University of Southern California Dissertations and Theses

Solvolytic reactions in the presence of added nucleophile

(USC Thesis Other)

Solvolytic reactions in the presence of added nucleophile

PDF

Download

Open document

Flip pages

Download a page range

Download transcript

Copy asset link

Request this asset

Transcript (if available)

Content SOLYOLYTIC REACTIONS
w
IB THE PRESENCE OP ADDED NUCLEOPHILE
by
J u l i a Ju e Soong
n «
A T h e s is P re s e n te d to th e
FACULTY OP THE GRADUATE SCHOOL
UNIVERSITY OP SOUTHERN CALIFORNIA
I n P a r t i a l F u lf illm e n t o f th e
R eq u irem en ts f o r t h e D egree
MASTER OP SCIENCE
(C h em istry )
U M I Number: EP41653
All rights reserved
INFORMATION TO ALL USERS
The quality of this reproduction is dependent upon the quality of the copy submitted.
In the unlikely event that the author did not send a com plete manuscript
and there are missing pages, th ese will be noted. Also, if material had to be removed,
a note will indicate the deletion.
Dissertation Publishing
UMI EP41653
Published by ProQuest LLC (2014). Copyright in the Dissertation held by the Author.
Microform Edition © ProQuest LLC.
All rights reserved. This work is protected against
unauthorized copying under Title 17, United States Code
ProQuest
ProQuest LLC.
789 East Eisenhower Parkway
P.O. Box 1346
Ann Arbor, Ml 4 8 1 0 6 -1 3 4 6
tA & y
Ui>>
U N IV E R SITY O F S O U T H E R N C A L IF O R N IA
T H E G R A D U A T E S C H O O L
U N IV E R S IT Y P A R K
L O S A N G E L E S , C A L IF O R N IA 9 0 0 0 7
c
' 7 2 .
S 7 H
This thesis, written by
J .tilia .. J u e SQ.cmg.......................................
under the direction of h£OC Thesis Committee,
and approved by all its members, has been pre
sented to and accepted by the Dean of The
Graduate School, in partial fulfillment of the
requirements for the degree of
M a ^ t e r . . . Q i ..Sclenae
Dean
Date FebruarYl972
THESIS COMM-I^Ei
iairman
M S '* €
To My P a re n t s
ACKNOW LEDGEM ENT S
The a u th o r would l i k e to e x p re s s h e r
g r e a t g r a t i t u d e to P r o f e s s o r K enneth 1 . S e r v is
f o r h i s e n t h u s i a s t i c g u id a n c e and h e lp f u l
d is c u s s io n s , w ith o u t h i s a s s i s t a n c e t h i s work
c o u ld n o t p o s s ib ly b e done# The a u th o r a ls o
w an ts to th a n k M iss Lucy Ja o f o r h e r a id and
c o n tin u a l encouragem ent#
TABLE OP CONTENTS
ACKNOW LEDGEM ENTS
p ag e
i i i
LIST OP TABLES •:
„ _r
LIST OF FIGURES .v ii
CHAPTER 1 I n tr o d u c tio n
i
CHAPTER 2 R e s u lts
5
CHAPTER 3 D is c u s s io n s 17
CHAPTER 4 E x p e rim e n ta l S e c tio n
37
BIBLIOGRAPHY '
51
APPENDIX
53
LIST OF TABLES
T ab le P age
1 , R a te s o f A cid P ro d u c tio n and P ro d u c t R a tio s 10
f o r th e S o lv o ly s is o f 4 - M e th y l-3 - p e n te n -l-
y l M e sy la te i n 60% E th a n o l a t 6 0 ° C i n th e
P re s e n c e o f Sodium R i t r a t e o r Sodium A zid e.
2. R a te s o f A cid P ro d u c tio n and P ro d u c t R a tio s 12
f o r t h e S o lv o ly s is o f 4 - M e th y l-3 - p e n te n -l-
y l M e sy la te i n 80% E th a n o l a t 6 0 ° C i n th e
P re s e n c e o f Sodium M itra te o r Sodium A zid e.
3. R a te s o f A cid P ro d u c tio n and P ro d u c t R a tio s 13
f o r th e S o lv o ly s is o f t r a n s - 3 -H e x e n -l-y l
M e sy la te i n 60% E th a n o l a t 60°C i n th e
P re s e n c e o f Sodium A zid e,
4 , Sodium Io n A c ti v ity f o r V a rio u s I o n Concen- 14
t r a t i o n s a t Room T em p eratu re i n 60% E th a n o l.
5, Sodium I o n A c ti v ity f o r V a rio u s Io n Concen- 15
t r a t i o n s a t Room T em p eratu re i n 80% E th a n o l.
6 . P ro d u c t R a tio s f o r th e S o lv o ly s is o f t r a n s - 16
3 -H e x e n -l-y l M e sy la te i n th e P re s e n c e o f
Sodium S a l t,
7* E x p e rim e n ta l and C a lc u la te d R a te C o n s ta n ts 23
and P ro d u c t R a tio s f o r S o lv o ly s is o f 4 -
M e th y l- 3 - p e n te n - l- y l M e sy la te i n 60% E th a n o l
a t 60°C .
T ab le Page
8 . E x p e rim e n ta l and C a lc u la te d R a te C o n s ta n ts 28
and P ro d u c t R a tio s f o r th e S o lv o ly s is o f
4 - M e th y l- 3 - p e n te n - l- y l M e sy la te i n 80%
E th a n o l a t 60°C.
9. E x p e rim e n ta l and C a lc u la te d R a te C o n s ta n ts 33
and P ro d u c t R a tio s f o r th e S o lv o ly s is o f
t r a n s - 3 -H e x e n -l-v l M e sy la te i n 60% E th a n o l
a t 60°C .
LIST OF.FIGURES
F ig u re P age
1 . P lo t o f em f(-m v) G en e ra te d o n th e Sodium JSn 14
E le c tr o d e v e r s u s - lo g ( C o n c e n tr a tio n ) o f
Sodium Io n a t Room T em p eratu re i n 60$
E th a n o l.
2. P l o t o f em f(-m v) G e n e ra ted on th e Sodium 15
Io n E le c tr o d e v e r s u s - lo g ( C o n c e n tr a tio n ) o f
Sodium Io n a t Room T em p eratu re i n 807*
E th a n o l.
3. A P l o t o f R a te C o n stan t v e r s u s Sodium A zide 19
A c ti v ity f o r 4 - M e th y l- 3 - p e n te n - l- y l M e sy la te
i n 6 0 $ E th a n o l/ a t 60° C.
4* A p l o t o f P ro d u c t R a tio -v e rsu s Sodium A zide 20
A c ti v ity f o r 4 - M e th y l- 3 - p e n te n - l- y l M e sy la te
i n 60 $ E th a n o l a t '60°C .
5. A P l o t o f Rateue© n? st.aftt v e r s u s Sodium A zide 25
A c ti v ity f o r th e S o lv o ly s is o f 4 -M e th y l-3-
p e n t e n - l - y l M e sy la te i n 8 0 $ E th a n o l a t 6 0 ° C.
6 . A p l o t o f P ro d u c t R a tio v e r s u s Sodium A zide 26
A c t i v it y f o r S o lv o ly s is o f 4 -M e th y l-3-
p e n t e n - l - y l M e sy la te i n 8 0 $ E th a n o l a t 60°C .
7 . A P lo t o f R ate C o n stan t v e r s u s Sodium A zide 31
A c t i v i ty f o r th e S o lv o ly s is o f t r a n s - 3-H exen-
1 - y l M e sy la te i n 60$ E th a n o l a t 60°C .
F ig u re P age
8 . A P lo t o f P ro d u c t R a tio v e r s u s Sodium A zide 32
A c ti v ity f o r th e S o lv o ly s is o f t r a n s -5 -H ex en -
1 - y l M e sy la te i n 6 0 $ E th a n o l a t 60°C.
9. T i t r a t i o n Curve o f H y d ro c h lo ric A cid i n 60$ 49
E th a n o l w ith Sodium H y d ro x id e a t Room
T em p eratu re.
1 0 . T i t r a t i o n Curve o f H y d ro c h lo ric A cid ( i n 6 0 $ 50
E th a n o l) i n th e P re s e n c e o f Sodium A zid e.
v i i i
CHAPTER 1
i
! INTRODUCTION
i
i
E ver s in c e IngLod and h i s co w o rk ers d ev e lp p ed th e
1 2 3
| m echanism o f s u b s t i t u t i o n a t a s a tu r a te d ca rb o n atom , *
i t had become e v id e n t t h a t th e n u c le o p h ilic s u b s t i t u t i o n
|
r e a c t i o n s c o u ld p ro c e e d by two d i f f e r e n t p a th s . The f i r s t
m echanism c o n ta in s o n ly one s ta g e i n w hich two m o le c u le s
i'
s im u lta n e o u s ly undergo c o v a le n c y ch an g e, t h e m echanism i s
b im o le c u la r and i s a b b r e v ia te d a s Sjj2 ( S u b s titu t io n -
E u c le o p h ilio -B im o le c u la r) • The second m echanism o f n u c le o
p h i l i c s u b s t i t u t i o n in v o lv e s two s ta g e s : th e s u b s t r a t e C
fo rm s th e carbonium io n f i r s t and th e n a r a p id c o - o r d in a
t i o n b etw een t h e form ed carbonium io n and th e s u b s t i t u t i n g
a g e n t i s fo llo w e d . S in ce o n ly one m o le c u le i s u n d e rg o in g
co v a le n c y change i n th e r a t e d e te rm in in g s te p , th e m echan
ism i s u n im o le c u la r and la b le d a s Sjjl ( S u b s t i t u t i o n -
E u c le o p h ilic -U n im o le c u la r) •
G e n e ra lly s p e a k in g , n u c le o p h ilic s u b s t i t u t i o n on
p rim a ry c a rb o n atom s te n d to p ro c e e d by S-^2 m echanism ,
th o s e o n r t e r t i a r y ca rb o n atom s te n d to p ro c e e d by Sj^L
: m echanism . Some r e a c t i o n s o f a g iv e n s u b s t r a t e h av e a j
\ A R (\ \
b o r d e r lin e re g io n * -* . * d is p la y in g b o th and % 2 i
■ 7
; c h a r a c t e r i s t i c s . Sw ain' p o s tu la te d t h a t t h e r e i s o n ly one
j ty p e o f m echanism o f w hich S^L and Sjj2 r e p r e s e n t e x tre m e s, j
6
j O th e rs h o ld t h a t t h e r e a r e two ty p e s o f m echanism s, S^L j
! and Sj^2, and th e " b o r d e r lin e " i s cau sed sim p ly by b o th |
I m e c h a n ism so p e ra tin g s im u lta n e o u s ly o n th e same s u b s t r a t e , |
i
| t h a t i s a d i r e c t , c o m p e titio n b etw een d i s t i n c t S ^ and S|j2
| p r o c e s s e s .
i
|
| A s in g l e m echanism o f n u c le o p h ilic s u b s t i t u t i o n a t a
j s a tu r a te d c a rb o n atom was su g g e ste d by Sneen and
■ 8 9
I co w o rk ers. * T h is m echanism may b e o p e r a tiv e on any ty p e
| o f s u b s t r a t e , i t c o u ld accomm odate t r a d i t i o n a l S ^ t, Sjj2
i
j and b o r d e r l i n e ^ b e h a v i o r . The mechanism'*"*’ r e q u i r e s th e
in te rm e d ia c y o f a io n p a i r whose fo rm a tio n i s r a t e d e t e r
m in in g a t th e Sjjl end o f th e m e c h a n is tic system and whose
d e s t r u c t i o n by n u c le o p h ilic a t ta c k i s r a t e d e te rm in in g a t
th e S}jj2 end. I t i s t h e b o r d e r lin e r e g io n when th e r a t e o f
fo rm a tio n and d e s t r u c t i o n o f th e carbonium io n a r e compe
t i t i v e .
The in te r m e d ia te io n p a i r can e i t h e r r e a c t w ith th e
1?
n u c le o p h ile o r th e s o lv e n t w jiich i s shown a s fo llo w s :
EX R+ X~
- 1
s
ROH
(1 )
A cco rd in g to th e sim p le s te a d y s t a t e a ssu m p tio n , th e
p ro d u c t r a t i o i s g iv e n by;
_R JL *.
ROH k
(2)
s
The psuedo f i r s t o r d e r r a t e c o n s ta n t can b e shewn a s :
k.,1 k + k [h] )
sLl s n i J
k
obsd “ K i + k s + k n W
k , k
^ = — ~...s — when kn (Hj i s s m a ll.
(3)
k
obsd
tN A
k
obsd
(k- l ;+ V ( k s + k a M )
k s ( k -l + k s + k n W >
( x + 1 ) ( 1 + m | l l )
( x + 1 + m ( l j )
(4 )
(5)
m = y k 3 and i = Jc_a / k s i a s x C D ,
k
obsd
/ kjj-A s 1 + m |u j!is t y p i c a l Sw2 b e h a v io r; a s x = 0 ,
kobsd / = 1 i s exP ec-fced "to b e Sjjl b e h a v io r. C ases
w here 0 < x < o o i s p r e d ic te d to show b o r d e r lin e b e h a v io r.
I t was p o in te d o u t t h a t a scheme o f s im u lta n e o u s ly
c o m p e titiv e S ^l and Sjj2 p r o c e s s would g iv e r i s e to th e
HOR
m
k 9
k
k P n W
U-RX R+r :
k
- 1
HOR
■ H nW
* M R
p r o d u c ts i n a c c o rd a n c e w ith e q u a tio n RN/ROH = k n ( l ] / k s
| o n ly i n th e u n l i k e l y e v e n t t h a t ^l n / k g = k 2z / k 2s*
i
j How ever, e x p e rim e n ta l d e v i a ti o n from l i n e a r i t y m ig h t n o t
| be a p p a re n t.
i
i - . ,
| I f p r e e q u ilib r iu m b etw een s u b s t r a t e and io n p a i r
I 13 1A
! in te r m e d ia te i s in v o lv e d , th e p l o t o f s o l v o l y t i c
j
i r a t e c o n s ta n t a g a in s t a c t i v i t y o f added n u c le o p h ile i s
I 1*7
; l i n e a r . Sneen v h a s shown t h a t i f t h e r e a r e m ore th a n
j one p ro d u c t fo rm in g in te r m e d ia te s , th e p ro d u c t r a t i o m ight
i
| n o t b e f i r s t o r d e r i n added n u c le o p h ile .
j
i
| P re v io u s s tu d i e s had in d ic a te d t h a t 3 -b u te n - l* y l
s u lf o n a te s u n d e r v a r io u s c o n d itio n s c o u ld r e a c t by e i t h e r
an S -j^ L o r % 2 ty p e o f p r o c e s s . By stu d y in g th e e f f e c t o f
added n u c le o p h ile c o n c e n tr a tio n on th e k i n e t i c s and
p r o d u c ts o f s o l v o l y s is o f 4 - m e th y l- 3 - p e n te n - l- y l m e s y la te
and o f ix a n s - 3- hex e n - l - y l m e s y la te i n aq u eo u s e th a n o l
s o lv e n ts , we w ish to c h a r a c t e r i z e b o th ty p e s o f s u b s t i t u
t i o n p r o c e s s e s and to exam ine t h e i r c o m p e titiv e b e h a v io r.
CHAPTER 2
RESUETS
The p r e p a r a t io n o f 4 -m e th y l-3 -p e n t e n - l - y l m e s y la te i s
shown a s b e l o w : 18
p y r id in e
( ch5 ) 2 cho + ch2 ( cooh) 2 ' * ( ch3 ) 2 chch: CHCOOH
CH^OH
(CH^) 2 C:,CHCH2 C00H “ J ^ ( CH^) 2C: CHCH^OOeH^
T.iATH CH „S09 C1
E i t h e r * 20: — I / ; cn?a i ? ‘
( GH^) 2 C: CHCH2 CH20 S 0 2CH;5
The p ro d u e t o f c o n d e n s a tio n o f is o b u ty ra ld e h y d e and
m a lo n ic a c id fo llo w e d by d e h y d ra tio n i n th e p re s e n c e o f
p y r id in e was 4 -m e th y l-2 -p e n te n o ic a c id . A f te r isom eriaar*
t i o n i n th e p re s e n c e o f p o ta s s iu m h y d ro x id e , 4 - m e th y l- 2-
p e n te n o ic a c id was i n e q u ilib r iu m w ith 4 -m e th y l-3 -p e n te n o ic
a c id . I t was im p o s s ib le to s e p a r a te th e two is o m e rs o f
u n s a tu r a te d c a rb o n y l a c id by o r d in a r y f r a c t i o n a l c ld is tilla r -
1 ft
t i o n . A dvantage was ta k e n o f th e d i f f e r e n t e s t e r i f i c a r -
t i o n r a t e o f two isom ei^ 4 -m e th y l-3 -p e n te n e ic .y a c id form ed
e s t e r i n 10 m in u te s and 4 -m e th y l-2 -p e n te n o ic would ta k e
m ore th a n 6 h o u rs j t h e r e f o r e , c o n t r o l l i n g o f e s t e r i f i c a -
; t i o n tim e p e r m itte d one to o b ta in e d |0 ^ - u n s a tu r a te d a c id
I e s t e r w ith l e s s th a n 5° /» o f c?y& -unsaturated a c id e s t e r
i
• c o n ta m in a tio n . The m e s y la te was p re p a re d by th e a d d i tio n
f i
| o f m e th a n e s u lfo n y l c h lo r id e to th e m ix tu re o f c o rre s p o n d in g
: 15
| a lc o h o l, t r ie t h y la m in e , and d ic h lo ro m e th a n e . Crude
|
| m e s y la te s o f 4 -m e th y l-3 -p e n t e n - l - y l and t r a n s - 3 - h e x e n - l- y i
| w ere p a le y e llo w liq u id ^ w hich w ere u n s ta b le and c o u ld n o t be
! 16
j worked up a t room te m p e ra tu re , M e th a n e su lfo n y l c h lo r id e
j . . . • -
j decom posed slo w ly a t room te m p e ra tu re and was d i s t i l l e d
1 b e f o r e u s e .
The p r e p a r a t io n s o f c y c lo p ro p y l e th y l c a r b in o l a r e
shown a s fo llo w s !
A, Trnw l q Nal®p
C l C H ^ C H ^ r C a C H ^ C ^ C # 9 hh^)
a on w ^-*-»-i-e,j3r H_0
anhy. e th e r e th e r,
A ch(oh) c2h5
A coO H -?0C^2 A ooci Q .2 H5M ^ Br * anhy. e th e r H^O
ea * in v e rs e a d d itio n ■
A LiAlEL
A c0Co Hk .-------------- _4 s A chC ohJ c^ , .
2 5 anhy. e th e r z 5
! 7
t
I A, C y c liz a tio n o f i f - c h l o r o n i t r i l e w hich was p re p a re d
l
j by th e r e a c t i o n o f p o ta s s iu m c y a n id e w ith tr im e th y le n e
! c h lo ro b ro m id e would g e t c y c lo p ro p y l c y a n id e i n th e
J p re s e n c e o f s tr o n g b a s e i n l i q u i d ammonia. C y c lo p ro p y l
' e th y l k e to n e was th e n p re p a re d by t h e a d d i tio n o f G rig n a rd
r e a g e n t to c y c lo p ro p y l c y a n id e and su b se q u e n t h y d r o ly s is .
C y clo p ro p y l e th y l c a r b in o l was o b ta in e d by th e r e d u c tio n
' an h y d ro u s A Ho0
A cs* ♦ O f f g t - e, her - Ag-cgH5 ^ A o o c 2h5
o f c y c lo p ro p y l e th y l k e to n e w ith l i t h i u m aluminum h y d rid e
i
i n an h y d ro u s e t h e r .
B. C y clo p ro p y l e th y l k e to n e was p re p a re d by th e
i c h l o r i a t i o n o f c y c lo p ro p y l c a rb o x y iic a c id w ith th io n y l
i
| c h lo r id e fo llo w e d by th e G rig n a rd r e a c t i o n and h y d r o ly s is .
i
G rig n a rd r e a c t i o n was done by a d d in g G rig n a rd r e a g e n t to
a c y l c h lo r id e a t low te m p e ra tu re to p r e v e n t k e to n e u n d e r
g o in g f u r t h e r r e a c t i o n w ith G -rignard r e a g e n t to p ro d u c e
t e r t i a r y a lc o h o l. C y c lo p ro p y l e th y l c a r b in o l was a ls o
an h y d ro u s Ho0
A c o a + C gH gH gx — t h e r — AeCOMgxjc^----- *— -
1 . C^Hj-MgX
AGOG^H- ------- * A c C ohJ c a
2 C0Hc
o b ta in e d by th e r e d u c tio n o f c y c lo p ro p y l e th y l k e to n e w ith
l it h iu m alum inum h y d rid e i n th e p re s e n c e o f an h y d ro u s
e th e r .
, R a te D e te rm in a tio n .1 ^ S o lv o ly tic r a t e s o f 4 -m e th y l-
i
3 - p e n te n - 1 - y l m e s y la te and t r a n s - 3 - h e x e n - l- v l m e s y la te
j
I w ere d e te rm in e d by th e a n a l y s i s o f th e t i t r a t i o n c u rv e s
! o f a c id p r o d u c tio n w hich w ere re c o rd e d by a R ad io m eter PH
I s t a t t a t 6 0 ° C i n 60$ e th a n o l ( 40 volum e$ o f w a te r and
1 60 volum e$ o f e th a n o l) ; o r , i n 80$ e th a n o l ( 20 volum e$
! o f w a te r and 80 volum e$ o f e th a n o l) . R a te s o f s o lv o l y s i s
; o f th e m e s y la te s a s a f u n c tio n o f added s a l t w ere a ls o
i d e te rm in e d i n th e p re s e n c e o f sodium n i t r a t e and sodium
! a z id e a t 60°C. R ate c o n s ta n ts , p ro d u c t r a t i o s and i n f i n t y
I t i t e r s o f 4 - m e th y l- 3 - p e n te n - l- y l m e s y la te i n 8 0 $ e th a n o l
i a t 60°C a r e shown i n T a b le 2, o f ± x a Jl& -3 -h e x e n -l-y l
! m e s y la te i n 60$ e th a n o l a t 60°C a r e shown i n T ab le 3 , and
; 4 -m e th y l-3 -p e n t e n - l - y l m e s y la te i n 60$ e th a n o l a t 60°C
j a r e shown i n T ab le 1 . The p ro d u c t r a t i o ( RU/ROS) o f
n u c le o p h ilic r e a c t i o n p ro d u c t and s o l v o l y t i c r e a c t i o n
j p ro d u c t a r e a ls o in d ic a t e d i n T ab le 1 , T ab le 2 and T ab le 3.
The amount o f p ro d u c t r e s u l t i n g from a z id e o r n i t r a t e
a t t a c k was r e a d i l y o b ta in e d from th e d i f f e r e n c e b etw een
th e i n f i n i t y t i t e r s o f t h e s o l v o l y s is i n th e p re s e n c e and
a b se n c e o f s a l t .
Sodium Io n A c t i v i t i e s . 1 ^- - — Sodium io n a c t i v i t i e s o f
sodium a z id e and sodium n i t r a t e w ere o b ta in e d by th e
m easurem ent o f e le c tro m o tiv e f o r c e g e n e ra te d on a Beckman
sodium io n e le c tr o d e i n 60$ o r 8 0 $ e th a n o l s o l u t i o n u s in g
I 9
*
: a R ad io m eter ty p e pH m e te r and Calom el e le c tr o d e a s th e
! r e f e r e n c e e l e c tr o d e . The a c t i v i t i e s o f e q u iv a le n t co n cen -
t
' t r a t i o n o f sodium a z id e and sodium n i t r a t e w ere i d e n t i c a l
1 w ith in e x p e rim e n ta l e r r o r . The p l o t o f th e g e n e ra te d emf
I ^ ■
| v e r s u s lo g a r ith m o f th e c o n c e n tr a tio n i n 60% e th a n o l
j s o lu t io n i s shown i n F ig u re 1 , th e s lo p e i s 54 m v /d ecad e,
w h e re a s, th e p l o t o f 80% e th a n o l i s shown i n F ig u re 2, th e
s lo p e i s 58 m v /d ecad e. The t h e d r o t i c a l v a lu e f o r th e
s lo p e i s 59 m v /d ecad e. The r e s u l t o f th e m easurem ent o f
th e sodium io n a c t i v i t i e s and th e c o rre s p o n d in g sodium io n
c o n c e n tr a tio n f o r 60% e th a n o l i s l i s t e d i n T a b le 4 and
f o r 80% e th a n o l i s l i s t e d i n T ab le 5.
t
K in e tic P ro d u c t A n a ly s is . ----- The k i n e t i c p ro d u c t r a t i o s
o f t r a n s - 5 - h e x e n - l- v l m e s y la te a f t e r s o l v o l y s is i n 60%
e th a n o l a t 60°C i n th e p re s e n c e o f an h y d ro u s p o ta ssiu m
c a rb o n a te w ere d e te rm in e d by g a s ch ro m ato g rap h y u s in g a
15% T C E E P ( T r i s cy an o eth o x y p ro p an e) o n S as Chrom asorb P
(6 0 -8 0 m e sh ), 15 f t x 1 /8 i n colum n. A te m p e ra tu re program
i
ra n g e b etw een 7 5 -1 4 0 °C was found to g iv e good p eak r e s o lu
t i o n , The r a t i o o f 3 -c y c lo p ro p y l 3 - e th o x y p ro p a n e to
6 -e th o x y -3 -b e x e n e ( AoC^H^ /ROC^H^) and th e r a t i o o f
c y c lo p ro p y l e th y l c a r b in o l to 3 -h e x e n -l~ o l( AOH / ROH)
i n th e p re s e n c e o f sodium s a l t a r e shown i n T ab le 6 .
I
! T a b le 1 . R a te s o f A cid P ro d u c tio n and P ro d u c t R a tio s f o r
j t h e S o lv o ly s is o f 4 -M e th y l-3 -p e n t e n - l - y l M e sy la te i n
j
! 60$ E th a n o l a t 60 C i n t h e P re s e n c e o f Sodium N i t r a t e o r
| Sodium A zid e.
S a lt aR a te bR a te a v e * m
A c ti v ity x U 3 seo- l x 1 0 3 seo- l l i
(m o le/1 )
0.000 1.78 ± 0.0 3 5.49
1 .7 1 ± 0 .0 1 1 .7 4 ± 0 .0 3 5 .5 0 0 .0 0
1 .7 2 ± 0 .0 1 5. 54
0.100 1 .8 9 ± 0 .0 2 5 .4 3
NaNO3 1b8? ± 0#01 1#s6 ± Q.0 2 5 ,3 2 0 .0 5 4
1 .8 1 ± 0.01 5 .4 9
0 .1 8 3 1 .8 1 ± 0 ,0 3 5 .5 4
1M03 1 .7 6 ± 0 .0 1 1 .8 2 ± 0 .0 4 5 .5 0 0.00
1 .8 8 ± 0 .0 1 5.20
0.318 1 .7 9 ± 0.02 5 .5 3
NaNO3 1 ^ g i ± Q #G 5 % 24
1 .8 1 ± 0.02 5.38
1 .7 3 ± 0 .0 2 1 .8 3 ± 0 .0 6 5.58 0 .0 0 36
1 .7 4 ± 0.02 5.68
• 1 .9 4 ± 0.02 5 .5 1
1 .8 4 ± 0 .0 2 5 .7 5
c o n tin u e d
[C ontinued T a b le 1 .
S a lt
A c tiv ity
(m o le/1 )
aR a te
x 10^ s e c " 1
bR a te a v e ra g e
x 10^ s e c " 1
Span
RN
ROS
0*100 2. 21 ± 0 .0 3
4 .8
NaU^
2 .1 9 ± 0 .0 3
2.08 ± 0 .0 1
2.16 ± 0 .0 5 4 .6
4.6-
0 .1 9
± 0 .0 5
0 .1 8 5
2. 29 ± 0 .0 1 3 .7
RaJS^
2. 28 ± 0 .0 2
2. 23 ± 0 .0 1
2.27 ± 0 .0 2 3.6
3 .7
0 .5 0
± 0 .0 4
0 . 318 2 .3 9 ± 0 .0 2
2 .4 2 ± 0 .0 2
2 .4 1 ± 0 .0 2 2.8
2 .7
1 .0 1
± 0 .0 5
aE rro r i s s ta n d a rd d e v i a ti o n o f l e a s t s q u a re s f i t .
b E rro r i s a v e ra g e d e v i a ti o n b etw een r u n s .
\ T a b le 2. R a te s o f A cid P ro d u c tio n and P ro d u c t R a tio s f o r
! th e S o lv o ly s is o f 4 -M e th y l-3 -p e n t e n - l - y l M e sy la te i n
| 80% E th a n o l a t 6 0 ° C i n th e P re s e n c e o f Sodium N i t r a t e o r
| Sodium A zid e.
S a lt
A c ti v ity
(m o le /1 )
aR a te
4 . - 1
x 10 sec
bR a te a v e ra g e
x 10^ sec” ^
Span
RN
ROS
0 . 000 4 .4 1 ± 0 .0 1
5 .4 3
4 .2 0 ±
0 .0 5 4 .3 2 * 0 .0 8 5 .3 2 0 .0 0
4 .3 5 ± 0 .0 1 5.08
0 .0 8 1 4 .6 2 ± 0 .0 5 5.58
NaNO j 4 .4 1 ± 0 .0 5 4 .8 5 ± 0 .1 0
5.66 0 .0 0
4 .7 1 ± 0 .0 5 5 .5 3
0 .1 5 9 4 .8 4 0 .0 2 5 .4 2
NaNO, 4 .8 2
4 .8 1
± 0 .0 2
0 .0 2
4 .8 2 ± 0 .0 1 5.30 0 .0 0
0 .0 8 1
5 .2 3
d r 0 .0 1 3 .7 7
5 .2 1 ± 0 .0 1 5. 20 ± 0 .0 3 3 .9 3
0 .3 8 ± 0.06
5 .1 5 * 'd b 0 .0 3 3 .8 3
0 .1 9 5 6 .1 4 ±
o
.
o
2. 97
N a l- 6 .0 2 ± 0 .0 3
6 .4 0 ± 0 .0 8 2.98 0 .7 5 ± a 0 7
5 .9 5
r k
0 .0 3 3 .0 2
0 . 295 7 .0 1 sb 0 .0 1
7 .0 3 '± 0 .0 2 2.07 1 . 54±0.07
NaN^ 7 .0 5 i 0 .0 1 2 .0 9 ;
^ B rro r i s S ta n d a rd d e v i a ti o n o f l e a s t s q u a re s f i t .
I d
E r r o r i s a v e ra g e d e v i a ti o n b etw een r u n s .
: T a b le 3. H a te s o f A cid P ro d u c tio n and P ro d u c t R a tio s o f j
: ' ' i
j th e S o lv o ly s is o f tr a n s -. 3 - h e x e n - l- v l M e sy la te i n 6 0 %
< E th a n o l a t 60°C i n t h e P re s e n c e o f Sodium A zid e.
S a lt
A c tiv ity
( m o le /1 .)
a R a te
xlO ^sec” 1
bH a te a v e ra g e
5 — 1
xlO sec
Span RE
ROS
0 .0 0 0
9 .4 0 ± 0 .0 0 9.56 ± 0 .0 8 6 .1 2 0 .0 0
9 .7 3 ± 0 .0 0 6 .3 8
0 .1 8 3
M V
2 1 .5 ± 0 .0 1 2 1 .8 ± 0 .0 3 2. 29 1 .7 9 ± 0 .1 2
2 2 .2 d b 0 .0 2 2.3.8
0 .3 1 8
M y
31. 5 ± 0 .0 2 3 1 .5 ± 0 .0 0 1 .5 7 3 .4 1 ,± 0 .1 4
31. 5 ± 0 .0 2
1 .4 3
a E r r o r i s s ta n d a rd d e v i a ti o n o f l e a s t s q u a re s fx i/.
^ E r r o r i s a v e ra g e d e v i a ti o n b etw een ru n s .
240
220
200
emf
(-m v )ig o
160 S lo p e ss 54 m v/decade
140
120
100
80
60
3 .0 2 .0 l i o 0 .0
- lo g ( Sodium Io n C o n c e n tra tio n )
4 .0
F ig u re 1 . P lo t o f emf (-nrv) G -enerated on th e Sodium Io n
E le c tr o d e v e r s u s - lo g ( C o n c e n tr a tio n ) o f Sodium Io n a t
Room T em p eratu re i n 60% E th a n o l.
T a b le 4 . Sodium Io n A c t i v i t y f o r V a rio u s C o n c e n tra tio n s
a t Room T em p eratu re i n 60% E th a n o l.
Sodium Io n C o n c e n tra tio n Sodium Io n A c it v ity
m o le /1 .
0 .4 0 0 0 . 318
0 , 200
0 .1 8 3
0 .1 0 0
0 .1 0 0
0 .1 0 0 X 10” 1 0 .1 0 0 X 10” 1
0 .1 0 0 X 10” 2
0 .1 0 0 X 10” 2
0 .1 0 0 X 1 0 “ 3 0 .1 0 0 X 10“ 5
190
emf
(-mv)L70
S lo p e ss 58 m v/decade
130 •
3 . 0 2 .0 1-*Q 0 * 0
- 18g ( Sodium Io n C o n c e n tra tio n )
F ig u re 2. P lo t o f emf (-mv) G en e ra ted on th e Sodium
Io n E le c tr o d e v e r s u s ~ lo g (C o n c e n tra tio n ) o f Sodium
I o n a t; Room T em p eratu re i n 80% E th a n o l.
T ab le 5. Sodium I o n A c tiv ity f o r V a rio u s Io n Concen
t r a t i o n s a t Room T em p eratu re i n 80% E th a n o l.
Sodium Io n C o n c e n tra tio n
( m o le /1 .)
Sodium Io n A c t i v i ty
0 .4 0 0
0 .2 9 5
0 . 200 0 .1 5 9
0 .1 0 0
H
C O
.
o
x 1 0 "1
0 .1 0 0 x 1 0 "1 0 .1 0 0 x 1 0 "1
0 .1 0 0 x 10“ 2 0 .1 0 0 x 10“ 2
0 .1 0 0 x 1 0 " 5 0 .1 0 0 x 1 0 " 3
I T a b le 6 . P ro d u c t R a tio s f o r t h e , S o lv o ly s is o f I r a n s - 3 -
| H e x e n -l-y l m e s y la te i n th e P re s e n c e o f Sodium S a lt*
C o n c e n tra tio n o f
S a lt( m o l e /1 .)
ROH /A O H roc2h5 / A oc2h 5
0 .0 0 0 .2 9
0 .2 8
0 .1 0 M O ,
3
0 .2 6 0 .2 6
0 .2 0 KaUO^ 0 .1 8 0 .1 8
0 .4 0 M O ,
3
0 .1 4 0 .1 5
0 .1 0 M , 0 .1 2 -
0 .2 0 M ^ 0 .1 8
-
0 .4 0 M ,
3
0 .2 3 -
0 .1 0 laOAc 0 .3 0
-
0 .2 0 RaOAc 0 .3 8 -
17
CHAPTER 3
DISCUSSIOH
The n o n l i n e a r i t y o f th e p l o t o f s o l v o l y t i c r a t e
c o n s ta n t (F ig u re 3) v e r s u s s a l t a c t i v i t y and l i n e a r i t y o f
th e p ro d u c t r a t i o (RM/ROS) v e r s u s s a l t a c t i v i t y ( F i g u r e 4)
f o r 4 - m e th y l- 3 - p e n te n - l- y l m e s y la te i n 60$ e th a n o l i n th e
p re s e n c e o f added s a l t ca n b e a n a ly z e d a c c o rd in g to th e
m echanism shown i n Scheme 1 . When k ^ /k g i s s m a ll, th e
s o l v o l y t i c r a t e enchancem ent i n t h e p re s e n c e o f added s a l t
can be i n t e r p r e t e d to b e a r e s u l t o f norm al s a l t e f f e c t
c a lc u l a b le i n e q u a tio n ( 6 ) ^ , w here k Q i s th e s o l v o l y t i c
ksalt ^ ^ ! + b ( S ait) ) (6)
r a t e i n th e a b se n c e o f s a l t , [ s a lt) i s th e a c t i v i t y o f th e
s a l t and b i s th e p e r c e n t r a t e in c r e a s e a t 0 .0 1 M s a l t .
27
S in c e n i t r a t e i s a weak n u c le o p h ile , th e r a t i o k ^ Q -/k
3
was assum ed to b e sm a ll i n a l l c a s e s . By s u b s t i t u t i n g th e
s o l v o l y t i c r a t e c o n s ta n t f o r 4~m ethy 1 -3 - p e n t e n -1 - y l
m e s y la te i n 60$ e th a n o l i n th e a b se n c e and p re s e n c e o f
sodium n i t r a t e in to e q u a tio n ( 6 ) , a b v a lu e o f 0 .5 was
c a lc u la te d * t h e o b se rv e d r a t e c o n s ta n t c o u ld b e r e l a t e d
to th e r a t e c o n s ta n ts i n Scheme 1 by e q u a tio n (7) and ( 8 ).
ROMs
kl
k n
- 1
[in t e rm e d ia t e)
Scheme 1
19
k x lO^see"^
2 .4
2 .3
2. 2
2.1
2.0
1 .9
1.8
0 .3 0.2 0.1
M .
F ig u re 3* A P lo t o f R a te C o n sta n t v e r s u s Sodium
A zide A c t i v it y f o r 4 - M e th y l- 5 - p e n te n - l- y l Mesy
l a t e i n 60% E th a n o l a t 6 0 ° C.
20
ROS
1.0
0 .5
0 .3 0. 2 0.1
A c ti v ity o f Sodium A zide
F ig u re 4 . A P lo t o f P ro d u c t R a tio v e r s u s Sodium
A zid e A c ti v ity f o r 4 - M e th y l- 3 - P e n te n - l- y l Mesy
l a t e i n -60 fo E th a n o l at. 6 0 ° C.
21
kl (k n f 3 a l t ) + k s )
o b sd . " + k ^ jsa i t ) + k s ^
When k „ / k i s s m a ll,
XI s
kl k s
ko b sd . “ k s a l t ~T (8)
- 1 s
A f te r s u b s t i t u t i n g k^ o f e q u a tio n (8 ) i n t o e q u a tio n (7 ):
k _ ( 1 + k_ i A s > U + k s ) v s a l t j
o b sd . “ k_i / k s + i + k n [ s a l t ] / k s
: ---------- — (1 + b [ s a lt ]) k Q
(1+ x) (1+ m (s a lt) )
1 + x+m [ s a lt]
(9)
m = W * = k- l / k s ‘
9 10
T h is i s a n a lo g o u s to r a t e e g r e s s i o n d e riv e d by Sneen * ,
e t . a l . , i f k sa1 ^ i s r e p la c e d by I& th e p re s e n c e o f
added s a l t , m v a lu e may b e o b ta in e d from th e p ro d u c t r a t i o
RR/ROS by t h e f o llo w in g r e l a t i o n s h i p : ^ * 1®
RR = ~r~ [s a lt] = m [ s a lt] f(lO )
ROS £ s
The r a t i o RIS/ROS i s t h e r a t i o o f p ro d u c t o f n u c le o -
p h i l i c r e a c t i o n to t h a t o f s o l v o l y t i c r e a c t i o n . I f a l l
th e p r o d u c ts w ere assum ed to be form ed by t h e way o f
s i n g l e in te r m e d ia te , th e v a lu e o f m was found to be e q u a l
to 3 .0 f o r th e s o l v o l y s i s o f 4 - m e th y l- 3 - p e n te n - l- y l mesy
l a t e i n 60% e th a n o l i n t h e p re s e n c e o f sodium a z id e . The
v a lu e o f x „ was th e n c a lc u l a te d by th e s u b s t i t u t i o n
av e.
22
o f p ro d u c t r a t i o , b v a lu e , o b se rv e d r a t e c o n s ta n t and s a l t
a c t i v i t y i n t o e q u a tio n (9 ) and d e te rm in e d to b e 0 .6 . The
v a lu e o f k Qa^ w hich a r e shown i n T a b le (7) w ere o b ta in e d
by s u b s t i t u t i n g x „,r_ , b„.__ , ei b ack to e q u a tio n ( 9 ) .
aV6* avc# aVc#
The c a lc u la te d p ro d u c t r a t i o s (T a b le 7) w ere o b ta in e d by
s u b s t i t u t i n g m = 3 in to , e q u a tio n (1 0 ). The co m p ariso n
o f t h e c a lc u l a te d r a t e c o n s ta n ts and p r o d u c tr r a t i o s w ith
o b se rv e d r a t e c o n s ta n ts and p ro d u c t r a t i o 's l e a d s to a
c o n c lu s io n t h a t th e s o l v o l y s i s o f 4 -m e th y l-3 -p e n t e n - l - y l
m e s y la te i n 60% e th a n o l can b e a d e q u a te d e s c rib e d by
Scheme 1 .
I f t h e r e was b im o le c u la r n u c l e o p h il ic r e a c t i o n f o r
th e s o l v o l y s i s o f 4 -m e th y l-3 -p e n t e n - l - y l m e s y la te i n 60%
e th a n o l i n t h e p re s e n c e o f added s a l t a s shown i n Scheme 2,
t h e o b se rv e d r a t e c o n s ta n t i s shown a s fo llo w s :
(1 + x) (1 + m [sa lt] )
1 + x + m [s a lt]
s v s a l t + k ^ ( s a l t ] (11)
\ JL -r A J \ T ill IfcJCU. OJ J
k o b Sd . = ( 1 + b ( s a l t l 5 + k z | s a l t l
s a l t
RH = — V 1___________ (12)
ROS 1 . „ s a l t
1 + m [salt] 1
k ^ was assum ed to b e e q u a l to 54*1 x 10” ^ /m o le s e c .
w hich was o b ta in e d v id e sup r a a s a c a lc u l a te d b im o le c u la r
n u c le o p h ilic r a t e c o n s ta n t f o r th e s o l v o l y s is <££ f r a n a - 3-
h e x e n - l- y l m e s y la te i n 60% e th a n o l i n t h e p re s e n c e o f ■
J T a b le 7 . E x p e rim e n ta l and C a lc u la te d R a te C o n s ta n ts and
; P ro d u c t R a tio s f o r t h e S o lv o ly s is o f 4 -M e th y l-3 -p e n te n -1 -
: y l M e sy la te i n 6 0 $ E th a n o l a t 60°C.
S a lt A c ti v ity k-eXp -fc
m ole/1* x i o ^ e c " 1
c a l .
^ — 1
xlO se c
m
ROS
e x p t.
RN
R0Sc a l
0 ,0 0 0 1 .7 4 ± 0 .0 3 1 .7 4 0 .0 0 0 .0 0
0 .1 0 0
EaS0*2
1 .8 6
± 0 .0 3
1 .8 1 a 0 .0 0 0 .0 0 °
0 .1 8 3
0 .3 1 8
1aM05
1 .8 3 ± 0 .0 4 1 .8 8 a 0 .0 0 0 .0 0 C
1 .8 3 i 0.06. 2 .0 0 a 0 .0 0 0 .0 0 e
0 .1 0 0
NaN^
2116 ± 0 .0 6 1 . 98 a 0 .1 9 ± 0 .0 5 0 . 30C
0 .1 8 3
NaMj
2.27 * 0 .0 2 2 .1 7 a 0 .5 0 ± 0 .0 4 0 .5 5 °
0 .3 1 8
RaN3
2.4 1 * 0 .0 1 2 .4 5 a 1 .0 1 ± 0 .0 3 0 .9 5 °
0 .1 0 0
MaMj
2,16 ± 0 . 06 1 . 99^ 0 .1 9 ± 0 .0 5
0 . 26d
0 .1 8 3
laN ^
2.27 = f c 0 .0 2 2. 20 0 .5 0 ± 0 .0 4 0 .4 0
0 .3 1 8
NaNj
2 .4 1 ± 0 . 01
2 .5 3
1 .0 1 ± 0 .0 3
0 .8 6 d
C a l c u l a t e d from E q u a tio n 9 , C a l c u l a t e d from E q u a tio n 10
w ith b = 0 .5 » x ss 0 ,6 , m s 3*0.
" H ^
C a lc u la te d from E q u a tio n 1 1 , C a lc u la te d from E q u a tio n 12
w ith m = 2,3» x = 0 . 57, b = 0 , 5 a n s k^= 5 4 .1 x lO ~ 5l.m o le “ 1
s e c ”1 .
24
added sodium a z id e . The v a lu e o f in _ and w ere
a v e . av e.
: c a lc u la te d to b e eq u al to 2 .3 and 0 ,5 7 r e s p e c t i v e l y . The
' v a lu e o f k c a l and RR/ROS w hich a r e shown i n T ab le (7) w ere
■ o b ta in e d by th e s u b s t i t u t i o n o f x&ve, and s a l t
i a c t i v i t y b ack i n to e q u a tio n (11) and (1 2 ).
: I t i s e v id e n t from T ab le (7 ) t h a t t h e c a lc u l a te d r a t e
i
I c o n s ta n ts and p ro d u c t r a t i o s from Scheme 1 f i t th e o b se rv e d
I
J r a t e c o n s ta n ts and p ro d u c t r a t i o s a s w e ll a s th o s e c a lc u -
i
j l a t e d from Scheme 2, and make i t r e a s o n a b le t h a t Scheme 2
! m ig h t be th e m echanism f o r th e s o lv o l y s is o f 4 -m e th y l-3-
t
! p e n t e n - l - y l m e s y la te i n 6 0 $ e th a n o l.
I
i
|
i
I The n o n l i n e a r i t y o f th e p l o t o f s o l v o l y t i c r a t e co n s-
i
| t a n t ( F ig u r e 5) v e r s u s s a l t a c t i v i t y p r o v id e s e v id e n c e f o r
i a p r e e q u ilib r iu m b etw een 4 -m e th y l-3 -p e n t e n - l - y l m e s y la te
i
and i t s in te r m e d ia te i n 8 0 $ e th a n o l a t 6 0 ° C. The l i n e a r i t y
(F ig u re 6) o f th e p l o t o f th e p ro d u c t r a t i o (R R /R O S)versus
s a l t a c t i v i t y in d ic a t e d t h a t a l l th e p r o d u c ts w ere form ed
from th e same in te r m e d ia te and th e p ro d u c t r a t i o s m ust be
Q in
f i r s t o r d e r i n added s a l t . * The s o l v o l y t i c d a t a f o r
4 -m e th y l-3 -p e n t e n - l - y l m e s y la te i n 8 0 $ e th a n o l! w ere a n a ly z
ed a c c o rd in g to Scheme 1 ; k ^ y O s ^ was assum ed to b e s m a ll,
and an a v e ra g e b v a lu e was o b ta in e d by th e s u b s t i t u t i o n o f
th e r a t e c o n s ta n ts i n t h e a b sen ce and p re s e n c e o f sodium
n i t r a t e i n t o e q u a tio n 9 (b a v e ~ 0 .7 7 ). The v a lu e o f ma v e *
25
k x 1 0 4 sec~1
7 .0
6.0
5 .0
0 .5 0.2 0.1
A c t i v i t y o f Sodium A zide
f i g u r e 5. A P lo t o f R a te C o n sta n t v e r s u s
Sodium A zide A c t i v i t y f o i th e S o lv o ly s is o f
4— M e th y l-3 -p e n t e n - l - y l M e sy la te i n 8 0 $ E th a n o l
a t 60° C.
RH
ROS
1 .5
1# 0
0 .5
— a r t
A c ti v ity o f Sodium A zide
F ig u re 6 . A P lo t o f P ro d u c t R a tio v e r s u s Sodium ,
A zide A c ti v ity f o r 4 -M e th y l-> -p e n te rs 1 - y l Mesy
l a t e i n 80% E th a n o l a t 60°C.
i
27
RH
ROMs
k- l ^
k-.
(in te rm e d ia te ]
k
• > K
R E T
k
s
v
ROS
Scheme 2
; T a b le 8 , E x p e rim e n ta l and C a lc u la te d R a te C o n s ta n ts and
! P ro d u c t R a tio s f o r th e S o lv o ly s is o f 4 - M e th y l- 3 -p e n te n - l
i y l M e sy la te i n 8Q$ E th a n o l a t 60° C.
S a lt A c ti v ity
m o le /1 /
^ e x p t.
x lO ^ se c " 1
c a l.
x 1 0 ^ s e c " 1
RN
R0Se x p t.
bRE
R0S< b1
0 .0 0 0
Nal'TO^
0 .0 8 1
4 .3 2 ± 0 .0 8 4 .3 2 0 .0 0 0 .0 0
HaJO^
4 .5 8 dt 0 .1 0 4 .5 9
0 .0 0 0 .0 0
0 .1 5 9
EalO^
4 .8 2 ± 0*01 4 .8 5 0 .0 0 0 .0 0
0 .0 8 1
Nal\T 3
5. 20 ± 0 .0 3
5.20 0 .3 8 0 .4 2
0 .1 5 9 6 .0 4 * 0 .0 8 5.90 0 .7 5 0 .8 3
0 .2 9 5
NaN^
7 .0 3
± 0 .0 2 7 .1 2 1 .5 4 1 .5 3
a C a le u la te d from E q u a tio n 9 . ^ C a lc u la te d from E q u a tio n
10 w ith b s 0 .7 7 , x = 0 .7 5 , m = 5 .2 0 .
29
e q u a l to 5*20 was o b ta in e d by e q u a tio n (1 0 ), The v a lu e o f
x 0„ D was th e n c a lc u l a te d from e q u a tio n (9) u s in g m ,
Or V G C l V ©
b and s a l t a c t i v i t y . C a lc u la te d r a t e c o n s ta n ts and
av e . "
p ro d u c t r a t i o s from e q u a tio n (9) and (10) r e s p e c t i v e l y a r e
shown i n f a b l e ( 8 ) . A ll th e c a lc u l a te d d a t a can f i t th e
i
o b se rv e d d a t a v e ry w e ll and make i t e v id e n t t h a t Scheme 1
i s a s u i t a b l e scheme f o r th e s o l v o l y s i s o f 4 -m e th y l-p e n te n -
l - y l m e s y la te i n 80% e th a n o l a t 60°C i n th e p re s e n c e o f
added s a l t .
The l i n e a r i t y o f th e p l o t s o f t h e s o l v o l y t i c r a t e
c o n s ta n t and p ro d u c t r a t i o v e r s u s th e s a l t a c t i v i t y f o r
t r a n s - 3 - h e x e n - l- v l m e s y la te i n 60% e th a n o l a t 6 0 ° C are.,
shown i n F ig u re 7 and F ig u re 8*
A l a r g e amount o f a z id e sh o u ld be form ed i f a z id e io n
24.
i s added to s o l v o l y t i c medium i n two c a s e s , ( 1 ) , i f
h ig h ly s t a b l e earbonium io n in te r m e d ia te s a r e p r e s e n t o r
(2), i f b im o le c u la r d is p la c e m e n t r e a c t i o n a r e in v o lv e d .
S in c e t h e r e was a r a t e enchancem ent when a s tr o n g n u c le o -
p h ile o w a s ad d ed , a earbonium io n was n o t an in te r m e d ia te
f o r th e s o l v o l y s i s o f t r a n s - 3 - h e x e n - l - y l m e s y la te i n 60%
e th a n o l a t 6 0 ° C *
Scheme 2 i s s u g g e s te d f o r th e s o l v o l y s i s o f t r a n s - 3-
! O !
i h e x e n - l- y l m e s y la te i n 60% e th a n o l a t 60 C, th e v a lu e o f b ,|
m and x w ere assum ed to b e th e same a s th o s e f o r th e s o l
v o l y s i s o f 4 -m e th y l-3 -p e n t e n - l - y l m e s y la te i n 60 $ e th a n o l.
A cco rd in g to Scheme 2:
k v s a l t
k ^ s s ° b sd __ 1 (13)
[ s a l t )
The v a lu e o f o f e q u a tio n (11) was c a lc u l a te d
n
u s in g b = 0 . 5 , and th e n was o b ta in e d by s u b s t i t u t i n g
w _ n j ,
c a lc u l a te d and i n to e q u a tio n ( 1 2 ). A ll th e
c a lc u l a te d r a t e c o n s ta n ts and p ro d u c t r a t i o s a r e c o n s is
t e n t w ith th e o b se rv e d r a t e c o n s ta n ts and p ro d u c t r a t i o s
a s shown i n T a b le 9 , t h e r e f o r e , th e Scheme 2 may b e
c o n s id e re d to b e a p o s s i b l e m echanism f o r th e s o l v o l y s i s
o f t r a n s - 3 - h e x e n - l- v l m e s y la te i n 6 0 $ e th a n o l.
I f b im o le c u la r r e a c t i o n o f th e s o lv e n t w ith th e
s u b s t r a t e e x i s te d a s shown i n Scheme 3 , th e r a t e and
p ro d u c t e q u a tio n s a r e a.s fo llo w s :
n , s a l t n , s
o b s d . = 1 2 + 2
_ tsalt a+*>a-n»lsaltl ) +
1 1 + x + m [ s a lt]
+ [so lv en t) (14)
k ” ls a lt]
EOS k f [so lv en t] + t ~/ b ^ ^ (15)
I n t h e a b se n c e o f added s a l t ,
31
k x lO^see*”^
2 .0
0.1
0 .3
0. 2
A c t i v i t y o f Sodium A zide
F ig u re 7 . A P lo t o f R a te C o n stan t v e r s u s So
dium A zide A c t i v it y f o r f r a n a - 3 -H e x e n -l-y l
M e sy la te i n 60f° E th a n o l a t 6 0 ° C.
32
RR
ROS
4 .0
3 .0
1.0
0.1 0.2
0 .3
A c ti v ity o f Sodium A zide
F ig u re 8 . A P lo t o f P ro d u c t R a tio v e r s u s
Sodium A zide A c ti v ity f o r th e S o lv o ly s is o f
t r a n s - 3 -H e x e n -l-v l M e sy la te i n 60% E th a n o l
a t 60° G.
33
; T a b le 9. E x p e rim e n ta l and C a lc u la te d R a te C o n sta n t and
| P ro d u c t R a tio s f o r th e S o lv o ly s is o f t r a n s - 5-P Iex en -l-.v l
! M e sy la te i n GQfo E th a n o l a t 60° C.
; S a lt A c ti v ity k
1 m ole/1* e x p t.
I x lO ^sec” x
"eal
1 0 5sec
- 1
RE RE
EGSe x p t. E0So a l.
0 .0 0 0 9.56
0 0
0
*
0
-H
9.56 0 .0 0 0 .0 0
0 .1 8 3
EaE3
2 1 .8
O
t « " N
•
0
-H
21. 9a 1 .7 9 *1.76
0 . 318
EaE-j
3 1 .5 ± 0 .1 0 31. 0a 3 .4 1 b 3. 50
0 ,1 8 3
EaE3
21.8 H -
0
— 1 .7 9 c1 .7 9
0 .3 1 8
EaE*5
3 1 .5
0
H
•
O
-H
3 .4 1
c 3. 21
_ " L .
C a lc u la te d from E q u a tio n 1 3 . C a lc u la te d from E q u a tio n 15
w ith b = 0 .5 0 , x = 0 .6 , m = 3.0 and = 5 4 .1 x 1 0 5 1 .
m ole” 1 sec” 1 . 'C a lc u la te d from E q u a tio n 17 w ith b = 0 . 5 ,
x = 0 .6 , m = 3 .0 k | = 6 .0 x 1 0 ~ ^ l.m o le~ '1 's e c “ 1 *
34
RR ROS
s
ROMs
[in ter m e d ia te ]
k |(H l/
RN ROS
Scheme 3
35
| I f a l l th e u n re a rra n g e m e n t p r o d u c ts w ere form ed by
| th e way o f b im o le c u la r r e a c tio n and a l l t h e c y c lo p ro p y l
t
| p r o d u c ts w ere form ed by th e way o f r e a c t i o n , th e r a t i o
{ o f two d i f f e r e n t a lo h o ls would re d u c e d to :
. a ; s
i RQS a ---- = - k2 (17)
I ^ 0S i j c kl
! k- l S
i
| The p ro d u c t r a t i o s ( T ab le 6) f o r 't h e s o l v o l y s i s o f
j iferan s-3 -h e x en -l— y l m e s y la te i n 60fo e th a n o l i n th e p re s e n c e
o f sodium n i t r a t e w ere o b ta in e d by g a s ch ro m ato g rap h y
a n a ly s is on TCEP colum n. From th e d a t a o f T a b le (6 ) and
i
j e q u a tio n (1$) t h e r a t i o o f k | /k ? was o b ta in e d , and k®
i ^ _ _
V ■
I c a lc u la te d from e q u a tio n (16) was found to be 6 .0 x 10*“
l.m o le ^“s e c . ^ i n SOfo e th a n o l i n th e p r e s e n c e o f sodium
I Q
; n i t r a t e . I t was assum ed t h a t th e v a lu e o f k® i n t h e
p re s e n c e o f sodium a z id e to be t h e same a s t h a t i n th e
■ »
p re s e n c e o f sodium n i t r a t e and th e c a lc u l a te d p ro d u c t
r a t i o s from e q u a tio n (17) a re shown i n T a b le 9.
The s tu d y t o d e te rm in e w h eth e r a l l t h e c y c lo p ro p y l
p ro d u c t w ere formed- from r e a c t i o n and th e u n re a rra n g e d
p r o d u c ts w ere foim ed from S^j2 r e a c t i o n was a tte m p te d .T h e
d e c o m p o sitio n o f th e a z id e p r o d u c ts made i t h a rd to o b ta in
r e p r o d u c ib le d a t a f o r p ro d u c t fo rm a tio n , b u t th e c a lc u la te d
p ro d u c t r a t i o s from e q u a tio n 17 c o u ld be m ore o r l e s s f i t t e d
to th e o b se rv e d p ro d u c t r a t i o s . F u r th e r s t u d i e s would be
36
r e q u ir e d to e s t a b l i s h i f Scheme 3 i s c o r r e c t f o r th e
s o l v o l y s i s o f t r a n s - ^ h e x e n - l - y l m e s y la te i n 60% e th a n o l
a t 60°C i n t h e p re s e n c e o f sodium azid e*
37
CHAPTER 4
EXPERIMENTAL SECTION
GENERAL;
The I n f r a r e d s p e c t r a w ere re c o rd e d on a P e r k in Elm er
m odel 337 s p e c tro m e te r and th e c a l i b r a t i o n s w ere accom
p lis h e d u s in g p o ly s ty r e n e a b s o r p tio n s a t 1 6 0 1 .4 cm~^ and
1 1 1
9 0 6 .7 cm . H n .m .r . s p e c tr a w ere o b ta in e d on a Y a ria n
A-60 a t 60 MHz u s in g t e t r a m e t h y l s i l i a n e a s s ta n d a r d . Gas
ch ro m ato g rap h y was ac co m p lish e d u s in g a 15/* t r i s - (2 - cyano-
eth o x y ) p ro p a n e on 6 0 -8 0 m esh Chromosorb P , 6 m e te r x 1 /8 -
in c h colum n on P e r k in E lm er 880 Gas C hrom atograph eq u ip p ed
w ith flam e i o n i z a t i o n d e t e c t o r . A ll th e b o i l i n g p o i n t s
a r e u n c o r r e c te d . The c h e m ic al u se d w ere r e a g e n t g ra d e .
A ll r e a c t i o n s w hich w ere s e n s i t i v e to a i r w ere ru n u n d e r
p u r i f i e d n itr o g e n . S o lv o ly tic r e a c t i o n s w ere ru n on
R a d io m eter and th e r e s u l t s w ere a n a ly z e d by LSKIN1 program .
A ll g l a s s equipm ent u se d f o r th e s o l v o l y s i s r u n s was s te e p
ed i n h o t d ic h r o m a te - s u lf u r ic a c id c le a n in g s o l u t i o n be
f o r e us,©» i t was th e n r in s e d w ith d i s t i l l e d w a te r and oven
! '
;d r y . E th a n o l was p u r i f i e d by r e f l u x i n g w ith m agnesium ,
| a f t e r d i s t i l l a t i o n i t was s to r e d u n d e r n itr o g e n .
4 -M e th y l-2 -o e n te n o ic A cid . — - A m ix tu re o f 37 g
( 0 .5 m ole) o f is o b u ty ra ld e h y d e , 78 g ( 0 .7 5 m ole) o f m a lo n ic
a c id and 75 m l 'o f p y r id in e was h e a te d on a steam h a th f o r
t h r e e h o u rs . The s o lu t io n was c o o le d and p o u red o v e r ex
c e s s amount o f h y d r o c h lo r ic a c id and i c e . The o rg a n ic
l a y e r was s e p a r a te d by u s in g a s e p a r a to r y fu n n e l and th e
aqu eo u s l a y e r Was e x tr a c te d tw ic e w ith e t h e r . The com bined
o r g a n ic and e t h e r l a y e r s w ere washed o n ce w ith XOfo hydro
c h l o r ic a c id , s a tu r a te d sodium c h l o r id e s o lu t io n and th e n
d r ie d o v e r an h y d ro u s sodium s u l f a t e f o r an h o u r. The
s o lv e n t was e v a p o ra te d u s in g a vacuum e v a p o ra to r and th e
r e s id u e was d i s t i l l e d a t 6 0 .8 -6 3 .0 ° C a t a p r e s s u r e o f 0 .2
mm. The y i e l d was 53$. The i r showed a b s o r p tio n a t 2970
cm“ ^ , ( a lk y l C-H ), 1720 cm ""1 ( c a rb o n y l g ro u p ), and 1220 cm”1 . ’
The nmr a t 60 MHz (CCl^) showed a d o u b le t f o r cP hydro
g en a t 5. 2 -5 . 5 ppm, a q u a r te t f o r p h y d ro g en a t 6 .3 - 6 .7
ppm.
4 -M e th .v l-3 -p e n te n o ic A cid . A m ix tu re o f 42 g
(0 . 368 m ole) o f 4 - m e th y l-2 -p e n te n o ic a c id , 133 ml o f w a te r
and 252 g ( 4 .5 m ole ) o f p o ta ssiu m h y d ro x id e was r e f lu x e d j
f o r tw e n ty f o u r h o u rs u n d e r an a tm o sp h ere o f n itr o g e n .
The s o lu t io n was c o o le d and a c i d i f i e d by u s in g c o n c e n tr a t
ed h y d r o c h lo r ic a c id . The o rg a n ic l a y e r was e x tr a c te d
tw ic e w ith e t h e r . The com bined o r g a n ic l a y e r and th e
e t h e r e x t r a c t s w ere w ashed w ith s a tu r a te d sodium c h lo r id e
s o lu t io n and th e n d r ie d o v e r an h y d ro u s sodium s u l f a t e .
The s o lv e n t was e v a p o ra te d and th e r e s id u e was d i s t i l l e d
a t 55-56°C u n d e r th e p r e s s u r e o f 0 .9 mm. The y i e l d was
4-7.4%. A n a ly s is o f H nmr sp ectru m in d ic a t e d t h a t th e
d i s t i l l a t e was a m ix tu re o f 4 -m e th y l-2 -p e n te n o ic a c id and
4 -m e th y l-3 -p e n te n o ie a c id . I n a d d i tio n to th e p e a k s o f
4 -m e th y l-2 -p e n te n o ic a c id , th e r e was one d o u b le t a t 1 .6 -
1 .8 ppm, one d o u b le t a t 2 .8 - 3 .1 ppm, a m u l t i p l e t a t 5 .1 -
5 .4 ppm.
M ethyl 4 -M e th y l-3 -p e n te n o a te . A s o lu t i o n o f 4 .7 4
/
g (0 .0 1 4 6 m ole) o f 4 -m e th y l-3 -p e n te n o ic a c id a n d -4 -m e th y l-
2 -p e n te n o ic a c id m ix tu re , 4 .0 g (0 .1 2 5 m ole) o f m e th a n o l,
1 2 .5 ml o f e th y le n e c h l o r id e and 0 .1 2 5 ml o f c o n c e n tra te d
s u l f u r i c a c id was r e f lu x e d f o r se v en m in u te s . The s o lu
t i o n was c o o le d and p o u red o v e r i c e . The aqueous l a y e r
was e x tr a c te d w ith e th y le n e c h lo r id e . The o r g a n ic l a y e r
and th e e x t r a c t s w ere com bined and washed w ith s a tu r a te d
sodium b ic a r b o n a te , w a te r and th e n d r ie d o v e r an h y d ro u s
sodium s u l f a t e . The s o lv e n t was e v a p o ra te d on a vacuum
e v a p o ra to r and th e r e s id u e was d i s t i l l e d - a t 32-35° C u n d e r
a p r e s s u r e o f o . l l mm. The y ie ld n w a s 27%. A n a ly s is o f th e
1
H nmr sp ectru m in d ic a t e d th e m ain co n tam in an t, to be
m eth y l 4 - m e th y l-2 - p e n te n o a te . . A s i n g l e t was shown a t 3 .1 0
ppm (m ethbxy.)'j a d o u b let^ a t 1 .3 ppm (d im e th y l) , 4 .7 5 ppm
4°
i
( d o u b le t, s a tu r a t e d CH), and a q u a r te t o f t r i p l e t (u n s a
t u r a t e d CH). The i r in d ic a t e d an a b s o r p tio n a t 1745 cm“ ^
( e s t e r ) .
4-M ethyl.- 3-pent_en=l-oJ.. ----- A m ix tu re o f 1 .4 5 &
(0 .2 0 4 m ole) lit h iu m aluminum h y d rid e and 84 ml o f anhy
d ro u s e th e r was c o o le d and s t i r r e d i n a th r e e n eck f l a s k
f i t t e d w ith a co n d en ser* M ethyl 4 -m e th y l-3 -p e n te n o a te
• u
(4*34 Ef 0 .0 3 9 9 m ole) was added d ro p w ise th ro u g h a a d d i tio n
f u n n e l i i n t o t h e f l a s k . The m ix tu re was r e f lu x e d f o r one
h o u r. The r e a c t i o n was te rm in a te d by th e a d d i tio n o f
h y d ro u s e t h e r w hich w as fo llo w e d by a s a tu r a te d s o l u t i o n
o f ammonium c h l o r id e . The o rg a n ic l a y e r was s e p a r a te d
u s in g a s e p a r a to r y fu n n e l and th e aq u eo u s l a y e r was ex
t r a c t e d tw ic e w ith e t h e r . The com bined o rg a n ic l a y e r and
t h e e th e r e x t r a c t s w ere washed w ith s a tu r a te d ammonium
c h l o r id e s o l u t i o n and th e n d r ie d o v e r an h y d ro u s sodium
s u l f a t e . The s o lv e n t was e v a p o ra te d and th e r e s id u e was
d i s t i l l e d a t 4 2 ° C/0.15mm. The y ie l d was 59%. The i r
sp ectru m in d ic a t e d a s tr o n g a b s o r p tio n a t 3350 cm "”'1 ’(-0 H ).
The nmr sp e ctru m showed a d o u b le t a t 1 .5 5 p p m (d im e th y l),
a q u a r t e t a t 2 .0 ppm, a m u l t i p l e t a t 4 .9 5 ppm and a s i n g l e t
a t 3 .7 5 ppm (-Q H ).
4 - M e th v l- 3 - p e n te n - l- y l M e s y la te . ----- A s o l u t i o n o f
1 .2 1 1 g (0 .0 0 9 5 m ole) o f 4 - m e th y l- 3 - p e n te n - l- p l, 1 .8 3 . g.
o f tr im e th y l am ine and 50 ml o f m e th y le n e c h lo r id e was
c o o le d to 0°C and s t i r r e d i n a f l a s k capped w ith a septum .
M ethane s u lf o n y l c h lo r id e (1 .5 2 g , 0 .0 1 3 2 m ole) was added
d ro p w ise th ro u g h a septum w ith a s y r in g e in to th e f l a s k .
The so lu tio n :-w a s s t i r r e d f o r 30 m in u te s , th e n c o o le d to
- 2 0 ° C and l e t i t s ta n d f o r two h o u r s , and washed w ith
w a te r, 1 0 $ h y d r o c h lo r ic a c id , s a tu r a te d sodium b ic a r b o n a te
s o l u t i o n and s a tu r a te d sodium c h lo r id e s o lu t io n . I t was v
v e r i f i e d t h a t th e s o lu tio n was a c d ic a f t e r w ash in g w ith
1 0 $ h y d r o c h lo r ic a c id s o lu t i o n and b a s ic a f t e r w ash in g
w ith s a tu r a te d sodium b ic a r b o n a te s o l u t i o n , o th e rw is e ,
i t was washed a g a in . The s o lv e n t was e v a p o ra te d and th e
r e s id u e was pumped u n d e r re d u c e d p r e s s u r e f o r t h r e e h o u rs
a t 0°C . The i r ( n e a t ) a b s o r p tio n s showed a t 2950 cm"1 ,
1485 cm"1 , 1175 em"1 . The 1H nmr a t 60 MHz showed a doub
l e t a t 1 .6 5 ppm, a m u l t i p l e t a t 4 .8 5 - 5 .3 3 ppm, a t r i p l e t
a t 4 .0 8 ppm, a s i n g l e t a t 2 .8 5 ppm (-SO ^CH^), a q u a r te t a t
2.6 ppm, t h e a r e a s i n t e g r a t e d i n t h e r e l a t i v e r a t i o 6 :1 :2 :
3 :2 r e s p e c t i v e l y . The ab sen c e o f h y d ro x y l group o f th e
p r e c u r s o r a lc o h o l showed t h a t th e r e a c t i o n had gone to
c o m p le tio n .
T ra n s -3 -h e x e n -l-.v l M e s y l a t e ; A m ix tu re o f 1 .8 6 2 g
(0 .0 1 0 2 2 m ole) o f t r a n s - 3 -h e x e n -l-o l(C h e m ic a l Sam ples C o.).
2.76 g (0 .0 3 0 3 m ole) o f trim e th y la m in e and 75 ml o f m ethy
le n e c h lo r id e was added d ro p w ise th ro u g h a s y r in g e and
th e p ro c e d u re o f th e p r e p a r a t i o n o f 4- m e th y l-3- p e & te n - l- b l
was fo llo w e d . The n m r(n e a t) showed a t r i p l e t a t 1 .1 ppm,
a c o m p lic a te d m u l t i p l e t a t 2. 0- 2.6 ppm, a t r i p l e t a t 4.1
ppm and a m u l t i p l e t a t 5. 2 - 5*6 ppm, th e a r e a i n t e g r a t e d i n
th e r e l a t i v e r a t i o 3 : 4 : 2 : 1 : 2 r e s p e c t i v e l y .
f-C h l o-ro b u t v r o n i t r i l e . A m ix tu re o f 42 g (0.6
m ole) o f p o ta s s iu m c y a n id e and 50 ml o f w a te r was s t i r r e d
and warmed u n t i l th e p o ta s s iu m c y a n id e was c o m p le te ly
d is s o lv e d . Then 175 ml o f 95$ e th a n o l and 79 g (0 . 5 m ole)
o f tr im e th y le n e c h lo r id e w ere added. The m ix tu re was
r e f lu x e d f o r one h o u r.T h e s o l u t io n was c o o le d and d i l u t e d
*
w ith 225 ml o f w a te r and t h e aqueous s o lu t io n e x tr a c te d
w ith 40 ml o f c h lo ro fo rm . The o r g a n ic l a y e r was w ashed
w ith 35 ml o f s a tu r a te d c a lc iu m c h l o r id e s o l u t i o n , 70 ml
o f w a te r and th e n d r ie d o v e r an h y d ro u s sodium s u l f a t e .
C hloroform was removed by d i s t i l l a t i o n a t a tm o sp h e ric
p r e s s u r e below 120°C; th e r e s id u e was d i s t i l l e d a t 9 3 -9 6 °c
( 26mm). The y i e l d was 60$. T here was a s tr o n g a b s o r p tio n
- 1 1
a t 2255 cm f o r - C l g ro u p . The H nmr sp ectru m showed
a t r i p l e t a t 4.0 ppm and m u l t i p l e t a t 2. 1- 3.0 ppm.
f •
C v c lo p ro n v l C yanide. ----- To 250 ml o f l i q u i d ammonia
and 21 gram s (O.263 m ole) o f - c h l o r o b p t y r o n i t r i l e i n a
t h r e e neck f l a s k f i t t e d w ith a d ry ic e - a c e to n e c o n d e n se r
and a d r i e r i t e to w e r was added 9 g o f sodium am ide i n 150
43
ml o f e th e r u s in g a t r a n s f e r p i p e t w hich sucked up th e
f i n e sodium am ide to g e t h e r w ith e t h e r . A f te r t h e com ple
t i o n o f a d d i tio n , th e m ix tu re was s t i r r e d f o r one h o u r.
E x ce ss sodium am ide was n e u t r a l iz e d by th e a d d i tio n o f two
gram s o f ammonium c h l o r id e . The m ix tu re was f i l t e r e d
q u ic k ly th ro u g h a s i n t e r e d - g l a s s f u n n e l. Ammonia and
e t h e r w ere e v a p o ra te d by d i s t i l l a t i o n , t h e r e s id u e was
d i s t i l l e d a t 93-96°C /26 mm. The y i e l d was 1 2 ^. The i r
— 1 1
sp e ctru m showed a s tr o n g a b s o r p tio n a t 2250 cm • The H
nmr a t 60 MHz in d ic a t e d a m u l t i p l e t a t 0 .8 3 - 1 .5 ppm.
C v clo n ro n v l E th y l K eto n e. M ethyl m agnesium b ro
m ide was p re p a re d by th e a d d i tio n o f 1 g o f magnesium
tu r n in g to a t h r e e neck f l a s k f i t t e d w ith a c o n d e n se r and
a a d d i tio n a l f u n n e l. The a p p a ra tu s was flam ed to d ry n e s s
w ith a sm a ll b u rn e r and th e n c o o le d u n d e r th e flo w o f
n itr o g e n b e f o r e t h e a d d itio n . E th y l b rom ide ( 3 .3 m l,
0 .0 4 3 m ole) i n 25 ml o f an h y d ro u s e t h e r was added d ro p w ise
th ro u g h th e a d d i t i o n a l f u n n e l. I t to o k 20 m in u te s to
co m p lete th e a d d i tio n . The m ix tu re was r e f lu x e d f o r 30
m in u te s a f t e r th e a d d i tio n .
A s o l u t io n o f 2 g (0 . 29 m ole) o f c y c lo p ro p y l c y a n id e ''
and 5 ml o f an h y d ro u s e t h e r was added d ro p w ise to m eth y l
! m agnesium b ro m id e th ro u g h an a d d i t i o n s fu n n e l. The re a c ~ i.
t i o n m ix tu re was co o led by ic e -s o d iu m , c h lo r id e b a th . Af
t e r th e c o m p le tio n o f a d d i tio n , th e m ix tu re was allo w e d
tOiL.stand f o r two h o u rs a t room te m p e r a tu r e . A f te r u n re a c te d
l i t h i u m aluminum h y d rid e was decom posed by h y d ro u s n e th e r,
th e r e a c t i o n m ix tu re was w ashed w ith w a te r, s a tu r a te d
ammonium c h lo r id e s o l u t io n , s a tu r a te d sodium c h lo r id e
s o l u t i o n , and th e n d r ie d o v e r an h y d ro u s sodium s u l f a t e .
E th e r was e v a p o ra te d and the. r e s id u e was u sed f o r g a s
ch ro m ato g rap h y a n a l y s i s . The r e t e n t i o n tim e f o r c y c lo -
p r o p y l c a r b in o l was 7 .4 m in u te s a t 120°C on 10% TCEP
colum n (6 m e te r x 1 /8 in c h ) w ith n itr o g e n flo w r a t e 30ml
p e r m in u te .
2?
P u r i f i c a t i o n o f E th a n o l. ----- Com m ercial g ra d e o f
a b s o lu te e th a n o l may c o n ta in e a t r a c e amount o f w a te r f o r
p u rS e th a n o l i s v e ry h y g ro s c o p ic and e a s i l y p ic k s tu p m ofs-
t u r e during- , t r a n s f e r . E th a n o l was p u r i f i e d by th e p r o c e s s
o f Lund and B jerru m . W ater i s rem oved by r e a c t i o n w ith
m agnesium e th o x id e . M agnesium h y d ro x id e i s i n s o l u b l e i n
Mg(0C2H5) + 2H20 -------- * M g(0H)2 + 2 0 ^ 0 1 1
e th a n o l.
A m ix tu re o f 5 g o f magnesium tu r n i n g , 60 ml o f comm
e r c i a l a b s o lu te e th a n o l and a few d ro p s o f ca rb o n t e t r a
c h lo r id e was r e f lu x e d u n t i l n e a r ly a l l th e m agnesium
t u r n i n g c o n v e rte d i n to e th o x id e . C a r b o n tte tr a c h lo r id e was
u se d a s a c a t a l y s t , l i n e h u n d red ml o f a b s o lu te e th a n o l
45
was added to th e m ix tu re and r e f lu x e d f o r one m ore h o u r.
P u re e th a n o l was d i s t i l l e d a t 78° C a t one atm o sp h ere.
R ate D e te rm in a tio n . ----- A R a d io m e ter c o n s is te d o f a
R ad io m eter ty p e SBR 2C r e c o r d e r , JSH m e te r 26, t i t r a t o r I I
and a th e r m o s ta tte d w a te r ja c k e te d c e l l was u se d to d e t e r - *
m ine t h e r e a c t i o n r a t e s . T em p eratu re was c o n t r o ll e d by a
Haake c o n s ta n t te m p e ra tu re b a th and was c a l i b r a t e d a g a in s t
•
a N a tio n a l B ureau o f S ta n d a rd s th e rm o m ete r. A R a d io m eter
G-202B g l a s s e le c t r o d e w hich was c o n d itio n e d i n 0 .1 If hydro
c h l o r i c a c id s o lu t io n f o r two w eeks and i n PH 7 b u f f e r 1
s o l u t io n f o r two d ay s b e f o r e u s e and a K4018 c a lm e l e le c - |
tr o d e c o n n e c te d w ith a p o ta s s iu m c h l o r id e b r id g e w ere u se d .'
T i t e r w hich was d e liv e r e d from a s y r in g e to th e r e a c t i o n
f l a s k by D4332 d e l iv e r y tu b e co n n e cte d w ith a T e flo n tu b
in g . The sam ple was in tro d u c e d from a m icro s y rin g e .E th a n * !,
o l was p u r i f i e d ; sodium a z id e was from M atheson Coleman
and B e ll; sodium n i t r a t e was from M a llin k r o d t; w a te r was
d i s t i l l e d and ca rb o n d io x id e f r e e . E th a n o l-w a te r s o lu t io n
was p re p a re d by u s in g 50 m l,75 m l'a n d 25 ml p i p e t s . S a lt
»
s o l u t io n s w ere p re p a re d by d is s o lv in g p r o p e r w e ig h t o f [
i , *
sodium a z id e o r sodium n i t r a t e i n e th a n o l- w a te r s o l u t i o n . |
The q u a n tity o f th e s o lv e n t u sed f o r th e r e a c t i o n was 25
ml w hich was t r a n s f e r e d by a 25 ml p i p e t to th e r e a c t i o n
f l a s k . The r e a c t i o n m ix tu re was s t i r r e d and a slow p u rg e '
o f n itr o g e n was th ro u g h . A ll r u n s w ere s t a t t e d a t p’ H 6 .5 I
I 46
I
| i n th e a b s e n c e o f s a l t and pH 9 .0 i n t h e p re s e n c e o f s a l t .
The pH v a lu e o f th e s e two p o i n t s d e c id e d by th e t i t r a t i o n
c u rv e o f sodium h y d ro x id e a g a in s t h y d r o c h lo r ic a c id i n th e
s o lv e n t i n t h e a b se n c e o r p re s e n c e o f s a l t w ere j u s t above
t h e b u f f e r r e g io n o f th e s o lu t io n . R e a c tio n s w ere fo llo w ed
f o r te n h a l f l i f e s w hich i s ab o u t 99$ c o m p le tio n o f th e
r e a c t i o n . D a ta w ere a n a ly z e d by 1SKIKL g e n e ra l f i r s t
o r d e r k i n e t i c p ro g ram .
The d e te r m in a tio n o f t h e S t a t t P o in t f o r S o lv o ly s is .
To 25 ml o f 60$ e th a n o l i n th e r e a c t i o n f l a s k o f th e
R a d io m e te r, 4 d ro p s o f 0 .1 U h y d r o c h lo r ic a c id was ad d ed .
The m ix tu re was t i t r a t e d w ith 0 .1 8 3 H sodium h y d ro x id e
( i n 6 0 $ e th a n o l) u s in g a R a d io m e ter ty p e pH m e te r and
t i t r a t o r . The t i t r a t i o n c u rv e i s shown i n F ig u re 9*
The D e te rm in a tio n o f th e S t a t t P o in t f o r th e Solvo
l y s i s i n th e P re s e n c e o f Sodium H i t r a t e o r Sodium A zide i n
6 0 $ E th a n o l. ----- To 25 ml o f 6 0 $ e th a n o l i n th e
r e a c t i o n f l a s k o f th e R ad io m eter was added 0 .1 ml o f 0 .4 H
sodium a z id e i n 6 0 $ e th a n o l. The m ix tu re was t i t r a t e d
a g a in s t 0 .1 8 3 H sodium h y d ro x id e . The t i t r a t i o n c u rv e i s
shown i n F ig u re 1 0 .
S o lv o lv tic .P ro d u c t A n a ly sis^ ------- A m ix tu re o f 0 .2 g
(0 .1 1 2 m ole) o f iiia n s r 3--hexen»l-.yl m e s y la te , 0 .1 6 g (0 .0 1 1 6
m ole) o f an h y d ro u s p o ta s s iu m c a rb o n a te and 4 ml o f 6 0 $
: e th a n o l was capped w ith a septum i n a 18 x 150 m m t e s t
: tu b # and th e t e s t tu b e was im m ersed i n a 6 0 ° C w a te r b a th
f o r 30 h o u rs . The s o l u t i o n was d r ie d by a d d in g an h y d ro u s
p o ta s s iu m c a rb o n a te to make a p a s t e . The c l e a r e th a n o l
; s o l u t i o n o n th e u p p e r l a y e r o f th e p o ta s s iu m c a rb o n a te
p a s t e was d e c a n te d i n t o a v i a l and two d ro p s o f to lu e n e
; was added a s an i n t e r n a l s ta n d a r d . Two ml o f th e e th a n o l
| s o l u t i o n was t r a n s f e r r e d to a 25 ml s e p a r a to r y fu n n e l and
1
1 th e n shook w ith 2 ml o f p e n ta n e and 2 ml o f w a te r. M ost o f
; t h e e th a n o l was e x t r a c te d by w a te r. P e n ta n e l a y e r was
I
i s e p a r a te d and th e n d r ie d o v e r sodium m e ta l i n a 10 ml p e a r
i ■
i shaped f l a s k f i t t e d w ith a d ry in g tu b e . B oth e th a n o l and
i '
; p e n ta n e l a y e r w ere a n a ly z e d a t a te m p e ra tu re p ro g ram r a t e
3 2 °0 /m in . from 70°C to 120°C w ith an i n i t i a l p e r io d o f 8
m in u te s on a 6 m e te r x 1 / 8 . i n . TCEP colum n w ith a n itr o g e n
! flo w r a t e a t 30 m l/m in ., h y d ro g en flo w r a t e 30 m l/m in .,
l
and a i r flo w r a t e a t 550 m l/m in ..
i
The M easurem ent o f Sodium Io n A c t i v i t i e s . ----- The
sodium io n a c t i v i t i e s o f sodium n i t r a t e and sodium a z id e
i n 60$ e th a n o l and 8 0 $ e th a n o l a t room te m p e ra tu re w ere
d e te rm in e d by th e g e n e ra te d emf a t a sodium e le c t r o d e
(Beckman 39278) on a R ad io m e ter ty p e pH m e te r w ith K 4018
calo m el e l e c t r o d e a s th e r e f e r e n c e e l e c t r o d e . The a c t i v i
t i e s o f th e s o lu t io n s o f 0 .1 E T , 0 .2 H and 0 .4 N o f sodium
48
n i t r a t e and sodium a z id e w hich w ere p re p a re d f o r t h e s o l-
v o l y s i s r e a c t i o n w ere d e te rm in e d . The s o l u t i o n s o f 0 .1 IT,
0 .0 1 Iff, and 0 .0 0 1 If f w ere p re p a re d by s u c c e s s iv e d i l u t i o n s
o f 0 .1 Iff s o l u t i o n s o f sodium n i t r a t e and sodium a z id e .
The r e s u l t s a r e shown a s fo llo w s :
C o n c e n tra tio n o f S a lt ->mv
i n 60fi E th a n o l, IT
0 .4 0 0 248.6
0 .2 0 0 236.0
0 .1 0 0
2 2 3 .2
0 .1 0 0 x K T 1 1 6 9 .8
0 .1 0 0 x 10“ 2
1 1 3 .1
0 .1 0 0 x 10“ 3
6 0 .4
C o n c e n tra tio n o f S a lt -m v
i n 80$ E th a n o l, I f f
0 .4 0 0
2 7 6 .5
0 .2 0 0 258.0
0 .1 0 0 244.8
0 .1 0 0 x 10"*1
1 9 1 .5
0 .1 0 0 x 10“ 2
1 3 5 .7
0 .1 0 0 x 10“ 5
7 7 .5
9 .0
8 .0
7 .0
6 .0
5*0
4 .0
2 0 .0 10.0 0.0
B ase ( f» S y rin g e C a p a c ity )
F ig u re 9. T i t r a t i o n Curve o f H y d ro c h lo ric A cid
i n 60fo E th a n o l w ith Sodium H y d ro x id e a t Room
Temp e r a t u r e .
50
11.0
9 .0
8.0
10.0 0.0
4 0 .0 3 0 .0 20.0
B ase (S y rin g e C a p a c ity )
F ig u re 1 0 . T i t r a t i o n Curve o f H rd ro c h lo ric A cid
( i n 60$ S th a n o l) A g a in st Sodium H y d ro x id e ( i n
6 0 $ E th a n o l) i n th e P re s e n c e o f Sodium A zid e.
BIBLIOGRAPHY
1 (1)* E.D. H ughes, O.K. In g o ld and C .S . P a t e l , J .C h e m .S o c .f
526 (1 9 5 3 ).
| ( 2 ) . E.D. H ughes and O.K. In g o ld , J.C h em .S o c. . 2 3 5 (1 9 3 3 ).
i ( 3 ) . J .L . G le a v e , E .B . Hughes and O.K. I n g p ld , J .G h e m .S o c ..
| 2 3 5 (1 9 3 5 ).
| ( 4 ) . M .L .B ird , S .D .H ughes and O.K. I n g o ld , J . C hem .S oc..
| 634 (1 9 4 5 ).
I ( 5 ) . V. G old, J . H i l t o n and E .B .J e f f e r s o n , J.C h e m .S o o ..
2 7 5 6 (1 9 4 5 ).
j (6 ) . V. G old, J . Chem. Soc. t 4 6 5 5 (1 9 5 6 ).
!
| ( 7 ) . C.G. Sw ain, J.A m er. Chem. S o c .. 2 2 # 1 1 1 9 (1 9 4 8 ).
| (8 ) . H. W einer and R.A. S neen, J . Amer. Chem. Soc* .8 7 . 287
(196 5 ).
( 9 ) . H? W einer and R.A. S n e e n .J.A m er.C hem . Soc..8 7 .2 9 2 (1 9 6 5 ).
( 1 0 ) . J.W . L a rs e n and R.A. S neen, J.A m er. Chem. S o c .. 88.
2953 (1 9 6 6 )?
( 1 1 ). J .V . C a r te r and R.A. S neen, J.A m er. Chem. Soc. . 88.
2594 (1 9 6 6 ).
( 1 2 ) . J.W . L a rs e n and R.A. S neen, J.A m er. Chem. Soc. . 9 1 .
6031 (1 9 6 8 ).
(1 3 ). J.W. L a rs e n and R.A. Sneen, J.A m er.C hem . Soc. .9 1 .
362 (1 9 6 9 ).
(1 4 ). R.K. C ro s s la n d , P h.D . D i s s e r t a t i o n , U n iv e r s ity o f
S o u th e rn C a l i f o r n i a , L os A n g e le s, C a l i f o r n i a ,1970.
(1 5 ). R.K. C ro ssla n d and K .L . S e r v is , J.O rg .C h e m ., 35.5195
(1 9 7 0 ). ~
(16) . O rg .S y n th e s e s . C o ll.' V ol. 4 , 571 (1 9 6 3 ).
52 j
(1 7 ). A. G o ld b erg and R. P . L in s te a d , J .C h e m ,S o c ..2 5 4 5 !
(1 9 2 8 ).
( 1 8 ). J . B. Rogan, J .O rg .C h e m ., 27, 3910 (1 9 6 2 ).
(1 9 ). O rg. S y n th e s e s . C o ll. V ol. 1 , 156 (1 9 4 1 ).
( 2 0 ) . O rg. S y n th e s e s . C o ll. V o l.3, 223 (1 9 5 5 ).
(2 1 ). M. Hanaek and H.M. E n s s lin , L ie b ig s . 697. 1 0 0 (1 9 6 6 ).
( 2 2 ). L .P . P i e s e r , "E x p t. i n O rg. Chem. 3 rd E d .” , H ea th ,
B o sto n , p . 285 (1 9 5 7 ).
( 2 3 ). A. H. P a in b e rg and S. W in s te in , J.A m er.C hem .S oc. , 7 8 ,
2780 (19.56).
(2 4 ). J . M. H a r r i s , D. J . R a b er, R .E . H a ll and P .R .
S c h le y e r, J.A m er Chem. S o c .. 9 2 .5 7 2 9 (1 9 7 0 ).
(2 5 ). A. S t r e i t w i e s e r J r . ” S o lv o ly tic D isp lace m en t
R e a c tio n s " . P .1 4 0 . M cgraw -H ill Book Company, I n c .
N.Y. (1 9 6 2 ).
( 26) . J . D. R o b e rts and R. H. M azur, J.A m er.C hem .S oc. .7 3 .
2509 (1 9 5 1 ). “
( 2 7 ). P .R . ¥ e l l s , Chem. R e v .. | 2 , 1 7 1 -2 1 9 (1 9 6 3 ), p . 212.
( 2 8 ) . K. ;L. S e r v is and J . D. R o b e rts . J.A m e r.C h em .S o c.. 86.
377 3-7 (1 9 6 4 ).
APPEHDIX
PRIMARY SOLVOLYTIC DATA
4 -M eth y l P e n t - 3 - e n - l - y l M e sy la te (1 9 .4 mg) i n 25 ml 60%
E th a n o l a t 60°C i n th e P re s e n c e o f Sodium A zide (0 .4 F)
Time ( m in .)
% S y rin g e
C a p a c ity
Time ( m in .)
% S y rin g e
C a p a c ity
0 .0 0
1 0 .3 7 .0 0
3 8 .4
1 .0 0
1 5 .8
8 .0 0
4 0 .7
1 .5 0
1 8 .3 9 .0 0 4 2 .8
2.00
20.8
1 0 .0
4 4 .5
2. 50
23.0
1 1 .0 4 6 .1
5 ® 50 27.1
1 2 .0
4 7 .5
4 .0 0
29.1 1 3 .0
4 8 .7
4 .5 0
3 1 .1 1 4 .0
4 9 .7
5.00 32.6
1 5 .0
5 0 .5
6 .0 0
3 5 .7
00
57. 5
k = 2 .1 9 + 0 .0 3 x K T ^ s e e ." 1
P a ra m e te r E s tim a te s and C o n d itio n s :
E r r o r M in im ized , S c a la r i n S y rin g e C a p a c ity
W eight U n its
S.D. Z ero , 0 .0 (F ix e d Zero P o in t)
S.D. I n f i n i t y , 0 ,2 0
S.D . G en e ra l V a r ia b le , 0 .1 5
4 -M ethyl P e n t - 3 - e n - l - y l M e sy la te (1 1 .0 mg) i n 25 ml 60?6
E th a n o l a t 60°C i n th e P re s e n c e o f Sodium A zide (0 .1 N).
Time (m in .)
% S y rin g e
C a p a c ity
Time ( m in .)
% S y rin g e
C a p a c ity
0 .0 0 9. 30 8 .0 0 3 5 .7
1 .0 0 1 4 .2 9 .0 0 3 7 .4
1 .5 0 1 62,6 1 0 .0 3 9 .0
2. 00 1 8 . 5 1 1 .0
4 0 .3
2. 50 2 0 .4 1 2 .0 4 1 .5
3 .0 0 2 2 .3 1 3 .0 42. 5
3 .5 0
2 4 .3
1 4 .0 . 4 3 .4
4 .0 0 25.8 1 5 .0 4 4 .2
5.00 28.8 1 6 .0 4 4 .9
• *
o
o
3 1 .4 00 4 8 .5
7 .0 0 3 3 .7
k = 2 .1 9 + 0 .0 3
— 3 -
x 10 ^ se c .
•1
P a ra m e te r E s tim a te s and C o n d itio n s :
E r r o r M inim ized, S c a la r i n S y rin g e C a p a c ity
U n it W eights
S.D. Z ero , 0 . 10
S.D. I n f i n i t y , 0 .2 0
S. D. G en e ra l V a r ia b le , 0'.0 7 2
56
4 -M ethyl P e n t - 3 - e n - l - y l M e sy la te (1 0 .9 mg) i n 25 ml 60$
E th a n o l a t 60° C i n th e P re s e n c e o f Sodium N i t r a t e ( 0 .2 N)
Time ( m in .)
$ S y rin g e
C a p a c ity
Time ( m in .) $ S y rin g e
C a p a c ity
0 .0 0 1 7 .6 9 .0 0 4 4 .3
1 .0 0 2 1 .9 1 0 ,0 4 5 .8
2.00 25.7 1 1 .0 47.4.
2.50 2 7 .5
1 2 .0 4 8 .9
3.00 2 9 .1 1 3 .0 4 9 .9
3. 50 3O .8. 1 4 .0 5 0 .9
4 .0 0
5 2 .3
1 5 .0 5 1 .9
5.00
3 5 .3
1 6 .0 5 2 .7
6 .0 0 3 7 .9 1 7 .0 53® 5'
7 .0 0 4 0 .2 0 0 6 0 .4
8 .0 0
4 2 .3
k = 1.81. + 0 .0 3 x 10” sec
P a ra m e te r E s tim a te s and C o n d itio n s :
E rr o r M inim i2 5 ed , S c a la r i n S y rin g e C a p a c ity
U n it W eights
S .D .Z e ro , 0 .1 0
S.D i n f i n i t y , 0 .2 0
S.D. G en e ra l V a r ia b le , 0 .1 1
4-M eth y l P e n t - 3 - e n - l - y l M e sy la te (1 1 .5 mg) i n 6 0 Ethanol
a t 60°C i n t h e P re s e n c e o f Sodium N i t r a t e ( 0 .4 N).
Time ( m in .)
^ S y rin g e
C a p a c ity
Time ( m in .)
io S y rin g e
C a p a c ity
0 .0 0
•
o
H
1 0 .0 . 4 5 .3
1£Q0 1 5 .4 1 1 .0
4 7 .2
2.00 20.1 1 2 .0 4 8 .8
3.0 0 2 4 .3
1 3 .0 5 0 .4
3 .5 0 2 6 .4
1 4 .0 51.7
4 .0 0 2 8 .3
1 5 .0
52.8
5.00 3 1 .9
1 6 .0
54.0
6 .0 0 3 5 .1
1 7 .0 5 4 .9
7 .0 0 3 8 .1 1 8 .0
55.8
8 .0 0 4 0 .7 1 9 .0 5 6 .5
9.0 0 4 3 .1
C D 6 1 .8
k = 1 .7 9 + 0 .0 2 x K T ^ s e c .- 1
P a ra m e te r E s tim a te s and C o n d itio n s :
E r r o r M in im ized , S c a la r i n S y rin g e C a p a c ity
U n it W eig h ts
S.D . Z ero , 0 .1 0
S.D. I n f i n i t y , 0 .2 0
S.D . G e n e ra l V a r ia b le , 0 .1 3
58
4 -M eth y l P e n t - 3 - e n - l - y l M e sy la te (1 8 .8 mg) i n 25 ml 60 i °
E th a n o l a t 60°C i n th e P re s e n c e o f Sodium a z id e (0.2 E)
Time ( m in .)
i < > S y rin g e
C a p a c ity
Time (m in ) s 7r i n Se
n m e v m in .; C a p a c ity
0 .0 0 1 0 .1 9*00 5 2 .7
1 .0 0 17V 5 1 0 .0 55.0
1 . 50 21. 2 1 1 .0
56*9
2.00
2 4 .3 1 2 .0
5 8 .5
2. 50 27*6
1 3 .0 6 0 .0
3*00 3 0 .1 1 4 .0
6 1 .3
3. 50 3 3 .0 1 5 .0 6 2 .4
4 .0 0 3 5 .1 1 6 .0 6 3 .2
4 . 50 37*5 1 9 .0
6 5 .3
5 ; qo 39.8 2 1 .0 6 6 .4
6 .0 0 4 3 .6 23.0
6 7 .1
7 .0 0 4 7 .0 00 6 9 .0
0 0
s
O
o
1
50.1
k = 2 .2 9 + 0 .0 1
_ X
x 10 ^ se c .
-1
P a ra m e te r E s tim a te s and C o n d itio n s :
E r r o r M inim ized, S c a la r i n S y rin g e C a p a c ity
U n it W eights
S.D. Z ero , 0,.0 ( F ix ed Zero P o in t)
S.D. I n f i n i t y , 0 .1 0
S.D. G-eneral V a r ia b le , 0 .1 6

Linked assets

University of Southern California Dissertations and Theses

Conceptually similar

PDF

Second-order nucleophilic substitution reactions of cyclobutane derivatives: A study of the stability of pentacoordinate carbon

PDF

The reaction H+ClCN to CN+HCl

PDF

The reaction of phenylmagnesium bromide with methyl B-benzoylpropionate and with diethyl succinate

PDF

The stereochemical course of the nucleophilic displacement of cyanide from alpha-ferrocenyl-alpha-aminonitriles, and model experiments for the synthesis of optically active alpha-ferrocenyl alkyl...

PDF

The reaction of styrene oxide with phenol

PDF

Kinetics of the reductive elimination reaction of trans-bromohydroxytetracyanoplatinate ion with thiosulfate and tetrathionate ions

PDF

The reaction of styrene oxide with B-naphthol

PDF

The reaction of trimethylamine with some inorganic acid chlorides

PDF

Syntheses in the fluoranthene series

PDF

Studies on the determination of thorium in the presence of rare earths

PDF

I. Intramolecular reaction of alkenyl substituted silylenes. II. Determination of the relative migratory aptitudes of a trimethylsilyl group versus a hydrogen to a carbenoid center

PDF

The reaction of 22,42-Dibromocholestan-3-one with N,N-imethylaniline

PDF

Syntheses in the thianaphthene series

PDF

A study of the reactions of phosphorus pentachloride with trimethylamine

PDF

The rate of aquation of the sulfito ligands in disulfitotetracyanocobaltate (III) ion

PDF

The catalytic conversion of parahydrogen by paramagnetic ions in aqueous solution

PDF

Kinetics and mechanism of the substitution of water in aquapentacyanocobaltate (III) by pyridine

PDF

The acid catalyzed isomerization and dimerization of styrene oxide

PDF

The chlorinolysis of carbon-sulfur bonds

PDF

The purification and study of inulin

Asset Metadata

Creator Soong, Julie Jue (author)

Core Title Solvolytic reactions in the presence of added nucleophile

Degree Master of Science

Degree Program Chemistry

Publisher University of Southern California (original), University of Southern California. Libraries (digital)

Tag chemistry, organic,OAI-PMH Harvest

Language English

Contributor Digitized by ProQuest (provenance)

Permanent Link (DOI) https://doi.org/10.25549/usctheses-c17-796137

Unique identifier UC11345350

Identifier EP41653.pdf (filename),usctheses-c17-796137 (legacy record id)

Legacy Identifier EP41653.pdf

Dmrecord 796137

Document Type Thesis

Rights Soong, Julie Jue

Type texts

Source University of Southern California (contributing entity), University of Southern California Dissertations and Theses (collection)

Access Conditions The author retains rights to his/her dissertation, thesis or other graduate work according to U.S. copyright law. Electronic access is being provided by the USC Libraries in agreement with the au...

Repository Name University of Southern California Digital Library

Repository Location USC Digital Library, University of Southern California, University Park Campus, Los Angeles, California 90089, USA