I . » s avmmm m scvraunm or m nsam tam m
or csaeuui omopitomoAisntca^

XX. IBS SDRHXSXS AMP ATTEHPtBD BUBHAL RSARaAHOEtBHT
o r ClGI^SOPXLCAfiBIJrB. fSSKD. SffiBR

Al l #** Injijftpdo

d M ilid to tft# Softool fo r Adransad Graduaio Studios
o f Mtohigan S tsto tfi& v a rs ity o f A g ricu ltu re and

|ygfc|iiH

tfto

SOiSIlOO is INMPtisl fu lfillm en t Of

mw&m oots fo r tfto degree of
dogtoe <w m iLm am t
Department of Cheraistry

1S$9

ProQuest Number: 10008635

A ll rights reserved
INFORMATION TO ALL USERS
The quality of this reproduction is dependent upon the quality o f the copy subm itted.
In the unlikely event that the author did not send a com plete m anuscript
and there are m issing pages, these w ill be noted. Also, if m aterial had to be removed,
a note w ill indicate the deletion.

uest
ProQuest 10008635
Published by ProQuest LLC (2016). C opyright o f the D issertation is held by the Author.
A ll rights reserved.
This w ork is protected against unauthorized copying under Title 17, United States Code
M icroform Edition © ProQuest LLC.
ProQuest LLC.
789 East Eisenhower Parkway
P.O. Box 1346
Ann Arbor, Ml 48106 - 1346

AGKKQW LMBOTf

a u th o r irltfh # #
th ffnf t t axidt

sepgMMMi m * #S3KiW #
%© P rft-ffaauoiir1jiflfp ? ! ^ H a ift

*W W3Mi y<i*liiWO■JWawpWKw IPmKI Wwwwl^W iM w IQIwUp*
m% tfc * m m m o t t k * m M m in v e s tig a tio n .
p»f| |£ frliK * <^ ^ ||||^ | ^0 th © Ilp jfl^ H
Gtmpuapnr tih o iH F S llM llih iS PTOeX^BM t> ]t& vid0d 0€ZV03Dal

o f 1958.

mnnnnn»tmim»»«

f ftIM

O f e<® M ns

P«#>
™

* * « * * * * * . - * » a * * * . * . a.

BP'P*^PW 7P iB^K'PBP '(P©IBP BrBP Bl BlW ^P"BP^PB» BPBP-® ^P'B*w W BpBP'Pp. B*Wfw|9‘ BP'* BPB** BpBP'BBBP^r* 'W

1Plt
B

P
M
II
$
&
1
IMIffi A
J
J
P
MM$($MW <
W
tMM$(M®&GM£Jk1!M
W fljftM
rt O
T
O
O
P
B
O
F
B
X
3
A
H
0
IS
C
M
£Q$?0&C&AL«a* . . . . * . . * * * * * * * . , * *

$

K
E
P
^
IO
T
T
iL
#
*
.<
•*«
..*...****•*"
«
»
***<
..«
•»
»
.»
«
»
„
«
.,,«
..#
*.>
***.**** 1
3

. . ......... . . . . .......................
V
W
■iLujyi

13

*■*
'•
■
»
■
#
*
*
♦
*
*
#
*
«
*
*
*
»
*
*
*
#
*
*
•»
*
#
*
*
<
»
*
#
*
*
*
#
<
*
#
- 1
3

Q
g
f
f
f
jjb
o
i^
^
JMMbttUM/WMMnt

fcI.
J jA-dMMHtot
w 'BMdlwPt »' * AIt * * *"•:#■* * # « # * * * * • ■ * * * * # 41« *« a# aa T.Ml
wpp JBww^wio 1?
»**««»»* * * «»« xu
IBrtitiW
^SlCf
S rii■*■f^rth^S"!^i^H
W it/lifffc * i#P-# <►
*♦

^

V

p it 1
OJtedP^ffldS” f lflffH*

s£

* * * • a v * • a #• a # a a

3F

3* W0B® 3uP3^0iSHSI?Ch*
**•-*«*****■
,rt' * ♦ • • » » * • • »

2U
21

*,*# * # t.1v a't ♦•#♦»#«*»«■***■■*****■•• ®* * *:t *•***»■»•*# «• Sfj?

A
t
f
t
^
s
r
o
p
iy
p
l'
w
f
'
*
«
«
#
#
*
*
«
*
••»
«
»3
3
.
M
ttl^
*»
*^
^
l^
o
*e
A
d
i^
l tr
lilja
o
r
o
iw
a
ta
ta
................
3
3

MmtiaMmm* tttw ra of t^ lo p ro ^ a a rtjtn o l ..............

B
.S
o
lT
tly
a
US
ta
d
ia
*

..................................

S o & r tu ti.....................

1
7
37

P
*
*
*
r
if
r
^
n
«
t
t
g
*
yf
f
ln
f
lr
iA
a
K ln atle Pim m Am m . . . * . * .

•**»
•.»
*♦
*.«
***a
*»
»
.»
»
»
•«
. 3
7
...........
37

t£wb«k«3 t * 4tfc4 *> | i i m j © i -jy n H f
^pP
WSHp1
®® wB(w*jrW3MP‘* •♦ ** * * * r#f1’* •■*■#* w-*

A
M
D
B
X
S
G
t
B
S
S
O
K
.

3U

................

t i

JJO

ii3

d
fO
O
M
f
T
S
Q
U
B
* (Mifll
F
a
g
#
A
*ttm At*ifli S
tr
u
o
tu
r
*P
r
o
o
fo
f2
~
£
4
e
t
f
a
y
Ic
y
c
lo
b
u
t
y
l
^yf^<T^ ; 3 f e y 11.t * * * * * * * * * * * # * * g.* * * # ' * * * # g * « « * « * , ^ N l ) i 4 *
• Aw® i»O iyO igpKl» rTQCTOUra# «« * * • * • « * » • * # # * * « • » # * * « # » * * # < » » » • * • » •
■d * ' S w
#$» ¥’*r»*ty *■*?*;■
## #-» | | f

f
^
i
i
v
t
f
h
r
f
r
^
T
|f^
f
f
d
i
^lt^
f
l
^
h
f
t
^
i.'ii'*m
um
,. ,,,-r
<
,, r
i,wtu,a^ tt u* ,, fyf
cm m im m o
fs
o
iv
o
i^
i#R a t * * . . . . , U 9
#■#* *
*■«* #■** * * *««•»■•»•■• 33t
p3wWBwjFyHP(w!wTR^^
*wmb>#T
Tf&yCp- 0# # # ♦ * #■•■* * * a-# # ON*
4P* KBBw 4P*lwr|pwlMkl«f * * *■*#-# • *#*#*•* #* *■## #* »•• * * w* *•• ** * * ## # *« * •■* * * * * * *3**
5*
* * « * * * * * » *s * * . * **;* * » • * * »« • » « # * * * # • « « * * # * * • # * • • » « 66
H |LWjMM '| M
■ tywm
XX

W
S
llttMi A
K
B
A
IW
B
S
)1
M
H
A
I*

’^.

^P^P^PW

^P^P ^P^P

^P

^P^P

^P,^1^P^P™^P'™^P^P^P^P ™^P^P^P

A* Syrt&m U

tfc
fr...*#
...........

7
3

A t S ^|^S iM lS 6iE lS 'tM? *^w i
-i&&wp typ
P M M B A t *#»!♦'* #*•%•♦#:¥♦** • * * * #•#* «•## * ♦ • * • * # *•#* p* *-* #•«#
M irfih i^ §1 flmitiikittrua tW a M ititll Offil sUtoKL *# ^ ^ 1 Q fthlKr* » • • « • • •

ft
T il

s
lb
W
w
** »<$*

7h

H^
ji

^ ' '' tt tt ' ^ SWW♦•"

iO
B
B
L
IS
a
s
sB

i

a

O

W

...................

0

0 0 && _0000 0 0 0 0000000000000

S

I

O

I

.

.

7
9
Si

x je m iiiM « is » * ...» * « ’* **^ M « ^
it f f a g g . .

g

#
!
»
■
*
*«
,
*
**
.
«
***#
.
.
*
**
»
.*
*#
♦
#
#
*,•..#
#
;..«
*•#
.*.. 73

M
F
3
H
I!®
fA
& **.*it
f

f f lP l f f .

“ ^p* ^P^P

............................ ©

...........

86

v ll

ojp <miw,w9

t.m f

T W Jt

'

F aga

^M5|ppWppWij|jP^^y|jj^p<^Pw^^P(^^p5iPwpn|#^P^wpw-PipP '# wP»P’wiPf•: w.p.'Pw .P1P•*#♦-# P1'P-ll P'JPIfcPP*<B-P"'B'.#]pPT..pr#
™

’w^WPpw

^p$ip pfj^pp Pppi^pfP^OAiPWW»

^ A ^ '“*'

,iu

” «PWp^FwRfflpypiw

|^1!pHilflipaii m< i n <ii i i i

S * ffitBtilffirt f 1 1Ki 21tt&& C cttifl'kttllfe ft #ng» **»«».•
'B^WPP.

[i ^»f
jH
pffPittff1
tj|pfr^P
lrf^
TpfS|Pjjp,PPipPlIf
i^P ifpitPfn■Ifniiiwfi
^PP^pTPW
ipEP
W3W

«8MMbV& 3frim<«oM«t*b# ia.Aawww* O iaxtm *... . . . . . . . . . . . . .
iMir^pft»

'M
l

ppf^p C^ppBlMpBP #0$?
j^ p jp ip p
BSypMk^ft

^09w’

Pjf?
♦»■»»»»»*»«»«♦*»#««

MNkfeitak- 'Mk&iti^P

51
pis

aj^Jip ^hgipfc^jfeiPpi^^taKtattiPSlk^^-

6 . M fflS N * 8*W «i « f S a w ® *!
■ *:# ! ; * - * * ' « ’« « ' » # « * « " * * * » * : < f - * ' # ■ * » « " # * # i » # * * • » # # # • * « * r #

jS
&T
JM
ililM
PPM I f i t e
"^
P
^ji*c
wjtM
r1
^^IL
^^pM
jJ’^fP^pipp

**> # « *

Pw^^F^llHwpP
[iPi^^^i^^P^B
IP^^^P
t wP ^^.B
pW
lJW
pn^ftM
w
^^P8SP'PP8w
^pP' -.^w
Pw
jwp
BP/li&
pP
^^P -f^kMLpKMPt^frsttttiP

5»
Jm.

^6l^fe3iy^BR21^^^y8jiSlfc38l

“ tIPW^PP^^■Pppf^^BfiPPPP'

*H^Br^i|fr»l!»- »lrl!^W*^^HWBp'

itiiiijbiiiiir Ini <^D£ Mcacaafi*^^'WidBti#’ nil. Lq43^B* * * *«* »#

Is®*

tit# S«i0liSti M lii^

^A^lMiM^^iBMibitiftL ajt-MM tf*fe*%dif y%ij| jnrt^ri^jifciif'fcki

^BW
i£^ifdb'i^w
tMlL
lw
r' ^tfuiil
;B^w Ka^*%

„* M
.# ,„ 6^

#ff '!^|^i9ift«»
W# <P.®#■# If #'• 1^Pt^ it Hi•' • '## it

11 . 5ti^1^«a1l'«ilrf.ii @# 0-ajjlSf^liQ
T*r7~n“ ^p fP r^ "” . M o il# ^■ B '?W"^||fT»PjJjp^fWjp!jjp^^iPi™MpRTspjWW^|(S WP
« « •*« *» 4 a ^ 0 4 a i0 B » * lii^ 6 1 « W t« r * t

iMPtiPp ™

l&Qp
Wf

•W'P rwWWfWIBIPnp^flp W

88

Ufc*
^pi^l W
. BBrMPtip|nFw»Blp(f:'!tiW
lW
W
P o#'
^TW*- O*10lBI.•^.-3Mi#
'■■W
W
PBPj^ti' I^*]p'w^P^W^,jp,,l^%
,,*Wjpypr'••P»^KWMtW^,flPPP^]pP-pwt(^WiOTpw‘W
*■wr
w y » in

8^5 mmmm-rn mtmr » ik ^ r a

%%^ &M%t^%*umA'm ft# 0m
0§?|i% Msliiap
^ tT t o ^ ia c a ^ U ^ W

99

tvtrl; *Pt*4:#l:fM!tt*iraa>
a t w O T ^ ^ ..............

90

j^ p l

A
t
i
N
b
f
c
A
&
P
'***
^&
fc®
JFra
iPIBP’ ‘m flltf M fAA^M Aiiiti^C ,1ifl%
fP^BBI^W
wR S it w
HppFP?
(F tPPBB ®PPPP.PP<PPPP'f ®f H

<f!L
pfP*

pc^wi^p^f m p *in m mm$.

A
a
t
t
f
c
A
&
A
&M itflif
T
t
t
m
r
W
n
a
in
iit
l
l
f
l
lS
r
t
A
i*^
f
f
liA
T
B
..
■
■
■
••■»#- &SL
PW
PP*'PW
^^p#
T
^
?
W
!«
^
P
iF
ti|F*PPt
*
*»
»b
•■.
• • '.w* F § ■
r*
Fw.b§

^
P
ra
W
W
i^
^
W
s
^
w
r 4pP
P

w
v w

3 j6 * SN &fi?2LyA^ < # PPM N tB W X m
piipp

‘^P
^
F jS ^ w

P*P

p.pf i f f *#

S
#»
iS' bW b*# P” "*^ $
■•w1®
c» Si<flPwjl3W
t«w'!* ^ F “ ^^(F''PFPPPP
iF vl8
r p Fi8
P Fi ite la * *

* P * P fW w P P ^ ^ T V •

R
jR
R
R
IjR
^
R
s
lR
R
^
^
iR
^

pfi* *
b p^
p-pp
pif ^
p,4
fj
pipp
>p ip pfp

^B.flfc

M

a
S
R
^
t^

UNSBi^MPfcPP
P^SfebbH6!PiMP^#i
M m rM itn rin f W*4**tt"
&
t
w$JFi&*i*+****-M**.*m>*+mm+
^P^^PP^PfSF* -’^P^BF 'BFjpF
p wW
*P. 9 W* 9 9-9 * w9 *FP9 9 w+* M
JpOr

^PP(P #

39• I ^

$ F ip

I

!IM I3m p e *

^

iMHIPiPf''lMI PBP ■PWBIiBWFppP'ibPl^ Ml -w**m ■»•#'#■*»#•#'»##j*«*♦•**•*«#•#wf
^dw^ifcjppk^ -Apk ’^aP
F
lrif' -ll^Mifr^^iiii in
.^rt# •1i^ii'*-Priifrtr

***
jhM

.||^9

#Pk

SPf|
^
WIW
B
IW
wP f

»
M.. lit-

p»

<
k
. ..,.a _,

<iP
M
|g
r
f'^ S

l* &

t

■ iM »

'H r * &

;fl# ftn
ririiitiiin
:n
^tfWif lSte«itoF
^|“ fl.
r
W ^p^
P
p
W
ijpwirtl* i ?p* * # * * # # #'iik.f ^ * b f i t #

M
jrw

W ^ l» M P 9 J
fc «k -J
K
H
U
M
M
4
I

Qm

SdeakM
I,^^

I®^*ji3? ^ 8 y t^ |iifb ^ ^

W « *— *

t
E
j
M
p
t
o
w
^
l
il
i
l
p ^
E
g
r
a
f
j
E
^
F
b
.PjP
,^
^
9
?P
B
P

^

^

/ * * * „ ,„ r i* h r i

PS5bOSSSS0W**

p pp p &f

^ f ^’P

i

f P'p ff

'
^
t
^
S
T
S

P
S
l^
iP
M
tfb
rik
^
S
I-j^
^
^
M
ibliiH t
M
lP
B
^ -iP
tj# ,%
P
i®
^
b
,
i®
iito
b fP
|||ia
ilB
?
riJ
M
ttA
fltjlia
^
P
.-H
t.'^
K
flL
h
rt.tfrM
.'W
rfl
'F
to
tjB
-F
ft^
M
rP
B
ft^
iiL
X
.
IP I# ®M0(iPTOi*^^
<*^
Vp*Jti«:5>
#lffiXMr
:M
^JW
wfcrtll^
lB
^^iS
PtftiW
EP*»
im
*MTjpS
L* m :* * m * ^#F
m
* i .W
***t*aafe 1^W'wfc -W pw w w w • p p^pwpwwwiPWpp
hw
,* M
Li^
b
P
W
F
W
tP
ib
P
fP
W
f ^
P
iP
P
, Jf ^
\Hj^r »
^
*b
P
.W
fW
i!1
, 'PP^^P5
<
n
v
«
*n

a® .

g yiC b M a » «

■w *«t» in ^
« t.

ai»iwB«^{^ «b*ww«sfc. ^> .1 o . . . . . . . .............

m n im * § f &^sm> )**3u^

^

|£@

wmmm*

«
M
t
«
f
e
eIn1
%
D
i«
M
»
-£
0
5
M
a
t
a
r«
* S0.1°C................... j
i
«
*

2 8 . a o lte a jm l* « f OOflSS iMMmr C ^rB l«f»paae«rtdiii?l IrtjtU R W o t t t fio #

pPipBPti^liW 3BHr w W f f i

9 w 9 tr

A t ^ <«P
(r
( tf it *f f<s
IM
^ c w
f Bf bff f pBi ff f ti f m
^ jjp

**^i|iW4-r iwV

te

H f 24SLS# * QflMdiMHt
O tm m
a » . 84ftaM2)fiK jt e ti 0 #0730(S W & m S ^ 3« ® »o ^ e*rtilB (? a to ifto w e -

wmfeato rn 80*

J®»

Mtmam-^ Wtme tb S M ^ c .

.

.

106

« l 0^36105 MMutr » » ^ ^ a a e « w j v i m f i# w > -

«B*l«fe* to 8®* Biwc»a*»iiQ*W*t«r * t ltf.0oG .. .. . . . . . . . . . . . . . . . 10?

3l«

a t o .o a a a MU#** s w ^ ^ ^ ^ i n y - i fjrifjju w o W tto m in m $ U m m 4 M W tow * * 5® » < r e « . . « . i d s

tt&lt w

^
# i# feillf# lik &$$!

k&iftMVlifrteife'
nirft
Wm4«»* *4 M . r i i „ ' i

!>m
ru—
l.
*•■■-* M * * * * * -

isiP A ;.4
5iltS*HP*|w*f
tte. WiH tilWil&MifekfiMK'Jii.ai
Wh.t aiw^*Jr**
li *ff-akL
#JH|to.mhwtlm
i
JPEP* j3tDi*l'lli(‘B'»*‘tWpjitnil D
Pfe
w#\#3
<i>1ffton«^^
in®*P feni' M rtMwiittiiilifflg Ttfi^fitif *4 0ri^r
(8^ jA
3®.® ®. w.* .* P* P * ® * P * P 1p - * w ® W a
■W
w*i|F <
3l*« S*8*n S |(*l* a t

0 <MW& MHSm

M t a t o t o t o ?C$ M ,a * m * y & W a k m t &

%§fa
ly
!P*P^ fiijf
JS
w S
f™ ▼o
W Tle -^
^||FO*
IPP
Bi1WP QdC$>l3»
y,,BWpr

im dM h to

frtyp*l* !WW•WfMPDIWIP^'lPP!1MF
J^Pi«uwf *WVriPWPSMp ^<^fl*-^^VVpPWV

f^tstmmM^§o$wm «§ s o ^ ® c . . . . . . . . . . . . . . . . . . . j i t

j^>
JMEr# flpOMwwdypBSW
*w
irifetii
l’,^#*!ff! •ia
P
PFPT^ff^r*|P
(•^P fm
J0

g ililili

fr t£ 3m m ~
h Q JT G * . . . . . . « . , . » . . , . * » . 121

lUEito^kwMT JK
IrtbM
* i lfi^ **totoutot^4^'j/*il tSMijiittdh>'i4'^tftoirfl~ 1EI%Im0W09P®^
Jtom
W ntar
« o * s ^«»»W^»-WW«»WWTW^WiV-WWiW
« s * # i » 6**«s««*«i H I
P*T:
PWWnP1IWI>P<^FWFr
PP" a
1*0Pt5|P §
4pr*W

mg mmm**$M W&$» i l

3S # 8* lw 38SiS- 0#

ilt t

0 #^BB|<S6

t^idQatosw®

w*wft$$$p mm0 IW ^

w%MM0m**

«e«toto to 8W B toJa^20?tottoP Bt liO .o ^ ................... US

J^*

®$&w3#w±0 m

a s ****# in p | ' » to « » ^ 20ie wofew Ms 5& ^3° c . . . . . . . . . . . . . . . . . . . u 6

JtO. a o lre 3jnMUi «C 0 ^ ® 6 3 ItoJ*** IM » lQ jw l^ « « to » g rl S riflu o w )a o w to to to ^

» to s a m * -a ^ M # iw to g 9 J ° o . . . . . . . . . . . . . . . . . . . U T

i i l . s ttto o iy ito n f v*Q $kT i m & m *i w i t o t * ft» n e is to p jw w riM il ^ ^ i ilM itftl. i 3B S096
Wpttl^ IKt» h0 ^L^0 *###•»■***#■•> 11#
y i . aB tw Jynto « r a s u m s n » l« r Hto#d flr t w tm n c^jstopwEoriM M h ^ s u to n o l in
M M wa*4 D|f UrtMP a t l» o a ° C ...............

li o

li3 . H lm T atO M a t 0.05208 s a l* * 1 Ktoad a»8a r to e * 0T b la p ta & l~
* ii^ o « t o n o l to 60j« to *o # ta -lt0i W ktor « t
• * • • • • • . . . . 182
n

Mlii|M < m

^

mKKmm

P *g £

M l* M b n la M b * « r 4M 8KS9 M O ** M M M «MM» M M * O w lfrp ro w rl■
jm
vp ^pp
w
|W
F'W
P
P
M
*N
P
P
P
P
i^
B
irn
^
|W
F
|^

i“
iPl~ "
H
"w
ifpn

M W ***,-mPP
4...........................
w
P
4M
v * vff f f

M

**#■impA wJiiptitJ
it
TiHrtfiiiil MMahaMfc # mmmk
pies^jp. * m m ^ m iW PpHPW' 4MP- wWWi pp

_.......
121
’f ▼ «PPIP*

,

jiiapurwpHip

ftlT ^ i C lo w a * - ^ W *l*r «% 6Q&sO

,

I

S

O

kA^ SilShitiSMIlAA a# IIA&IN&II. Ifliiiflmif fcfrlflttliriiirtitfflitiilfrtfminn*t IPiift IMhiiiriifriiJi
KMI
^ ttw d k A M tA ‘ A k « Ifc& k iQ ^ V f
WiwiWP III. 'JBUSfedf
r*flP lipmiBiPPyjwp'fHWKPimr ISP lilriWv.'Wi
# * * * * * * * * *fcittl>»'
JM»*»
!)$¥♦
il|'
j?. OiO&fSISP
lAiP
'r,'»n' ” -S iiip(i^|p
rTgr»waMr(ffff^W
fW iw
” -w
,r^“ '1 “ *F M
■“ ™
flw r.1~“^WlPWjWA™wH»
d
A
ltfto
A
fe
lfc
y
iid
k
i^ Aml

MMUVfM1
A P I■lH

* * * ±

k ft ,

* ik m

t»

^
frfrrlE
g
khirtf^iiiaiitiai

j b p v v m‘vr
^-tiiZf
¥ f # * f %* * • # ■ ' # # # ♦ # « ■ i i ?

thN
|

P**» iiilB p i Wpffp liiP WiPPWif UP *«r#y

«*n *

m

ft#

S0 * SMMMSjMlil f lf

u M

m

&

* &

* * *

*+ ■

y k

jr f m

m

,d .

_

* *

* * * * * * *

I f irfrUfr MUiMMiA ' flhwkata* *W«a

Q«iOBVSI M iM P 3W M tt®3i»fW i$»& yl. M i 3tta«9-

«*<% ■>» M l TOM lit M M M ija g l W M ep i&

jSk*

im

326

ojp 0»C^S^i jtoSs3^’
fS8%£llWW* • # • * • ! * * » 7H BllRWU»HjO* WrtMp;i | «9* i r o » * * . * * * * * , , ' * * . » , . * * l&
S M iftM M M M riM lti Sin # 3)1' flto arimo W

W *»w A b a * < r s , » « . « . . . . . 131

5 3 . 8 «asrrtjBiS* o f Q M M .m m a f< il^m > 0 ! ^ ^ ^ a x i^ x
m fpp> .*?l*SB8p0P^S^i failJpP Am W *® m?*** *# ** «» JfcjMfc
S t * $ i|p lS «#

S te F : I^ B iM N ^

l
^
f
c
f
c
.

A
^
w
4iP
w
ip
iP
|®
W
P
^iP
^
P
^l^P
iP
^P
^|IP
P
' PP

S^illWlSltiLS A#

't
n
f
f
w
r
t
t
f
i
i
i
i
i
w
^
f
i
H
E
wuM&te mb,*TT “

w
w
pjpm
fw
^piiw
pr^M
>jP
P .w
if^
p
ip
^
w
w
'

MQSLflti?
|jm |M iS W P lS ^W .' « M lP

a
*
-*
*
#
*I
l
k
O
T
^
p
P
A
P

^y“ • “ “ p wp " • “

fc#Jp 0 ** **#**'«##

Af A SetiLwlaiiels
#«4dij^pL i t e . ^ i 1w ^ , f f l i g^
SM jOm m wiurtirtB | » TQ^£ M 0m m *$ & » ii« r «A U>«8 0 ..................

336

glgA Salw lsn^bi ®£ $ J 3&?3T WB&Mf

IMjnucmwwtwlMi la W

ISrtM* m 60.1 3 , . . . . . , . . . 337
3dL

tffim

m

m m sm . m

mm

f*« *

3t ^ iwWip^PBj^y^ro^

wwfflSyjrPKW wfiwflHr

ftrin w K ro taa to to la ?0£ W/aaaa-SOf Ite to ra k 60 . r o ,
# * 9 o3IW»2aM»J»: ,«p < M ifi(% to $ s t. ;% # l« p M fg a iM M ^
*w^g

WlnA^Pi!* jyto

jv ft

138

>

&» MatoIjWiK of O.C«$?$ M « r % «laMt»|g^^

Wwi*i«*J«)M(i)rtlnt,(l to Botf Mea^An&Otf ItaW * >4 ,t o J r a '..* .. . . . . . 1LO

SsS^Pii^WSS erf S»^B0S6S-

,*!y^fry^^iigrll-

i& ?o^

0 *

B & ln

f m n t iM

wttor #fc ^ ^ S * * ********
®£

$kk

M ix ® 3 M I^ * m

JtL&L

&u mkti/fr jf%■ifHSI=l»^tt? %3Ti(fr^t

iHriittiV1*!unfitj^a*l>Jlliitnkruirt

M fto te te u m ta te it to jj
®y * mwSPwwWm mmm mWBm WmWa*(M* « k ^

^

M M H * * « M. m

te te r a t 1*S*?C.. . . . . . . . . U*6
®2£ v-dfiisw|^p sm^mSr IIRRSr^!^
« » H M > n » . i « < > M .............

68 • S^lWlSlilS -OJt 0*Ofclt& ItotLaff

ll» 7

<^>^ ,it^ r

35e±mo*w»iw»tat« to 7*^6 S isam m -30 %Mjrtuar a t k9.9® 0... . . . . . . . 1U8

69. QWiTOf tote Jbma the Sfl0t»oJy«t» cwf 0.oacS3 itsiiur MtthyiW

m m * m n ? ? .« » ...m

« .M .,.« « ..,..« .....

fC . Sotooavsto o f G.OQP7 to la r to te yto e rtK U g ro ilyie ia to

' W4fl»o*was«feato to 7-OjStteaw «H ^( Water a t t o /o

i¥

ISO

?1. St^toaS to te im a tea te to o ljra to o f Q.0&aa7 to la r to te y lo
iw r te ie g r e ljrto w U fflja E P tfto o s w a a a te te t o T ¥ O to ca a o *

j(«
lW
ite
ia
n
^
^
**»
»
»
<
i«
«
****«
*»
«
**»
*****......................

<jf A4,

3
S
1

? £ • S o X to 3 ^1 & q£ 0*02285 M o lw
1beii!X^o.^a«wt^: im 80 # T ^ im m ^ ^ 0% t%tar at k 9 *9 Q0 „ » * * * »

1
3
#M
tM
l Mi $xm t
fe
*S
c
O
m
a
g
r
v
d
t
e
-*f 3
,0
2
0
2
6m
a
rH
a
tty
*
*
ta 3o$ v% mmm**
20^

?U*

T*W
7
5
-

w&t^r at
«*£ O .^B M 3' M a r
frif3 B < > r» ^ o o ta ta la ■
water at ^ 5 *i®a.*.*a*6 *6 **.****#****.***a

a
#0
*
*
8
1
8
$M
ar a
M
M
g
r
l
U5 *l

70 ^ A
o
a
t
o
n
®
2
?
*
3
^W
a
t
e
rat

ia

& * iH fJ w a a Spoctanus ff it 0 > 9 lo p ^ j!^ X < s a m n 7 l m n a io r o a o « ta to .,
t # X iiW

i l tjfr ti# $ a ^ o f

18

*®* '? *p w r w *i*w up,T^g*Tif»i o» j’Wwwseiwra jfjw?as*<yv

wo

r^FOiNKnp^OK

® f aaw suga®;^

is

U* VatmmA 9tmHmm--*4 % aa®pm g0liM iri^^
.* _. j.

■E®■? n O ^ 0 4^ 0 A ®

! • 3M m m &

^ ■*.

T riflw w o -

^.

0 -i®10 . 0 0 ' 0 ' 0 ' 0 ^ A 0 -0 0 0 0 0 0 0 0 0 0 0 0 0

o ff i

*

lO
tirffr
O* £l#KF(Prf?6»

f *

l'W
]M
k

40*

^t0

,11..T
h
M
l1
«
M
.jjk

0h o
i«iM
f*
M
i^
f-ik
-m
m
.f
a
-jflt

tfc
W
k
tiM
rtT
*t6
*T
m
M
h
lf**lM L & t

OX

,jft2
^
m
_
~■
*
'ja
-i-jt.m
«
a
.-l.j_

J
*
L
lJ
S
P.

l

0 0 0 0 0 '0 0 0 0' 0 0 0

#0
23

. • * * « »# - * * * * * * * * * *

25

.**.*.*.♦ **

26

tititiSJ
h
f
e AiM
-J
I'i^
ft

^
ft'riM
h
jrL
j/l'ih
lk
.J
^
J
k<
jM
.^
I9
P
MmW* I*^Sm*h2iltjfciiittiri?
.rXw*»OX
O*
* * * . * «»* »* * . «* i . , 4

u
iL
a
*»
1
J
*-.-.

.^
-_
■
..j±. IjB
tfit^
J
ta
A•
»
*1
--j rift jjfc

^piteppPBy® os* yjbs^^sSM:.
-^
W
a
i*
.*
>■
^
■
iJ
f
c
i—
L
k
,.-.',—
.^
U
ij0
L ii

^

H

6« 3 $ £ M iii Sjsoert&ttsii ■«#

J
m

It

k
jt^
a
lh
.

28

a
jS
f
c *
O
b
>
.M
K
.

F y y *£t3.i30
* «*«*«»« * « * « «* * «.# #

..................—
J
h
i .>
t
K
.^
...^
-A
--.»a
t.i.^
b
i
_
—
^
J
B
t.—
a
.-j.-^--^,A_"
-•—

jH
n
b
u
u
fc

JO

^ .

#|NiPSM % OX
XTXXM&&3FQ**
*•**♦***'**'•■•»!».*#.#*** * * ##«*'#-« «'*»**# ar*# • * « # « * **:*»i» **.«#

J®

$HliPWiWNB*»* 4-®•* #•* m*#.'#* ¥ t ••%«(8•##'•!*» * « ##'*»#» # «»* * **6 #* *'* ##•*«'#«» # S5
its
idaatiBOffii
5Cr
«^r-v»-w
•^w
« ^-w
« •-w
*«
•#•«
• »wi-w
« •w• «^«^» • « « • » « • » « * « » « * « • «
•f**™
wV“ W*T 'Bioxaaaa
IV.H^WI.P*F/pW^WI &&
upw ^T
»r- ■
t»>r^rw
i^.w

5
|fpr6

13* f l s i ttf lo g (8^8*% } VMHMM t «»*• tts» 8»3vo2jn^i o f Foi»
fr
lO
a
c
n
^
o
o
o
ts
ta
ofc
A
q
u
o
o
u
sB
lo
w
s
a
o**$
>..*•****•••• S
7
lit * 7 M o f lo g (V a -tC .) iMENttS t fo r t i » S oloolyttt* o f a te *
te rM Ctotaino!} f t e l IN l M W artfleo tio a o f O ycl«|a»pytartisyl“
tr 'ii%1m 1 i ffty 9

1

in jq $

ataiaw i0 p r .* ..» .* .* .* » * * .* * .* * .» .. . . . . . . . . . . . . . * * • « . « . . &

x lv

#
IM

$ £ d ra s $ * Q m M m «§d

ttl

p& g*

3$ * f $ * l «*£ %m (W & *% ) 'fm m
“

16.

"‘

"'

% im

tt*#

©f

fra JQ%
i ♦*********«*»**#*«*»*»*»»#•«*##*»«*#***

fk

H o t of aogtoiwaoo w n » i t Jut to* soivoiyaf* of Methyl4m $<£i3£

3S«
^ ^

J lM M il <#■ c%a
W’

t j a

>

^ ^•©•fW
^fcJti^
pT*t:*©►pteygnsA
jV» 'WMM
P^Pwpm
>^*n||##*•*»**#**,
■'*•» w

*7®
“

U * P t o t , « f le g k t o * i* * l / J to * to t »«tw »ls*4» * f CytOeppopsda l£
■^*FiPM^4i. 4*fW
*mAniwmwm^WmS^m

so* ftois

©Up

®$ %®$ k v*f#kh& V * * w 4ft*

©&3&d£3§rX

S I* FM% ©£ &Ag k i M

1

^fcfWiSr rthtoto

% I9ftl&
JHIlwHar*» * # * • * * « * A£>©

®i ^J© pp© $fi*

In : ’JC^S $Sc@c88^if»S0^W sfc£&***»««»««# nffiy

i : |/f #»* mt* $&3»© )a*** ©c

* l* M J * fft *1*?^ ,

22.

-4 wa J&^Hflf' 1^ 1%

Jifft §®$£

1%%* ^ v r t t t t t v v frjgft

« t le g It f * * # * * I Jt 9m to * SotooljpotB o f to ittic g ra ly l-

2}< ? to * o f lo g I . M M l 1 / f to * to * S to to lp to o f Sortafioyolja.mAaisri m&tommmMm in r a i t a n * 3i | { M a r . . . . t . . . . . too

2i*. H o t of lew k w w

S/f. f i t to * Saiw jjw ls o f MortrtcyolyS?*

e»«ra»yi wifiseKiWNweeiwe s».o o p .iw o (t*M w j» wwtw**»»****»» u i
S f• M

o f' lo g It ywema %/t pm t M Sotorolswla o f 2~u«rtejrl-

©
s^xlobutarl.
wpfuw
.'
m
^L3r.-fgHt'%

*

#

4^5 "®
$t^M,
~~'-fi'Wm
mw^mrmf^K9^ m m -,tJpt w

^ *“ •” •” *” * “* •^

26. H o t o f lo g k w o n l/E f» t th « Sotewlyale o f 2-2krf^srl«
«7 olot)Wl9 l »l£3Moifo«W«rt®to In fg jf DJaawno-lOjS H td m r..

lf&

27. P3»t o f log k v«nM« l / f ft» t e Mkelsf&w of Cjrolaiprofyln
o
tf
c
t
la
a
a
r
liiig
r
lf
r
if
lt
t
o
iW
B
o
e
r
t
w
t
ois6
0
g
D
ir
o
a
m
*
ljO
*W
o
fc
o
r
.... lit

Si.* f ie t o f lo g k VWMIO l / f : lw tb o SolirolyelB o f <^olajwo)f?jdm jl^ fim s m B 0 . Itifto w w o o o ta to t o fS # D io a » a « -3 0 ? W a te r .... 166

19* Plot of log Sc VWWWO l/T to t too- Soltolysla of CytsloiHfoiiyaia
o
th
y
lo
a
r
tiljv
l. to
lflM
o
to
w
s
o
ta
totoS
O
J
fD
io
x
a
a
e
a
o
fW
a
te
r.... 1
6
6

1W
f il,

JUS

I
0$ lE T O M Q E M W A lS I

OF GM&XN
e^Wadra^AHBIHOIS
~
w
'wwpopa*is imaPP^PItoPPPVIP*HPMp*nnppg^P'

I

I » m w p n a irt w f tm

p a r ts , M b

tm

p t a 9 < B M & swart will tw trfladi
•

M H U

III

JSHW jpwnw i iHPwt

9M»

*|W*p*i^

Sa^tttilsS* wm
mtipBBB'
i -^ie-sywrtWPwejpr
Hir1|irflBrtwwwnw
i^iii*

vi^vwt|PCPPWi|pi^Hpmr

mmmmM

X

th is tfaeois $m sditoQSad o f 1sho M itt, ho^i as?# cor&opnod
nH& «?^l<>p3?op5yaoia?biii3rX «y#fcoa** 3&ch paH id ll b© troofcod IM$«gm$*3y
fo r # i# purpoo© o f c la rity . & * 'port*
w usf x *

mm*

m * s y n th ® » ia *m i 3 o x w 3 a rg y i o f

CoyfettflLti Cyo3ops^fiyXooi%i>yioXb
PABff l i t Tho Syxst&ooig m&

of

#

thwtaaX

C
^
X
o
p
io
p
y
X
o
o
^
b
ii^
lH
is
^
jg
r
lS
t
f
a
o
r
*

of

f

to n t o i i t o

to ts i la M s to w iiiiiilf t t o

*

* to fty n is to ia & to to M * to to ^ ito to

Mil tototo
U
r
ttofy
to
to(1
)m
t&
*A
M
to
§
to
tot
s
rM
m
to
Ms
M
lto
»
:r;

to M to iife IM toMtoto to to ir &ww toatotoM «sto as l i a
to & to t o r * * to M to to to to H

im

e*

«»„
«e» i^
j|jg * *>'*')* I*I- ,*-..
.jMf • * * * »

:cx

f

HXSTOl^XCAXi

MM&3&& my*\mm mm wmmtiMw m m ^ m la jjo X vo lyt*^

afHfwtWit

m m /M am , pm w uw M jr KmwMW o f < l*lo o a li*a ti< m o f tbo p i oaootaram o f
% t* doubXs bond ia ttw ta a n s ttio a ota&o. Eme, * u a la e le a a le r rils p la w
mmA im m a liy ile agrstam ( I ) mgr bo fa o ix ita te d fajr nm m m m ooatefe*
tooMMfe ta th o ooblouls a&Soligr f*ras otraotovm suefe as IX * and XX b*
J
fe
W a
m
fr
ttto
v
b
ii

a
life
M
«
M
M
o
fc
4
k
tiU
^
In
hiaa
fr

u
a
h

typ m *

Iw lf lB #MEr 9m MUWKEnyWli AP XX 4«

t * qst

mm ■* 9 * <* i

a*

♦

m » m * os*
tt A
w

f

h

- ch •* oh «

. xT

in ** <m

IS ¥

itA* <
n
^
b

betws$& tii© c^Xopropan^ iia g

^ Am
ir
n
iirt<
1 a-*%- \
«0GDX<S
OOsa
\X / *

4^9^8931^. I m HLw^

ciiaJ* x~

#
?
Im
A o
lb
V
n
JM
-' %
hTvniflf ,AA

fc
fe
rtfc
MB w a il OauBokJI* ilitT
O;

tb o

itk
n
-m
-fc
**! ffi»
b
ito
i*in
iM
frM
J
f ifl ■
■in
J
b
iA

Wl® flUL?35ywi»j@ fl^ww9B8jj^' *P845mW>* uJJHC?- SMS 4B6p®S5X1®Q

t$ Im f t ry1i*«8ot'ixr4i in

tsSoad tha oom.

oi
XX 0

I nnb
iiioaj-^A
nita
h

%

^

Tbm, b*a» tsfeo o f

flh ifttit jf t t ? r i a) in

in

aolvojysis o f cyolopr»pylcart>lnyl

atheixaX wsm ho Mama jfa n tn r than P^raathyl-*

s03g& dU w U a ( I f ) sad oyeIsp»sgft«aa*lJB3rl bromido (XXX b) solvolyzed
26 bLsoS ffeotor than a llja b » *ld 9 {V a) (2 ).

3

08*

• X

08*

ZZZ ft* X •

?
C *
» 08* »

Cl

If

uifc,

X«ftr

IK®*

X * © * 8% « /

A

® , * « - £®, - CH, * 0 * SO,
«
B
*.• ®- O
B
,* X

TX a
f ft, . X«* 1®

n .

x » o -s o ,

AJJPwj KBfl K l8nUBKl045lrlM«S ®JT

©wWBap P lfl^

ffi-jtyaufr Hfoyfcay*
feWW
jMiiii.l wmii^aw
*!
IIW MBT iw

# * -^ 4 ^ ^

yJULI. K /
sawt XOOO

WMuA* ^fc-si^m^ajMa^hiafcjrtbiX-*! -fSiViirai'fjgM■ ^HtTT
|VJfc jfa\
mf U / *

!H sidi ^scsflp't^.oiiA X

s y s ^ to s in t t t t l*

m m m t% *& a s f3dc <i f jit fli i® l #

at,

[^> ®
U

TOC t»

tn •

[>

Hr

®,

fix A

®

X

x,
111 o

k

f t * pN M iw ti «3*o i nd ioota parf& olpatioa o f te a ojroloprapaao artag.
2& te a kan3»o3f|&» o f

otOmfcla and cgolotortarl

teXafiM * (TDDt a ), m l la te a d la io tiU a tlw i Of oyeloproKjriUwfedivlandBa
CCEt d ) am ajmAtatylanltM (U S b)» te a fm a n M » o f jaodaota m s
te te lH *d | h$$ apaOopmgrXeatbteol C m a ), Itf*
am

(W H o)

a X iy X a m rta n X (¥ 1 b ) ( I } .

xxx 4 . x m hr.

rati
mgM
Rpm
'te^Ba
ap^t.ejp x
mm•~ ci

¥■¥¥
¥ m
fM
•Lii m
w$ A
•■ vft

tojj a¥ *m **“jH
ttll
vAii D
T O X e * X • €H

m ix 4f x * oso#
'C
5
i
a«€
$«
►
C
H
*■
<
*
Q
H
2
* cm

m h
T tt

aO & tidX vftLfi ft#

flwa iftiiy )laaayftwtimt o b ift-w ia lii ( 9 ) awC

* m >1ffllia'W I maftftjfctawtmmtal^yMfr-fedi l &TYT fit) ( k ) amtm fth a SftBtt
|fcfimafoaii$ftf

©f

aB n^LongK l}!

aaft eyoiobatyl aoartata* ***» forawd la • aa&io o f 2.8 to 1* fta w
x«*a& a warn awjuXatoad (2 ) la te m i o f a m id taterooiw w etoiv o f ayci©iwwiM^ aaadt< m ^t mtwl

f*ttM«wtefc «(&tih ft ftlo if and ftS8S&M ia llS r

liarwraapatelo aaaoUoa to aOXgXeatfolagX daaim tew w .

<
*»
*C
H
-C
H
-C
H
*

□
M ik . jCi.

'iu i i k

^pH9 nwPA

rinit iti»nih

^W^Bhww* T p ^ t

^ B w

ntMli «*4 «isi

^PP^Ipli^pPwi^^HfcJp

iiitiAxm wl~ n itmi
SP^B}^^KP«P®pi s(|e^KPPIbpP

**

#
* m m * W z

s
*
>
0
H
§
i»
.a »C
H
j|* C
H
*• as

u>-

ay* ®

* <

m

k if t

im a£ to* typ»*taw» in ttm sehsns, totm tun « ttess-foM
—ft* o f ayjwstay «o th at Urn two aatfcgftian* group* o f tbs eyeaoparopune
tiiilwinltrni

n a g Mmnm • v il'n lm A w ttb tb * maagaWs mUtojUjmm group* tb * c M
•frw M M wpuOlgr

mmmg

th * atnrawd aaitooa «toa* Sa «**fa

p m d tte t.. O il* « w tb s cam wttfe tb * eyal<rt*rt*m>l.. Hawwa1* la 1b*
$mm&t m rnmm at c“

(W * *» tb « r tiu a 3 3 .3 *)

*w *> th * t p a t t it iS tgr 1b* ao»*«aw*4fisX ±afe«naadiat* w ft found « t fib*

o u& U tal carbon *to a , end w a y g it* (ra tb o r tb m <6.T*> * * • Ants* In th«
$S»£iyE*;' m » IflftS

]>y>.yg|

Q$3t$ jtt®s(53!yBii&j03®

shot ^n i

vm im ( 3 ) . 4

|>

IS
dwawft

c h * » o * so * <• o$ 8 .J h lh M it

is t&e
wttttfelral

0$
)^%ks&

^^>>600 » o “0 j^ s

%0 g lttt ft^ ty
f 2 jl) » Algo. t &0 tB&tifo&X fith fT .

tm&u* m
iwi.%
m
mCOnditioiiSa ****** mfrlhr th© aiLhtrl sHtiM^* QSlaf a fte r O lffllt
<j<nynf ££&
4BIWm a?tti?i&2£
PfPWWfbr

’tM ttt ttEssr*
^ WUrw^ipW'W^IWf''*iiWi^^bsyQL
^feJsi^s?
^
' jb^
^PWWW
fa “.r-.^—
-,r«*w^ JEte3t®ififcci
^ >
.
-— •-■#”

7*,^ P P titfl 1341 <QPwBK>t &HmWWBW$ w Hwi

)

P^PHPPPP*1

wlli«**t* la <bl»rofn»B a t aa^Mtwl to rawranM n ^ U U y to allyloartilBya

1|p^.*M
i P*ia
+n**+4tm
m*td$ m itta
n ll JiwrwlwlL A# th
mffli1rt!k)i^<ir1
lttO ia ftr*w
PS|||0i P
I0 (nPa
|0 it1
iMai*M
vwMV0 V w ^PMMw
••■•PWWPWn^
'stipbi|
i^p ^
P|pJ'waw»w*F*»
'Wi' **p»v«wnp

7

€$$ **►(99*
I
QH

«MfM
*# Ihistitu.

•*i*

-a .

» OS#

w *w , &*
e # a» f a'
® KNU^Ii jFttKJOWs
4r
|^ > »

CH# * 0 - CH# * CH# - CE * OB#

®

* G
B
»

©
*o
#
8
J
i
l
K
8
%
j
W
E
W
S
'S
S
E
^
t
X
1
^

Im
s
w
b

© I *fchfiHp|7 #iil^i@ Ni $&

W69S6

s
o
3
y
B
o
3
j
y
8
!
S
L
f
l
i

@ ieiSiif: jfedLtoWfcdLos# <00*2

9tt£MSflF&jMdr J*&3B

3S*€ttKEW9jQt§8Kl
*&
*mm- $mtemm»

^fclL

jMtA'^lAitaii^l’^#amKJBiuhfe

P^wyESpv^S^I^^Kp^P w^P

$
$
£
M
M
i
£miMmm

*
$
H

-Pfc4St1^i-:
Pk’T-

Jlfc
Pl^SS jp^^^wkwv^wS^0^Ppi^9ii^P
^IrvAX'i sPPp^P 3^P®^P®^wpjPipw!®^pPPm

m fflli
y
’
f
;

y
g
*
%

4^>»AifciK |igg|i«MM| w m * n e tt i^ ls i^ ils iH fii^ w m m *t$ksM ih iiiif^k&sfc

t
f
t
w
i
l
f£oV$B&&9 t
i
H
I
%
^ .ftw t ^

/ «

* K /'* ‘
\

>
.

l <
I
$ * 0

o
a
rm
f
e
a
a
r
0

HO.

*

fa$ BXmtm *> jo
jtUfP

96%

90$ m o u n t -

28*

ttMVBJS IbJ^^lttdStW.'ttfeMh ■

1T3LR ^ ^ tiylyATIWjfc JwwlHI«*^C#*

IQ * U fp

f* *

'B8bk>
rifc

/^MtMk''v'Wttttbft4 fejjyh-A*^kto^fc^A u.
-fiB^WWjJtM
r^<A^JKIbW Jw I9^8ISWin(I w
CTBIJ^ wSI a ^ sFBWSI jK$SwB

fldLt^W 6 t& tt io^jsn& 3P <MP

&$$$§*

f M # jjn ^ ^ p g ro rl^ ^ d a in

sSntosttP■tn tbs* o f Ko§iowKr imA iSni^lsIS CH) ^n
3 t$*<^lX>OhOli«Srt«EH6 - y l

I36bs

^tbaEpi^swMi ajt■

. t 3^Q bl0P9fiS ^ R t« *

nJ£ %foi> %$n^tn iB®8l#n®8l$ xtliig int. n

jg'^nig^ty#

l t o l t it a «M .lit? - to p trtd ttfn to to to * *o l»» 3j«to rw w tio n .

For

tta a ftlit* to # to to o ty ito o f >to lo i»H o rtetoyol«9B (IX a ), * cyoloim tgyldiiiiFAtiirft With 3^fcilfiS*

ff0 OBlfi'fcri<3 ttigHiJiAAiiwmn.. 4«

9

•p aim a:vM im ii. i * vapavtM p . t»

t» lao tiw w itiuww «m» v b Ib -

|rifa^LBrijljL^i|A* ilkftfltjftiMftibtifeMt #?HliP'
HMfettdkriiM
nawspi nsgmnMI; **jp f # t - w
8w(p JWPSF

•X

xx » , x « 01
XX te*

X • 8*

XX »D X mm

4IUh"I#’?' lf i« ^a^ftgytttdLViSy o f th
#
IP*”
SlUikifttfMNttfMVAitfbSlk
*"WPv*lfpM(*W*

{H

**
^4
<f^4h'g4ppftii
W 'FW:#P*<*w»t«iMi
kTffUJfTi^*Pii^f|WPfWvram
^Sf<pBP^ *&***■
PP'-Jpw^Ppfcp
ijPF tw
jpVV
iMWPK
^ff
HWMM a#

<g|F

^9&1fSbL j#hSk.«ttS ^SkStafcjfdlAftSj^k

AffNr w*W3T J3*^W**S£rw

-rfw.p
*m W w «w4.Vwjyf»*,$| w*
W P v J Wj^'^USKi^? o

* ) o r fcfas b ro a& d o ( IX fc ) m i J ^ h y ^ o s s ^ ro rt^

W t is ^ f g it b o fe s r

pgppfegnBgi*

lo 4 ]b i jfblX oW Sjaff
t$ r lib s

(XX e ) { $ ) *

%

ooeorddlag
aoX V O lyE lS i f

^ w a M <wt

rlU dg fo y * o^sirsN wS*

OH

T W jw tw te ( 9 ) , h e n a n r* o b w n v a d tb a fe tfo * M a fco X ysU o f th * H w a w *
lliH
lMjy
tim
Jf it
'g|^|j|Sllftim
jpPP|;^P|pgm
^SppNS
gMP^nw
OSlRI^
SANP' fT
m SWS
^^'j)pT

.itk*it*4i 200 * * ««***» #»a?fcjMP 4han> til» jk : A#

xo

^ww^PflP^^w^psi^ WWw&mm&m&yp* • i l SM m H - WP IpFWSI W P 9 iPHr vpWIIWMMHHmSP ^KBwHKEBT1*
*6#t
appU^ SBlA-''^iM^!lhS!Wj^hllP‘
*aww; # wwii'Vwi'^pl^F -™

W?l ^^PapiWIIHIa SIfPPP ^WUPPIWBbBaP ^Mfll
Am lA i^ lb A tt
^r^^hmp iPwWAu^iMRj^it

131 ||U;JE ^i|\
Tfliiia
P^Pfc
PPU
jtd
. 444
^.JT fiMKPIfe Awfllwi'
W(fflPiwwm H® 4toltf6'l3fiMb
Pw
^®4AV^I|PiP|w®P*®f tut :#&
-^IW &
W
p&
“&
Wfei-BMI
HKHrMMHHV K
SPiWPf^P P
PH
PW
VRF
Ajl**
p 4
'®fc
PPn
®a
ljBm
Pm
ifttA.

ia^hYi

,»

m*m W in ■n^UHUhMu l*PWH^r«itl',A.li-WP

j|,M<iMiaii■linaaX

^-*t wt .at.-t.^*.- - A.J —,

# 4 »W 4*

*W

A\

W J W W ftfll v M Up AA • /«

•'tf

S a, I - cl
X te * . X «•
S h * anfc®

$X

•* x • o - w g - v y M i a ,

CB&

M

fh & w f/U j/S L'

«dU#
•wP^pPM’
po Hmlv

#k

^
uw p ^ c rw rw i sop

H

% itin i saen iB!iM»tt iA iA ttt o f-' $&& taEewyidfttS m ik cm isrdbsftj^r

ojn& opw p!^

HajacndaUEV

ijp itU I, tfe rti «*» Hot « « rti*tfly •a U a fe cto iy. Because

e& puyiftostloti d iffio a ltJ i*# , the kin etic

mOc on c^oprop^oH A iatfl

chloride, breaWe load bwaseaasalianate v u not done on pore (less than

SI

ftifffw
rt) «
w
|w
w
w
Ib
» fla
»
i iste
am m w atm o
f«
g
N
a
n
p
r
a
n
r
ii»
a
lt
iv
l»
itlH
S
M
i.*
nn
y
s
ln
fim
r
y
iw
te
y
ln
r
w
H
S
m
a
r
t
k
s
a
te
y
!a
t
e
a
>isw
>
m
»
>
T
<late
a

P —

» -at'fiwteilwiwiwSfM aiat mid, i t «m> a te m W U iM te s t te a

ta
a
te
in
s«
m
jd
a
a
t
e
t
a
a
S
lyfirtea
a
tfa
r
* Q
a
ap
w
r
p
m
m
a t te
ag
g
t
a
a
te
4'MMHibiildK olBak&L^jpbvb

'totinflklifc

othMtidMWiMMUfe
jmA*astffc^tjtfi
wmm W pPBy#*w
pttSrWf WWw^WI

■*-—

^jh> m.

j|

®WI%¥»w3CTwP

a
h
a
a
aa
a
s
m
a
jm
*tm M b
aa
te
a
ta
i.

AX©9#. t&O o nly fttOdlAO 031

fta ^ t wurl n»rt*l,*nrt| 4m J f i i t ii i

ftifeMtfMMftttM&ifc kflMftfe l&MMttfc. JftMt jfrdisAtoatfc^lfcat
gfcMriAf/A4>ltA&
OPteTJ(^ppte®O®0O^|p^g
aW^A^^WA1 "’'PW i3* 0A4j)fcWMOlPW^W®r*l|t|l’
V t F t^IW’ft tFRtp^WOftA
IjUaA

i t t l WiilH

tm

o

f

th te

tetr»« w
aa«te fcte Uw 4fcm 4
Sf^te^Pr frjhwf
l^^**te#te ltetetatetatlfrteteter* WfHPNH|
ate
BRjF
iMPte^teMte'ter^tetete

'¥4 l wjjAutejBak 4f^tlfei3lUi3iiitfttid0tHfcWlhi^k jtfftAAtfttdf

o
f
c
lt
o
f
c
o
t
a

Jta*»

.iPs'^F

&
$
&
lv
&
t
l7
$
$1
&
#
4
#
*

g
g
s
w
W
ls

PttKiA.
i », JjttagteJl
eO^tttA^jMkWNb tdAkAitK^
tet.
Jti®t JK
ZI IWBwRsjpw AW*
XtiJw*. JRJ& tw^CWIr
0$SX^w!M*w
JTQSF

pte^SlPlifeiEtW^StSji th « A^
<Sb3jlW6klti8S^M^NMl ^

a n te M iit
tite
ete^^^
a'PPPFF*^P(PtFWF

aftvafl

4i.Hp

BraiP^A
pwIQ3Lfl« doKSB

Wftrtpiftaaj <H««# ggg(f fjf^aa

^J^p(S^jElW^IS*^i^!^F^4EMS3S^Jk39^3L. tNMFO pM^fll?sii a life®®®

1NHNI f^ttttsi t® b#

iP ^M b© i^ a d lly p«3?lfl®ciltf b at tb^b?

wm t»
ob
M
rfo
r:WiM
a^gtigtil ®|f <^y^Xoppo|^f3Uwsa^^

F
iB
a
a
a
s
r
, th
»trltb
i^
J
^

wafi ppflpBFidl i^ i Ibausdi to b® ®ftti^a^st03?y

fo r ld J » tto
tb
#

o
fth
«t
»
l£
lt
3
i©
lo
a
e
A
f
e
a
t
^©
fiM
m
e
l
tW P tlB r^ at^ ^ k a ta a Vi^fi J o in t ly iN N ttl 1?®portAd (3l**3S#3M l) a

tbA «t«3rti o f tb© p rim e ? m d mmm&mp alcobol# wsr® 3?®po3*t«d[ to
Ao3»%f«a b f

tikm m m * i t m

•x ^ h o lo *olvoV»0d b r lO ^ *o « g rf^

tb© esters o f tbo to r ^ jo r
B 0€M ^ o f tb» O o ^ ^ r^ A

12

wma&rtMp

ftyfttem s I t vs* miio ip a to d th a t th e

trijttju to ro a o e te ie * o£ th e G ^ 3 ^ s ^ ^ o « a ^ s lm X e wmM e o iro iy s e tg r
e l? fy i* ^ x y g ^ n c le a v a g e *

ro S K B S H M ,

33

D>
Xa a<tay, S**l»

u ttfc m

mwi

•te a r m i 80«® g* (2 .1
m u

6oo a£L* ®g

I* A fte r tk®

«f

fftX f

JS*ft ftft I f t f t

ftttft ft

msMi (b o ) in

*f 1 6 0 g.

(am find oosMsiCLf hoars)
fo
rmftd
ftltlc
m
«
lt
o
r
n
*
*a
tr
o
®
»

w s

aprt t& ft

ftlfts ftJ B ttft

o
f6
0s
&
-o
f
« « t« rf 60 ffil.

SS^o id * o f liotigr* fUo fto lsftto ii

« **

f& ta rttS * and til® ftlftftto ift

# m ) m r a%- room

ftftlAift ftMMftkftft ftllft

o
f other.

ft& fttt ih k o tiiQ w a r

ihft ftolroaft roaaovod*
ft

313 i*
mate*

J
f
a
f
tothor

||® f t d fia la iM i

b 4 >. I 2 3 .s-121i. 0 ° , i^» U tfO l,

ttw tfbMtei g u t • m m fm v m

( u u . , m *b».) la ttw m p a r

OyaJojawwawethyl tattoo* (tttjiplioa ty «»• JCUteteh ClrtMUal Co.,
}&2>nm1em, WiaoeaMte) m i ntineto to oyfttogawpptowfetyS^^

wtiog a

p*oe«&tr# Mwimnw to toot fo r agn»Xopa?c>5ya««*ij»)X. too f& tid of
•toafcol «■*’ 8?f, t*.p . lSS2*0»Ua^®,

l«ii321» tto oloohol goro *

gxsft)c {AUSlL » | 13 & & & *) I I I

J
to
A

-

jo
u -d
fc
to
W
N
ii*0
A
L

w
iM
i,

j23^R9 *46013044? IP w P

it

T iff Mi w ^dkrJf

/ \

O\

h
M

m

m

_

0$jjr iwOtwrt* «&# JSffiirlMSji ^4 0 ) • Til© p h y s ic a l

■fm«

iMwawft

»fc Q#|$ im l .

&|k Om*^wo»lfl.mto*» IlM^gl. %*§i '#&&$&? FtW^0tS8^tS3t inttl' UifSd Jbap
01* ffrf1^
o£
H&Hi th#0®
Qal&mM a $g|0—
E*ei0r
OMMtfelUFfeh IfWffa
.^.J|^|^ p^|>y|
| JbtS&ojji <^t$fS8db0dtokg y«|y^f||^o»
fia iM o tM»aWw« tsm a

{d id o $ ? l in h ^ih a tiit^a o il MuMiiM ftk L

» to N M H B ^e a r

•ad a JrtatJar j*«s*w Atr« eo3aaa» oith packing of typo «<J* (o ilix w M j
^ il^^iiN liJ ^M N it P ifflp .O ) .
i__,,
(J
c
^
jfc
...^
.—
jt■
-.’
^
8p00i
xJiti'A
l 0af
H0fi>
0a— hfa-M.tuM^
j

a ll fsmpKl

i j

S

I

l

S

'

^

J
iM
iw
'^
■
h
o
f—
.d
ft iK»*

s c ^ m
s ^
i1

th m # %# aolam*

i

f

l

i

f

i

f

i

B

o'W sndU iB

u
^
.»
■
—
■
»
% u
iM
&
^
rfi^
iA
»
<
tM
M
i^
L ■
—
<
^
%toi ^ jfi
jJ
b
jitf^
mm
it pkH^w
m
x
's
ox
xu
p ,» .i* ox

^rpt of aol»m anil 1M tdae

go# *1^»o»>.oi^wMKw«i> ■ 4ja m4w>#.m I- oX th a TTWirti^Bim «««{§»f»4imf».ft tw > lis t e l*

15

Wig

b#.

•ifaMtirwvm *

qm h I*

#*»w 'yWwyipwpPPiw APdlipiRWPGW wWr 4mi6laM|y it in»rj~ cfarCA%^mA^JLmW4Pl»llP-A» wWWr

«* i.o m », ag* u u & r*

M fin w m « (W tc aold (3b.J» $ ., &.$ m l*) and banaoyl obloaida
<8U $ ., 0 .6 a » l» ) mam aland in « zoo-m . xmnd-bo«teaad fla n k , and «b*
A S jttlfc 4 cwwumH

(
^
tS
b
s

*cm
tiw
iudM
*4-caM
t 4 n m -*xamlmm^4
wah
H aaw4PpapMim
mmlwmnrn
.
■
fw
T
rJ
P
p
p
w
^
m
T
^
*■ <
fw
J
IW
m
H
W
p
m
B
(4
W
a 4
W
'*^
4
M
P
W
P
4
P
P
m
i^
t

*#** 6n»
^
p
m
M
|p

w
f
c
g
g
f
if
r
lf
f
ln
h
t
f
f
f
t$
&
H
2
j
O
O
*
3
a
s
3
L
e2
*
o
^
o
^
*
t
i^
1
it
^
is
s
df
X
s
&
k
*w
id
^

i|ffff-$fa ^ 0 Ta| f

|^igw^yi>w(y|y g$fajgf#.g^

ft*y flffiff |)hT**y^liyfiTil f f l w M hSUl'-.v'!#’

g*M§ #n» 4femfr4fti*A r^*fc*toai!% rth'tmvf^Am jaanfl WN^fem^ 4m 4dkm fwwrtam* « th fiP *

A
U
t
i
lS
2
l
L
3
j
0
I
^
B
S
il®
H
W
H
t
o
'i
&
i
D
K
M
H
l

A 30Q~k3U

A#%#3»

%$$$& t
N
8
8
6
B
^
N
|
6
P
W
t
8
t
l
l
N
I
#

£Utf& 4Si$fc$ H^LtAai & EiSHSi&fcrg rfc ta w , A

m»yiww ^.^nAnmmamw iaWl 6 <
3w«"fli*4.rea» ftjaayitt <g^gW
ttw» wmwmnp
mam^n'wrnmppppmpa^fm ©

4
ViP
S
P
4
*W
W
1
W
* m
o
m
m
o
p
p
p
m
^
P
W
P
P
ffP
^
^
t-

H«g
t
frii
a
*>0 m
J^
S^d
L
.
«#
?
p
if-m
n
n jjp
m
rn
w ^

aafaydawm P M * and c ^ o g . ( o .i a o in ) car andten apfarido. a o a te tin n
a t t4 ® f . (0 .1 c o la } » f '<Q a^^m «dlM M ai4. In $0 a&. « f amgclmim adbacr
4ifjJB
MMm
i diQjd
tSP
M
w
tWinBwy ^.p'fp
AfK
ab
giufgjm. *wSww|6ltt|6yi|
CHnbSpX
w1m
^EC
l^^^^^wP^WH
R ^rtji|
^PPP^AmmdjA
^^^nT
^

A'^j^fejiltewfr

ttnjuM

nftaawam m * m dtew d and atsuwm fa r ttm o r a lx Aoom.

mPm? ttiS9

16
tHfWWtfaa of tfc* aodim (W it of Q» aloo&ol «m oooluj la aa
i« * M b M i a m lstton o f lafttfttaaxojKHrt^l ohlorldo in msrnrn, pxopaxod
•ft VMMimwly ftcftm&wi* atfdaft own? a pwlod ©ft ftiftom oUutm . A ftar
th * « W w n w « MLkvM fin? fifto o a s&mftw I t ms filftm i M i ttum
•rtww tad i i M

mmA
w
< 1
1

Um » u lth 35-jftU portion* oft lou-oaM 100 aodlaa

amdt tftmmm ngjUfeli

i raiLm g.

AI^mm idono iifto *oMjam» ywdLgw***

siwijhgug to p flSXfi&K&u

*<aMifetftite»A, m m

*k»Mi«*fifa * fl1 it4 iiifri

'■
’■ :■

*^
p

h
m
mM

W
W
W
lft.m '^
p
p
M
^
A
' ftW
'o
C
T
p
^
W
M
W
’’P ^
ftW
P
P
W
ft-1

^
W
W
PT
^
^
W
rjW
p
* A
ft®
"

ftM i M i tfeo fira s tte a b o ilin g fxm 3&M&P o u t o o H u rto d ,

m
t
m
M
IIN
N
P
^
p
t
P
V
M
P

Froot& eniaftU u

33-Ji f . (80ft) oft spO piM fpSi*
m
M
qI in
f
t
J
O
M
m
u
M
f
t
a
f
t
*
, ft.p
.1
6
6
.S
»
1
0
7
*
5
°
»ftf91
*
3
5
1
5
- S
b
*u
tte
r
|p$g$g j(JbBS*3L*g |k ^ i^ t ) In
ia fiT O rtid ifiip lM R s o f U s iit y iS ■£#

y |^ > y

T tEfeS

£** F lg a rp Xo

Cslo'd few CJ^ar*0** C, 1*2.871 8 , ti-^o

m m * c, U3 -2 ?. lt3 -3 1 * 1 * b-5 1 . U-U7

A.

^ N g u g • o # 1§ ■• QFa

5 ftl« wrtaa* w*8 fM p ttw t &m» fiJ30 | . (O.ot* w »l») oft w jriastcsols1!*

/Oot^kjlyini

M Mftrtooiuttti** «rt«**liatto %£ ikhatf 0>x*

t)3*l£lMQ3?Q*<*

m v te te . B ja ftlllirtte n «aw* ?*U t s - (850) oft w w taleyolylotBA dJigfl
ts ifS w H ro M O te te , ft .p . 6U.5 -6 5 -1 ° a ft 18 * » -* *g “ lJ O lO l- la ili0 « ls *d few ^ic^Jn^aP o*

Ite n ft*

® t i8 i< jS if 8 , 5 - flii

fi» 5U-63I H* 5 J 5

Figure 1,

vO

CO

O

O
vD

O

uojsspustreaj; iuop uod

CO

O

Trifluoroacetate

(0C14 solution).

i—I

of Cyclopropylcarbinyl

CO

Infrared Spectrum

co

(microns)

On

Wavelength

17

Figure 2.

Infrared Spectrum

CO

CO

o

o

u d js

spjisirsuj, 1 ^ 0

O

CM

o
Trifluoroacetate

(CS2 solution).

CM

of Nortricyclylcarbinyl

(microns)

O.

Wavelength

18

8

r*

8

GH . o * C *> CF*

>

m
A
w
$vm
*mj*&*k,w# P K U w S9n6l4X#§flro|Py**8in«^yX

wMt pFf^plB^rWwj

a * p s tw iw u Q jr t e w ilM , fro m 8 .8 0 g . (0 .1 mi») o f e y o a o ^ p jfla M ttg rl*
o n h ls o l ( th a t gatra & a& sgU poak 3a tfco »**»*? o b ro n iotograpii) and 2 4 0 $.
(0 4 . * » !• ) o f a o d ln a k y M U tft la 100 a ll. o f co b yd ra u i o th o r.
©£

A flo ta tio n

O h io rid e * tM e e fe l %ft o ra v lo u s lv de»e®4h#d« wbs addad

la %m s to a t** l& t&e e le cto ra te e o la tio n eooXed to ext to * befclu Bm»
■egAiitfrae «eggt tft& E T& l ISO h M lV f it $&&!& taeftHKffitllX'e * lilt lM d . wm ilwrf
tttiP ** tto * e f^l t t 1* %$* * j - p®aHSS9B o£ SS6t*N$tt3MI .SodlttJB bfl, ft*1%^ i%ft ffttpl
3,©BK*o!ld H B tW * *H I

#|NUf D * 1 * ffit* ,

A fte r reffiOVtog th e a o lv e e t

<1^1 $ ** to *e n is i A^*ii^ti.-jy> ^ fw ang^ n. 0|jdM M *i H w ft ***** th e

1^-11 ijf ^

55*85° i l 80*9$ mm am e&ltoetoft* Wm^mmito&m ttem #i * «e^*stoe©
QOlllHRI jjH?# ISP^%|i0®S0: e ttk b .p . 5IM &P a t 8 0 *9 0 w . am i
ag® 1 •3 $ 8 3 * 1 .3 to .

to * vapa*1«4m «na.t»grs#i ( fi# * * e 3 ) had tfc *1* * mla

peak* (Axial «# 8 isto«* 10 a im * and

33 *£ & •)*

JtiB CfflllQOfiflKlttt. 1 .2 oatati 3« eieflMhaMse^aPs

tisdXbios^aoetatej,

to e ** n lH be

M fm edi to

X il jgftfl^fchflM* Wiww>ayfl4,.4<w> w# e v o l(}.

e Isrgiyp est?ae#e &f tjfl*

fla o K e a a a tg rl ^ 4 » fl0 * , ra p a r a tm a w to g n p b y ia U o B lw d th a t 1mm o f
CoagMMamt 1 and m o « o f Oeapeaeal^ 8 HttBP f036®ttd •
A tt^ te

to se p a ra te O aeptm M ie 1 # 8 end 3 by fre o tlo m t^ o n n e re

t»M.wj«aaaa<^1
_ T
th e VaeOP
ae^eJ|MPai(ev^BFemB^emw|aiawaF®
ei%
eeam
^^M»
r ^e^paeoeM^ hft
■we^li8■ ^MMBdittiMiiliiMtl tw %Mitt WfflilT<ltil# ^KiiMttdh
■p®e*e
^
(OaK0M 8 a « m ili tlhm *

31 aA n*. Id a la . and £3 a la .) .

S o p a ra t*

20

Figure 3- Vapor Chromatograph of Reaction Product in
the Preparation of Cyclopropylmethylcarbinyl Trifluoroacetate (Analytical Column).

10
Component 1

u i-

Component
Component 2

Minutes

&

w ^iiu 4 M P H w%
. wpm iQnMPwwiPmf jo^*F«yB9Mi gpVv v n w jtvq ooaycwiwrog
b ttb an « M a iW p d t f o f a t M M 985, aa ia d io a ta d by n |a r
«feMHNAasmpt^. Canpoaawt 3 aa* abama to b * c g n lo p g ttp y lB rt^
p^jt

^ii^iW i w& '
jgy j^pfay«

w^mKwehmvV WWH

8jP®dpH*^ JBwFW Wjf vHpTOF

_

i

'*•-’ -

..

Cw^omanfc ^ bad b .p . 57-5B9 a t 80 m u asa b jj8 1,3578-1.3579. Bw
In fta ro d apaetrea (Flguva b ) ta dl oatad tb a t I t m o an. a a ta r. Ibara lit
«a a b a o ijjito n band a t J 4 J ^ t wad' th a ra t« alaa aband a t 1 .8 5 /k ,la tfca

a
U
fc
jtf* m
w
l m

ju
t*—
m
**| tfsirriiW
M
tiiiii>
n
»
'i s \i

m|[4Ml*4
X331$g

jf ^lU W lit i

*

th a aatar (o.go g .) at* bydrolyaeei by ttuddag a tib
jarnH ttm

g&, of 6 H

W6ti$ ^ rtW 'frfofllf UtiMtibt -W l% *fl>

■otojbdOPiiS* #*¥* tfao S iclyp^ts Wtftf# drtodi o rip
'

1

SSB»

i*Hff

jpstiMb

lltfU fjiilkit*

^hiyfe wwi

n&Pfe %ta% © f

#- <&

wofoem

Affetip fix tH 1*

u n i ofe^ffitjQCKii frsisi i44ms

m%a%&m$ sup* ■#*?# {reported **p.

&£%$&

l..^.f;ib%^«>t»t fTONL

l^ ji^ t

Tfru# j&

'UtiS'fc

■^feiSs a a to r $j i

M *

O
^
M
R
C
p
W
N
fi

C*Xe«d. for

^

a# W*l6 j H, l*.p8
^

Fanadt C, U6.S1, MuSUi S, 5 4 3 , 5-30

™
-»*r 1
.3
5
8
9
-1
^
5
9
2

SMr lamaMd apaatww (Flgova 5 } indlaatad tbat it wmi m aatar.
J a n . C«lo»d. fa r O ^FaO ,* 0 , U6.15) H, U-98
Found* C, U548J E, 5.12

oo

\n

o

u o fs s p u s ire a j; qneo «i©d

of Cyolopropylmethylcarbinyl

vO

(microns)
Trifluoroacetate

On

Figure In Infrared Spectrum

Wavelength

(CC14 solution).

22

Figure 5*

Infrared Spectnim

Q
OJ

uofss-pusirajj; ^u g q **©d
Trifluoroacetate

(microns)

o\
of 2-Methylcyclobutyl

Wavelength

(CC1,

23

2U

toOW w im no bands aoar

too M W la fm ro d opooteaa o r m a r

3 4 3 /t- in to o tnfronod spootam .
8«m m » U |M

o f 0.26 g . o f to la o sto r by to o amo

pm w M ta* m p rrn iM M ik r dooosiboa ( M

as o lo o ho l to to an is fro ro d

OpotoMa (n p o 6 ) d iffo ro o t ito a to to o f eyotopropyim tojftaagfei& ol.
lb * in fm o d

119m Am m

o f qyotop»|qam ^

(to g a * 7) ia

laetodad fo r eojgaa&aon. too easbon to te s c b lo rliio aoUttoaa d id n ot
doeolorLso bretons in oaatfean to tra c b lo rld o . Ib * jfesaytaratoano o f too
U X ocboi,

roosyotoO isod fm a potoolaa* M u r, aaltod a t jp -io ® .
0«a**d. fo r QjjPialJOa* 0 , 70.22| B , 7-371 » , <5-92
K*w d*

C» 7 *M ltf H, 7-371 V, 6.85-

S o w to m Q *y o ta lli*rtlo B * fro tt M o n o , eoxtoa to tn w h lo rid o , o r a o to m o l;
614 n o t afaaspsa to o M O .tine p o in t, fa a tto a p t m

n b to pm paro too

3#5»diM«rtoans<>too,, toot noprodoto M tto a g to rn * m m tm p m ta u m eooM
bs obtalnad. to o in fra m d apeetm o f to o o o to r (Coiqpoaoto 2) oaf o f
too. a&oebol boto contained 101 absorption poto to about 10 J * to to to
jQttQTli# sSiBB'Sbsdl

lib#

fUj&g (23b)o

to o aloofaol porUm o f to la o o to r in probably Z -M toyX eyolflbtoanal.
Soto In d ic a tin g to o stru o tu ro o f to la a lco h ol am dlaouaaad in too
oa raaalt»o

T
to
lP
p
n
to
fP
w if**

p nmpVtwvWm

f»H to 4 jh y ifty iiiir ih B iy t

N#v«j?thal«»#. Goasgomnt 2

b# w fw tiM to a#

-J
p
- M
tonaytotoiW
PW
to to
toto
to
w
lto
to
ito
to
* to
to
to
|K f#to
iN
P
*o
P
n
#•

#V

In tb # jw#bflrita cta r o f 1% f# ifb fH if f -r

C yoloprapytoaU gfl^arbiaol (174! g ., 0.20 a e ls ) and to lfltto ro o o o to o
«oid (254) g -, 0 J 2 aolo ) warn tonad ia a 5 0 *to . latm d-bottoaod fla s k .

Figure

6.

Infrared

Spectrum

CO

Q

u o T S s p is tre jj; ^ u ©q

Q
CO

(microns)

Os

of 2-Methylcyclobutano 1 (CC14 solution)

Wavelength

25

CO

uojs spueuBaj; ^u©o
of Cyclopropylmethylcarbinol

(microns)

On

Infrared Spectrum

Wavelength

(CC1* solution).

26

ft?

•a ft to * a ba te r* tomam w arn. A fte r w tftoadag to * e o la tio n fo r oaa-fealf
b * * r i t bad brnoa* ta lc t a t and se O ed e * m s stopped, to * soteteM t
to * to m *U m *d to im tn to soon ta q p a ra tu r* fo r 20 h o u r*. A fte r

to ia tto t w tto

a ft. o f totw v to * K t r t t n m s aactrasted w ith io*-o oM

$0

10* sodtoat biaaxtom at* u n til to * mguiam la y e r m i m in t , and to m t t

ugg tf&tth&d 0 x100 n lt& twitaa*. Hha orattz&o
W
to
P
to
w
* w
p
ip
p
iW
to
F
ta m

to
1
"
to
P
t

m
lW
P
^
w
^
^
to

«mmi

U
to
H
v
V
P
* to
m
#J
p
itto
F
to
to

ov«r imaniMriiiffi

tolfto* m & distilled, b.ju 1 0 ^ 1 2 2 ®, »g* 1 .3 6 3 9 -1 .3 «lt?.

wm
W m
V
^
|N
m
M
P
^
0
P
V
n
M
|p
M
M
R

Infrared

a**l»*i* of tot* protest indicated th a t It m s p e im x & r (about 9 0 *) .
Smatovlto^ttontpl t*lflH>»faas«t*to.

Xu &

®ie yield was about

- Cl&liten fXaarie,, f!t$4M w ltli &

( u ttf f fl T ig flff

jftyyf

pSsos 0# gXcupti

fiTlffofl j

o f th« IM

<*f tfc t fla sk* H i plae«$

H|»

M i M iS

0 *5 0

®tes#% to M tte *

SfeyB

g. o f

*

A mi oadjdiaiiig a o lu tiio a , pro*

a iiio iifia g Xajo g* fc* m k i 0jysiipw tii0 QaJajytuPii^® in

liuto jgjft ^
to
'to
to
ta
.’tto
to
t^
to
to
^
m
.

4
1“
^
S
.j£
?

~
m
, to
to
d
S
^ ittiitii O
T
ijllitiW
h

O f iM lS 0 8 * g U S

£${,*

j
A
'if

Ito
to
m
to
A
to
d
h
adta'V
M
h

O O |$ 0 S 9 ^ |? S t0 d l

i ^ y g l ’lto g rj to a ii ay M a rf < S $O pH tlS 0 til3 ? 9 1 t{ $ l I I I # f fltff f ff 1

tfc tft *****

aatoztlaX

4
1 C
r

1*5

f tlf il
f t t 8UQ& A IM A #

slow ly* Affeoa* f.^,1. q£

iMtifctinP

to * wdLdisiag agent had teas added {20 adm tes) m o tto s m * applied to
s tm s -it osar as m oh o f to e ergm to enspsM to* as p ossib le .

to * w ater

la yw r m i m ta rto a d w ito potasaisn eartonato and to * organic lijw

iioniiTiitnrl ultfe a wtaKftjtiiit dhtoBBW* Ai# Wsdo oriEaniG Sjbfw wei.dtio4

^
P
to
^
®
W
0
P
p
0
r,to
^^^!tto
* ’W
to
to
T
B
P
to to
to

.-ta
s
tawj^ww to

0.J2 g . A fte r drying « r*r D rta rito

—
- -^

...

P
l■
»

m infrared

iuto

’** te
te
w
^
jp
*1.*

spactrua m * obtained

to to bad two paailc* is to * eaattoagi regtm (flg o r* 8 ). to la ox idatio n

Figure

8.

Infrared Spectrum

co

CO

o

Q

U 0 Tss-nustiBj£ q.u© 0

CM

O

(microns)

On

of Chromic Acid Oxidation Product of 2-Methylcyclobutanol

Wavelength

(CC14 solution)

28

mm m p h n m X / <b®*# t® y iild

kmtam fw w

< te* « o iv w i> o a a ia g t f M w l.
80bASj|fe JfSaSlMAlfcfkAifc ~

rfafWgAjfrjfc
«iiw vnnM w wweKuguwanww
jubiowPPbl iprjsrbjbto iVKSr wcixwGi«90 W3JW& 0 ^

•o & iu t fcy&cncld® .

8 » b ta d a «o3at£<m mm a a W ifiw ! w ith ooaa«i& r«tad

b g rtfcw a lilo rie « & d and octx-actad a ltfa o krtto a to ta M b lo r ld * .

wx«w

A ft« r d ry ia *

vmroQu %«wTOaj^ri£io sojj)wsom mmr w sarow * tn# SMSNMdi fljpMiKn

•PO iiwB *1® 'PlJIWPWsMW* Qk w lf

<5WlraQXl@f* IwjroS^pwkOwl jNMUCg*

Tha oavfeoft ts tra o b X o rijiia m*iiiBfi% |,^if- «H4 n o t g tw a fotohfH *vA V fokyfo
t i i f l _ ftlth a ia h

.. vmA&n MarfUla? a o n d itlo x ia - S fV fi A

py^H hw i^ll iSPFB*

X? 8£L • O f nyir^gH.ir^ftj tafc^tfefo fcflfrjt hS&R d& iA d OTAF

|R$XfAtA

and d lttH X a d , mm &Mw& s lo w ly 1 *6 0 g* ( 0 .0 1 6 ml*) o f <Jtew!ii»i& tv la K $ & t»
To tk ia y n llo w ©©aplax p i added te>p*&aa w ith s w irlin g o w

a p a rte d o f

tw e n ty is ta tte a a aeO tation o f 0 .J 0 g« o f 2 -B » ^ X o y o lo b u ta x ^ l la 8 m l* o f
pyy^ ^ t i^ i^ t lt ih la

^-m|y t fo-** p 3Eli®fl?$l ADA b ro i& l* 1*7*1 111 %MO bOttaPS I t

mm mmry darfc P m *

The asO & tion was s w irle d fre q u e n tly f o r 16 hcnare

and tita n 2 0 a l# o f w a te r added and Kdxod th ro u g h ly *

The aspacm* ao-tot*

ti<w * was oactrootod t& re© tia o a w ith ® r*a 0U p o rtlo m o f 20 $ h y d ro c h lo ric
add.

A fte r d ry in g o w

eodiam e o lfa te and rmmtmg th e s o lv e n t th o

In fra ra d apootium (J lg o ro 9 ) on th o om do m uddao had a s tro n g oaTbonyX
psidc a t S*?5 /»» a n o th o r p o p a t 5 . 8 6 / 1^ aoead a a m U a r paek a t $ « A jm*

30

CVI

1—I

o

rH

©
a
•H
XT
•H

£

ph

co

q

i—I

©
xs
#ri
o
•H

ft
E
*H
E
O

vO

«
U
& z'— S

£
o
•H
+»
£
S i
—1
O
E m
-p
o h*
© rH
a o
CO O
O
Vi
o

XJ
© 1-1
Jh Q
cd q
u CO
-p
"a £
M X5

CJ\
©

u
a

O
CO

noTS S xuistrejx q.ueo

<M

iM U fm rti ffir ttn r ty t i

ailtflntwtlllll

40km IkllMlilMtf

fagr « t* aatbMI a f afaaad, a>«o. (1*1)
.

4
R
mK
C
m*1m
km
M
& iwR^p8wS|RHF*

WS^Ef*’* tf^OfcrcTtT
#M o liO a i b t e t m t' tp iw M M iM i# U nran# * liS « *• *«»*»•»«« H i**'
•pUmA ao jaaa* 9 » fra o tto n a , b .j» . 37*39®#
M teaflupqlfttw tw w (raporfead fe«tp. 37*&0)»

m m

aollaatad «ndl uaad

m

9 m ra w in io * fra c tio n !, b .p .

33*W °» dUonld tM aabO y a»thja*»«^o3fifcut«» (raportad b .p . U X .7 °)tfea dUjonraa gamm%or m t
jH ffttfr ftl jp$^®tiwltottt^i3ii6<4

ftp «

fbaomra (lt$ ).

m i' f l t l p i

A 300-n a .

a iiXtrogasn, to to t j flwr*%>i to

it wffiH ffiify' a jffr tjy i!1#!#### ws2»y® { u tto ipqy a x lt

to o n

V B tif) y fj #0

###•' g,

mwirtuaailtt #Cfl&aM##d dXtttJftiJltf JtaUMtiL* farattAjttriw*wc? t
y iMBffy y f c M ili m d j .

Xu tii#

feojK afeattijdL d® (ifc& J i n

tXwtte m* |&a**& tt« 8

m

#0A

of

M jO m l . © f jfilib s R ^ M iS ^

«.

g« (0*16 mOo) o f froafcly diatiXXod

( b ^ i 3 ^1 2 6 °) bo#®# to & fto o y l^ o t^ ^ eto*a?ato i# $0 sol* o f digl^ao.
X# a 2S0«mt<» 3-qgKik*# fla m e f& to a i a lto a s p ir a l ooadaasar
o^mno^)tjipd to a twat#!* b itto to to lts p # mu#! #& to la b fffofli to # dtoos#Ki#

gam rator #o to # i

my gmtobItoat to to

to# aoXution to to# fla a k , waa

sOaotoi to « t g * (®*2X a o l# } o f to # la w to a a la r fflOHfctoiiOcI l-a& tigrl<sgncloW H b # ' t o $0 mX» o f aato^M aa to ts ra to to m to fto d

to # fX a#k o o a ta to to #

to # o to fto aaa ^aootot to #a toaNMkXt fe a to , m l b o to iXmik s ##v# # tlr r# d
a lto wa&mWt

to # ^su o m wa» fto to to w ^X i id th d iy n ito o g e s i.

32

fit* ■odion bw fthydrld* aol&t&sa m a added to the tm m tr lfla o r id * otfciyl a th a ra t* e o la tio n over 9 p&rlod o f oioir h^my to gonosr&to
(l*£) *

A fte r s tirrin g m ad d itio n a l hmx %he « d t to tbs o le fin reactio n

£X«iKc 9tt» <31»oosm9Gt«d and tk * mmm diborane in th« generating £ M
vaa hltirolyaad cautioueiy «d*h tb * ad d itio n o f a a a ll y&mm o f i« 9 *
H it o le fin raeotlon flu a k vaa aaxLooad irlth & droiralnff fbnnal ^
JiS aflU Of 3 K eodins hydroxide m a added a * fa s t aa foantng p arad ttad .
fitta %
$an . o f 3Of hydrogen p w n M i m e added over a ported o f oaa boor,
fit* le a -s a lt bath m a vaawvad and s tirr in g continual fo r another fan ir.
A fte r filte r in g th e atoite s o lid obtained and washing l i w ith eth<» , fit*
*•a
9
8
«^|HU|k
fc
tfta
M lA
fc
w
t.J
9
. 4
fc
9
9
i9
-9
9
M
M
tt^
9
w*w M
^MH
wtiM9n99fl A
w9*F9
vvpu'HwW S 'amwt
Wdm
w^pHOPuiR

fe
fife
n
fe
ia
k
id
lk
tfc
9a£ttTw?v9a n
0909
IB tW

0tb9T| 99(1 thd OOIeMIKKI OJPgaildtO

OV®T «ay.^wM|f%im im l ftifat .

D is tilla tio n

tu p p m ra d to glam two

main freactio n *.

fba f ir s t fraction

( 6 ,0 g .) , b .p . 130-132.5®, ng* l.!t3 C 0 rl4305 g ar* a phengrlurethane,
n .p . 7 7 .3 -7 8 .0 ° a fte r ateiraral re c ry a te llia e tio n a fro * hexane.
c a lo 'd . fo r 0*JS*aJW*i
round*

<3* 7 0 ^ 2 l H , 7.37} » , 6.93

0 , 70*28} B , 7 4 0 } H, 6.88

fit* 3,5 -d im tro b m a o a t* o f th is fra c tio n , a fte r several re o ry a ta llia a tlo n s fr o * 955 ethanol, bad » .p . 9?*5*98*5°•
Oane'd* fo r C a#s#a°e>
fooadi

c* 5 1 4 3 } 8 , b *32l 2, 10.00

c , 5 1 4 5 } 2 , 2*41} 2 , 9*99

fit* aooond fra c tio n , b .p . 336*339®, «§* 1.1401-1.1412 gave a

aup. 111-112®.
a m i.

The yield of this fraction t?as 3 .0 g.

C alo*d. fo r C *# ***)# *
m om *

0 , 70.22} B, 7*37} » , 6.93

0 , 70.20} H» 7.2ltJ * , 6.87

M * « J W H ttl& te 4 b « » « ttt, a . 9 . « H 9 ° .

ia a i.

0,

A a lm d m a ltin g

0 «lo*<i.

for

si j*3 l H, k.ISi M,

VnnriM

a , 5 1 4 0 a S , k 4 0 # K» 9 ^ 5

1 0 .0 0

' « * <*>• IjS - d tirttrn lH n tffit t at « M 7t*6X°» B it M pm tad m ltttig

it
tS m 3 #S^l8 ltep*eaeot*t

it £ 8 .5 *J ? *5 ° Ck?).

o f 4h& t& ftu rfttV ifth ttM ©£
^®^p*~

4pSt^9^8flfcMS^3hlP

tad of

9 m ra p oy tn d

walfcUia point

-I# 1 3 9 *9 ° IM k l*
jfcflsjt-

^H6@P9(NPP^|pi8MElS

flfofr in £ r*r*d spwtafitifi o$ xi&tl&Mfcp &£ ih s

HitIfeM ff
^@|J^s3y0^^

ja th l&

iiHbttiH tH btlbttbJ?

'%2|&% 1D$ '$|t4l

jflfrfrffi

in th is mm$M*

U*U osfc 1&MMN& SNW^QflSil ild i< $ lt6

t$MSISHKOP

■aria aatw r «m papastd by a swtlaad analagaus to th a t fo r cyclo p ro n rla a rb liv l trifla c w o a e a ta to . M »thylw rt^< ?y8lyl««cbinol (6 .8 0 g . ,
0 .& &

m l* ) la 85 m l. o f aahydrooa * to * r m a addad to 1.2 g . (0.0? m ol*)

3k

o f H t e 'l g f M i i ta 25 a& . e f e th e r.

A e o latio n o f M flM m w ftg fl

«tt«K M e la 90 m l. -o f e th e r, pNppaad fr o * 20 g . o f trlfte e s n e e n tle
•ftM and M> g„ o f bamojO. ah lerld *.an d hearted belev 30^ fta r two h ou r*,
■am added la t M B t r * * * * m tnatee.

M eM lU rtito a « f tin t erode product

pare 6 4 g ., b<#. 8 M 0 ® aft 33 a n ., ag* 1 4 5 0 6 .
t|M l OSMMIK1&& O jf fiHX1#
bswiainiiBintfe
wetat
J^ffriW
w
PW
»IP

^.ItaBbaftnsfe Hi

w
w
A
X
S
mm^^PIh-

Solrolye&e efeodlae

#mm a&tBBBQM SXl*.

Bhfll

^taftdwi*4 ftrtVi

w^tiwW
^P^^0P j
2
p*
W
N
B
®
» ^r^P
W
w
P
tw
W
r

$o3Mtt* fe.p. §0*5*83 .X° «& 3$ a s.* *sg®
M il M 9 & M l IN ? m titesN&M *

nw

•*—
'^tyaiff-inM^

antdttMidt

™
3i^^P^P((5H
w
ff

A e«xit«r ftM U o tt

M ewtawift 1 0 1 # th ® iil^B ttP B Id M M lX M t &£ t i d i

fra c tio n .

Anal, c ia o 'd . fo r O gifafgO gt C, 56401 8 , 5.59
Pound* c, 60 Jb« 60.951 H, 6.61, 6.71

& t& *

H$

^ N iiid i !iM ? il' ©NNRPWii o s H i#

MIsSJBSid Irosa Urtl •d & l

m*- i M

f

M S y g ^ y <^iyoMtogyttph«

SgftMMPBX SSNMPH &£ ^3^X^|J3?^^|3^3k083P^4jBK3X W68NI pJWp&lMSCl 3LH gH
Itt

-A (g0H^(M®ttdl i80gA3lto2Mi' H®? Iri^iW
^oldLo ttluwSI^® *

nm itiMMmmdt:. *A4tk\

TiS
&MWWfr ggrtMWPd 1WW?®

amatl&&*&** 4$ 4>H»4s. jtonft fttm l ftTyr ^ ty y l

«m^

ftvifbaMranaaftnfea, £ran tto apsa^palafta) aoid e h io rld o and aodlaa ookOo>
p K fg ftM n lK ln ^U iln .

lb * llp ild mfaum whpo traatLoaatad and «ba a o lld

a rta n t aw«» araofyatalllaad imm patrolaaa athar <b.p. 30*60°) on fro a
atolMlwPi a tb a n o l. H>yaloal ooaatanta, jdaSda and aaalam a are gLaaei In
.M O # ! •

Figure 10.

Infrared Spectrum

CM

uo-pssTBieun3.xj, q.neo

(microns)

On

CO

of Metl^lnortricjrclylcarbinyl

Wavelength

Trifluoroacetate

(CS2 solution)

35

bO
-B

36

m

0
0

rt

04
S3

S*•&

a

#*%

O

r|

%A

Hi

*!

$

%&

<n

s
&4
ft-

&

0*

s*

05

&

¥Sf

0

1 ■■

I**!

HI
*

Hf

.M A
yjStfc

f*
q

•

4

ik

"*

4

3f

> • 8 o2M39«&» StKdlne

PlnaBBW w « pur i f i ed fegr teeaeteo d o f H a ea r (2 U ).

Cooduetmo*

eaten aafepUed fear fir * Twee L . Hy» eee bqployed fo r oaklng tip w fe fw i
n Jjrtw w *.

m e letaleiaaee o f th e eoa3»(rt«BM w et^f and o f the n M

atatenee m

as h ||h th a t I t eoelA n et be Maanraed w ith th e wwfcuvteitee

fekftfe *****
wpP JKST^^&fKi Sjjr CwJCT^

S i# ktiwrt&ci »tudiaa ©nd
t-n
-r
v
-,

u
e
ie
n
iin
.

rp^m'TT-

ww^r^wtp

O lw Wft|p i8 ilU W JBHRm^CU!MCI«
***& ****

in m t aattriad o u t in iudNsap»

'"r*VW^1VPfmMEiP
p
^
F
^
p
n p
p
-»
p
r
«
m

T
^
jp
p
^e
pqmj&Wwtt

d ta w a e eeferente o f several v e ip fe pnr oent e ra fe e ittm e .

’F
W
reT (■
ftw
p^
H
M
r-w
*P
M

Predaot

nmiyiHL* to r m e e t o f th e en te r* ms alee carrted e a t in aatbanollo

jAAd
^
k
fc
-M
lL

M
t£
fa
iM
llM
W
k
tf3 M
r
ik
e
te
w
^
W
P

a
m
S
t iM
fc
jn
ffiP jitet3l3lhriifallim
tatdlbtw
iat
M
'fk
tk
-ttillilii
4&
jQ
IKE!#? inUSl^r
»0*iMMI*

dfcfcufr' pj^wa«*^
tsNfi

■dfffyfl

T
p
l^
^
p
jjr^
^
Q
M
P
©
#
'

4'tah

y

d
M
tfk
iM
M
H
J
#
eW
pirt^^^XW
F

J M

%
A
|t

-ji&
k
.d
M
!
r
H
im
a
ft
fc
r
a
i- - P
e
a
e
fc
k
A
P&1I& Um©
W2ImQ&W&m
m
bjft lA
tat-M^^^o
iT O a se tia t*© #

£$$ S lE ir

enpfopyfr /w y |^ Sl>S

* j

#C ap0m&m%*3&O*0@S^)e0SO m%mmlteM&m©f e#i<a* in th© ^©rUniaar

3®

•o to w l. tto ti p m m m MU>« «W to m
9& V M U w *

m b

W m *m

**U ta o *M M *U M U .

« * • * prw rtflw ay f a r wrtaes a f irifb ts m a a a tla aaU by

a « * m i w « rm
"P

’i * P

•» *&
4kMb kffalM,4®*4tffcvttjb Jbth'Jitk
w» -jBwMUftwBf wftff

a Mk
P5M »yp

MBwirttOr^i-1^.^ ^

HJI I Ww m HIm W^ P P #

’i.jM Mt4tAiMM ■a#

Sp^tiiPhkP^^fc•

■-^P'^PPP^^RP’^P*' P*PP“ .-.

WppjHH

WtMfeftMHM

/<■»'**

ta p !

A# ffr -"tftflft

Jfeil^PPPPiPPdtJNWakM^^^^lfcpP iP%

rtJ lliA Q P w t p rfa iM tttt

U^^fi. ■bmUt'%-^kPalPuJ^ t^BmPP '^^PmPP

’PPBffHB^ff'^PPPp|IP*P!IPpppPPi|[p' “ w:w’wl'*pp

i^yyop|ip$ isMi' ^ ^ li- "te^'1spipiiiyft 'jiii' t^p' i» i^
ilM p p iiliP jjOJMMArftuttwjk MMgg*
» lia
M
iiin
i' m
# liM
iM
ftitfB
lili^plip
lr kppM
«pi*i.p».•
PrP
jp
P
^
^
B
P
’fP
P
P
^
^
P
Pp
'^P
'P
-P^
^
^
p
M
f^
p

B
jp
'P
IP
p
m
p
H
P
V
P
I^
^
^

!s*^^9|j^998^!p

MMUi iMJIUWJL
Jww#OT«S*P

ippjyutm

••

p b p y ittftrttT iiii

B m i f l l l i r . l t t | 4m

P
*^
p
M
p
^p
p
o
p
j^

'p^'^ppp^1■

fiqWT
<»j».**A
.i«iu*
yyi
y>«y
4BA
MMBPlybB
H uflff e ifjf B
aawrM-'ft
tt.P
P tt
pqlPPRpM
^plvi1. W
w^pWp
^piwP
PPP
pBJi |^p®
rpr p
n‘®p^^p#Bp'^^p awt#
wf #j3tiafc
pPf*- *^pipppipppwp
pp^pinipp^ppamart^iai
^BBPpppp IMfflB
^ppr^# - afjgp
wW'p*p

4
m -Afujm.
mH*!
!■
lam rW
ttrunt
appp
p|f|aPpr ilAwMgMMHM
qHjyBWpWWpp>»Wi -^B
PPlrp#P*#
,'>^^p^^P
*PW wn*W &M - atraft ■«£
^P* idalai
bbpppiwp' ■feheMrlRi
iP»PWiWH.i p

jp t e S y iS S t o d t ii

{ * ) So3ro39«ai » f 8 ^ 1 a ra » j^ o M b i*g rl tiie ia o ro a a a ta ta la TOf
(B M o H ^ ««M p * t

6 « f.

#*B lF IU P p

»

<s.ii (>l o.og> » ia ) «•»
6 t**o l*a S la ISO *1 . « f fO jt d ia ttM ~ 3 0 £ w ater M l natBtelnad • * 6o° fo r
60 boom , A fte r <x»oliagt tte a o ia tio n twa> a a to ated w ite a attea
vn
jjp
'^
V
M
fciiH
p
ijp
iP
W
^ W ipi

flp
M
Q
P -O
f
^
W
P

^iP*PO

wPPB^^ ®
|H
P
JP
op»t®
W
fflP
H
l#

‘w^^W
^O
O^W ^W
»O
pp* «
P
*lr^
w
p
M
in
H
"i

-P
W
lw
K
r^B
r^P ®
P^H
W
R
p^B
^IW
R
»#

jlteiks
1
fe
S
6
,8
^
B
-#
®
^
|^ |
•jttnjf
mmm i^^tifiltililltilt"
* W * lw if fpwMMrawW
i16®
HW |iiHWBi
WRSflpB:
if ™

W&M ws&tl ifcm i § rail*

«HH

ntf®t^
L
—
«BWF^

^toiv®

Mli&txlifts o&ootvan &t th i* Ofttdo

IM H M JtfWlba^bXtt to im

(A2bi#3L«# 23 tittn r )

m
B
M
P
r tfU|£ljHiQpiiw

' jmh^i |k

s^Lupe ( i& **

mA .

f frtiirffrrffr ■

(til S o l^ ls rii# o f

^ 00$

<li«s(ssttift^3 0 ^ # ^^ g |A f,. .uli j»eftoc*
Q ^ l^ a ^ ^ o ta M iQ rl tai!l£GBewe»«e«liAtt (B 4 g ., 0.®5 m i» ) « •
StiHoHWdl 1b 200 41* o f ?oj( <Si®0cias^*30!S aoteBaol cn l w fi» » * i fo j* 2|g
I 9B
9W I*

Af^nr

Sbs B itetihtiii iM i fi?«otlofiujtl^di

n SjMblBB

noSniWk* SbS' li^fv^1* ^ 0^otrm ^ o f j^ # fliS S

******* nfe alhfttlit <1-^ al..

•n
w
il!|(P
!^
®
W
w

^If.’t a # ^ h # *m»I.

4

-lip
p
ir T
P
^
W
flip
d
IP
lW
«
B
P
H
P
:4
P
'li^
P
'P
*P
^
"
6
P

..

■
W
n
p
f^
P
P
P
p
P
'™

-*
iW
b

SfittBti#

"P
W
P
tP
P

0H aih
la
WtokgtAA
urn
faliW
itfi
p
P
#
iw
i^
w PlwW
oli1
W
wW
lw ♦
'W
'O

*LW
B
^
^
P
i^
p
l*^
j^
g
|B
*

ytfimk ^^ M i. . # #^' jain-) sHM^lajssotls to that o f fiafc^M^I#
• gt

a a ib y t trin a e rs « » tK to (lb )«
^fc@06Wlii'

4^><a eifiBsfceiltV^ *ila4»fwiiwi^:ia» ttf

<10^

n
M
lp
H
P
w^
P
P
llllo ^
w
S
H
v '^
P
P
^
4
w
#
(P
M
w
®
flW
^
P
^

hnd #1 on^bo^ggfl

hffii^ ^40NNMi

^™

Umi 1* 1»

^

fr»stl«m «, eontolM ag aM rf^r

(A n il** 11 ada.) and Uta

« **a fi« tt wHt«r ( t e a l., j> a te .) a * laB teatw t Iqr aagar oiuroaa*off«4>y M d
Wk&Jfw W **

hP

A ttm p tid salaroSancts ^

*rWaom~

&&*&&& ill: UttfcflQ* *4 ISdP*
Q p t& a V fV f& m to ^ ^

t » if l * ow iw « ts »» 0 .0 0 g . , 0.C U 6 a o lo )

1 ^ >*»twd aftfa. 10 & . a g w tfc ta r «t jfO^ fay »m nty»-fattr boayg,

in
■*w
wp

AtfflnsF mkH
'M.itP-w"

iffijAf*

"

;, 7*5*"'*y ^ q p W F

1S tW ® tid L 696HB

n U flttt*

f ld f

vk& ofm'$ ,iw
iy
i ■ *WPppppp?WP*w inm
■**&*&■**&
*PW
^^ppp-.. *I!|P
PPP<PNPPP *P<W

' Wl

">,

flHHUPFP

P & fo fiX * J T O d f

4fa «

TPPPIfPTPIWpWFW'Pf^wpw

f i& t i& iijiili

itt

If t iM

iiMr^-M%itfbW»llf

p r v ’l t t l i ' t j^ n

.

P P P I

s a fttw fe t^ w t

^pnlp^^jfflpWA'

f r w n ^

< H ff lT*i l f MF fff

*PltfF

m m im

y ^ f H im i

il&Pfrtt&ittd a*»«t1iw!t4si ,srtwgi jm
im
m
em

Vwvkp

lijb

tu u < a
PFtWs^P■
P
PW
PW
F

ijljl

H O l . 't t o l i a l t l J I

j » m w tiWM

9 mmA

f* \
'
^W
l mL. M
y #y
$«M
*$
w «^iw
«iu*Mb
#^V»'iite-/b

€N f

mm

wfc Im*®
'iftSMk:

**muk

4 4

tt.s *a t !'A

J K jfr

ums^I

|d k

i p N I ' l l w w ^ i S I®

ss«

?fc ^JfL dM^^fcJ0F^frb%
4KM

4
9
te
4
jh
w
A
B
u
ft‘ttM
feiA ifc
rtP
M
jjffiT
.'fc
J
lL
lJ
rtJ
m
U
t'--ifr-J
d
L
-rtL
fi)M
L
^
L
-M
k
- W

■i^^gpsjyB^pyp^

^ s i

^s^afp p f p ^ p

mtm x

Jm^bSK'

A A

4 li£ ftl!*

AjElSllay •aflMWwgftwa* *|ri||.

$& ^j&$

W
fm

_
w

*h|i. g$2&tlQj| ***** ttX&tfAtflMd tfcPiKI ^ ai|<t w lih lii s£L««

irife a M & M a -a r tl ‘w e e p e r
PpP^-P^P^P^jp* 4
I^F.iiiiiiA
Pt^PP!P»t*F^^
pf!pPwP
W^^pspjpp

Afedb^rdtt

is ttw

4^ ^ i! t %

{MwgMfe m * ^ w inin > t w t »

tt^

* i ifii <*■!>• iWlt' llft’

lip ilP w l ^

jw g ^ ljM r

iO T I

%k£&8t®

rifclfablV

|i« h »

lA S It t t t t d L t i l

m^XjtM%6 m WtSMtfa, & £'
unpp

^

J*\

i^|

mi^S

ip.M^jrsfc iW-BjM

M&Zm&
^ 0 3^

^ [ it f f e in t t ^

W

* ^ O O X *tl

^ lA

liiBlMii.

49m IB I

* p I irift.’feftH HTt h r t i i t w i .

VmmvfQCk *

"F*»sppp ip,

;#?^¥ HS«# W W
$m
8&M i- WEIiia#

B S tt

033J &£

e t h f f liP

wp flfig
g w p jS
f ^ ^ l* ^ ir ▼

a »x i

it |a i

.

xmMm $rn Qmmfc Qw w p w <totE»wtoeM^ (*» « » • o» SO0* S p*s«i« « t
jppi|Hv^PI||«'PwrlM H l * P W p

a
“,

IF^QBiil?
*R
^WWfww

5

^ WBl©^t^LcflEKB'
<pfpi,'*PWWF
ip^pppwwppp^

W
t i E tfff.
tt
*^. ^Pl^«

'".'W'ippw11!1 m ' W * w *

•*

3^ t i^ 3SSttl?6lS
«sjm wi'-v

3

ittilStiB tifW

3^ 8l'

S lS ^ ^ L iG N
d»^»
■"■B
w ^w'

«M rt tH i» ^ « » «a» <^?i>«p. o# iO « te .) » • d ta H ^ rl « tti« p .

Xba to e m a d ^w rtanui o f fm o tio a %
w
> 0>m$>Q, 39»St a to .) ecwfcslawl
lia » *p « jo a JMMUS obsrao^KtiJSftlo o f W oloohoX, tfa* (^roiopifoiwno siag«

'^P^VP'PfPpV^^pw*

3# iSwNhSisitt tibxm
tt§3&»1 JMWHP’ «#
^^pp^^MIP' iPvm
^p^PFPi^P*w 'li*
^«JP&&&0O ii^iBjpP#^
w^ 1

JSMUiyLott.
* &«
•lt<hii
miI.» .V ^npp, ^M
iSiMlifcL'
jSlBfllliiliMtiL
hA
feitaMk
^"P1pw.hw 4
■)SB
■j|H0BF jffSSWIttl1
^■jPk w
pilpwiJfcl«iBi
’^ipjp^Pflr vMiNwv,^
UffWFVIfcwS4M
MRmipinPPQMI^ w
^Pb
W
P» iW^pTw
'WNHMMP:M&tftL&MBl

-t#) SllSbl^lyEte

mo&

Mu MmMJIm

In

Olt

SSfaiftil

'3i4iN£tE

m m -j^g

to b# mo tn ly Hm ttttttftB ttftsftl ttttfcm . So '^pB^xrpKU^^m^o^ms^ks^L n a ttttttt
tttthtttt* m itt e lttittttttttd * ******»** yfya^f^s ^ttstttt iHttm foym i I f ttll^ySy'm Qnttitti
jfiLtttt^iSttl OOisi O tttttttttttti *
A fte r rdftaxtMg 10.0 «> ( 0.06 m itt) o f j$ p n a £ j» te a y 9<& pur* ojrolo*
)a ro j^lM te yle » u & lft]rl tirtjpafflyo«o«t«d» la $ojf « ta iiitt* ^ l sttH m w l f t *
32 tea®# sad Hum £r*<MomMag te * tto te tte th ro a # te a tttew a p ira !
#*3»e*» la fm ro d M uOyttts teMMd te a t tea ante jwodaote nm * rnm&L
txlflH n m a e a te te * a>^wrtfayloyotetetea»l m i m m m m fVtegtti a s te r. S a l
« W—a * anaanfc o f oyo3Bpi»ig^a»eth7aoai*di©,l n e th yl « te o r natt alae abmm
to fea a jw te a o t fcsr aoapoteffia w ith te a te ftw w d ap»otw*a o f

(11).

m

m thanbio

to m

Mtar (S.0 g., 0.C9 ap&t) «u «3m

£i&
ijM|!n1fctejk'4w
!i2%
wwrwAX
W' rniiltfrlri

c!mm w w

% dftnni l>2i 2 wrartj

f

c

-

rm tfm e d t o r
#

4

k

12 fcotuv in

MMM
M
tip
O * wMHW dPwhfeCllAjS
*
wa»T
y«
M

UtMM tttast m tto & X teil&oroaiavtwte ad agr^ppc^UMfefayltt^iByl
SSlS^SL

jMPotSinyfe# f ff^- TOTrartt jfoaraafld I s

dtffitnl imtfftfft
W ^ “'
'p.-^^.w

hmh *n«m JMgfi&JElttl*
w?

-Wto- a»ipi^>IW|H''MiWiW

V * / $SOi$l^j|jyp3U6

» d » « g fe a r ( 3 .2

0 $

y & tM

)

m

3m 8868^690*

« .»

0 .0 1

m

t i % m 9 & & !to g 9 & fa to

idfeJKft UkfcJki^K&lftilHihtttdMMitJf dfaf

i* ,

9 9 $

om & * * «

v m m i' to rn

to m

x m S 3 m *&

to

r

12

im

a m

o n ly d tr U r ia fe l* y v o O a w t*

AW mJHRNHPP'IrV!
*« SM 4

n w i «e

efeM susd &$©<$ ttm
«nr,

to

XIMKURIt AND &38Q8HKRW

A . % • Abteaptod SteuotoiiMi P roof o f 2-H atoyi-

Wtit m%W, tMrntxmi fW » tfaa ro o o tio n o f (^lefn«opgrlM l^ja««xM nol
PMfe te lfta o ro o M tp l. atO oildo o r txtO u o ro a e o tio ao£d, had Ah* m m
•MOyCU • • eyoXojw ojsyaaote^

triflw m w w oW A o, bo* dUTfoanmfc

l* ft« « 4 and n m r ia fra xm l aboorpfcioa a p o rtro .
X*6 £>J&* «nd §& 3«23 juu

lh o a&wwo* o f ham * a t

tim flwr tty ^

a yt G ottitflxi in ® m l6«

propaao K ing. H ydrotyaio v&tb boao g ar* «& hloohoi «ba*o b o ilin g p o in t
'dwaajdA
OfeMfejiaJwuw
dtiAMitiaHaiom
mommuht w tf& w pQ ire ir o » w ) w
\fi^ u ia<T
ufij*%
i, /\ obog
winoAAioa
wuitioaiuifll d
ppfw
mvXm
aa^A*0»f|.Ji.<Mi4>i oiW.^ £
%
*k«% *»#*
U#*«r*

1F**a
mmADjO
uA wA1V
AA ^maoouoa-*■
/« »A w
eos*AO
t v ip i si«u tcaito
ici
w1n»A xs>

iMtf»iMMijl«M*it«* lilOQilOl ■ fKmm mum ha
wwiri■
«m'^ma

v

W
1^
W
flB
fiW
Tm
rw
^
r ^
n
p
^
|P

*v»*v *» th ti in£raz*ed

0*•*j*io c p y y o jp p ^ ^

o f tfett ftii& r

ft Kavwl ak«ftwtA<aw

ip
n
N
B
J
pW
P
W
^
^
i

to
p
p
p
p
P
^
M
iM fr ^
P
B
!r*n
to
*

os* t& tt a lco h o l. Both o f thoao

WXtftolfien 41,4 hav$ a bso rctlo ^ w—fe» «# about 10JL 12#* w iiiitin mat tan fi&G&ibati
t& 'Sbs c^^2jolsiSj6iy!i

(^Xfe) •

Sn CMMrtb©H lt#^yiME?:h lftyi4 ffj| yyy^t jpyow
ISEUmTI

$&%

iflHy
4

^$Jt$WWSi^

\®»P*

th«i 3 #gao4

l

-

^

byoaiss

/»

353s*h1C>)
Am

W

pP^torO

gmr#: a #»ijM # >!|4N noBXtaSdi beXow voom tM a^tt.taf@ «

A aaaroh o f th o lib o m to ra d id aadt d iro lo o o aogr v&xtP al«moX
<o^iaoi»ii*irH^,»«il4roar to 43HM fiXOOttoX Ob'tildUaSi JE^Ift
P
a
lW
i^
M
P
4
K
P
|im
^
B
)P
P
P
r
w
p
p
im
ffp
M
M
P
|^
H
L irtt

m
W
1
"

*■
*

^^Pois^,,o
arw
w
^

111

,m
ip
i^
m
p
^
w
r

thftS iB *
siwwwbiw

“

& • «0«moa. la pM m toar a -^w th s^yo ljo to iw w lji M biaii «nt3d haro gaoa a trle o l iamaam* am th is rw ild •aooook fo r tho d lfflo a lty fa proparing
a ta
ntoH
w '•
rfflHalffM
WlM
t-iMM
* • *•*»* *M
* T lfflit
'» r *•
WttMmjf pm

Aaa

ti

tlw alaetol te * mdobiiMuma, Mioto kM

* toarmtwrlktlu lafinuMl a m U m tfik akanspftiMi *fc afecwk 5«6>o>(21a),
to m iiiw m h itw . Sato w M rtto * «pn» i» o to a i « |*b am * to m am.
totoWftlto
£&
<mMf
c ftM
!>■**.
mm
mwW
ti pAmmifel<M
fiftftk .W
ftt
H ^ I.i. pii ^tlftiflf* ftBd P
pftW gffltfhP ftftftP
W
Pto“ mtopP
M tihom
WgHt&mW ftP
PMMWWft|plftRMpiP# fPmiM

•tooto. # *6 ^ * . IM to ft o xidatio n o f ea^Sratftnon# to rto to lv o ft w ito
fttoMWpft o f to ft «^yeClolwttaEEi(<» & to i la M

mnooamn (20)«

to totoa$ft imp m dm to
M
M
M
M
flH
^
liM
U
jS
b
ftk
’tfrik
ftH
ftb
^
B
k
'

fc*sstototofftltotoaml from

a
.jftirift
wMKto pP^wwml^maJliS
UMSI fH; aftmtMMUfcaMSkftftiitoM w*
u
h
m

A
to
w
k
to
iM

W ftm m m m W iyX Q R ^ ^

^
M
lb
N
M
h
P
k
^
M
^
to
J
M
b

*

U sing a am aynthM U o f aiM Ataiai ( k ) A ) to a l la raportad to *fca*
ftf oladSlBSji ifafQ

mdL'ttiMy o f

^ :jff^ iw|m^ iP to to#

t o t o im to fto to *

ftft£ft tottttoftft#

ofttototol fm n x^MPViiMpPicP
to to to ® p p to fttto n il <^**1^ 71
# wbsp&

jpSflMQCy ftftf tPSSttoWSSf* lftxO& P P M3iJW0feM^L ftb tft$ llft$ f3P©$ll tip IPftlfftftlSlpHPnft
$ f ftrwnli^.ttyywYo^
U p pdUftR3^f t o

rw l tiT ljO jlH irO A C S to to ftttft ft «ftCKJ£*lft£'Sr & lQ O hol*
tftsHctoas^r ftto to o to t o l n to cw w p ftip o to to to ft to w n o a ^ lo ^

to d p to to b S sa tiil,. to **

*

to to ftft to d ftto r& ln g oX oC to *to *

or tot* ayttthaadu of aloofaoia &*ftft not
Baetstiftto in toft ik3J*bmlL ffttoitPi §a ayelo&atan© tottofttooftft*
ft * W&9

S olvoloP ift o f ^ lo ^ j^ O o « a M iii5 P l M
3 0 ^ totor to 4cP totft

r#OC^WT&)B

t o i t t o l i l i to ? o £ c&oxanfttofttolfifti %

ctooftfttograjptoy ftto tiy Ito totoftxtol tototsmo*

o lto to to lM tto n *

vtoor

th«rft mui no «vid«no© of

Ito n to ft ftto o r vto r«|Jtooftd u lth n«toft9tpl# to# o»ay

w m m m m p »»

p w

v if M

i M V ffQ ^

•SfW W ipfl^

S^Wfl^kS^MtoNS

3W3II SilWfiflMNfcS

.

ym<—m i’ftitdim.- tug
A frit aannkma*. r lm rm itr I lf 1*1 h>«.a im iw n Y iw I i W
* #l Him*! mfii—iM irl
™
w
w ep»W wffVK^^MMN^p^PPWVM^ tHMPlF ^nw
V ^ M a iiih S w S w w V p v W

"tofjr

3 E 9 w H H iw H ip

4iME^fc36uHflWSfe.l6flflk

^K W P

^

I p - e s * - © • a - a r*

iWNN003»

0
II
QFS •* O ~ 0 <* <B3
TTfci^iJjWt•simtf'iivM ^1 in■ieiA%i^ifl'fc
JeEea«Ul3h3Jn^

jAiirti ^fcuwA^H &**&
jfc. *S iw
ftMdlbiwi
ik&U
i B IS i fgsBww
*^MMMdfc.
weet* A*lv jnj||tBW twvg

wtOgr sw tbyl laridebwmMtfatim and 2-sM*tgfl.cs3>ol«*«tBaol.
AaMSwaOOL^jfi

mato&Oa In v r t t r , an a tta n p t w

wp^HTJLf»OyO'ftfitWy fttfff 3b9 SKS'll WvtJPjT

nude to aotawljnM tfala as ter in e s te r.

Vngr l i t t l e aaleo lyela eeasraed a t 5cP during 2b boum , t a t irapor
cfereastogiepbjr on th « p t H l inSieatad th a t asm Z-sstfcylayirixilmiya.
til£ ts o re a a e *a te « w y r—wtt than «■ * in th e s ta rtin g e a te r.

M3m, tb e

M M t IN M N M

m

i

te l* *

^l^fc^tW
MtfTMll‘I iM O
tttfS&fil
mm flfii^iii^ifrlnniB
mimaa*! uluuitiWl it
i»TitP
at ifftri
mm
ininili
fcift
nwurniwii*!
m
ifliiHHpmii wpiWiiHW'
TwwKl m
PWP
w^lwPHMyPMmypmtjt*3N0K^pft
Pw
jHIIW
wP<M
MPMM
HP
PP» ■f^ua**!
■^jrtMw'
pwEVj^#!^

Mtliga«wrt)iJD 3d tx lfla o x o a M te to im

a l*» aolbrolyaod in 60# aoaioaa-

1*0# m *« r (fegr *o 3a » ) a t vM Qwk. Vtpaar tfurcoatogm pbjr anft H a fra n d

M M » » t^ L

fttfifayX

M fe M '*

iteww o£f

9«»*MaHkWg»i,l

-

# fe 4i* tt&& fwtfW8$t jb i iwil&fcBji&X ishim n®s f^ iffwHt. in ttos- iM F th i^ llo

^^K^j6GBM8E^tiP®

3K^^^GSJiSCSE3i3®fe|jJr I^Ek
^^Lsytyww*

’ttk #

*>jf

i

fflnff^hyl

4lh l!P -44BiioSBS^rd^l& ishttfe tit# MX^oXyftSUfr oijt c^^Xo3^i?<3^3^ 3Lra(art5i3^^C'5®a?fefJbHiy!3L
a^jp
p
p
p
p
B
W
P
P
iB
P
P
i***P
'•W
^^F
P
ir^P
' J
W
lW
P
*

p.

r *

^ -m rm m
*p
. i.1

’V^w
SA
m
^
m

H

" > - m . • a - o * o ii

^NL^tM,jUfrffi. ifv

n
y y fe ^ g r y ^

0Fa ~ a - 0 - o s *

fka ^K^viMildbiLttrl tirlflttororaertat© prfcWiaaably tfouXd arlso tl&

Iw M w ati m tara, « ** m l* noald la m m produce th * m attyl triflo a ro M «t«t« and tfeo Z^wthjKLcgrBlobataaQl. A nor# eo^?iot« deaarlption o f

ut

ttw vnriM kO * wa r tim t— o f » 3 a ro 3 jw la o f ^ ^ o p ro ^ x w ^ jrX a a itttH g rl

i«if3a<rea«fls»aft» ic a hs jtewt 3 * tt> wwUwi on m rn a m t k im
c . 9m

$ h s u #£k i odt

Be&reagtfa arts*

o jt

jttMMraBWul. H » 4 o h ^ tu n * aattftfr.
^Rbii tl*iiiflrt.1 m m if iiii ti £fcXX&titii& Is #

$© iS3bB I 'f

.

tn u i a M M tt& ftl lif t
mekmm mtk%w*iA.*kmm j*fe i W iiW il *^M PaPWj idM iwn ai.

th #

%I*K

* » xuui&ifftdHEfctMi

f ffiflft IH8FS: USUtitiLly' jToUbDWBdi $&

$O‘60t eoaqp&sfciOB.

T lltm fitl f

* *&** mi*%mm%
wm&\MasagagMmi mm*x%m■
m^mmmmii law- th ft SiSilStiL

}§8r&Br

.lt>**w JbwN» .

< **3 0

S a»

A te te X

♦

A ttl$

(3 0

jm to m t M m to M & m riA tm
*»
PI n

W
W
flB
P
f-^
W
lP
P
^
P
lP
l fw
P
«P
^^w
*

(X )

< *)

^ I n i A i t ^ -—
f

—
•
t
t
'- «
(■
'■
."'p
-ff

X • s lo o h o l o r a s l4 ooaM asbratloa s i tin s %

• - n * m*m omtwaton&jm » t Urn t .
par s ftw rt-o ^ M r o r pouodo flrp t-o rtfw ro so tlo a «bs labo*rstod fo r* o f
$$i*
g rtfe
*P T
Jteaw
M
tii MBiiftiaiil- 4w
j[p
*Pp#l* wn
lp
tP
F
^
fp
^
p
P
WlW GF*Kck " f* * r9 ^ " *p

.

la (a /s -a t) • k i.

£2)

* •

wrnmmm (ohm) « f

to *

mnM«n s t

Um *

sm I

% * n tfM n w

(e b a s ) * f t o * s e lK tla s a f t e r i t M l

AWHMJIWQ @QJ)9vlBiiw 0 f i r ft $?4BEH*C« OX WnrWfW, J$011$9c
H^Kfeflifc
nnTir«iil>ilt l>iBt I inn 2M
4fto filliriW
iiH oinsnif^
mittm-inn .>1 f
wpiM
lp wwlwTOWTOftWlI
I’^ g■rn |liW3(|E^
(S
S
fe
K
H
M
L
-

a*.
.miossihs mtnfc
,-g^ HSSb0Hi .H I
1*0 <KNaB«0lSBBMre

settofAa
s
>
A
f
'S
ipw^pwinisisTOilip A
wjk aaww3M&m&Mw§
w va
moom s

( m i) is jw o p o rtto o s l to ( a /% - 2/S )

( • ) la m » w M i i to ( a /% - a /% )

903&Q#

2m ( * / * m i *

m

A£‘fc«r c ^ w e rtin g to- baa© 10 1^ oyy|

*■*%■

(3 )

jpffi .0yy^. yij^|y|»-fr^'| y||s tfOSPMB# tfe *

068^p@POS8OSs^S t$ttQQ£MM$

ao g < V » -% ) - f c /8.3) t ♦ lo g ( % /% -% )

(U )

I*s » equation (U) i t 10 sees th a t a g to t o f lo g (iv 'ft-B *) versos t

f o r » H o o t order re a ctio n a a U
vfaioh is

wfuX to

( i / 2.3)

g iv e « s tra ig h t lin o , to e slope o f

and whose

in te rc e p t is lo g ( % /% • % ) .

to *

slope* O f «1X U jmo obtsiaod ia th is th e s is were oslo u ls ts rt hy to e
aatoed o f lo s o t (g u n s (26 e,2? ).

gens n o n -lin e a rity o f too p lo ts o f le g <V»*R*) w n w t eight be
n y ta fcto doe to oavetara o f toe p lo t o f speoifio oonductene* versos

*

m M saaoantratton. Qatranbtsaa te r th is o u ra tu ra ware
t o bii

earnidarad

bAaj&itefe
IJ
nPu'ttenihBra-tfiinM#.
n iMtttnrnt t m n a # fIelBta* 1J>4»PW*^WlWte*
4 ^ * w w f c w l Raisf
Mi
•trwteWMilsia {fete
1P**P |T<*
ItWiMl w
WHIP

w ill and bananas tea lit e W
i« n » «

jo w , w

aw ora 4b wob * oorosotlsn am f a lily

* »»»%• «c a*«

VWIfllWWB *b tWMWl ttrtKBWWKS IW\- iMfc

lilIM P #

W P lm ii wmMM&ttB w$ l i f t # In

t # } f J* anti jf.

ISb# m in t o f th #

awtwfflgi#tjw vw
4n
c<nT
aw!H
aP'T
itlis
itt
An
#
aRHw
nNtiw wrIusi TtrTKTtft^vpyt^iM
W
®
r™
' o
'llf*T
^
^
^
w
iV
,4
P
f n
fliM
w ASbit wtHHiftiTiBrtfti f ri ****** «
n
W
(ra n

^
^
^
J
w
^
W
P
W
ip
p
ip
q
te
P
*^
®

flfoggff

latum V aitt* $# fft.iff** glfSin# - AH f^jf m # Id lX itlO «**♦■* gQNI glSNIft

In

9 t® fS

tixo Appm*&x.

W&& n

®£ tb a it it #

I n th in

s ith th o rn raposiad by M offat and Hont (3 ii,lS ,l6 )» iH w rtgrl trlfte o ra aeatsta sas prepared and aaJmSjpssd in faj£ aestons-30 $ ra ts** (by votena,
te a aotean* sand by M offat end Mant) and in W * dteBane-3 0 * ra ta r (by
w rt# it, a aateanb mad in th e k in e tic iiM Im in th in te a a ia ). A value
»*

o f te a a p e e ifia ra ta eeasiaafc a£ 6 .1 xXO

«*

«se

. a

.

a t iiF in aqaatma _6

aosfcms « u

obtained, aeapara* s ite te a

„1

reported ra te s o f S.$ x 10nas

te a ra ta constant fo r th is eater in tee wjpecme diom ne so lve n t a t U5°
ra a it .7 x 10“ “ « « * .
(k »

7 .1

x 10

te n s, oya3nja»pytea^

se e.* a t 1*5®) and n -b a ty l tv lfte o ra a s a ta ta both solvolyee

a t abate th a mm ra ta .

.

so

a
muxsmmasB

ffMMSSSQBSMHESSB

9,

mmmmm

16.8
1»0
So

U S .o * o *a

.8 a o»5 5.8U a o.oit

2.32

: . j a 2 .3

U .c o a o .c t

9 J $ * o .a

.? ± 1.5 13.5 t 0.8
w
w
iiiiu
im
n
n
w
w
u
w
iig
iw
.i

6.10 t 0.2

Si

3 0 1k, M S

mm

m

0.631

3 **5

± 0 .?

1».0 0 £

m

i

PfiSBSBBSSS®

M W
tjr ■ «mmw^I f l Jfcl*
,;|pt"
'^148

«,C

60

|Q
N
u
h
m
h

1»0

1 7 .8 * 1 .6

so

3 0 .8

60

W t.T * »

6 . f t J ± o .0 7

10.1 * 0.1

a

K O tl 5

sm x m mat at*mum. wet m scx.ks.2sxs m
» " It

k»

%A&

50

ft*

to ^

sol"

i. f *
k*U ± 0.Q3
12.5 ± 0.U

<M tt'
1^4
*.« !

f» io « a . |to ta o f ta a d ata am *ham in V tfa m * H » 138 a a l 13to ta w * pn&» tao d ata fo r « ^ l« ^ R ^ ja a m ia y a (lig s m ax) and agrol*p m p fiw ta y a m m iiio rl

(ngm

32 ) ta d fto ia m io a ta ta M la do, TO and 8 0 *

a p ta ta dlaom a mm omp«radi. Vigom 33 la » |O a t « r ta a d ata to r fe a r

S ta te Q& t& © 'S B X v© l3r#ls A * * * se e &&Jio&i,fid 4 » 'fa M a 5 *
w
yim
j|fe ili ta
J
fc
m
*
®
;gjm
ttie
g
ta
.
A#riiw| A
iPBWff
TpBfiiMilff
^B*ifc» A
1V1I9
ii# g»i>*

***>Jfit

i®

AMMMiVMIfil A
ife
4
®
iV
^
^
&
V
h
fl!®
!*1
i

00lV03ty&® t i Sfe&Sfe ffiH*

4tan madfeaw
•
nJppfBIota
BBP wtowa
tafe^^taPp ^a*aj.BSttS
T*|Paap
f^ w m * k a m iw k i wf l q #

BA
■tata foa*
•ftpF ^

****1. IKslf&fe
«Pflt#a pPp’
Alta*
HSva^dn*^ ta
Br ta4ita*M.m dttofem ftbfi'Btrf Ttird

Mtawtaa ifes*®
■ma
&temma^
mm
rtMin»fnwta3
f i^^ ’^mt a Akafc
*tarfejfl«»<
IH ite ll&lw
ftta
^W
"w W
lff1
m
P
H
W
-W
'jp W
P
w
1^
"
F
m
P
PW^ p^-pm
tataW
»iiiitaPaTW
^*ta

d
W
H
ta
fP
B
p
d
p a
m
a
a
jjC
T
fP ^^P
tap^fP
JP
'W
^W
liP
'taP
taP
'W
TtapP
P

mam la Figaro 11* ( a m
liH r ii iP in iMit n l

taatawyta

A ),

ta o aatam

am i ig4ttm4i4m AaAm v*m iStiS

j^H 4^%%ng^% V«JS ffflff^iff Ha& m f t1^ 0# 0b@

00^0 0 ^^^**

aataoa M lxtara la ta ta a Iw S Iw IA ibI i»33«»3j»1* ta ta o om taata.

aaUafmahory

aate m natanta m m obtalaad weOy fo r ta a a lo w r ao3ro3m lne «a tarf
P m ta ^ U s r^ A ita l ta ifa a m a a ta ta ta .

Xta la t t w pox^Loa o f ta a sOota o f

lo g (s /» -\) tmmm « « a m lla o a r (a m fl# > m 30*) and fm a th e alopo o f
fe ta poftaoa a£ t a t gnptai# abtah rapew m te ta « a o lm ly a ta o f th e alotr
aatav* m ta o ew taata fo r ta a m am am ** ° f 2-nefeyi*qr«a0btttar3.

55

Figure 11* Plot of log (R/R-R^) versus t for the Solvolysis
of CyclopropylcarbinyJ. Trifluoroacetate in 60, JO and QO%
Aqueous Dioxane at 50 . Data from Tables 1k , 21 and 26,

0.7

0 .6

J0%

o.U

Log

(H /R -R *)

0 .5

0 .2

100

200

Minutes

300

Uoo

56

Figure 12. Plot of log (R/R-R ) versus t for the Solvolysis of
Cyclopropylmethylcarbinyl TrLfTuoro acetate in 60, 70 and 80$
Aqueous Dioxane at 50 . Data from Tables 53 $ 56 and 62.

60$

0-7

0.6

Log (R/R-R*)

0.5

70$

0 . 1*

0.3

0.2

0.1

10

20
Minutes

30

ko

57

Figure 13. Plot of log (fy^R-R.) versus t for the
Solvolysis of Four Trifluoroacetates in J0% Aqueous
Dioxane at 50 . Data from Tables 22, 35* h i and 57.

0 .6

(VB-E*)

0.5

Log

O-C-CF.

CH

0.3

0 .2

0.1

0
100

200

300

(Minutes)

Uoo

500

*1
‘ IT

o

\*s

**s$

A
#%

l
9

#4'

m

**%
94

4

*

cv

9*%.

•|
#4*0

#1

•r

ft**

59

Figure lU. Plot of log(^R-R^) vermis t for the
SoIvolysis of Mixtures Obtained from the Esterification of Cyclopropylraethylcarbinol and Methylno rtricyclylcarbino 1 in ?0$ Aqueous Dioxane at 50 .
Data from Tables U9 smd 6iw

l.U

Log(H/H-R*)

1.2

0*8

0*6

gh3

I
GH-OH

0 .2

TsSS
Minutes

to
te il3 » o * m « iiil* (wfaiefa « p M

w ith in 1 0 * w ith thorn Obtained firm

WWiimiJiiRH' v ll W W PW®w R f f f i r / IPHIrV

* * t* r

w lW BW m iS 3S30ar

in it# tupmmMmmm{a n a * M

im p* a ll

<m#M& in te i* mum,

fw w iE ip vBwwv &XI f*0» < ^iV2Q3aft^ Wmrm Ol5®SES3WP OH «® ll JpwPp OSnPISr*
*W*m W*mfwm9W Jfw r ipW ^C^JQirvSM^pqK^v w» <J|rCSj»|a^^
w
»
w■
■
■
” ■
■
■
■
" **»▼
•wwwm
,W
B
i"l

(mt•b■ii ll •3*>4-'fofl«tl
# tslHI
rtia
t\f^ ^
ftjtla
m
l(frthlWl
fW W
ftP
flMO
••w
w
'W
M
W
PPr ?Mi£4&0tt
J
P
P
"
’>
pP
*W
"f1
P
vp
"m
w
W
K
W
' A
wm
M
(W
p^lW
!P
**w
p
^W
w
?W
' P
W
*. .•
^P P
m

t
m

f
m

Sdjiotlc data of $b$ falsification s&s&ur® w w o about J M M f alonor

**1^ y f Kff ^ 0

HftTiff H f '1^#% |j^fiyi‘iffr S s tW fa y

0 0 8% fn f3t t®dUB<l^^iWOSIOSi^l^O»

ISiO fH^NB OOEMNftOE&O S^II^OlPtOlSi fo y
!88fiiSijE5i3®^

^asa

OS^SEf-*
Hyy^n iflfepw; |m i*gi
attHa&i&o n o #

JM M ^I
tfe # ^ a t ^ liii

£t flS Lighli CflflUPVOtuyO*

* f ik i. f i

(o o o 2^f$s?o i | )

-tiW O lS B IW O H . W S ^ 'fO S d O O t

f4PftM
ti> a
pptU
ntiiM
M
ty'jl- afc**
P
p
W
*l
P w
W
p
H
p
a
^
B
P
^
m
S
^
*- ig ite a iN to d

too

tS^iflW ^IPOw

tiis t gt®fo tfeo jt.ir!'if-t4-|ftit; fWoS^s iJjoa*

at p * mmtim (in So* t&mma a* fcsf)
m t» ooaHM Bt*.

^bO hlgfclH? fNBfeg*

nt 'm
m
oaalap
ta
dmw
aw
ipmifo p fc m
xO
iiaai
#w
M
iP
p
l' *
wW
piiMf J
■
P
I^
m
JPu
t#
*w
*P
fW
^
w
P
- a
w
n

w
j
^w
P
^
x
M
W
'

jfc
h
fe
.^ n
.^i^ifn -Q
'-n
a
i if J
lT
^
M
k fi!*1
!^' ,Aff .m
P
iM
i^
M
P
i'M
p
p
fh
i
w0
yooctaLOH
\ixi
I w iw
-i H
p

$M

*nH*

a

bm» of abatrt 35-1*0*

aai • Madam o f P a s t

p
Q
'P
i'iftfip
M
^
lilU
iib
iif'- tM
/ was
uaoa
ia *.
iM

90#

of

'ilfiW
lh
*!' fc
ilP
T
i^Pi'AiifH
H
iim
' iih
%
’iiil'ii

h i

3UUi owwotBT# o f tlw kfn aU s data fo r titd * w te r 1 *

p M M i^ r <Mo to la t m a a l rwtovti o f ths ajncO oproi^iott^XeartdB ^ trt.»
fite m w e *a *e te

teifteopoooetste iM sto th«a 1103* 0^ * * *

c l * nem aniO *, te i aSmir# *M » then te * »H giM a o vtw .

61

Figure 15. Plot of log(R/R-R*) versus t for the
So lvolysis of Cjrclopropyljuethylcarb igyl Trilluoroacetate in JO% Aqueous Dioxane at 50 - Data from
Table 57*

0 .6

0.5

Log (R/R-R*)

o.U

0.3

0 .2

10

20

30
Minutes

ho

Iflto lta il# ftit to a

«&**♦*>*»» ■#W*«a th «

y v ip M ^ n a t »»a«iij®*i*a?te^^

M tS aam aaaftiibft mao gm *

mend pOsta (aa« Hoorn 1U# a w i1* a ).

$ » ktm fclc paata toa? th la « rtw

& ftd siwsih tsfe&rtwftir t o M i i t& ttx i Istasso ifoa?

£3jooi'o&2«&ftt&
r.
mm. tm ^si.m w w "♦■: •■ •'W

■^re^flpeiy s^

te l* *

*ipFwT
PN
M«WFr ■•*Pftr flf foa
S^HW
p r-^ lf muftfllltf' bar

jfjtflit m& &&£&&■iaiiifeim ftoh# M
m
%
**nftai&tet
bgf jBygtis^j®^* *W$jT
%

.

-i f ^ ^ ^ ||. $ j$ ^ a s

^ 1|| ^ '

080* $ tm J U lli^ liititt

l^bSSBBES

|||$|N p 3j3F ltib || *fffff%#y

0<£' ^ t# 4NH%Wi 1Mtt9$b

tta l ^

(iirjiJtTA|'.vti »

In $ fc£j| ^ f* * - Ss

.flffiff1^ f f il W l0 l^ ^ y t f o g

-|fe'lp&^b ©Jt SSI^ij|S^iS@bBN| W T fiffifft M W

^yym bi; % &

&&

*•*•» WWWr

£g$g} SS^PSW i6 ) & ’©•SSB**-

tlb # iNNlfiyBibBMEidis ®s& ^ iiiJ i fffiite fr immi ipjfKbi&i $ 0

vm uti ta r tb a aoU'oJyaia a t th * AMrtav a o lw jjw la g a tta r*

am » vm aa a t ^ .* p lo t* a t
» t e « t l# t U n a

vaM tM to nam aada M t i maw

f« p th « t i n r t p m « a t « » i

M

m

M ®

^^ii tl,iteA-,,|t"h— ---^t j-^l itf"*!mnihUffcii
4^6Q|)^M
Nwl^
^WflPiit,i^^iil@g^EWWHWW^iHPw^ W W W ^ I W P l H P ♦

30S«tw ta r,

k

im a g

d a ta ,

fm

ta

th a m a p *

Jlyk fiSfilin 4'ttt
jH ftstiriitiiW ■
# ¥ |!lv * M IV}! ^fiBsKBsP®

* B.aaOO*** 0 4 a a a .*X ( « * » m u m ), m ao a t 50° , te 8oj6

#M H M M I0gt m ta r^ k • 3*5 x 1 *T * m « .
to m O vsa tto t «Oop«

a t

(m» ra n ).

ttar. la t t w portdoa

a t

»o a tta a p t «na aada

too ownrao.

63

Figure 16. Plot of Resistance versus t for the Solvolysis
of Methylnortricyclylgarbinyl Trifluoroacetate in 10%
Aqueous Dioxane at $0 . Data from Table 68.

35 0

Resistance

(ohms)

UOO A-

3001-0D

250
* 192 ohms (calculated)
o
o

200

%

- N >
~0"

2k
-2
Seconds x 10

16

-O '

30

36

&

i4 n iu ia l» « « e tlv * tto n aMVggr, 1 ^ , m a fta la u la tu 1b lb *

t o i k * «

w ku &

(% fe * 3 £ ) ( V * > ♦ 8

P lo ts ® f 3U^s ^ iwnmhi l / l fo r tb s n u n la vw rleua aolvm fes t$pmt 1b
M J S U f M 3S to 29 In tit# JteSWMdE*
qi#

^

Aft#r

t&a si### by th©

9f i M B t f&fiysi## tb# a&iiy&tiaji #yirtar wsui <*ttiiiMiB'faii<} |Von

v fa tm M » & #98? © a k w riftlt

’

juio rnmaxpy o*

flKkjIk,

J
IM
U
U
&
^
k
B

tS
*
k
iB
»
MB
tfb
?
J
# ^
ta
a
b
A
r'A
'lM
te
m
id
k
lJ
ljM
k
iU
M
’

/o o l#

«

ZaH f tm# ©#&©iyix#»wJ jeto® #h#
.^
V

1
1
J
lh
l~
l#

.S
tffc
fc
/'t

d
E
fc
s
^
^
fe
S
M
* J
k
-%
*iriifc

S
to
te
ttJ
E

S < |lS ldLtille

^fejt #nfcmt*y ©£ activation.

A 8 # im# ©©n.©®!*### £*©ia tti© J&rrinit

m & m te jm ( 2 6 ) *

m i
,»^.JL»

^

A0?^/l

^ ■#■ A H /H5P

©
r

A $* •
« tu w »

h »

iu •

n u k « >

2 *3 H

l#g ..(j ff o

c o n s ta n t, 6 .1 0 * 1 0

*

J « |i ~

« r * S tta n a
« **•
**X

Boltaaana constant, 1.380 x 10

arg dagra*

(0)

*»&

aolocsla

,

T alura o f A h * w& A S * £ar tfao va rio u s xm ottom «xw lis te d in
M O # ?» fh s A 3 * n lM i w » th s wpttomoUo mmu o f a ll o f th s A 3 *
ioOmm M Ctcolstssd fim i ffp s liM k (3 } fs » «Mh K obtained fo r * gtvon
•s ta r In «aob solvsnb. Xhs H M M d s tls b lo a fro a *« & ansa valas is
a ls o given#
®£ p a r tic u la r l& ta re e t a re th e a lx d lA rltd o e o f th e e a to o sle A m
a&
ilMtti&MfellMii-JMt 'jW
Uj'^
p

fjftail' 4&ktt tfettfct AWhafltniOfii^ ro^iAr^tfcr to 'ttoifl*
aM
M
^ft^
M
ee
M
rH
lSlpLle
fcB
iKpiN
ktiW
ihW
Hto
fe^*!toP
PlaK* e
'Vik
SP
'oe
et'to
eP
jP
BM
tS
jBiw
pjM
pS
W
f^dM
W

fia y i ^ reijiH ^

,, jwm# OesMxM^ y i,^ ^

e
ta
M
fe
to
M
llO
S
B
I# tilltim
to
tfc
.M
U
lto
M
K d
fc
fe
t-^
u
* p
Q
iw
^
O
r
tfc
^
ta
rtrlM
ih
n
a
n
H

WlSSrggr Jm Ww ®3PW *®3f

•
’•flfla
ti-iw
A
f'ta
T
rft^
't

ftHii4nm<Vl an sutommmmti to th f l m *m *
—
■
‘-^^1#‘tm
^ m%

.n
a
O
a
.ta
^^

al Jl *m.
JSUNW
MMw*

A S9ipHpfSliW6ifc O f t bOiflj1 Wffiltffffl f<te&t©P$* S A ill thflO# Obll&|$©d $H o th e r © ttldlae
iff gixen to M A e 8*

!Ui#

mmik 'Wo Vm9 IffWPw^llP wfcf^y

o f the prim ary alcohol© and
0- SLL{HW!l&jySI 'flBwPB^Pw wICm# OJt wjWjypptlTO

©ato&3$0l. IISPO XO llrf^Valp

XIOpR^LlNI OtltflrOpiea#

l i t th e s e oeaea th e ra te o f eolxolsnsdLe is © o n iro lle d b y th e h ig h o rio n *
te H ltm

o f g ^^^fyjtr

is^tont tb # ty j, -fl^ ^f ^ ii^ i^ fi^

xu& sroaptipisi fiflncs e^hsiiaasff ox i^ i^ v e tis ii p p to© ©oxTo^Bdii ox
tHPiJDs^wsootetiS #yf*
ee te xe o f to x M o is r A lo i^h o is EtesiSioiS b p JbCfO’t
1yy^ Saaslafi* (1 2 ) •

I bo

to tiho#o fo x
b ^

( 1 5 ) sod bp H a rt

e x# i^ i^ gp w h ile th e e o tro p lo o e re

r o to tlx e ip p»«^PL# b e t © t il l n o g a tix o *

th is ia d ie a to s th a t th e ra te

o ^ e tr o llls ^ fe e to r in theee eeee© M th e oleavage o f ^ ie eQJsyl^oxygm
bond (id jifflh nosOiS haaro * rO U U v o ly Oarse o a orgjr w q o ip w a a n t).

u

2AHL& ?
H Q U til 8 S B S T O B : t& fr
Q& S S M to

MfflSW EXQN PQ& WM SCSil^M BXS
^ SE38S3B8 f f f ilf iM F
■

a w ttm w a w M s M a w #

Am
£& & *
‘M8«*WM«**W«MM*!»WMM*«M*iim MiWMMMN^^

A ar
*t*« u

fJtt •A&JteaA
eatriaioyl

10.fi

IM.
,*,« B S A VI!e|1^
*m

184

-W (4*04

-*5 4 *0 .1

-1 2 .3 4 0 4

A f
'

A jr

a

it e i»

K s£ L *

*# u u

«*33 -SL.140.1

9 J£ -50.5*0.1

314

a«t

-U5 4 *0 .1 12.3

<4(3040^

843 -£SS^±0«X

324

-13.0*0.1

21(4 -0 .5 6 *0 4 8

*

|

m m m m m m m mmm m m m m mm m m m m m vm tm
mfMB$ / » M llillE * .

munm *«ft <»«a«gTAtnr AtiaimatJt

.xiaftw aaw tt
$&Xir#tt&
«t^*W
w^»«>www»j^i»i»ww!ii>nr<iwi<i>in»i><W
!M
p>it»>fi>wgiHaiii<i<aiifflir>1ingttmm
tiu»iiijit*»>wiii<|»i»wi»*ai^^>t<w^!ii^«>i(iip|ii)ii.i>i.i»«bw|<wi»i»»iw^ii

©£
X

}

yySwtty
S ^ oj^

M
qt

It

to M U # 4M f*f to «*& *#

-H S8
ao.r
jj> , /

Affair

AS* £ © ' # $ & * ( k ^ s d#)

:' # f #
*13 «#

10.3*

-SU7®

Stli «1*®

« 4 .t#

Jt
ifr<»ifrdi*l .hiiMi fr^"iyfrihiM«'?l' liB'JfrlA'Vifri'fif jm tlrftjiln'A~iifc W A s . l M i & ■^^'WEJ^MiW4ijlW*i<#ik^v6ki8k
JEliaMi A-fr.
imMi ^M^m
UR> ®an^®P^^P5r
^
W F
m t
*+■

^ -v- w

lit * L

smIsiMNRW JWR-jf

-■■ ,^.^.Jbi.%,. -•— Jlfr ,M| iiiJMhlMtefai'J^ A

A b M f c A A P 4 t * * lJAMhaitJi4.iikd&)A.*b.AtMih,

«8RS*0&®I^

>$«)

«.3b

...

IWNfrlBill Ijjtilli

A

66

#
Z
t
V
v&EMMjLmtrJ&rtWIN

1%3* 0fgMm6 Dnn th» m&w&uu&tf. tmuLt•

th * t

tb»

«k# Ayfajfc 4rYiil#*lYtrnw^tft^mATir—— - --•*- - * j w
4 W ^ Im —______________ ■ j u u i^ u m A
W
»
*
v
S
f
e
w
tI
B
B
s
M
p^
s
B
S
M
B
U
Ij
«
P
C
W
H
P
®
B
IM
g
j
rp
H
R
p

*
*
w*!
#
W
W
|W
*
*
W
i^
f
O
h
«
P
Ib
H
Iw
S
»
«
u
^
j
p
E
W
H
|O
X

J
R
X
2«
u
9J
^
K
w
ia
P

f*o» w th anpl y ia sr» a ll iM M lilc tt u lia i ih * io a iw rfjjg aM btatM (99b,
*4 H rt*

jw f j

~4fo*fc,te
xot

I4*e
tfc^HUJtlk

ttfrpfcptjtfe
A% . ifir
p
?
jL
W
4
g
r
P
«
M
i
lOX 111

*ww ■- '■
■■l'^""11'"'pf

GFa

•
r
*TO-' WW.

n

«0 • 0

» K♦

wXXJw*®*^®©

iAiaaittJL jjWS l - |W-g M[, „, *t* ^ J L ri- # r tii i*

■Wb^wwlF

H
jO
■
*
*»
*
>8Vjj|
wSw^P

■FWff

■

f

OX
a J I

—• —^ liiftfm iir — ■
— w ■* m m A

n
• 0 ** S •■—>—■» GF* * 0 *

***A&kMMA # m

P
IJ
P
Ip
P
n
p
p
P
P
P
P
M
N
P
N
ilP
M
P
i

<M

SOU

1Po 0$ 161® pto<S p^|yi

W
W
?
o
t
Q
^
o
X
o
^
t
E
^
d
p
y
S
i
i
i
i
s
H
b
&
^
S
i
O
S
t
i
^
b
^
j
B
^
S
k
n
f
l
f
^
f
e
^
S
L
o
6
3
^
f
l
s
^
a
s
I
r
i
t
-

*%

©
x
^
^
x
«
o
i^
«
s
o
^
»
w
o
o
x
w
a
jx
»
8
pw L w t «
jj^
x
w

so3?i^2^ls 3 j|g , Isfe&ii SilNBF in ssWsdQB^ ’111111# fisfofl¥#rTyff

#1

1

w

♦

u
*
y
o
x
©
jM
P
O
|
^
^

if wt

B y fi& ttlo & ? 'fti& h th a lio is k 0 # H&xfe

ft##
m
to
ls
ts
ly
s
iS
’o
i?
t
h
i
s
a
t
o
r
o
b
a
b
lv
JJ
P
W
I f
T
^
»
w
»
»
p
p
iw
ifa
*
',P
■
*.''F
*

1
f
e
3
^
J
L
*
*
SmdbdL £1 2) 1SJi©
iB r ^

t
h
y
o
u
e
&
i
n
'■
W
M
P
*1i
ww

4
<*w>ay<m*4«*» pipBp-^li^^PrJWWpyO^pp^iO
1ntoT>mrti1f iiififfi
«
i jfls.*iiiia»A-t*4*W ipl *W*™' Wf Ifeft
■ifcPWRO^jpWBBIiPiOr
wp%y~p .
VPW
ww*wf%F ^o!LXow4iifi!'
"W "^•Obp0pFw'i^w*piMi0|B^ aohanoi
if w w ip f liw w

m

S o lro ly u m
toy
iS s it o i

BgQ

OF* * C - OK

%I
\ I

o£ %&& xwtiPiEWigiisdi a3<stiQl snd awaurewQntof
®&

'H&&

y*^

^

H m ;j^ t in iim ^ f.

at

$|1

q£

fun $

tjlMS

fryrfjim ^ygr ly ©JJ

mtmm®i ta rfcia ry alcohols* (m 0mmh&m), Mm ( 5 0 ) hm*taft«d
O
*
l|
JH
8 » 6 * 08
m2®*
H i

▼

** rt--^- --

H

jf iJ

*G B
ll
I *• 0 » <M
♦
ft/m
*W » J |

y «»

-—
**.^ - r j g p

0
II
B * 0 * OB

♦

A
K

KSWSKf *aT fu*s

th a t* Hin o M tr fo r t& tft elooraga t© ©ecaa? w ithout aold cataO^als, the

?o

m&M&tm icm to bo M

mmM bo mm

or tbe eaioa to bo

forwtd thoaOU* be io tt b w ic , or botfe** $boa t b it, m l oouuildarlaag tho

m ^Tyw* 0$ mm trifluoroaceiataa mi ott&o|®©|jg^^

cud

ayoV}**

i t i t ovidont tfcoi tb# it« b illt3 r o f mm ttooadary
•m tm lw i i©» (

P > gh-gh3) th a t io foraod i t

tb e s ta b ility o f th e y tim ty m ^nS m ion (

ly g reater than
£>*$1* # th a t vm id b*

f tiM f i f el]^l~<ncy&en euMfani had oaoerred) to ollotr fo r the observed
dmCiity of laaohan tgKMi- fo r tteats toe m ters*
IM
* •fe iwW wdfl mmmw '^tJfe
mm

Sv968wlw

Wm£3kmw

fe^tLIB
oW
l^to
si«
i0i■
R
L»nH&
eP
fc1!|■f!litM
ewm
t& i«
|l
mSNmm1tiA
mmm.
W
#1
^H
JP.1iha^k:S
W liiijr
wFmm

$Pt$ mWBTO fw /

0JP

miHk■mtikmm

jKMMTOwSfte FC3?

rmtoM wtifr ttd flttO I^ iM y B te tt to solvolarao v lll a lis l*
cMtyeeen f is t lo iie

tb e

r ln s m is t b e ***!& **» in

it iM ljy d J ie

ion th a t i t forststl*
Itey

aflftloflrr. wMjy frJ h -t^ la n y is ttrl^ a ^ 4 *y to <1 */*4

to iv o i^ ttt b r

mm mm mckim&m m mm ^MJmmmm%m o f 00^mW ^m

m***nan gta^fe4m&\ ~

B
w
^
^
P
rT
lP
O
"
fc
^
I^f0K^wwfW0^ W
P
W
|N
B
J
Ib
B
*
>
®
P
b™

$*&, im

t& t

P
ffB
B
B *P
*P
P
fl^
P

a > jfa s la y a ly le « rt> in o l aay b«

r t t t o f s^lto lssiS ’ o f tho a tttr o f

•
^
B
'1
n
P
1
B
P
P
P

mkssUmmI

^
P
P
P^
P
P
P
P
B

P
B
P
r

'W
^

to • g v m to r xwCtoMto o f «to*> lc

Stemtii o r to an «ir^pyi|<yBh^ ttotetiyitjjr of tb i oeiboxiiujR Ion foraged in tfeti
«mM la oonbxaBl to too to ifi» o t» a 3 « to to o f ^ X o ^ jy J U o rth y lo a jb ia o l.

$11 SOTEH3TC3

agM BfcHiM Ef

n

BfTSCOBGTXCSf
ABr -fl&A
A.*4A4
A^u4vfefrAhA4f
Atr flAttM
&
WMMmww Jpr^w^t Hb &!tt ^h^Ali
'^nsr^p ^Mfw^MIRwiM
BiW "AAAAfiHAsiAiril
fSiWiWfiqBS^WEB^S^Wis Vmia
M
v
*wPb® hpHW
iP 4
M^4UMHPS^0AippM
WS^H
w
Jte
A)AdllMlfklti£fcAli^l 1
4l^m
6kB
*Sm
HW
tiflfc'm
1l 'S^RViSPRgpfflWPAB
ttMlkiHilMiNlMKAfe
4bMi^fc^kui4WfcttAMhttiifM^&
mwmmBqpwmm
lAm
vam
0 * 43f|yijMiP|9drvr^

akm^)

AifcAi%hJ^i^fc V */ *
pZlSAQr^ vWMKP

Sa tfcla ath ar to * cyclopjopane rin g la in a p o a itlo n aaalagsa* to th a t
a

«f thn eartwa-oartww d o u frla to n s la a U y i jfe a q d athar (n )

W#

o f jp*tiy^ p & sa ^l a th e rs fo##

Studied hi# two

h&nr&b<Wi wt&%fy&&(32 *33) *

Ifcecimfc fWflpk has banei

cosiQomsd v ± th *tha D -O l&ls& h re a rir^K a fiiftn t* { 3 k )*
$3&tB ft lttC tU fa i

o f H ^ t^ 1 lllHRSBlMMPy fo ?

o » $ » o * o * s « c
T
i t
I I

Sm M M

toad w t t * n ^ it « y tea in a lip h a tic tM U * te a t, aa in an

ta s l a th a r * r a a in y l rtfcar* »
pbaaal atoara (3 3 ).

p a rt « * an aronatlo M ag , aa in th a

Tha raaavaagananfc la bast rapraaantad by a oonoartad

a y a lla wwrhantaw, w ith to * fo ra a tio a « f a dianona ia ta n a a d la t* tolefc
than anaUaaa to gtva th a e tn a , product.

T2

CHa - CH « CHa

,GHS * CH ® GHj|

simtlaritlee between the cyclopropane ring and the carbon^
carbon double bond are wall recognised (1).

It was of interest, there*

far®, to determine whether cyclopropylcaiblryl phenyl ether (1) would
undergo the Glaisen rearrangement * A plausible mechanism analogous to
that already demonstrated for allyl phenyl ether, and in agreement with
the current concept of the cyclopropane ring, can be envisioned.

I
A partial increase in the positive character of the o-caTbon atom
of the ally! group in the Claism rearrangement has been postulated (3U) •
Urns, in accord with the postulated resonance structures ascribed to
the cyolopropylcarbinyl system in unlmolecular displacements, it was
further expected that cyclopropylcarbinyl phenyl ether would undergo a
Glaisen rearrangement.
this part of the thesis is concerned with the synthesis and attempted
thermal rearrangement of cyclopropylcarbinyl phenyl ether.

n

A,

#

ff

iM ta s i« r # " llm w s w le r

a»l») &£
asai

la m
*g*» o#& m ^ s )

%&**«
p

la £% p|p»
* . Jd&

£&» HT
H v to ** h m m *

'B it- $*

a ttlM r ft*

m 3*1 * *.f

aa&£ a*fe5 A tt a A

i» r ^

ta a a^3arwaA *««#

t|4*tf& 9«K l is . go s & , *?X

& a il<
«ad

OS

) $& *

*4

13

KSPEKM BM Cft

A . S y a t b t t is o f O yolopw jylO ajtfeljaiya Jfe iM yl B th o r

£ ^ 0 8 * . 0

flrth a 4 J k ,,,J I M

im p

#

+ f J f o J M it o lt ,je a n

J 3 l«

A 300-aO.. ttu ro -m o k o d f lu k , f it t e d w ith * Bwtbibmrg B tiw w r,
J'OjfiLttJC CtolldSBSSP# thiSJ'fflOlftiri&AP #*** A dlPOpplUg f^U98S*X VS#
2 6 .U mU © f

m&f * f g * (0 *1 m l*) o f

to **3

In AH icMS^AAXt h a th # p*1^1]Si#ni9U lfoi!Q rl o h lo x'ld A

(3##0 g ** OO. w ol® } la J ftr iU ®# wbijyO Aiwi d fc lo rid A m ® a tid td la fo r ty *

—

.^..gfc

A M J i.

JHfaMift

J*#dfeaifc

liii^iH tflf

MttfcIbJift

fttodllrJt tMlttitiuA Mb

HU** OX «BnBi5yf3SEHl CnDUJOXILwO IvwEI MH9MB® MRS PMXuP3*lg
fO X h#0 feOttJP# #

^Ql# OO-^ iljMwStOBO 18801 36l#168tMPftiila.COd V11W1 fj? WX * O f 3£^ ]K

MjXOXSLO MQuSf # « #

rOM3JSa«8$ 003011 *■? *

SOpMBSotl MhS 1 h8 ftffiO ffltf %
&
j$W
3t
c k lo r id * .

iiiir t iM ii All

flw w S U * v

13ft# JMgWffm WWPi

OHO# #&$& t 5 sfll* o f a tth y la iM i'

lb # A ^ b la id asrtfcyi®**® G hlo& id* ® o3atl© a m i e x tra c te d t lim

M a® * K ith tQ tiL*~parblom o f io # *o ® M 1 4 K « h lita p i« a o id aad d rie d
o re r p o ta m la a carbo n a te *
Th# ml&wak mm vwemA a t reduced prooaaro id th a® h e a t a llie d *
? b * r« « id » A m

a ro d d iA h a ll*

H a m l o i l m i d im a lv e d la 50 a x * o f

w fcydroue o th e r and added (3 0 a d m ito s) to a euepenaion o f aodiujs

to

ffanmcfcto, prepared tows 250 g . o f p b « i» l and 3 1 .5 g . (1 .5 *> la ) o f
•n ito n to 'too nfll. o f a to a r, in a > 1 . toraa*aaakad fla to m ta d w ito
&

M tix M>wtor ». tudBhtte
W
P
iM
pilinnVw &&&&&&&&»
^
M
R
to
p
>
'W
W
^
lR
W
to
iR
R
W
1
R
W
to
nS

R
R
P
S
w
to
B
R
to
R
lto
'^
W
to
^
^
^
R
^
iP
"
*

d v o M lB fi: l^ u m g i

•ad oeolad to an lo e b a th .

to t e o la tio n « n than attoxad to aoon

t4B&>«ratttr« fo r f ly * d in •

fha ssM M ss ttog filte re d find

tin e a in to 10£ ifcKttna bydroxlde and tw ie a w lto w ater.

i lx

A fte rra n w rto g

to * aotoanb d to tilia ilo a yielded 1 .0 g . o f eyolopropyieartitorX phenyl

atoar# b .p . i«5»l*8* *1 2 an.# ng8 1.518?. I t gava a negative fam rle
ofolori.d« isjHi'ta

t h ift ttisektetiaS u ra 110% losalyiiaii* lu i i t dirf ta rn fllH tt# 1!*

tokttto4/*to*t
totoKtotfetoiii.'feto 'U
«»*§
«M B
ijfowtofe^totoi
■Ww^
R
n
P
B
R
^
R
I^
P
it
R
B
^
to
to
BtoRiRR^RalF^R*

H
F
F
to
to
W
**^R
*Pv
^b
w

(M clzttm
brfM
i 4jh* HflTTltl
W
F
P
F
W
Bto
F
P

»» r« A tfl4 rMgttoavtoBtorfl \v& to fH ^ tototow^. toto&kftd$ »

(a ) 2,;M »biren(»oyi!^^

phenyl ato ar (3 5 ).

Fotaeston ta rtd a *y to to s to * (0 .5 »»1») wee prepared * » » aaeaaa
anfcydrooa te r tia r y to ty ! aloahol and 20 g . ( 0 .5 mole) o f potaaatoa to a
t o l *# teree-neeked flaafc fitte d a lth a Serahberg e tlr r e r , refU m eoa»
daoaer# to arw w aiar and a dropping fu n n el.

to a aaaaaa ta rtta x y b u ty l

t l pahni ana vnevad by d la tU la tto n and to a potaaatoa te rtto x y butoxlda
diriad a t about loo® a t 1 « • to r fo u r houra.

A fte r 000lin g to an le e

bath ttd breaking ap to * potaactoa ta rtto x y butoxlda v ith a glam rod
and a lto to a a tir r a r , to a w hite ponder waa covered « ito 165 g . (1 .2 nolaa)

n
o f a&3p2 pbwagrO. atemt wad WOA . o f H tg rin w p ta te m .
<326.^ g .* 0 *5 k>1«) a w A M

aL M e tta rta g la m

In n f t n i

te w .

iw a A M rtttjr texw d omngo-md and la te r te o w a t e a t .

B»* a tx te x *

S tirrta g « w

oawfelnuod m ad d itio n a l flv a te a m cb ro w t nqporaturo * during A t e
w a M ltio tH a 200 a l. o f psnteM a w addad. A fte r pouring ia te
200 a l. o f r a te r te a organl# laarar a w m psrotod, th e Ctfgaesua liiy w
w te w ta a oam r it e 75 AL. o f pantena and te a ewbtaad p w te w a o la iio w
©¥&!* H IM fteelllXa S llM W Itt'# '

aowa W M <wa|te|| a llV l lahwwarl

e th e r (333 f • ) e**§ i*X *t a * ©C n g fe e rle lj b*p. Xt$*>126° a t 1 m u w&lah

$&&cs

npW Mtewtef

■
W
^
W
P
*
^
W
^
1
S
P
,P

te
Fw

M
^tar
iw
re
L*mp z^ax^tal3JL;&a%i.Q^i
J
flM
W
f W
a
B
W
te
J
te
fe
A.A
w
M
N
1
P
U
teA
P
r
te
P
|W
-.^
p te
2
^
^
M
W
W
M
flfe
k
a
itw
i*'A
H
w
te
q
,2
A
te
H
W
P
. frois
9 ^-

o te a w l te a p ro d tet <31.5 g»« 215) ted a s a ltin g p o in t o f 53*51** *

jg £ . G ain'd. fo r Qxlf t u $rgQi 0* 39-231 H, 3.271 Br» 52.32
Ite W i

G» 39*21* 39.06* H , 3 .3 2 * 3.311 B r, 5*.W » 5 2 ^ 7

I t l l S&8tdha6M,OB ©Jt ft

rtfifrtra yft

twrt t&finS'X, ©tb®? (3 6 ) •

re fin x

A %~1* lam se-neoked ilmsk ma f it t e d w ith m o f f ic i a l

©©ndessBerp Ew iB bw g e$£$rer

100

A. o f 955 a tew o l*

A
A
B
.%
te
\'JF f tm
fte 6
^w
<
W
^
M
2
»
A
w
B
te
P
w
^
■
‘M
P
r an
^
^
W
te
te
^
F
w
Pte
B
W
a
'W
u
F

a dxeppi&g fteiinal aw^ vae ©harged wjtffii

6© g . o f away niokal a llo y and 30.0 g (0.033
,,w
;B
p
?
jd
a
A
^
w
»
A
fA
^
^
te
A
-o
w
w
a
te
a
a
^
»
f

'©ia©*ift!L
th
efWr.“
te
we
” ^
A
aT

tamt a m idtfo 600 A * ® i 1 0 $ m d t e

H *la tzsdxtstiuna
waa
e
*
w
te
p
^
^
A
A
w
.g
p
te
W
te

(ana 2»mr)»

Edition «a»

0.lm a t t o f e bmmm Warn nm m ia a d a a ti^a potiod batasm th « baas

bagm jra&oiing w ith th©

a llo jo

B10 ao M tlo a w

rafluasaBdi

a n a d a iti^ m l tw© h « , fS lta x ^ l, aad th # f ilt r a t e waehed w ith lo o *& •
© f 1 0 ^ e o d im h ^ rc a d d e end t lm

w ith liOO ®a* ©£ p e n ta » e .

H ie aqueous

X a^er wa» peared lu te U00 nX* ©£ o o m e a tra te d i^ d ro © h l© rio a e id acadt th e n

76

a
o
•H

-P

A
O
CO

o
o
is

S
1?
©

a

(X,

o.

a I
QO

VO

o

CM
uo-pss-pnetrejj; qxteo

Tf

,

e d e e w tw l te e t i n

w ith 1 0 0 a a .-p o r ti» n a o f penfcaaw .

: « m W k *< panfcm a e o la tio n # w
« w p rw h ic t 0 . 0

J k ttm

d r y in g

th o

a o & ttn a u lfa & o and rem o vin g th e eo lvao fc

g .# 6BjQ ( t la t lU n t l a t ii3 -5 5 ° a t 2 m b.

®a» jwodaet fow * cmvantX ro& ictlo ae were ooablmd and fra e tlo a a ia d

g h e ip l a th a r, b « . 51-53° a t 2 m .,

: te # *»
. ng* I . 5193.-1 .535? .
& & .

11 p m a negative fo rd o a h le d d * t u t .

c *io » d . fop OjoKiaO*
F o h *}i

c,

E , 8 J .7

C , 81 . 11, 8 1 0 6 } a , 8 .8 ? , 0 .3 tt

a * Attonpted 3Btemel iisam ageiiesrt o f
ttM & L m t * r

On> a&« o f avoSfltoBofflslanbSHBfl shamo! eth er m
a1aa0i*ph«3?l*3 pn&G&p®3pQ $&$*
M a ta k iU

ja tu ^ J fe b 'd k lA ^ M .M id f r -

nlk&aa

P td a ^ -^ fo

ww0 ©EflwKSjOtWE* t»Ma& eCBSt

a

hwesi # 'IHif
n

^

» ip J

ffiyf-i*

>lf*mPiiii t "

wkifee~tllLiiAt

reflm cad f2111 1 a t
lost isafiBB jfttS seg&G&zwb

a H tJB t

Xw^w w l® ^ ©X

■ i'fcn .n fo i

iw iu

A

w»0 |RiSlIrcXI*g WWWIJF*

lysgyjpy fot.a^i 414 W b

4Ch*> jjggg^ 4MN& flgPfflltBHHA*
A oiseh-ml* pa'PtliODi &£ 4^4 ®t*h®r n ^ i &©©,%©& in $ #jm|,#4.
vo3tt»a was aupsoalm ttfLy l l jf u , a t 500 1 1*° fo r ta n h o u r*.

fo e in fo *

raa apaefcn» o f th in s e ta rla l a m id e n tic a l w ith th a t o f th a a ta rtta g
« tt« r .

Both a fta r js *0 » *ta g fo r a ip ta a n home and t f t w heating in a

sealed fo b * th e fin a l M a te ria l p er* a negative fond® ohlortdo te a t fo r

Figure 18.

Infrared

Spectrum

CO

s

s

uofse*FuistrB aj; q.u©o a e j

o

o
(microns)

On

Ether

i—\

(CCl* solution).

rH

of Cyclopropylcarbinyl phenyl

Wavelength

78

HBHBJffll JOBS' DISCU3SICB
ptm&k «tb er v a * properod by two lntapoodoab
awtlwda, a * etttiUiM d is m fo U tw ia g nahmm.

*m

o a ^ ,, a B g *^~ ^>0» * e * m
f\a

Q

-o -

- t

qhjK

^ I

isB S ffif xu&jcijyit 4uu.oy
W K , 9 5 ft S#«tOi

/ V o

« <J8„ - «i » GH# * a w * *

.S S l
«*wrt1ftwoftww l

aefeh^t

( 3 ) ilW W ' i& O tlll
t a A-fekaittttl | | f | i

^

y * 0 » SB

IlNfffc Sb#

o l

ttn y ^ yt«M^a«id m m l

^jwtfc tfOSylfldbe disintiyi vim

ftanH4 war!

in fen vmMienfc n&sk

INI6WWI' i^fc- l^ ^lTtl? b t 390FH SlWlllS fflHPH $$}#

f

r AX&O* th ft

Wkawtoww^fiffa 4a» rtmnalil tuft, m afe»P«fflBl» aauljHnmlnil4ft

♦Kan tttW I

ai

i& v-^ro*^^i-lv
p ljttr a

MWHi *pP
M
#
aLhrttti^
&&Q&V&
MR
&p3&
8&
« ■’frls a tttio n
*W
Ip
®
f»
>
^■.
a
^
p
^
W
T
a
p
p
^
w
a
p
a w
wttiwp-ff a W
m
f
lff Sh2 tyD
Ffjpwv

>
tp
Q
£
g
tp
|P
a
llW
m
J
p
p
?
flP
> QH*AW9A

W llT |» i* i)» lU ty fo r p n n c M f *

80

MMLomfomm I mm foaaa poatia*i© d m infcaroodiato* in th e
Wn9&tm o f haloforma e lth potassium t-b u ttn d d * <35#37*38>*

$*a

iirtar»© d i& t* dibiaocartHwao n U X add to o le fin * to g Ire dthaloeyolojm p w ** d e riv a tiv e s .

a fte r

(36) o f th e

propane cofflpound obtained in th in $*§*£#* the product had illa U a r
( t if it iM l p?e#«rble§ m l an id a n tl& a l in fra re d apeotrua m
SM
.1 th a t obtained
by tfo* H r a t aynthetio uieihod* % e second method *a a used to prepare a
s u ffic ie n t q u an tity a t

phenyl e th e r fo r the a&tawpted

r* a rr * ieig*isas& ♦

^8w
ftlf'jUrilii
etraki^eaA ISwP® -dk.4toMMifc^iMk4Kj8MiaEatiUakWia' vdfc*filt'
t^ iB-dfcw
Waai IftpMSt

tan to f i r e hours*

„..l^-l4tV&ft
mMi&1Lu. M
kAMkJvid Mm M
t^dfciaBtail jfejftjifc itffa.de
** +$m
m«Q>
3F#BwwMSlJl
JMw&wCiO

^*utt w a solreisfe

as dixshaisrfL eth er o r

tff
asAttNfcetfftlfc.^aM
i di'Sejm o w l 'SHW**
tekaaafctih e
sbeii' ■
n8b&a^ 1111
pei^a^h1
.-^®. ja-dr
aamrittw
uieituaMi^
iaem
Mk*B
te^^a
4frk ^se
8*e 'xicx#
vetfadfc
<W|^jy*ip^j^PBiiwjgrii
j>wim
hiiwata*wp
maaaw
\ jl? /9■* t•***»
®* jth
B^eew

g reatly affected by aoetlo sold o r diaathylanl l l ng ( j f ) *
Three atta s ^ ts to osne© a cOysliNisptiyp* rfla^njaa^snaaa^t o f cyoiopropyOL**
oaTbltfyl phasyl eth er a r t aade*

the eth er aaa fle e t rsfluxed (SQU^O)

fo r »iK hours and then fo r IB hours,

in th e th ird abiaapi th e tim p

a m heated in a sealed tuba a t about JOgPg** fo r tan hours*
ijtlb u red ap®K5truis o f th e heated

^0

In a l l
a ith

th e a ta rti& g a *tw i*2 . and ao paMMm tmvio ch lo rid e Umt tor phm»3M
namm t^hm m m na^ ..

Ti 4iHh> awmdMairHa th a t daa®itS &

MlrihMl

CMlfiDJt!!®?'!*

enebinyX phauyl a^har a i l l m t uadorgo a th arn al aia ia a ii*ly p » ra a rra u ^ *
a n i i and th a t in th is particsular aaaaf th a csyolopropaua rin g is not
analagoua to th a oarbospoarboa dcsubl® bond*

m

%•

% * W W im m m v rn m «r 4rti»pw«A*Ertiiwi, aa«*i!t*n&l.~

*■ *

^^vsl^P^^A JiaffSSI^ 'TOruiSi** I W&& p& ffyfflifm 4tt& IMWfflXiJiffi *SjP
A

^ '< 1 i* i >% 1 t e in w t o t t a^

MW&^Hv^pHl
tb * a * a la a & *a a 4 b a to n tfe *

f » U n i n ite s «*£ m tim 1 ® m &

Ww IBBm S
«o3gp$39M l

« ^n m

«

®

P

m m f& l& m M

^ “W P li^

-M s^H aqflgW i I t a M iu

o s im itto M ^

ww*

H a st* tp « & q p n 9 9 & »

gbm
3M®tej^9L IM iO eom K N m al# t o l
M q&

*

im m ^m m X &sm

le d

s a ii^ rl ft* il!!!» M m tt* $ *l*

3km ftfswer
m ^ m lm ^ ^ im

t& m m m ?

m ^ m k’ ^ iM is m rnm m k •-:** # :^ ? a ^ « s lk
rnMWX tffclm r*
m&mm&v*

1to®

^ l^ ^ s s d i a $ $ w * te>- £&&■%&?$ wkth
m teatfl ts ^ & & im irn £ « te
a*$«r> «*?

«&§& <&A9gv*& ;i» $ *a a # ® &^3$t>«K.<.

$Kf

'ilm ?*£<*$$, s ^ im l a ffa sp *!* m 5

« f ^vilvm$5.«s?. fe? m il o f *ii& maiM&'B 35$% ssss-

«trtt4s$ ’
wfitfcfe ite# modmijlMUi

ikuNNa*

m i w%j$mem& %&

t» y l^ M

m «*#*&»

(p m e m lk ly jWiari/Hs £ m *
fg «

Atom,

0m m i & s m **& w )

01

"3U ®»* 1»lf3*M »aftafcaitaa o f syo&ap<ofyUuufe£aol, a o rtrlo y o J y leaxt&aol and dg^epM fg O ^^

ware prepared and p o xlftad fcgr

wamatAouO. w th e d a . a resweagad « rt« r efcieh i* probably 2 -a e ttv ltp e M M M t tsrtf3JK«»*o«fc*it0 waft alea foraed during th e ayatheai* o f
9W n^||p tiJMSffOO^^ 99|9b9^pr 4^?

vOOk-wwOktJOOnn^tOt^niAiO^^OHlvwPtn O'

$£* $|t#
Of frolVoLvaiS
lifl
fQllsmd
"
P
I'l 1
»
F fwlittt
^
iW
ip
-^
ip
M
F
^
p
jD
iW
IW
r Of
w
^
tp
a #Mapl
.tp
p
M
^
^
p
Q
p
n
ffy OO&Saftt
^
^
V
W
r
-'P
F
'D
P
^
w
W
W
^
P
P
P
^
P
r 1
^w
a
p
p
p
p
rw
tp
re
ip
w
w
e WB^hlOlSpSF
^
^
T
O
T
^
N
p
M
g
ip
-o
w
pw
-n
W
fc

m Sm i^Jk$

J^Jr^3^^3rC4^*©«»TA«yMgrX 6*»a |r*wRPlOyrJ^^lM»OPK^^

fl&OX^O&OliOtiOO inl^OijfOOi fejP

f$00iOI4e

oos&dLOjjrl* t^i*3^ttoi^oootHtt^o o o ^o lyio d
m m W iffm

aOO%tMLJ>LMitelkPP^ii-AiiMlk
iiMli
vlfo*
JIJwOl^gteOOvOMO

tsntyX %ai*f

jtkgtifajO

mm

w#w*

ISftttSj 0^Ol|3$SP^|0^M
'

^tfofidaolic ^Oowoo to ffv o

tflim'nMrtli^ tfteiMvWdw^tMkancfO: ^NhiMi'40&fk'n 4ifcjMk.**
**lf MBnfla
*lfl' MpOliiOfclbft ippft 9nw < iii*i j% ■■■
©yojJ»pt3^p^^
* ftJJUP9*
^am^^figrBUO*1
m

in &otlun3n& ,|^ yo ^ ily mol^ylL 1&£fXU0VO0OO&0t&

om l 2^soHsthyl^2y©1^1^%oE!!oX *
Orii^fr 9lMfrn'M liiI ^ i f ini gii liifdii m O h frtir

9

0

U rn o tto o o

dU rfu *% llMrt ^ilPPaO l i w A

ymM
A

iifc

o ^p o lo ^o ^^iln o i^i^ln o scls^^s ^^

OSm^mrvm^](P *l **0B3O *I# 90 W W w w O u wgr
ibN&

j^«M0MMNfedttJift0Mr

jtFif iMMjihf iflfcJMk

iMbitik

OlMtlHtiifc'^diBdMEMk'riPdMhdA:

l u M

o o lw l^ o io in mtibmmX or $0 %wMmwM® ^smm to yto M ®p^prswl~
■I» m A1hi ■■ijfll ■*- r t

11O i i i f ' ^ t

WttmB^k VWiMr* IB9
weotffcf tfcnn^t

ifiiAinOfciMi

'<QM*kok

'iiHin^t itii

appwKHI w pTOWWIB WSfcW
aKliiktOOOOOkiHBiitfk

^tdOL

T¥M9Mri> m Pit aril#*1* fe iift& 'lM

rMnwoKttaont M A l« r p pesooatae* o f aaatiiyX irtfb io ro o e o tirta
(iwwam dbly orladme f » » roozrsRged awtor) and 2-M othyioyolobttt«»l
M s * aOao obMxvacl la those m‘3m%f$m* & » zw tM , solswot «£fecrfe« and
a a ^ R ^ lM and entbaa&iM o f a B tlw id ra fo r a l l o f the eetatrs axe ooaa la ta n t w ith th e aaohanistlo poatailates (bead oloaaegw<) naatloned
^AuHHRtA
•wetFWw*

3.
1 s t «aO d s e t ba *n *A fla d .

taiCtm tteaaata&a w i «3ao prnpand
A f w k b M tio stadias on th s Japan* w ftar

in dic ated th a t i t s o lre ly M d by slkyX-ojgrgsn fis s io n , and th a t i t was
w ssy isnn a tisM i#

a * ^jpitnyaaiiyta nntdtfyii phswpi sthss? wan fspspsasd by tan indspssd^

li*

m * ij& m * B m * ,

u$L-*f {

to

% • * » ? • *m aum * • * >• »* a iy iti,

Mgnta OAenietay,"

m a to e iN M tt* DM BsMk, H S it, pp. 2MWB*»« . .

* • 4 . D . JfcftW t* « k i * . H . M u n r, J . in . M m . S ee., J J , «JQ9 (H A ).
J . e . B. l « p M

end s . S ie g e l,

jr.in . Qfee*. S e e .,

&. 4. s . KMmfe* m i f . e . GBsMwe, 4. in* t e

3J»5 (3 9 5 2 ).

see*, gg, A A (H A ).

5 . 4 . C . KBMMM matR . B . M an*,. jr. in . (R um . S ee., 2 J , AS2 ( H $ l) .
6 . 4 . S . M a r t * , I I . BawwRt M i B . in a rtro n g , <1. in . Oban. S e e., jfg ,
J ltP (U VO /»
T* 4 * D . Bnfaerte M l W. R M W tft, 4 . An. O w e. S e e., Jg* M *3 ( H A ) .
* v # I/#

ft* 4U

#» to n CM #* £##«# j|J *

9*

Me

3^0# 3P• ^SSHSt* St*

j$Sfl)$#i|&3Sty^

: w * f w * #9IX«Nro 8wB & *

|i9P >|r»

KHi Kmfto sw tto p * ^f* to * dsto« S&*.3
ij|£E8E& Slift Si# O^C^(2fiBBS03P#

1fi## jfcfiifl#iMS48ife. Cy&#s#*toj(dL

jPttSflS?®*

01sj#®(p9(j4 5^*

A . S . S . Femwan end 8 . B . Inngsar, <1. An. Ob«n. S e e., J g , 106S ( H A ) .
3 2 . B . Bast M l 4 . M. S M I , 4 . in . CAM. S en ., & , 3 *0 (H$S>).

33* ®» R. Keeewer end S. V inetein, J . in . Sham. S e e ., £§, i«3U7 (H S 6 ).
A . A* M M

M l B . B eal, 4* in . C M . S e e ., J g , A

is :. A . M M

mat B* BMnS, 4 . An* M an. S ee., jfc j, 2?8S (H 5 8 ).

(H A ) >

1 6 . A . aaRM-OMt B . S ent, 4 . An. fflum , S e t., J ft, 2082
$.7 * i *

to y to s s l#

(1S59)-

# it o CG^ptosc t o t o i

PM UaM m # Bee B e k , H A , p . 1031.
18. V . B . V M M

ami 4 . H . M itaany, 4 . in . S tan. S ee., |g , A lt (H A ).

m

» . « . to * m O M n p f, K . V . an m O m , * . 9. S w fa r m d e . s . a o o rt,
# * t o . (to n . S o o., Ja» 3595 (ism *

as. x . «r« D**j«no» mm x . Bejwesko, to r ., & , to (3908).
to * !»• *» BXUJttgv "»w -In*iw *iw a apowta* MtCoaplM; (aio w O **,"
^fe|M to Btofcloa* Joha V tlo y and Sam, 9m M , 3958, (* ) p . JJk9,
( * ) » • 30.

2 2 . X . to ro a , 0 . s . K&mtsemu aM H . H *ria , eiww. B * r.( s®, 343®
(3 9 5 7 ).
■
* -»
S 3. 8 . X . P ot», 6 . S . A rth , B* S . 8«p5U»> m d I>. B . Sm rett, «F. to . Ctow.
S w .* l£ * to 8 (1 9 5 3 ).
<£*$#■ #** “ •

JrJMMNPpjp

3*301

vIJjBSBMaWK^y^j

*2l3uPS-

. 8 . 6 . Hootb, Bcvtao, 1941, p . 2 » .
M JL*
M 'Rmawm
1DlM
feM
toriw*fekt.9#m
ytMMfead It*
131 lift.
«3>* 4t»
It* '^frktojJk'XMtoKifctolk' ljBl;^tf^fc**yto^ujfcp A
V

W E

Sou*. Bur

**te,

tofiitotfAIdL^tk jj^uuli
WX&

-Mf i?
4FjkW
2hwto*

jriHtefcr

J9S6, p . «M 8^J£»3T *

t t * F*
J w | i # M ilM M ia , <jfc All Fourth S tttto n , to & w -H ill Bock §».» 9m X a k , 3949, (to p* 370*
( b ) p . 356.

• a » w* iwwiritoiMlg wBBto #* tofKwciQWPvrp:
M

©x toxj^rawiipnnitoiA. aipipfr—

W I3 j^ t m i &mm$ $ m S M e *

fit *UJjHSMVl^toSp
*"%**
*P -8#* *&*FmMjS
t .jUrtW *lkttk*X y.T TXfeWWoBUIji.
Xt
«?@4 S3*
to*
># m m w Vtol «• ISyZifcBig*"AXilSOry *3* m w fJFOwwPltolS^
HfnnniintMiiri-ft7-4^1 'R
**^~
mwi^.f 1
1M
7 p«** 4*y53*
Irt/J
xtoMiSr
f w w * jn m
m *JWiW
7 #,j)#

Q« !£.*

^S%E1liWbfl3PB yp^f

^f| 0^*WB*,Q GtlfifiOlJPfepy'y®

aam toi K r*w & ty prww, xthite*, to r M

, & 53» (a ) p.

0») p . 752-78*.
3 0 . J . E ia a . " H ^ ilo a l QrpBBle caaasdittoy/ to to w B iU Book 0 o .# 8nr Xorkt
3 X 4 (to p . 3 2 .

J3.* A . 3tiralto3.«*«r» «Rr., (to w . toM «# ^

571

(3956}.

3 2 . D . a . Z u to e ll, G to#. to w ., ^2* ^ 5 (3 9 4 0 ).

31. D. 8 . to to d l, W gpaio to to tto w . V o l. XX, J<*a WH0 7 «k>8 <aw,
to r Z ork, 3pti4, p . 1 .
1(1, _ mM JillTft*». Rltetito Atoii!htt>tBlfi««a

JpJi *

*
W
P
X
PM
tM
to
lP
to
M
to
B
U
P
to
lJ
l:

iW
V
^
M
*tX
®
to
VT
P
W

to
!P
fto
X
lto

V orlag, B a rtla , 1957, p . l»(3t-i*06.

to
F
M
P

Cfa&Sgk&m* W lx a ato
^

to
*

1+8. H. Hart and R. A. Martin, J. Org. Chem., in press.

.1$*LS$«>

4«*J

i**+<4tb *4 <
k
>
^-v,-',

^

£
*!*■
*
':.^i

,U •£t;v
&*•£.-'
fW *
•$«*»/

^-A S flS

3 ft «*3

S

# *p p

2f
>,,iT.
-. *

^

If .®
M v’
,. .<
*

•.*■
*
:>
;vr
:

j* * *

4

. J i4

'*-.i3 X ?
> . ^ 'i
_

lif>

' «
A
>•??
- «',>
%»
-v*;

* -V
-

US

~
'

’^V T

.-.*£'

*#■*#

'-■ £'%»

*£*;,
SI:
;.-•

.f*v-'®
- .• '.
:£ ? A
<2||fc*?'

■■■•*
^ W iil
-***- ■?'*-4$^

■"■- •’ ^ 4 .
k ;i £ - t i #• .■;/*'■ ^
„•.-.. .-.u
, *. ;. •.

“
' •*
•
•r
: -'•*,>
-.'■
•

® /5
,;-4
^
:->
■
*•«*. j

^ i>
;£
■
»A
4
-.. * ‘. -‘-**.'£± V
-v
~
*%
>

M

mmm

;>
iii

I

Iiw
i(|p
1
|K
«
B
|«
I!*.<

8?

T ia . t u |
m m m m

in u u t
XK 6Q ^ OXSGU

* M * f a im

k » l M * X0“ *
It • 3-CO. X 10"># * 0 C ~ X

90

O f 0 * O till Kr»^A» g m A l,B9F,X lS i2 B IX ll
131 6&S l|08Um»faMfiffii £f Ii3«3r0«

9MB

MMMMMBBCN
B

I
?

10

¥

to

as
n
is
Uo

1 ^ ,» 1&*9 ohao

It * 1.7? * 10” * n te .” 1
k « 2 .$ * x l< f * # • » .” *

n

lifAww

n
n

u

a#

n

a>WTffaVf TfrtA*^T0f1!Y« Tfffri,l ^ <?y^

mam a* &«c*o»

1gjW<!f11^

0OBSH

n

%

l$sti

w ^ J L —

^ T 5 %
tfifla
fa,■
>

i?
0

3

s

*

I

'9 M 0 4

9
30

«o
*0
*$

u
>*o
,»0
■
*81

S
39
m

n

WL
iS

m

g

*

as

0 * 3 8 tt
0 * l$ 9 r
o .U ld l
® Jkm
O J0»

&

*9
*1

JT*

30

•

i f iO afas®

Ik * U *07 ac 10~® a te .* ’ 1
»*
* i
k«6
.?
8a
c
1
0 mm*

°"^® 0U

o ^ i
Q *$ klZ

9k

ts !2 a a !s a 2 & m a i± £ m *e £ s s t

9$

9*

n
Oo

MMMtwrn m »o«s warn wamwmwwam, pm m t& m m
m

t#

m m n & m

v m m * * m ^ rS T

m

i®

¥
m
m

85

o,

m

o .im
ojeo B
o ^« o 8

tag

0.33®?

300

o o tm
^

a y o o ju w

k • 3 .3 ? * lo “ * ■ to .**
k * $ M

* J O ** • » . “ *

mmmm or omrm mm
m m

m orm itntuM m w uim m

tat

‘o.

5J8SS8ttS883SSffl

K M
%

10
*0

&

o .o w a
*

...

I

99

HMH.1 gg
vnm am m

a, • 3 M «*»»

k * $ J & M 10 *ln.
It * s>4 t * 10~8 1M.m%

mmmm

ipMMWH

wmm

ion.

108

mmmm m omm mm mimmwmmm&jmmmmmim
x* aof wcckmbmo* mm a? to-re.

M M M t
I
Jflfcn*

jaflgiySB

*** TTZ
iiwijwumiininwni

t» W » 'lii''
k * 1 -3 ? at 1 0 ** iia . *
k * t.3 2 * 1 0 ** .« •* .*

f* » p i $ $
T *« « *» ■

im_*uw

'*+m

-w

^ fir W w4^

9*¥SQmmm- w mwf fv

^

T

9mm^ m m

xr to# mmim>4o$warn xt $qa?o.
■ H H M M M n n iM M R

t
m Kk

-

«

J t....

* * * iT

20
bo

<a
12

120

li*o
ly

180

200
flWp^F^

as
ssmi

W&

Its
352
380

380
U 00

0 J j260

oa»U76

\

%Sk

imi'i

y f lf ftiB 9 ft

8(&$14SJft C f 04.015 Mfum OMygPBOITXOAaBI IEtL fSIH JgQ ftW gttIK
IK 80< M CBCM IM IQft V A S R AS 5 ? ^ 6 *
a m s s a a a w s je s :

R pn

iw a w M a

t
m£ r *

m
to

IflitO O

IfcW
9)

4 111

10ft

•max
m m a e m or 0.07300 m u x .
at lo f

2T0
W
30
1*0
m
»
TO
60

b
t

warn a*

s m

?c .

30609
6830

li©

330

0.3J33
800

0 *3§ 0 8

0.3666

210

0 .36 IT

820
830

0.33ST
o .i*iii*

21*0
JL « IS O O o to *
*
.8

«»
1c » 3 . 5 7 * 1 0
a ia .
k * $.95 x 10**8 «w.”1

MT

CttfeBJO

scmgmks or ouxao$ nous aaaM sseusAuum mnsommmn

n

60%m m m 4m

husr m i#3Fa.

M

W

M M M M

*

lia .
0*i5S 8k
f l. im
» »
«o

b

308

0.

0,

040*

231

a lo

0,

120

0,
0,
0.1
0i

X$9
16$
3 ^ .0
1 3 0 .0
W .0

.

110*0
0.JH A

\ «* 55*0 -4m*
k • &#3f at 10*d a to /**
k m3 *9$ %y

f m&*~
m

u *

fc • JU?9 m k T * w ls *« r*

k * 6*Jtt k llT

»•©*"*

im

M U M & iK n car &

eeO S B Q K U S K H S
0.

:
ass

assasssaaK sajisssM a^^

saseaasssas

0

m

k

* f.

Ic • 31*

mw

v&m* ^
«*4
«S
m 20
M r#

rnmm

us
fM T 3 $

H I

11 &

in

*

*

*

«
soft

r

W A m AT S?-<TC .
w B ossw cw araB w

%

M m &m m m sam
I f lif Mgwflfri
ST**,

* i» .

MM|WWNIPm
20

« 0 f# g

*<$3©
0
#
0*
0

»
100

t« ft

0Jb&M»

200

0
0*

0«i

280

ISO©
£Ufc>

o
0
0.2803
0 , 2m

0.3010
0.3326

as
:-i2o

0.3226

m
$20

0*3
0 .J J
0 *3 6 jS f

SbO

0.3W S

&60

mf!% ohm
k m A *5 0 m V f* ia te /*

It * told 3E itf*0

MMM

m

110

■'

"» •

0 * tttA tK to.*

S9^P03b^iS Qjt $$M|
pMWliMWflway^^

k a , W ltM

19ft&(iKK£B&

*a *

l& ^ e re

obtalnM

fM M

tb t

<« #ta w»MwiuAiwfc<am <g# ffelp**

1aO*Iaa*o«wt**i# afaJLeii alao oont«da*l SHwttqfl.-

e y tita lm ty l M U B aa vN »ita te . Aa 2 H a a ik 9 l^ r< ^ ^ ^ fc rtJ ^ a w tta ta **

(fea&ew t l^ a o ild
e&jf

Kiwmffcy WSKP9

Sb iflbs lito s s ), igpy* s tra ig h t tfo f# 0$A tfett aslope
foj* tfe£$' fflttiKP $01

S

IS O

5
H
®
4
5IjJ
t

MiMaMaaemiigaaiiBigaiiaiaaeMiBMegMa^^
'"■*
" ***

t
« **

% •

3 S .7 o ka s

.
-a „ „i
k * 1 . # X 10 sda.
k » x .8 1 x lo * 4 a a a .* 1

R
W » l* ^ -

»

jftfeCHi fi? m npttnyffyjMMBHHTL^,

W 1#$W
w arn
'mmm

wmmm.

% » j& 4 > < *■ »

km 1 M m 30** *la .~ *
k m 3 .02 x 1 0 ** * • # . " *
immimii n wi»np

a *8

jliiiuwjiiiiwiii»*ai^i(w»w<>^

ifirtuiiw

■MMMM

k m

& id

iMMPMMM)

1These data used only for Figure U9* page $9*

m

to u t so

mmsam m

m u

m

*

m t w m m & ® 3$ m m

n
m

m ^ ro .

it * 300 t»io«

fe » S.31 * 30“* a a a .*1
k * i. < * * a o

*•*■«

v im x

m m eam

w

m

e m m m j& im m m m m m p m M m o tm m
m tojs m < s m fr% o t w e m m t o j r o .

9m

mmm

mm
%
rtJbfefc
<6Bl6p#

0.333U

o .i
043.
0 .3 & 7 0
0 4 0 *7

^

* 328 etum

k • $ 4 0 s 10

<%

m%

sin.

k»?
.?
?x1
0
“
°«
*»
.

cagy jp i

tjo

«0«tate, 3hto tofrtop ®ate*» also
i^ k n iN B ik rfi^ fe - « n ^

- iifttliik r ^ k

# ^ u ff: liiy k td H u & iill

w W !# ^ a jL u ii

A

! , , , i^

JL*1Ue

tasijnbaoi^-*

^a^a* t>he paftotLoft 0&a^tlfflnv
-1. ^ ^ .n iti dm. j—

QlBllflyB^E # 0 # «!»«0«*O p j^ lS lI JBWP to # ##*Ito9i##SMI # *

iwniftit4rt«- Q#8|ar that

*#«>» (abo^ro to# iftfoiM*

^^MMkdMkaAwa^SLsi i i ^fai f i HnMAb^^

od? to# ■
& *& * to**# « w a thd iit^^itfl $&&#&&&

to to# Ito to #) yyp uaeti to ^ItfffiflMitog to#

mmmmm

mmmmm
ipiiltwim

i hi

mmm

mmm

133

m

M cn o ^

^'WP^P^^pW «^wjp. —
*'C.fu x m

mm

m

< ro *
tfr x » ^ m :^ ^ r jf.itiiB :g ag

iW W liliyiiSEttSR

w -J U *
^ itn g
turn*
G

1»

% *■ # 4
k *

•jwfeaq&i
P ’ *»1

m%

JC 4P . m il*

«-as.
■*
“^
^ -«*9
a "
Is « X *0 § |£ 1 0
M ft*
..

H it

«r 0

m
Utitt $&&&£' i p t y i t W

w

t f i fflifriff sw-

p # a * p * w fs p * w ^
»

1

^Y T T Q

o.am

0
0 4 ^0
%

nt %&& &hwft

it « 3,^1 x 10*** ■*».“
k •» 1«?2 x 10 •*».**

iw

%
«4»*

*

»,..

« *■ *

m

- jam

mLl ^

It

tiMfcft

.».*».

tUpw *$©38®

m£ J f

x J 0 '.

at»“

k • i» 4 ® * lo “ * w w .* 1

mtmmtu

nmnmMmmmm

*mkMpmk

ifa o

nwn»»te_»

■MrtllWWN

nimipnjwftmimLi

iMpmwwmm.1wiwwn<

m

90U K U K S R

W Q,<SS$tit

m m m a t m im m M M m m a t 6 o .icto .
OHM

m

M

%

XclOk '<WiWwP
* * * • X *>

< ta i
mm

s°

■ f*

310

km

0

I
0 .6 5 8 7

aoo
2M »
8100

0 .8 1 1 8

3000
% *

-

,

,

k * ii.O? is lo” a4a»*'
k • 6.83. x 10m*

ifiw m m tr f t fc * < & * *

d tk & tfS lS lil

ISm M
ainS
t
S
&
a
*6
U
,6
6
,&
,?
0aad 72 a
m
tfeoaa obtaiaad d ixveU jr «

« » jU
v
n
v
aanrtar. TUa date im fsb laa 6S, 67, 6?, 71 *ad 73 war* mlat»
IjdNid fvtam ’ttsu iM ffHrfriw
%Mym
fryy9***^ vfi&i* o£ 1^
# f %m
ftg m k

n
*rt o
fth
itt th
a
s
ifl)*

V bm m

Ia
M
*rd
a
tam
m
4
»
ife
liA4
tr
«
d
r
i$
i

U
b
m
tu rn ito
t
e
t
otb
a»
a
*»
*t*i a
o
lv
a
ly
a
lam
f
c
ao
o
n
a
t
w
r
t
aA
a
rH
4
*a
rta
r

31*

1 .1 3 3 5

JL * 336 ohm

W 3L&

xm m m m m & am m m
a
4MMMMMN

MM

i!pwwj*a»Mi*"

ik &

UtT

M
ftW
IM
W
M
p

we***

tt^ln1rllTr‘Tr“1 ^^^•^lr^''r■'“^^L^^^^“'•l^^^"'^‘‘^'a'^'“'^l^■■^i“ i‘■'‘ '‘^u'"^^^'■.... ■>■...■>

.„

mmwiw:

mmmmm

mmm

13*
vtaa x 32

aawcosia

m

o«qeasg acua

saowfanm m m m asti
%
tufoejafi-

W»

a » g f* f

O U iitlS
o ^ m
o ± m
04*815
04 *5 0 0
0 4 (5 ® :

0.g&>8
0 .^ 0 ®
0 .0 3 5

0 .!
^

» 370 ohs»

353

n o u n

w > 'r iiil. H . II> iiM J ' * l llW K» l W *

I w H !(IW ^ !g # l ^ < l t i W W W * i W i P > i il » W W j l l ) > « W f f M H W ^ ^

W Wn w » H B i i ^ < W l « < W M M t W | N ! I I M » W I ^ ^

0.600
0 .7 W

JL * S IS aiuM

*

■ " ' _a

k * 2 .1 3 x 10

. „i

b4h.

f c « 3 . & x 3 0 " * w » ." 1

a*
■KHB-a **L
m xM M m . m

o < # 9 k i w a rn r n m m m m m m m m
w m ^ m m m j ® i& a r o .

m

m i

*u .
*mmWm
©<
0*1
&
©I
G 4&&

w

n

0*2
0,
0 *M
0<
0,
0|
®*
0i

2i

k * 1 < B X 10

B&K.

k * it.# at 10*** «•#.“ *'

155

Tim.K 75
s e s m ts is o r 0.05123 «o u s ih w tx i, ra ju K w a c s rA ta
XX T©.W A O W W -29.3* WMHR A t 1*5.1 0 .
wsae&m
%
aflbu

a
otawi

15

w

0.0318
0.0588
0 .08U6
0.1086
0.1323
0.1563
0.1798
omJ6
0.2279
0 .2511*
04769
oJm.
0.3253
0.31*91
04738
0.3957

825
¥6

§

Jo

262
Wl
1?2
in
1S5

?5
90
105
120
135
150
165
180
355
210
^■1PPPH^
m
2l»0

#0
132.0
123.0
116.5
110.0
33M
100.5
97.0
^ » 58*0
IK

tow

JK XV

a
i • ^

S&ft*

.1

k m € » t l X I® * * o m T

156

Figure 19. Plot of log k versus l/ T for the Solvolysis
of Cyclopropylcarbiryl Trifluoroacetate in 60% DioxanekO% Water*

8 * 5 2 kcal./raole

Log

k

-3.

-3-7

-3.8

3.0
l/T x 103

157

Figure 20. Plot of log k versus l/T for the Solvolysis
of Cyclopropylcarbinyl Trifluoroacetate in 70% Dioxane30% Water.

E

« 8 . 9 6 kcal./raole

Log k

-3.9

-U .2

3.1
l/T x 10

158

Figaro 21, Plot of log k versus l/ T for the Solvolyois
of Cyclopropylcari&inyl Trlfluoro acetate in 80% Diocacane20% tfater.

Log k

Sa * 9.82 kcal./inole

-U .5

3 .1
l/ T x 10

3.2

159

Figure 22. Plot of log k versus l/T for the
Solvolysis of Nortricyolylcarbinyl Trifluoroacetate in 60% Dioxane-UO# Water.

1 1 .5 k c a l./r a o le

-U.0

-U.1

3.1
l/T x 10*

3 -2

160

Figure 23« Plot of log k versus l/T for the
Solvolysis of Nortricyolylcarbii^rl Trifluoroacetate in J0% Dioxane-30# Water.

11.7 kcal./mol<

no
o
i-3

o /t x 10

161

Figure 2U* Plot of log k versus l/T for the
Solvo lysis of Nortrieyelylcarbiny1 Trifluoroacetate
in 80$ Dioxane-20^ Water.

Log jk

13 .0 k c a l . /m o l i

3*1
l/T x 10

162

Log

k

figure 25- Plot of log k versus l/T for the
Solvolysis of 2-Methylcyclobutyl Trifluoroacetate in 60% Dioxane-LO^ Water.

-3.7

3-1
l/T x 10

3.2

163

Figure 26. Plot of log k versus l/T for the
Solvolysis of 2-Methylcyclobutyl Trifluoroacetate
in *10% Dioxane-30$ Water.

Log k

- U .l

3 -0

3 .1
l / T x 103

3 -2

16U

Figure 2?. Plot of log & versus l/T for the
Solvolysis of Cyclo propvlmethylcarbinyl Trifluoroacetate in 60% Dioxane-UO^ Water.

-

1.8

-

2 .0

3.1
l/T x 103

165

Figure 28. Plot of log k versus l/T for the
So lvolysis of Cyclopropylraethylcarbinyl Trifluoroacetate in 70% Dioxane-30# Water.

-

2 .8

-3.0

-3 •h

-

3 .6

3.0

3-1
l / T x 103

3.2

166

Log

k

Figure 29. Plot of log k versus l/T for the
Solvolysis of Cyclopropylmethylcarbinyl Trifluoroacetate in 80$ Dioxane-20^ Water.

-3.6

-li.0

l/T x 10'