Table 4.
6J&.L Cald. for C9116: C, 87.0; H, 13.0
Fgwad: C, 87.16; M, 13.17














PMCVWIZA? (lX SUDIEES


A. R-souls mi DibeShuio


T%4 pI*Wblllby of g110%tI1 4 eyel lymef1:atiea an

aI ecetSs.Aiab1% whiit thS series of *lof1.T is less tlam

*&I& tbo diallyl type of iommmr.. It Is a6eo6sry to get

swelote 1, 4 Pelymrtsuteriestie all the butedieaa

type IWtrM, aWW the residual 4double beads Mlt not riev

set. Tsqused ke"H am*, I Ziegolr type eatalyst Gy*&e.

wS asus Ohiih has boom rspwtod (59, 60, 61) to give

a1..ot 00*1'ete 1,4 PQ0Yetla#sti.in T7166 aysto imolvus

tke use of Utmtaivle tatvS.elowide 6o trbt*Wmtyl a1 iawm.

Sire4 tore are sW variables in tlp Ziegler type

polyme1ittIem xystom, several diffor2at variart.e re~@

tried b-oIoe soluble polymer w" fe &". 'he order of

OddiItOR of tkO .eMpo*eatu (*MMvr, tilbwtyl 8,191imm

MW tLt"Sem tot~e rltds) vas t em to be qaite eritt-

cal. The ey w ibAwt p.,wr w6 obtaLMA' in tMe

polymmlr"atm of dede obeseiw go by o4)mg r

first, tb.. t*iL up1 .I `blm, aaM flually, titaabum

t#4Ia0 tde, Tka Obmdr Of t etrIm ft tM order of


4S


CAAMRR III







ThO PS`Y*k $"t& VWO PUr 04 #m O at
%U0 PIA14 of k19NO 6 t1UtSet. TA4 Eto 44M Gar**
&wised In TabbIo S.

Tha PONFOOV44 of l,3o9fL&.6edin~e~ur~m tin-
saltd In 17.$3 pe900 yIY6S at O PbYm. (N thisy, 47

pettmt Vqpolu The iifiirod d sp.#tri of %Ae, pelyaw

(rw so ptet&tsm bemids Fol)wt) sbnd a week bead at

1639 41, 'toiek 1i *s nIOmb to Po5idual Inteowzl d.*Ie
baM (64). A b&M of *oilv inteotty at 9*e. i0A1.

onlto that the remnw4l~ dsAle boe have a 'Lra co-w
ti6mti*... Week oasptloia at 9" sorl pil *97 mal

0s 4ttpL~bwtei to P"adM btvtadkofyl or viwyl srerop

P.ory aati4i~ eif me$,8.O~~t xA a't
sea fUvl. W t&* $w oPeatioa em1it1l a& for
tka raoaattr ia 12.5 p"Oea# yeld of a p.Yw was

obtatae; hot, ts 1 thea 10 @pe@Umt e4his WOO
s.luhlb@. ft pretwfu1aS the eati13't, is*. ad4ing the

tolLo Yl a um. twe Gai tttG&1vM totpeklevi1 f~fa

an d ll wif th*e m4Ktae to age few 30 )nLvt6., sad tben
a4dlI.g the a o, the yrlild .( polymer vMS ralood to

17-5 peroont, of *isla 10.w50 p4renet vW slIa. The
laftGid 6postrum of the polymer (po64iu1u brmlie
Pellet) "and a bead o **dlI Intesity at ski Qie o t"

uoLgqneh1 to reSldual daqfl. ben. A Sttefg baW at
965 r*'l Iadicates that there ow tpaz* doshle bmS* I
the polymer &ad &*other bau (wed iuomk) at 72% on"
l the prOstmee of ekS doable b S. Vek bsherptol n









TATI $M

POLYMRIZAUTION C TETRAMIR


111* il $veRt MuineTr tn1*S If
ge. Tite7 (m
g. moles Tettar lralT
rr~l~~Tltt~rhd fta


1,3, ,ll-Do.teettrt a ta


1,3,6,8emat*etraeae


3,6.Di) thyl eneec ta-
Ell**1.,7


10 0.8
10 0.8
10 0.8
10 0,6

10 0.79
10 0.79


5x10'3

6.xlo'3
6.7x103
6.7xl0-3

5.9x10"3
5.9x 10-3


xlo-4

6.7x1te

6.7x1Q-

-0
$.9x10
5.9K1004


* all polyoo.tatins earritd *at at 300 in heptana
* l.--me err, alsminv trilsebutyl, titanium tettachletide
2--trils utyls alueli ttheamlr m ttrashloride, Ml64 wd
by 30 minutes g4Ing, tiken eawmor
















M*4ijet of
Tr 1,* I
At&a~ss


*tot Ot
AMu tt I o


Ih'.~'is.
(-)


S1 I1Ir6


s io-- ib
Iae*Aeble


11. 4ml* 1r4


7.aler

lroe4


0.67

0.14

0.01




o *
0.30

0.19


O.U7

0.11

0.08

0.11


0.44

0O28
O4Io4

0 EZS


__ _I_ _______________ I_ I__ __I__ ______ 1 ______ __1 ___
- -- --I I -- I


L


- - - -. - - - - dP O m -0 -


__ _-1.







at w' do' W6 S 6bb tuaw or% *me WIWI o "ag
d~sq' VW left. Th@ *e S*S 5 I$ easpet1 *l tbM











Yb ,4Iymr h Y~ atieft of 3P,". 1N&Uy1we kd6*&e 1 ,7
wt @#rtid out wader co"Itt" Idwelterl t4 00*0 used
L
for 4l~ALdbsPat... The polymrerwa eiv t&Lw In 50 ot-
sent y&Old, of whieh 44-74 ,oteont w" solub. Attms
to #t M M Infiepod poetrya of %et PO I)' were Mb.








Smog I CPb 1f1.ak1ii jf ~Lkauya~m




1EW~1 CWV. ftptsra *64 ebtaAMMi fre S*ok %ad pariftod
by' VW~ha 04th $Si*alfw6 &4910, P*"&&IM Pcin Mt$ 00116.

Ue~ a 4IH164)ag fpI. litktow a*1dm4 vb The
Pse~flb1 kh%& SW et4Ore OVt 0diin.


A Ow1l (10 tow) vial equippedV 0~~ rubbev swu
to t UM" 0 "t~Lq 06"18 -e fixed To& Plaiad I* a









V"Mm 4#440"W Mlll OV"Wiwddid- P*@W~t#*d *Alftoa


*ODe6 tin.
Selutiont of ttL440bvt~)l 41atim ,Sd U&~ tetra..

ethlalde lia beptsf we" mro up sad plmoe in mall

floks, eqwippod vitk 4"ookeh arra.@ed to that tke flaks

"aid be flushed with Mtfg, amuile solution was boia4

dlrtwn i*Mw S 5yriad.
?be vial we$ rgmw0 t1s the oeleitera &ads~ *wine

S nltrogwt flembed vgrLCq*, 5 oe. of keptame vm mdod

tht"b the *4M 4a6p. M was it.11 4w by I ec.

(Sc10""3 m.4**) a2 LJ,~,lads'daterae To this was

added 0.6 s.. ( 6*1 a*leo) of the keptome *l)ut~i .1o

tvri'sebpyl aamL. This its followed by 1 o4.

(5*104 molos) of the **lutie f tiuiL tetrachloride.
TUe Wyrtago ia.41 wes fommod from t" vubbi' sav, &ad
the polymorilatiee "S *Ilsee4 to presso with osioUlowa1

SttriaQ for 21 howr$. At "se and Bf %khit time the vial

666 opened arW the esfeoed latf 30 So. of mothopael.

The pvelpitatod polyrmr we, osked wLbA sltkhn*l sa

dried at 0.5 m for X4 howe. The yield its 0.15 s. It

woO pMied ift a Soiik~t *ktratttr sad 4*1MtP~e cefiia-

uoq~ly Wlth Mt bea**e tfr 6 h~**S A Solubl pVelymot
of 0.07 g. w4 Obteaimd.










US ass"que W*" for tke Po~rwrisat Ln *I t
008PMfs Oft *M~elnl to tkst dIwibd fey 1,3,93,ll-
dastu t9f f The data tre 60~isbd In Table 5.










UARWN IV


WdMMART


IDtAW duirvs4iy" of hebadtern. Mre bnn pspved.d

wki~ok are fwactiomlly eapable at 1,P Interaetion beumept

WW doubie beads. TMe ultrwielert tptra of thos @sb,

pQ s oe: d*%srWA" .4 aMow-r*d to t"h tptrs of

vir~s~v=Windg disuse. This msw '- o eyatkoLsts, p#rbwr

ti, an d,.ettal date tre dsetbe'd In detail.

The tattataS &il GUO4 d4vriati in yeftisea of

Xnfiin absorptle a eps rSeepd to axilIeg dleaes.

Thbq~o dietiateg are explained iR terms rf an intecepatial

intetevitr betmon tUs zv .a njuateq ddb1oe boft System

beftk in the jrei s&tit. &md in t he e)ectteoineaily

stlvatad State* Th e atweetivi hI the gremr State is

token to be at 142.t a Pe.tlal expla*8lea9 of Whe Sao*

of Oyelepelymerlitil of 1-6 didnes.

The tetratass wofe poyirttisd to yield partially

soluble polymers. Infrmred study of the sltuble free-

tI A didatod thst at least tor des.Qtetrzone and *a,.

*tratP&4, the peolysrtb oo"46tod of "0 Welie Strutwre

pr q6.d








BI LI L RiMY


G. a. Butler A. Cgm9ww 6ad W. L. Miller, J. Ag.
@A taW O2., 3615 (1956).
2. X. Stasld er ran W. NXMtw, il., 1159 (1934).
3. c. wallins, l A& AS g. ~ts., U., 41 (1945).
4. wo m. SH. OscWe r, I. S9h"y j10 (1944).
5. W. ,rlma, T. Hoi u d R. J. Z elt, jl. E~T l1 .,
4 45 (1953).
6 L nKa a i J. COS,, t. Ar*. tJ* Aja, I, 1006
(1954).
7. A. rsAtaRa, M. o. Aty.n, ir.y. t IM*I
a;, 431 (1969).
6. R M. nma, 4. ASUUa LU L-., 1s 535 (1954).
9. L. E. IBl and H. J. Ma/ted, P r ^I L u mifw


10. J. D Field, 1 0Eas L1, 3, (906 (1960).
11. A. CrA. m ,r ald .. a. UaTI, J. AUs. .i ).&* .
5464 (198).C
12. J. F. Jews, J. J- atB Sgi.,w % 15 (1958).
13. J. F. Jea, 3L. UAUL! Sk-9U, l, 513 (S1954).
14* tUmaL. Wrl,- 44- 46, 281 (19 1).
15. G. B. ttler *iW M. D. 2asRto, J. GLA QMg., L2k
309 (196C).
14, Bstl r RiA K. D. BtFlia, J. JA. g ,
2 T12 (%96).
IT. 4. ft" V%, 41 92aS IL Ulm


is. F, Js, F. {Iut l U#*D 7 (1958).









8 a C.' 3 a ow Lad 11A W. tWm J. *.
R. ?. i. *U Ji3 s V.* i. .** 9jalL.,


21. C. S. tr*Ol sA RA. S. Vee. fed, J. RA. am*., I,
1641 (1 %Q).
*t. W. I. GtbIO, 4 rt e* 1)59, $143 (1961).
13. r* llted, M l f io., Pj fb (19M9).
47. C. 5. Irftvl I R. D. Vftt, L. 6. m W., sI,
SYTI (1957).
8$. r. Butler *el K. D. BWrizn, p. toSc. C .m,; a,

Wo (0%b).

t7. C s(. Mrvl ad J. D, Sltll, j. g. I .,& 8 .

26. C I. it -, *t a., Y, iinakIa J 6 t I I-18.
I$40 (191).
s1. r. C. Lmase, '4 ., 1, 8 F1g 7 ( Aiti).


4t9 (1961).
30. Q. a. D"4*p, ~! SL, J. 4 1w. i., & 9 U 46 (1959).
310. R. c. Ltibl, grJPI.A. it, 807 (1958).
32. O. ML*61tate anS A. Xvirik, lM.X atU^, U, 641
(196a).
33. W. I. Ghibs sad J. T. M*ray, J. PZlUM bL., 4
1211 (192).
34. L. R. G. Trel.ar, rL. k&I. | v., J 345 (1943).
35. R. N. Mawrd, 3i. arjm IA., 535 (1954).
36. C. rvel asM W. I. Gatrisea, J .~. a.,
3 4737 (1959)).
37. RA.W. We>r,,, d l, U L.., 7- 7676 (194I).
38. E. A. ed, ,, , gi, I ,9. 379.






39. I. A. *M MI A Iad A L

44. W4l4taa, b. t9 a )., seso (191).
41. 4. miCft-, A U.L. ZGL., L, 4t01 (1955).
43. v. er~tei1, (, J. "gl., I (l) .
43. A. karotk, ra. v ifazmuLm v 954).
4. P. C. am14t, i. M. ~ I ., Zir 3L73 (196).
45. P. R. aSry, a P amI j.., Il, 5as (1969).
46. S. IAL n, L. tM ~ ik., $,, 45Li (l 96).
47. E. b Per or *an L. A. Goldblatt, A. .w iL.e
710 li1 1195G).
48. R T. OT 'Camr aMn L. A. Gldblatti, AgH . QI.,
1a7t? (1954).
.49 T. T IoW.o, W.* *. ODitist_, Uliverlty of Floride,
Agaeti, 1961.
50. 6. VIMUt a MVd U. SeLlkepf, Si. MU., 2v., 319


J.. QM. %a to be pabII*Ad.
5Sl. R. C. Krl &ad T. F. Yos,i ; I. QW. U 1082 (1956).
53. 6% C stf T-Mslk ft sa mk D. vv
Htettlan ,II H; lc!, ?m l, J., 175. 8 P. G .
54. i me" t e, vl. II, Inter-
", Idia-I.!,4Mw -bk.
55. R amtm&usa", "L bl. QUMI .U 6a9 (1932).
%6. L. c. Jm, Jr. *&W L. ,. TV t, aoL-. I@, oLL
tf8 (1955).
57. 2*i sr, it H., Ag., 80-11 (O1 2).
58o. wIUig, *.J ^sL, Lo-*27 (1958).
59. c. C. mk1, l- 1A L L.,0 1 1694 (194*).
- C, -,. no"" It it., tfaMs Pik
L A& MJ& rw>^y a&, r957, to GMWW$r .&




.
64. QJ e g i 9

4'A:"t .qML .k~










BIOGRAPHICAL SKETCH


Maurice Alphonse Raymond was born on January 8,

1938, at New Bedford, Massachusetts. In June, 1954,
he was graduated from Sacred Heart Academy in Central

Falls, Rhode Island. In June, 1958, he received the de-

gree of BaGhelor of Science, cum laude, from Providence

College.' While pursuing his work toward the degree of

Doctor of Philosophy, he has held two summer psoitions

doing research for Koppers, Co., in 1959, and COin

Mathieson Chemical Company in 1961.

He is a member of the American Chemical Society,

Delta Epsilon Sigma, and Alpha Chi Sigma.










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