SYNTHESIS AND SGLVGLYSIS OF COMPOUNDS CONTAINING
THE CXCDQPRQPYLCARBINYL SYSTEM

Joseph Mario Sandrl

A THESIS

Submitted to the College of Advanced Graduate Studies of Michigan
State University of Agriculture and Applied Science
in partial fulfillment of the requirements
for the degree of
DOCTOR OF PHILOSOPHY
Department of Chemistry

1956

ProQuest Number: 10008513

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I

ACEUOWLEDGmei?
The author wishes to express his deep
appreciation to.r the help and encouragement
of Doctor Harold Hart during the course of
this investigation.
Appreciation is also extended to the
American Viscose Corporation whose Fellowship
Program provided personal financial assistance
during the academic year 1951^1955»

ii

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TABLE OF CONTENTS
Page
INTRODUCTION............ #..*.**........ *,*.... *
DISCUSSION OF S2NTHETIC P
EXPffiilMENTAL

R

O

C

....

E

D

*♦
U

R

E

*..♦

1

S

6
25

A * Syntheses
....... ....... 25
Bicyclopropyi K©tone..................................... 25
Di-(2-m©thylcyclopropyl) ketone........... ............. 26
Finely Divided L
i
t
h
i
u
m
.
27
Cyclopropyl Chloride.
....
28
Isopropyllithium.
29
Cyclopropyllithiura.
29
T r i c y c l o p r o p y l c a r b i n o l . 30
Other Carbinols Containing the Cyclopropyl Croup.#....... 31
Dicyclopropylisopropylearbinyl p-nitrobensoate........... 31
The p~Nitrobenzoates of Several Tertiary Carbinols....... 3k
Bicyclopropylcarbinyl p~nitrcbenzoate
36
Attested Preparation of Tricyclopropylcarbinyl p-nitrob
e
m
s
o
a
t
e
36
Structure proof of 1*l-d±cyclopropyl-U~ehloro~l~butenej
oxidation with neutral potassium permanganate ......... 39
The Reaction of Tricyclopropylcarbinol with Concentrated
Hydrochloric Acid..
..........
kO
The Reaction of l,l~Bieyelopropyl-U~chloro--l~butene with
Aqueous Potassium C a r b o n a t e h i
The Addition of Isopropyllithium to Ethylene............. kX
The Attempted Addition of Oyclopropyllithlum to Ethylene* U2
B. Solvolysis Studies*.. . . . . . . . . . . . . . .
l»3
S
o
l
v
e
n
t
s
U3
Staixiardissation of Reagents*.*
....
U3
Kinetic P
r
o
c
e
d
u
r
e
.
h3
Product Analysis.....*.#.*..
.
.
.
.
.
.
ihi
Proof of Structure of l^isopropyl~5-methyl~3~hexenyl
p - n i t r o b e n a o a t e 50
SOLVOLYSIS RESULTS.
A. The Hates
B. The Products

..........

52

.......... ....................
52
.................................. 66

vi

TABLE OF CONTENTS - Continued
Page
DISCUSSION OF THE SCLVOLYSIS STUDIES*

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

A* Recent Concept# in Solvolysi# Mechanisms**.*«*.*«..*.**••*»•
B. Previous Investigations of the Cyclopropylcarfoinyl Systems*.
C. The Present I n v e s t i g a t i o n *
1, The Nature of the R
e
a
c
t
i
o
n
,
2, Effect of Structure on ..the -Rates., **♦#*#*#**
3* The Driving F
o
r
e
s
*
L« The Internal R e a r r a n g e m e n t *
5. Mechanism.**..•*.*••*.*.•.* ***i*•..•*•••**.*•«**•*«••*
....................
6. The Energetics
SUMMARY

............. *....

77
77
85
95
95
96
100
105
108
Ill

*.... ........ .... iHj-

LITMATURE CITED........... ........... *....
APPENDIX*...........

116
*»..... 119

vii

I M S OF TABLES
W

fage

X# Preparation of Certain Garbinolo Containing the Cyclo■P&0&9&'

*****##«***-*•*■*##>##*#$<*•##*.*#■***'***#*.#*:*-#•****#•*#* 32

t# Fharsioal properties* Yields and Analyaet of Several Tertiary
GsrbinoXa Containing the %sl*ipre$Q&
»«»«+•«.* 33
3% Melting points* Yield* and Analyses ofSeveral p-*Httro~ banaoatsa#'*♦♦•******#
*** *##*■*##**♦**■#.%#'#■€!#«##■«#♦**«**.*« 35
It* Specific Rate Qonotants for the SolvolyslB of Bfeyelopropyliiioisronarloarbiiisrl t^Mltrobensoate in Aoueous Bioasane»*.*.«*, 61
$ * Specific Rate Constants .for the SeXvolysie of Bi^(2^eth3rl^
ca^^3be^Hs^sr^.
j^mtrob<meoete in Aqueous -~
.

BXoxaHcie***-«**.**#«««*$*«%*#:**,*.##*.***♦*#♦****#**♦**«*<»**.***■*■** 62
6« Specific Rate- ckmabaaia for the SoXvelysis ef MAioproj^X*eyclepx^s^Xearbinyl j^Nitrobenao&te in Aqueous l&oxane****.* 63
7* BfeeUie Rate Constants for the Selvo3yiiie of BieyGlopropjrl*
carbii^rl p^Mltrobensoat© in Aquaous Moxsma***.**.**•******** 6i*
8* Specific Rate Constants for the Solvolyele of Triieopropyl*
carbinyl p^Ritrobensoate in.Aqueous.m m m & 4f.o•*****«.«*:«.**•*** 65
9* Meier Eaihalpi.ee .ami Entropies of Activation for the
Solvolysis of Several p*Bltrebensse&t«s in Aqueous Btoxane*.* 67
10* SisXvolysi* of a ,a-* enBnT , Y ^LtBethylellyl Chloride*******

62

IX* Relative Rates of Solvolysis* of SeveriX p-Hitrobensoabes in
Aqueous Bioiosu&e***.#*******«•*««*******:*********#:***■*♦***#**» 98
If* Rearrangement of Several p^Hltrobemoates in Aqueous Dioxane
AS a Function of the Water Content of the Solvent*****.***.*
13* Solvolysia of 0*007005 Molar Bicyclopropylisopropjlcisurbinyl
p-Nitrobenaoate is 95$ Bioxane * $% Water at 60°****.*.**..* ISO
H u Solvolysis of 0*006185 Molar Bic^loproi^llsopropylcarbinyl
p-Nitrobensoate in 95$B±oxan© * $% Water at 60° ***......
121

vili

LIST OF TABLES •* Continued
TABLE

Page

15* Solvolysis of 0*011214 Molar Dicyclopropylisopropylcarbinyl
p-Nitrobenzoate in 90$ Dioxane - 10$ Water at 25°*.**...... 122
16* Solvolysis of 0*01808 Molar Dicyclopropylisopropylcarbinyl
p-Nitrobenzoate in 90% Dioxane - 10$ Water at 250C ••••**•**• 123
17* Solvolysis of G.Q095U9 Molar Dicyolnpropylisopropylcarbinyl
p-Nitrobenzoate in 90$ Dioxane * 10$ Water at iiQ C .•***•*••• 12U
18* Solvolysis of 0*008258 Molar Dieyclopropylisopropylcarbinyl
p-Nitrobenzoate in 90$ Dioxane -10$ Water at ii0oC**,**.**.,. 125
19. Solvolysis of 0.008175 Molar Dicyclopropylisopropylcarbinyl
p-Nltrobenzoate in 90% Dioxane - 10$ Water at 50°C*.♦..*..,* 126
20* Solvolysis of 0*008159 Molar Dieyclopropylisopropylearbinyl
p-Nitrobenzoate in 90$ Dioxane - 10$ Water at 50®G**.******* 127
21. Solvolysis of 0*01255 Molar Dieyclopropylisopropylearbinyl
p-Nitrobenzoate in 85$ Dioxane - 15$ Water at SfrC.*.. *..*.. 128
22. Solvolysis of O.OO7038 Molar Dicyclopropylisopropylcarbinyl
p-Nitrobenzoate in 85$ Dioxane - 15$ Water at 25°C...******* 129
23. Solvolysis of 0.008261* Molar Dicyclopropylisopropylcarbinyl
p-Nitrobenzoate in 80$ Dioxane - 20$ Water at ?°C**•***«*.«* 130
2iu Solvolysis of 0.01012 Molar Dicyclopropylisopropylcarbinyl
p-Nitrobenzoate in 80$ Dioxane * 20$ Water at 7 0 .......... 131
25. Solvolysis of 0.009522 Molar Dicyclopropylisopropylcarbinyl
p-Nitrobenzoate in 80$ Dioxane - 20$ Water at 16®C#********* 132
26* Solvolysis of 0,01019 Molar Dicyclopropylisopropylcarbinyl
p-Nitrobenzoate in 80$ Dioxane - 20$ Water at 16°C***.*..*., 133
27* Solvolysis of 0.009368 Molar Dicyelopropylisopropylcarbinyl
p-Nitrobenzoate in 80$ Dioxane - 20$ Water 0.009525 Normal
in Sodium Hydroxide at 16°C................... .
13U
28* Solvolysis of 0.0088U5 Molar Dicyelopropylisopropylcarbinyl
p-Nitrobenzoate in 80$ Dioxane - 20$ Water 0*009525 Normal
in Sodium Hydroxide at 16°C•••••«•**«**•••***.••.,•*•**.*••* 135

ix

LIST OF TABLES - Contlrmad
TABLE

Page

29* Solvolysis of 0*01235 Molar Dicyclopropylisopropylcarbinyl
p-Nitrobenzoate in 80% Dioxaa© * 20% Water at 25°C.*.*..... 136
30. Solvolysis of 0*00972 Molar Dicyclopropylisopropylcarbinyl
p-Nitrobenzoate in 80$ Dioxane * 20$ Water at 25°C.... ♦•*.. 137
31* Solvolysis of 0*00930? Molar Dieyclopropyliaopropyloarbinyl
p-Sfitrobenaoat© In 80$ Dioxane - 20$ Water at 25°G********** 138
32* Solvolysis of 0.009022 Molar Dicyclopropylisopropylcarbinyl
p-Nitrobenzoat© in $0$ Dioxane * 20$ Water of 25®G********** 139
33* Solvolysis of 0.005522 Molar Di—(S-aethylcyclopropylJisopropylcarbinyl p-N±trob©nzoat© In 90$ Dioxane * 10$ Water
at 16°..********...... ....... ........ .... .... .... .

11*0

3U« Solvolysis of 0.005U98 Molar Di-( 2-methylcyclopropyl )iso~
propylcarbinyl p-Nitrobenzoate in 90$ Dioxane - 10$ Water
at 16°.............. *.*.******•**.••*.... *.*.........

1U1

3?* Solvolysis of 0*0062140 Molar Di-(2-methylcyclopropyX)isopropylcarbinyl p-Nitrobenzoat© In 90$ Dioxane - 10$ Water
at 2?°*..***.*.**....******..... ***************••»••****•* 1M2
36. Solvolysis of 0.00629U Molar Bi-(2-methylcyclopropyl)isopropylcarbinyl p-Nitrobenzoate In 90$ Dioxane
10$ Water at
2?o ******....... *...... *........*.... ......... ******* 1U3
37* Solvolysis of 0*005975 Molar Di- (2-mebhylcycXopropyl)isopropylcarbinyl p-Nitrobenzoate in 90% Dioxane - 10$ Water
at 35° *****............. *.... ************.........

1UU

38. Solvolysis of 0*006258 Molar Di- (2~m0thyleyclopropyl)isopropylcarbinyl p-Nitrobenzoate in 90$ Dioxane - 10$ Water
at 35° *****.............
.*.***.*.*.*
****** lit?
39* Solvolysis of 0.006952 Molar Di-(2-ra9thylcyclopropyl)isopropylcarbinyl p-Nitrobenzoate in 90$ Dioxane - 10$ Water
at 35° **********..... *..........*.............. ..*.*.. 1U6
UO. Solvolysis of 0.005625 Molar Di-( 2-metbylcyclopropyl)isopropylcarbinyl p-Nitrobenzoate in 80$ Dioxane - 20$ Water
at rC.........

Ht7

Ul. Solvolysis of 0*006059 Molar Bi-(2-m®thylcyclopropyl)isopropyicarbinyl p-Nitrobenzoate in 80$ Dioxane - 20$ Water
at 7 C
..... .......... *******........

Di8

x

LIST OF TABLES * Continued
TABLE

Pag©

U2. Solvolysis of O *008950 Molar Biisopropylcyclopropylcarbinyl
p-Nitrobenzoate in 90$ Dioxane * 10$ better at 60

1L9

h3* Solvolysis of 0*00931? Molar Diisopropyleyclopropylcarbinyl
p-Nitrobenzoate in 90$ Dioxane - 10% Water at 6tir ********** 150
U a, Solvolysis of 0.0102U Molar Dii©opropylcyclopropylcarbinyl
p-Nitrobenzoat@ in 85$ Dioxane * 15$ Water at 60° ********** 151

kS* Solvolysis of 0*008655 Molar Diisopropylcyclopropylcarbiriyl
p-Nltrobenzoate in 85$ Dioxane - 15$ Water at 60° ********** 152
L6* Solvolysis of 0 *0092^2 Molar Diisopropylcyclopropylcarbinyl
p-Nitrobenzoat© in 85$ Dioxane * 15$ Water at 70® **t**»•••• 153
U7* Solvolysis of 0*01096 Molar Diisopropylcyclopropylcarbinyl
p-Nltrobengoat® in 85$ Dioxane - 15$ Water at 70® *.***.♦.*. 15L
L8* Solvolysis of 0*008783 Molar Dilsopropylcyclopropylcarbinyl
p-Nitrobenzoate in 85$ Dioxane «* 15$ Water at 80® ********** 155
U9* Solvolysis of 0.008L82 Molar Diisopropyloyclopropylcarbinyl
p-Nitrobenzoate in 85$ Dioxane - 15$ Water at 80 ****•««**• 156
50* Solvolysis of 0*007015 Molar Biisopropylcyelapropylcarbinyl
p-Nitrobenzoate in 8Q$ Dioxane - 20$ Water at 60®G..***.,**. 15?
51* Solvolysis of 0*006933 Molar Diisopropylcyclopropylcarbinyl
p-Nitrobenzoate in 80$ Dioxane - 20$ Water at 60°G*********, 158
52* Solvolysis of 0*007.637 Molar Diisopropylcyclopropylcarbinyl
p-Nitrobenzoate in 80$ Dioxane - 20$ Water at 60®G.,******•* 159
53* Solvolysis of 0.0119k Molar Diisopropylcyclopropylcarbinyl
p-Nitrobenzoate in 80$ Dioxane - 20$ Water at 6QG********** 160
5iu Solvolysis of 0*009i±8l Molar Diisopropylcyclopropylcarbinyl
p-Nitrobenzoate in 80$ Dioxane - 20$ Water at 60°0*.******** 161
55* Solvolysis of 0*01123 Molar Diisopropylcyclopropylcarbinyl
p-Nitrobenzoate in 80$ Dioxane - 20$ Water at 60°C«»•**«**• 162
56. Solvolysis of 0*00U06? Molar Diisopropylcyclopropylcarbinyl
p-Nitrobenzoate in 80$ Dioxane - 20$ Water at 60 0*,.******* 163

xi

|»31f GF t iM M * Gonitnned
Fage

57. Solvolysis of 0*00579 Molar DliBopro^lc^loprowlcfiUJ'bifiyl
p"»Mibr©b©n»o&t® in 60% Moseane - 205 Water at 60 Ce^ f#MrM
5®. Solvolysiis of G*OOB570 Molar Biisop-opsrXejrolopropyXaa^iiajrl
p-Wtirobe&ao&t© in 805 Dioxim® - 205 Ifeter at 7CP0 •*•■««♦##**
59. Solvolysis of 0,.008626 Molar Mi«opi?o|^leyol0|^wlea3^iB3rl
p-^ltr€%«s3soat« in 805 M m s m ~ 20% witter at
166
60* Solvolysis of 0*01015 I^lia?•Mlsopropyl^
P-Hitapofe^ooat® |n 805 W$m#m m 20$ Water at IlCFO**.«**#«*** 16?
61# Solvolysis of 0*0115$ Molar Biisopropylt^lopi^pyloarfoiByl
p~Hitrobeassoate in Bo% Dioxane «* 205 *fet©r at 80%* **#.**«.** 163
62* Solvolysis of 0,008986 Molar Biioopropyloyoloi^oijrloarbii^l
jHKttrsbenaeat® in 70% Dioxane * 30% Water at hO^C,##««***#* 169
63# Solvolysis of 0,009^35 Molar Diisopropyleyelopropylcarbinyl
p^Kitrobanaoato in 70% Dioxane *> 30% Water at Jt0*O«««**•+«»♦ 170
6U. Solvolysis of 0,008528 Molar MisoproKfleyclopropyloarbinyl
p^Sitrobenssoata $m 10% Dioxane *■ 30% "Water at 50®$****#***** 171

65. Solvolysis of 0*0G®9l# Molar Diisoproi^loyolopropyloarbinyl
p-Mitrobonsoate in 705 Dioxane » 30% WkUfc at 5G®0.,*#.*,*«. 172
66. Solvolysis of 0*009296 Molar Jllisopi^pyloyelopropyloarbiinyl
p-Hitrobensoata in 70% Dimsan® ** 305 Water 0 ,0091*10 Mortml .
in Sodium Hydroxide at 5C5*0**********************.*♦...*•*<
6?* Solvolysis of 0*009068 Molar Diiaopropyloycloproiorlearbinyl
p-Kitrobenaoai© in 705 Dioxane »- 3©5 tfittsr G.009&1G Hormal

in Sodium Hydroxide at

****•*.**#**•*•***•*«

63. Solvolysis of 0*008832 Molar Diisopropyloyclopropylcarbii^rl
p^iirobenao&te in 705 Dioxane ** 305 Water at 60®C.*.».***.# 175
69 m Solvolysis of 0.009320 Molar Diisopropylcycloproprlearbinyl
. p^Hitrobensoate in 70% Dioxane * 305 Wbier at 60%*.***#*.*. 176

70* Solvolysis of 0*006235 Molar Bicyc3opropylcarbinyl p~Wltro~
bensoate in 855 Bi®x«ne * 155 Water at 8
Q
°
a
*
177
71* Solvolysis of 0.006897 Molar Dicyclopropyloarbinyl p*Mitro*
benaoat® in 855 Dioxane <* 155 Water at 80 C,.**,# * . * . . 17®

LIST OF TiBUES * ConfeUwed
fBU

Page

72, S olvolysis e f 0*007173 M olar BioyolopropsrlaarbiByl p -H itro bM ooat* to 8QJ* Sloxana » 205* Water a t 6 C r < S * « « » » . . . > , . 179

73. S olvolyato o f 0.009806 M alar D ic js lo p r\w L o « *b to y l p r flitr a banaoata to 8qj{ D toM tn, - 20J* W tter a t 60°C3* , *•■■#*»■*«, a. «»* w«
7b* Solvolysis of 0.000038 Molar Mcyolopropyle&rbinyl jMBitro-*
benzoate in 80$ Manana ** 205 Hater at 1#$.

101

75* Solvolysis of 0,0073141 Molar I^G^lopropy-learbtnyl p-Hiiro*benzoate in BO$ Dioxane * 200 Hater at 70 0* .#*#•**a*****'V** 182

,benzoate in

76 Solvolysis of O.OI063 Molar Bicyclopropylcarbinyl p~Mtro~
805 Dioxane** 205 W&tar at 80*

I83

77. Solvolysis of G.007900 Molar BieyoloproiyXcarblnyl p-Witro~
benzoate in 80% Dioxane «* 2G$ W&ter at §0%.****#***.*..**** X8I*

78* Solvolysis of 0*G08ii72 Molar Triisopropy3.oarbinyl p^Witr©*
benzoate in 80$ Dioxane - 205 Water at
79* Solvolysis of 0,01056 Molar triisopropylcarbinyl p-Nitrobenzoate in 805 Dioxane <* 20$ Water at 60 0 . , 1 8

6

80. Solvolysis of 0*0Q9SU6 Molar frtisopropyloarbinyl p-Hitrobenzosi® in 805 Dioxane * 20% Hater at 70 0..*. *•«#.«„***■*»*. 18?
81. Solvolysis of 0*01099 Molar triisopropsrlcarbinyl p-Nitrobenaoata in 805 Diim m * * 205 water at 70°G*..*....

188

82. Solvolysis of 0.00033® Molar friisopropylcarbinyl p~Nitrobenzoate in 805 Dioxane - 20$ Water at 80°G
83. Solvolysis of 0*01020 Molar Triisopropylcarbinyl p-Nitro~
benzoate in 805 Dioxane ** 205 Water at 8 0 ° G . . ..... 190
8b* Solvolysis of 0*009809 Molar Triisopropyloarbinyl p^Mitro-*
benzoate in 70$ Dioxane * 305 Hsiter at 60 0*..**•*»*.*.**.*. 191
85. Solvolysis of 0,008576 Molar friisopropylcarbinyl p*Hitro~
benzoate in 70$ Dioxane - 305 Water at 60°G......

192

86. Solvolysis ©f 0.007870 Molar ’Triisoprcpyleaibij^rl p~S?itrc~
benzoate in 705 Dioxane * 30$ Hater at ? 0 ° C , .

193

rH*

U8T m

t m M

~

Ctontimed

TABU

Pag©

8?# Solvolyeia ©f 0.008670 Molar Triiaopropylearbingrl p**Nttrobensso&te in 10% Moxan© - $0% Water at 7Q°C*.*..*.....*..** 19k
88. SolTolysta of 0*007985 Molar Triioopropylcarbinyl p**$iiro~
benaoate in 10% Moxan© * 30% Watcar at 80°0...********.*.*♦» 195

89# Solvolyala of O*01079 Malar Triieopi^learMayl p*Hltro*
benaoat© in 10% Dloxaa© «* $0% Water at 8
0
°
C
.

ativ

196

him OF FIGURES
FIGURE

Page

1. Infrared Spectrum of Di~(2~m®thyleyclopropyl) ketone (neat)

7

2. Infrared Spectrum of Tricycloprppylcarbinol (neat)..*......

12

3. Infrared Spectrum of Dicyelopropylisopropylcarbinol (neat).

13

U* Infrared Spectrum of Diisopropyleyslopropylcarbinol (neat),

li*

5* Infrared Spectrum of D±~( 2~methylcyeiopropyl)isoprQpyl**
carbinol (neat)..............................*..........,..

15

6. Infrared Spectrum of Dicyclopropylisopropylcarbinyl p-Nitrobenzoate (mineral oil m
u
l
l
)
18
7* Infrared Spectrum of Diisopropylcyclopropylcarbinyl p-Nitrobenzoate (mineral oil m u l l ) . . . . .......... 19
8. Infrared Spectrum of Triisopropylearbinyl p-Nitrobenzoate
(mineral oil mull)........*.**.,..........♦*..*............

20

9. Infrared Spectrum of Di'*(2-m@thylcyclopropyl)isopropylcarbinyl p-Nitrobenzoate (mineral oil mall).........*....*.

21

10. Infrared Spectrum of Dicyclopropylc&rbinyl p-Nitrobenzoate
(mull in mineral o i l ) . . * . . ............

22

11. Infrared Spectrum of 1 *1-Dicyclopropyl-U-chloro-l-butene
(neat)..
...................................

21

12* Plot of log (?f » V) versus t for the Solvolysis of
0.009720 Molar Dicyclopropylisopropylcarbinyl p-Nitrobenzoate in 80$ Dioxane - 20$ Water........................

5U

13. Plot of log (V- * 7) versus tfor the Solvolysis of
0*01158 Molar Diisopropylcyclopropylcarbinyl p-Nitrobenzoate in 80$ Dioxane - 20$ Water................. ....

55

11,t, Plot of log (7^* * 7) versus t for the Solvolysis of
0.01158 Molar Diisopropylcyclopropylcarbinyl p-Nitro­
benzoate in 80$ Dioxane - 20$ Water*.
....

56

xv

tIST OF FIGURES - Continued
FIGURE

Pag©

15. Plot of log (vf - V V^/Vj.*) versus t for the Solvolysis of
0 *02158 Molar Biisopropylcyclopropylcarbiiyl p-Nitrobenzoate in 80$ Dioxane * 20$ Water.**♦,..♦***•♦*•#.*«****»

$9

16. Infrared Spectrum of 1,1-Dicyclopropyl-l-astho:xy~2-methylpropane (neat)......
.....**.*..*.***

69

17. Infrared Spectrum of U-Isopropyl-5-methyl~3-heotenyl -p-Nitrobenzoate (mineral oil mull).....,...***........*.........,* 71
18. Infrared Spectrum of 3~Ctyclopropyl~3~methGxy~2,U-dimotiiyl.........
pentane (neat).

73

19. Infrared Spectrum of h-Isopropyl-5-m@thyl~3-hexanol (neat).

76

20. Molecular Orbital Structure for Cyclopropane*.*............ 102
21. Molecular Orbital Structure for Cyclopropylearbinyl
Carbonium Ion*

102

22. Plot of log k versus l/T for the Solvolysis of Dicyclopropylisopropylcarbinyl p-Nitrobenzoate in 90$ Dioxane 10$ Water..*......*....*.....

197

23* Plot of log k versus l/T for the Solvolysis of Dicyclopropylisopropylearbinyl p-Nitrobenzoate in 80$ Dioxane 20$ Water.......

198

2I4.* Plot of log k versus l/T for the Solvolysis of Di-(2~raethyleyclopropyl)isopropylcarbinyl p-Nitrobenzoate in 90$
Dioxane - 10$ Water.,
.....
199
25. Plot of log ks versus l/T for the Solvolysis of Di-(2methyleyclopropyl) isopropylcarbinyl p-Nitrobenzoats in 90$
Dioxane - 10$ Water...*.......

200

26. Plot of log kr versus l A for the Rearrangement of Di(2-methylcyclopropyl) isopropylcarbinyl p-Nitrobenzoate in
90$ Dioxane - 10$ Water.
....

201

27. Plot of log k versus l/T for the Solvolysis of Diisopropyl­
cyclopropylcarbinyl p-Nitrobenzoat© in 85$ Dioxane - 15$
W
a
t
e
r
.
.
.
.
.
.
................ 202

xvi

H i t OP FIGURES - Continued
FIGURE

Page

28* Plot of log ke versus l/T for tho Solvolysis of Biloo-*
p^opyloyol^ogyloiurbljaarl p-Hitrobensoate in %$% Dioxanet9+ Plot of log kp vermis l / f for the Rearrangement of Blleo"
propylcyclopropyleafhi^rl -p-Niirobensoat® in B$$ Moxane%$$ Water....***********.***..**,*******....*.**,*..*.*.*. 201*
'

i

\

r >=
•»

30* Flot of log k versus l/T for the Solvolysis of Diiso**
propyloyolopropylcarbioyl p-Mtrobeuaoate in 80^'Dioxane *
. t< #
203
•

'j 5 I ‘

: i l

31* Flot of log k0 versus l/p for the Solvolysis of Biise*
.XjropyleyolopropylearbiiQrl p-Hitroben&oai© in 80# Dioxane 20# Water.****.*.*.*******♦***********,*****...*****,**,...**** 206
32* Plot of log
versus 1 /f for the Rearrangement of Diisopropylcyclopropylcarbinyl p-Jfitrdbenaoate tn8<3# Bieacan© *
20*
**************** 20?
33* Plot of log k versus 1/f for the Solvolysis of Diisopropyloycloproj^lcarbinyl p^Kitrobenaoate in 70# Dioxane30# Water***************^.*,»*************«*'«***•***«*»'**.**« 208
3k* Flot of log ks versus 1/f for the Solvolysis of Dlisopropylcyelopropylcarbinyl p-Mitrofeensoate in 70# Dioxane *
30# miter.***,*,* . * * * * , * * * * * . * * * . . * * * * * . .

209

y~>. plot of log kr versus l/T for the Rearrangement of Diiso-

propylcyclopropyloarMi3yl p^Hitrobenaoate in 70$ Dioxane30# miter*»«**.♦***.**,,**«,*» +****.************************ 210

36* Flot of log k versus l/f for the Solvolysis of Bicycle**
propylcarbinyl p-Nitrobenssoat® in 80# Dioxane - 20# Water*. 211
37* Flot of log k versus l/T for the Solvolysis of Triisopropylcarbinyl p~Hitrob©nz©ate in 80# Dioxane - 20# Water*. 212
38* Flot of log k versus l / f for the Solvolysis of Triiso-

propylcarbinyi p-Nltrobenaoat® in 70# Dioxane - 30# Water** 213

xvii

maoDffcitiOH

1

introduction

Chemical evidence supports the contention that the cyclopropyl
group shows characteristics of unsaturation (1,2).

For example,

cyclopropane and its derivatives readily undergo addition reactions
with halogens (3) and hydrogen halides (U). In general, addition
reactions of cyclopropane derivatives occur more slowly than corresponds
ing reactions of similarly substituted alkenes (2)*
Extensive studies of physical properties, such as absorption
spectra and dipole moments, also demonstrate that the cyclopropane ring
is unsaturated in the sense that electrons are available to conjugate
with an adjacent unsaturated group (5)*

In these studies, the degree

with which cyclopropyl groups interact with unsaturated groups is
intermediate between the activity shown by a saturated group and a
vinyl group (5,6)*
The type of chemical and physical behavior discussed above indi­
cates that the degree of unsaturation of cyclopropyl groups is somewhat
less than that of the alkene linkage*

On this basis, it would be

expected that the reactivity of the eyelopropylcarbinyl system (H)
would be intermediate between that of the corresponding saturated
system (I) and the highly reactive allylic (vinylcarbinyl) system (HI)*
R-CH2-GHa-CH3-X

I

H

CHg-X

II

H-CH-CH-CHS-X

HI

the enhanced chemical reactivity of the allylic system toward
displacement reactions Is ascribed to the delocalization of the pi
electrons of the double bond in the transition state*

For example, a

unimoleoular displacement in H I is facilitated by resonance contribu­
tions from structures such as IVa and IFb, which may be summarized
as I7c.

♦

+

R~CH*CH~CH2 X

X~

IVa

IVb
4*
[R~GH-GH-CHb]

—
X

IVe
In a similar manner, the reactivity of cyelopropylcarbinyl systems
in unimoleoular displacement reactions should b© enhanced by contributing
structures such as Va, Vfo and Vc which m y be summarized as Vd and Vej
but judging from dipole moment and spectral data ($,6) such stabili­
zation should be less important than in allylic systems*

3

Although cyclopropyloarbinyl systems have not been extensively
investigated, wii&t information is available shows that this system Is
unusually reactive.

Thus, the ethanolysis of eyelopropylearbinyl

benzenesulfonat© (Via) at 20° was 11 times as rapid as that of allyl
benzenesulfonate (Vila) and 1000 times as reactive as allylcarbinyl
benzenesulfonat© (VIII) (7).

CH^CH-CH8*-X

VIb,

&*C1

Vic,

X-Br

VTXb,

X»Br

CH3
GH3**GH~GHa~GHa~0~SGa<

CHa*0~G%*Cl

VIII
The rate of solvolysis of eyclopropylearbinyl chloride (VIb) in aqueous
ethanol was kO times faster than J3 -methylallyl chloride (IX) and cyclopropylcarbinyl bromide (Vie) solvolyzed 26 times faster than allyl
bromide (VUb) (8).
Polycyclic systems which contain a three-membered ring also show
remarkable reactivity in solvolytic reactions.

In aqueous dioxane,

the rat© of hydrolysis of 3 ,5-cycloeholestan~6~yl chloride (Xa) is about
10® times as rapid as cholesteryl chloride (XIa) (9a,10).

Solvolysis

of 3,fj-cyclocholestan-^-yl trichloroacetate (Xb) yields cholesteryl

k

triehloroacetate (Xlb) as one mi the product* (IX). Furthermore, Xb
aelvolyse* with alkyl*oxygen fission, whereas XXb solvolyae* with
a«^l*©5Kygea fission*

Xa,

XmOl

Xb, X«*0013COO

X Ia ,

X*G1

Xlb, X*GClaGQG

The remarkable reactivity of the cyelopropylearbinyl system
certainly cannot be explained by considering the cyclopropyl group a
simple but less polarissabls analog of the vinyl group*
It was the purpose of the present investigation to obtain more
information concerning the role of the cyclopropyl group in solvolysis
reaction®• la order to do this, compounds containing the cyclopropyl*
earbinyl system, especially those containing several cyclopropyl
group*, «we «y»theai*«d. Tha solvolysia ratss of these compounds Here
then studied in detail*
The synthetic methods will be discussed first, followed by an
experimental section containing details of the syntheses, the kinetic
procedure and the structure proof for the solvolysis products*

5

The methods for calculating rate constants, a suimsary of the values
obtained, end a discussion of the solvolysis products follows In a
section on result**

the detailed kinetic data is presented in an

Appendix* Following the section m results, the present solvolysis
data are discussed in terms of current concepts of uniiaolecular
eolvoiyse#, and the role of the cyclopropyl group in solvolysis
reactions is examined in detail*

BXSOUgSXQH OF OTSTH1XXG FBO0OTIBSS

6

DXSCUSSIOK OF THE SYNTHETIC PROCEDURES
A route to secondary and tertiary alcohols containing one or more
cyclopropyl groups on the alcoholic carbon atom m s desired, Tor these
alcohols could then be converted to derivative® whose solvolysis
behavior might be studied*

Important intermediates in making these

alcohols would be aldehydes or ketones containing cyclopropyl groups,
and/or a eyelopropylorganometallic compound.
Bicyclopropyl ketone (la), which afforded an entry, via reaction
with organometallics, to polycyelopropylated alcohols, has recently
been made readily available (12)*

The procedure has been modified in

the present work, so that it is not necessary to Isolate any inters
mediates (13)#

The over-all yield from Y -butyrolactone is about 60$.

The homologous ketone, d±-(2-melhyicyclopropyl) ketone (lb) was prepared
by an analogous method*

,0

G
CHa -

HaOCH3

GHa - Cv=

I

/0

CHS - GH

B

I
Jft

R
HG1

*
E-CH-GHg-GHjrG-CHa-CHsj-CH-R

la,

R~H

lb,

H»CH3

The infrared spectrum of lb appears in Figure 1

r*I

H
r (

O
r -J

oj
c
>
<D
O
*3*
O

O
&
r-'l

VO

4it
.3?
'?
C'J
•r-t
n
Vf
o
R
F
v>t
o
o
P-,
0>
V&?
j-3
r*

t—3
a
r-j

O
Q
VO
-3uQfss^uiSin^^ q.uOQ jo,^

o

&
i't

8

k readily available

cyclopropylorganometallic would greatly

facilitate the synthesis of compounds containing the cyclopropyl group.
It had been reported that cyclopropyl bromide reacted readily with
magnesium, whereas the chloride reacted only very slowly and income
pletely (lit). The only method found in the literature for the prepara­
tion of cyclopropyl bromide involved bromination of silver cyclopropanecarboxylate at -70° in a Freon solvent (11*), This method is
tedious and limited to small quantities because of the explosiveness of
the bromine-silver salt complex. Cyclopropyl chloride, on the other
hand, was more easily obtained by a method suitable to preparation in
quantity*

The procedure described by Roberts (15), involving the vapor

phase photochemical chlorination of cyclopropane, was used,
Because of the uare&etivity of cyclopropyl chloride, the preparation
and use of cyclopropylmagnesium chloride did not appear practical.

There

was, however, some reason to believe that cyclopropyl chloride would
react more readily and more completely with lithium than with magnesium*
It had been reported that cyclopropyl chloride reacted with an
ether suspension of lithium so vigorously that external cooling with
dry ice was necessary to contain the mixture (16).

The major product

was cyclopropane, 32% of the chloride being reduced during the reaction
and an additional 10$ of cyclopropane being formed on hydrolysis*
Other products were recovered chloride (21$), dieyelopropyl (10-12$),
olefins, acetylenes and tar*

It seemed likely that eyelopropyllithium

was an intermediate in the formation of certain of these products, but

9

its presence was not established.

It was also reported that no reaction

occurred between cyclopropyl chloride and lithium in methylcyclohexane *
Synthesis of eyelopropyllithium by the normal method for preparing
organolithium compounds was not considered practical.

Ether could not

be used as solvent because secondary and tertiary organoHthiuffis cleave
ether at ordinary temperatures« Although some secondary and tertiary
orgsnolithiums have bean prepared In ether at low temperatures (-70 to
-40 ) (17 #18)* this was not considered feasible for the relatively
unreaetiv© cyclopropyl chloride.

However* low boiling hydrocarbon

solvent® such as petroleum ether have been used to prepare lithium alkyls
(19).

This suggested the us® of pentane as a solvent.

In order to

speed up what was anticipated would be a sluggish reaction# lithium in
a high state of subdivision was used,
When cyclopropyl chloride and finely powdered lithium metal were
refluxed in pentane under a helium atmosphere, the lithium was consumed
and replaced by a suspension of cyclopropyllithium and lithium chloride.
The structure was proved by carbonation to cyclopropanecarboxylic
acid (H)# identified by its physical properties and infrared spectrum.
Helium m s used in place of nitrogen because lithium forms the nitride
when exposed to nitrogen, ©specially warn nitrogen (20).

It was feared

that with finely divided lithium, this problem might be even more than
ordinarily serious, although no critical experiments bearing on this
point were performed.

C00H

n

10

G^lopropyllithtum could net b© Induced to react with ethylene, Pierces
under similar condition© tbe addition of IsopropyllithiUBi to ethylene,
followed by earbenation, gave isooaproie acid (HI), identified by its
physical properties and infrared apeetrm*
GH*
GH-11 *

0 % a CH#
gh 3

(X) coa
(2) if

v

<3Ha

OH-CHa#GEa«COO!

t it

No dilsoajayl ketone (IV) was isolated (18)
CH*

0

ghr

By treatment of either cyclopropyllithium or isopropyllithiura
with the appropriate ketone, the following carbinols were synthesized
in good yield*

trieyelopropylearbinol (V), dlcyclopropylisopropyl-

carbine! (VI), dlloopropylcyclopropylcarbinol (?H), triisopropylcarbinol
(VIII), and di-(2-meihylcyolopropyl) isopropylcarbinol (XX)#

11

V

ch3

CH,
OH

m

C

OH

OH

CH.

GH
GH.

CHV

vn

T1

gh 3

CH
GHS

C

CH,
OH

CH

ch

CH

chs

\/
CH

CHa

/\
3

ch 3

CH

C—

OH

GH.
ch3

GH.

vm

IX

The Infrared spectra of the pure carbinols V, VI, VII and IX
appear in Figures g, 3, U e**d £*
the lithium salt of each of the carbinols VI, V H , V U I and IX was
treated with p~nitrobenzoyl chloride to yield the crystalline p-nitrobenzoates X, XI, X H and X H I respectively* The last of these decomposed
to a yellow liquid when allowed to stand, and was quite sensitive to
moisture*

j~i

a

e-i

i—5

XlOTGS-JIiSTmS^ Q,TX©0 *5®^

12

13

o
H

-t-i

i
a
r—3

o
rt

•r*

iJ
©
r-S
■— )

P
i
o
'w
M
&
O
Pi
ro
-4
O
&
«p>3
«
o
a
8
■Qp1
©
mPi
©
rf
f
-4
t-J
f3
»*
©
QC1

O

o
w
ttOTsefcrsxnjJc^

•H
(*«

vo

O

-2F

Q

uo^sepisTisja ^ ^ 0 je<E

o

Infrared Spectrum of DiisopropylcyolopropylcarMjaol

VO

21iourc

to

(neat)

I

—I

v0

oo
t

o

uofBSfcrsxr^J^ 3-u30 &°«t

Infrared Spectrun of Si-.(2-ciethjdcyclopropyl)isoproi^/lcarbi2iol

to *ri

Figure 5*

(neat)

O
r~i

p^niirobeiasse&te (3OT) m e obtained from
and p-^itrobanssoie mid in the j*r©«@nee of femiae*
aaXfoajrl ©bloride in pgrrldiae eolation, using a proeoduro patterned
after Broeater (2*L)«

17

The infrared spectra of mineral oil mulls of these esters appear
in Figures 6, 7* 8, 9, and. 3D.
Attempts to prepare trIcyclopropylcarbinyl p-nitrobensoate from
the lithium salt of tricyelopropylcarbinol and p-n±trobenzoyl chloride
or p-nitrobenasoic anhydride were unsuccessful*

Treatment of the

potassium salt of tricyclopropylcarbinol with p~nitrobenzoyl chloride
did not yield the desired ester*

The method used for the preparation

of dicyclopropylcarbinyl p-nitrobenzoate also failed when applied to
tricyclopropylcarbinol*

The reasons for the failure to synthesis©

tricyclopropylcarbinyl p-nitrobenfcoate will be more profitably discussed
in a subsequent portion of this dissertation.
The product obtained from the reaction of the lithium salt of tricyclopropylcarbinol with p~nitrobenzoyl chloride -was 1,1-dicyclopropylH~chXoro-l~buten© (XV), identical with the product formed when tri­
cyclopropylcarbinol was treated with concentrated hydrochloric acid*

18

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Figure 8 , Infrared Spectrqm of friieopropylcarbinyl p-Kitro'benzo&te (mineral oil moll).

to

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noTGGtuiBimaj q,ti©o <XQ~

figure 9.

o

Infrared Spectrum of Di-(2-4aetbylcyciopr&p^l)isopropsrlcarl)inyl p-Hitrobenzoate (mineral oil mull).

tfavelgngth in Microns

a\

23

fhs iftnstttV# &£ 1$X*di©yoloprepyl*j^efo3^^

m * proved

% r oxidation wltii potassium permanganate to <li^loppo^a ketone and
£ -ehloroprepionle eeid* Both products sere'identified by their infra­
red apectra*

C

OB

H5

35?

^KMnO*
11
**

0 « i 0 * HOOG-OHg-OBy-Gl

Furthermore, shea l#l-dicyoloprop3rl-U-ehloro-l-bnten© m s refluxad
uXth aqueous potassium carbonate, It sas reconverted to tricyoXopropyicaybinol* identified by its infrared spectrum* this reaction will
also be discussed in sore detail in a aubseipent section* the infrared
spectrum of 1,1-dl^clopropyl^-chloro-l-butene appears in Figure 11*

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25

SXFB&XMGBItAXi
A* Syntheses
Pic.Yclonropyl Ketone (13)

o

A 5*1* three-necked round-bottomed flask was equipped with a
Herabber® stirrer, a dropping funnel and a reflux condenser.

In this

flask 69 g* (3 g* atoms) of metallic sodium was dissolved in 900 ml.
absolute methanol.

Wien all the sodium had dissolved, the solution

was maintained at a gentle reflux and 516 g. (6 moles) of Y -butyrolactone (commercial grade) was added dropwis© with stirring over a
period of 30 minutes. The solution was refluxed for three hours, after
which time the flask was ©quipped for distillation and the methanol
removed in vacuo leaving a highly viscous residue« The flask was again
fitted with a reflux condenser and dropping funnel, and cooled in an
ice bath.

Before the viscous residue solidified, concentrated hydro­

chloric acid was cautiously added with vigorous stirring until the
mixture became more mobile.
increased.

At this time the rate of addition was

After 1200 ml. of hydrochloric acid had been added, the

mixture was refluxed with vigorous stirring for one hour.

The flask

was again cooled in an Ice bath and a solution of ?20 g* of sodium
hydroxide in 1 1* of water was cautiously added.

The mixture was then

26

refluxed with vigorous stirring for one hour,

the flask mas then

equipped for distillation and a water-ketone mixture mas distilled
until the strong characteristic odor of dicyclopropyl ketone was iso
longer detested in the distillate,

the arsons layer of the distillate

was saturated with potassium carbonate and the upper layer of dicyelopropyl ketone m s separated,

The aqueous layer warn extracted with

three 1CXM3U portions of ether,

The combined extracts and the ketone

layer were dried over anhydrous magnesium sulfate and distilled through
an efficient column* The yield of dicyelopropyl ketone, b,p* 56° at
as
lit m , , hp 1.U65U, was 200 g* (60?£), This preparation was equally
successful when 3 moles of commercial sodium methoxid© was used in
place of 3 g* atom of metallic sodium*
Alternatively, immediately after all the Y -buiyrolaetone had been
added, the methanol was removed by slow distillation at atmospheric
pressure and the last traces removed In vacuo. This variation shortened
th© time required for ike synthesis and did not affect the yield*

G%

0%

The procedure was essentially the same as that described in detail
for the preparation of dicyclopropyl ketone.

The best results were

obtained when the methanolic solution was refluxed for three hours and
the methanol removed by distillation in vacuo* From 600 g* (6 moles)

27

of Y -valerolactone (Eastman Kodak1s practical grad©) and 180 g. (3 moles ♦
$% inert

material) of commercial sodltua methoxlde (Matheson, Coleman

and Bell) in 900 ml. of methanol, there was obtained a 50% yield of (di(2-methylqyclopropyl) ketone, b.p. 66° at 7 mm.,
Anal. Calc*d. for G9HX40t
Found?

l.U600~l.b60lu

C, 78.21; H, 10.21

0, 78*08, ?8.11| H, 10,39, IQ.kk

(Analyses in this thesis were performed by either Clark Microanalytical Laboratory, Urbana, Illinois, Micro-Tech Laboratories, Skokie,
Illinois, or Spang Microanalytical Laboratory, Ann Arbor, Michigan)
The 2,U-dinitrophenylhydrazona was prepared (22) and after
recrystallization from 95% ethanol melted at 101*102°.
Anal. Calcfd* for C1sH1s N404j
Found?

C, 56.591 H, 5.70; N, 17,60

c , 56.88, 56*9h$ H, 5.56, 5.51; N, 17.1*9, 17.53

Finely Divided Lithium
A 1*1. three-necked flask equipped with a Lablin© Stir-O-Vac
high-speed stirrer (obtained from the Arthur S. LaPine Co., Chicago,
HI.), thermometer, condenser, and gas inlet tube, was charged with
1L g. (2 moles) of lithium and 100 ml* of mineral oil (previously
dried over sodium). The mineral oil was heated (helium atmosphere) to
230°, the source of heat m s removed and the molten lithium was whipped
into a fin© powder with the stirrer.

After the suspension had cooled,

the stirrer was stopped and a gas dispersion tube was inserted into
the flask so that the sintered glass portion touched the bottom of
the flask (the lithium particles float on top of the mineral oil).
The system was closed and a vacuum was applied to the open end of the
gas dispersion tube, th© mineral oil being collected in a trap.

The

lithium powder was then washed with several portions of n-pentane

28

(previously dried over sodium) * Although ve*y fine shiny particles of
lithium resulted, this method of removing the mineral oil m s somewhat
long and tedious. Alternatively, the lithium powder m s filtered with
suction through a sintered glass funnel, washed with pentane, and

poured, with psatsas rinses, into the reaction flask* Mien this opera*
tion was drnie rapidly, clean lithium particles were obtained.

^ > — 01

Cyclopropyl chloride m s prepared by the vapor phase photochemical
chlorination of cyclopropane,

The apparatus was essentially that of

Heberts and Birstine (15), except that the recycling system was eliminated,
the reaction chamber consisted of 250 cm* of 0*? cm*

Fyreac tubing bent

to form a planar grid which was illuminated by two Ken-Had RS sunlamps.
Gas flow of reactants was regulated to approximately 0*10 mole cyclo­
propane per minute and 0,033 mole chlorine per minute,

Th© unreacted

cyclopropane and the chlorinated products were caught in a cold trap
and the ©access cyclopropane was recovered and reeycllaed,

In a typical

preparation, there was obtained 500 g* (6*5 moles) of cyclopropyl
«
so
chloride, b«p. 1*3,5% Up
X.U080 from llu3 moles of cyclopropane con­
sumed,

a yield of \&$*

The reported physical properties of cyclopropyl
m.
SS
©hloride are b.p. U3*U3 , n^ 1.U079* The infra-red spectrum of the
product obtained was identical with the spectrum reported by Slabey (16)

29

for cyclopropyl chloride*

No attempt -was made to purify the higher

boiling polychlorinated products*
Igopropyllithimn
CH3

ch3

A 1-1* three-necked round-bottomed flask equipped with stirrer,
condenser, dropping funnel and gas inlet tub® was charged tinder an
atmosphere of helium with a suspension of powdered lithium (11* g.,
2 moles) in 300 ml* of pentane. Isopropyl chloride (78*5 g«, 1 mole)
in 100 ml* of pentane was slowly added with vigorous stirring over a
period of about two hours at a rat© sufficient to maintain reflux.
The mixture was refluxed with stirring for an additional hour.

An

approximate aeldimetric analysis of an aliquot indicated that about
0.6 moles

(6Q$) of isopropyllithium was present*

Cyclopropyllithiiun (23)

l>
A 1-1# three-necked round-bottomed flask ©quipped with high-speed
stirrer, condenser, dropping funnel and helium gas inlet tube was
charged with a suspension of powdered lithium (9*8 g*, l.U moles) in
300 ml. of pentane*

Cyclopropyl chloride (5h g.» 0.7 mole) was added

in one portion and the mixture m s refluxed with vigorous stirring for

30

ben hours, at which, time essentially all the lithium had reacted
resulting in a suspension of cycloproj^rllithium and lithium chloride.
Acidimetric analysis of the solution was not reliable because of the
low solubility of cyclopropyllithium in pent&ne.

The reaction between

oyelopropyl chloride and. lithium was, on occasion, hastened by adding
a few drops of ethyl bromide to help initiate the reaction,
'When carbon dioxide gas was passed into a solution of cyclopropyllithium at -70° and the resulting mixture acidified, cyclopropane*
carboxylio acid, identified by its infTa-red spectrum, was obtained.
No dicyclopropyl ketone was isolated,
Tricyclopropylcarbinol

OH

To a solution of cyolopropyllithium in pentane, prepared from
9.8 g, (l,h moles) of powdered lithium and %k g, (0.7 mole) of cyclopropyl chloride, m s slowly added a solution of dicyclopropyl ketone
(77 g*, 0.7 mole) in 30 ml. of pentane*
stirring for 8 hours.

The mixture was refluxed with

The flask was then cooled in an ice bath and

300 ml* of cold water was Slowly added.

The upper organic layer was

separated and the aqueous layer was extracted with three 70-mi. portions
of ether*

The extracts were combined with the organic layer and dried

over anhydrous magnesium sulfate.

After removal of the solvent, there

31

Hfci obtained 20 g# oi unchanged dicyclopropyl ketone and 7h g. of
^eywiopre^ylcMblnol, fc.p. 88.5° at 10 w»,# n^° 1.48*5, a*6 1.4802.
the yield u&s 70$ based on the amount of cyelopropyl chloride need or
9U$ based on the amount of ketone consumed*
ifta l -

Gale*A* for CloH10Oi
Found*

St 78*89) H# 30*59

0f fS.S*# 76-60) H, I0*k9* 10*65

tfsing procedures analogous to that described for the preparation
of trf<^lopropylearb±ml, the oarbinols in fable 1* sere prepared from
the indicated ketone® and organorastallic®♦ the physical properties,
yields and analyse® of the earbinols are given in fable 2*

;oh
W r,

the lithium salt of dlcyoloproiiyliBopropylcarbinol m e prepared
in p m t a m m l r m t m pr&rims&sr described from 26 gm (h g* atoms) of
lithium* IS? g* {2 moles) of iaopropyl chloride, and 220 g. (2 moles)
of dicyoloprepyl ketone, the flask sas cooled in an ice^salt bath and
a solution of p^nltrobeiusoyl chloride (223 g*» 1-2 moles) In 1800 ml,
of dry ethyl ether m e slomiy added, and the temperature maintained

32

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33

3h

between

and 0°,

The flask was farced In lee and allowed to stand

Kith Stirring for eight hoars*

The mixta*© was filtered and the

precipitate extracted with hot ligroin <b«p» 66-75°),

The extracts

were eoa&ined with the filtrate which was evaporated in vacuo. The
residue, which contained unre&eied. ketone and dtcyGlopropyltsopropyXcarbine! as sell as

hb®

yielding 80 g* (22$) of

ester*, wastaken op in ligroin and reciyetallized
the ester*Small amounts of p-nitrobeasoie

acid ware r m w e d bar stirring a m m ligroin solution of the ester
activated, almaina*
from ligroin*

The ester was then recrystallised several tines

There was obtained 66 g* of dicycloproi^lisopropyl-

earbiayl p^nltrohenaoate, m.p, 111**115° with decomposition*
Anal*

GaleM* for

G, 67*3Gf H* 6*$>8f H* 1**62

foundt C, 67,271 H, 6.8l| H, iul*9>

Going procedures analogous to that described for the preparation
of dicyclopropylisopropylcarbijisrl p-nitrohenaoate, the p-nitrobanzoates
of several of the tertiary oafblnols listed in fable 2 were prepared.
The p-nitrdhensciate of the secondary alcohol cSioyclopropyloarbinol was
also prepared, by a procedure described below.

The esters were

recrystallised from petroleum ether (b,p* 30*60°) or from ligroin
(b,p. 66-75°),

Grystalliz&tion was sometimes induced by cooling the

solution in crushed dry Ice.
given in Table 3*

Halting points, yields and analyses are

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36

tbs method is essentially that described by iraimter and Ciotti
(H), |te|*eitrc^033soie acid (16*? g *, 0*1 mole) was dissolved in 800
ml* of warm pyridine* The solution was ©eeXad and bemenemOfoi^X
ehXerida (If*? g** ©*X mole) was added* The flask was eosled In an ice
bath m d <&cy&2x>pr®pyl$iirbiml (11*2 g.,,. 0*1 mole) (prepared by 0* S.
Curtis* Jr,) was added is on® p o rtio n ,

The mixture was kept at 0° for

tw© hours with frequent shaking* The solution m u poured into 1500 ml*
of a mixture of ±c© and water and was filtered immediately, yielding b
g, (15$) of ester*, The product was rsexysballised several times from
petroleum ether to yield white granular crystals of dicyclopropyl^
eaabinyl p^nitrobensoat©, m.p* 7b~?5°.

(a) From the lithium salt of tricycXopropylcarbinol end p^ultrobemBoyl chloride.
The procedure m u similar to that described in detail for the
preparation of dl<^lopropylisopro|3ylc^blnyl p-nitrobensoate. To the
lithium salt of tricyclopropylcarbinol prepared in pontons from
lithium (7 g»* X mol®)* cyclopropyl chloride (0,5 «©!©* 38*3 g*)* and

37

dicyclopropyl ketone (0.5 mole, 55 g.) at -70° was slowly added with
stirring a solution of p-nitrobenzoy! chloride (O.k mole, 75 g.) in
hOQ ml* of ether, the temperature being maintained between -70 and -60°.
The mixture was stirred for 2k hoars at -70°, and then filtered.

The

filtrate was evaporated in vacuo and the residue taken up in petroleum
ether and filtered.

The solid, which had m.p* 185-190° (lit. value

193° (21;)), was p-nitrobenzolc anhydride, identified by its infrared
spectrum.
Other experiments in which the p^nitrobenzoyl chloride was added
at the reflux temperature of pentane (twice), at 0° (twice), at -20°,
at -U0°, and at -70° (twice) all failed to give the desired ester.
The confined residues from four attempts to make the ester, in
which a total of 2.9 moles of cyclopropyl chloride had been used, were
distilled through a figreux column.

There was obtained about 60 ml. of

dicyclopropyl ketone, b.p. 56° at 16 mm., and 212 g, of a liquid boiling
from 90-98° at 5 mm*

This material was redistilled through an efficient
o
so
column in a nitrogen atmosphere, b.p. 82 at 3 sea.,
1.U998.
The infrared spectrum of the product had bands characteristic of

the carbon-carbon double bond (6.06p), the cyclopropyl carbon-hydrogen
bond (3.2Up), and the carbon-chlorine bond (13*75n). The compound was
subsequently shown to be l,l-dleyclopropyl-Ij.-chloro-l-butene, identical
with the product formed whan tricyclopropylcarbinol was treated with
concentrated hydrochloric acid.
Anal, Calc'd* for C10HlsCli
Foundt

0, 70.37J H, 8.86* 01, 20.77

G, 70*28, 70.3U H, 8*90, 8.8lj Cl, 20.86, 20.79

38

b) From the potassium salt of tricyclopropylc&rbinol end p—nitro—
benzoyl chloride*
A 1-1* three-necked round-bottomed flask ecjuipped with a high-speed
stirrer, condense, dropping funnel and gas inlet tube, was charged with
5*9 g* (0*15 mole) of potassium metal and 80 ml. of benzene*

The flask

was heated (nitrogen atmosphere) until the potassium melted*

The source

of heat was removed and the molten potassium was whipped into a fine
powder with the stirrer.

The potassium suspension was cooled to room

temperature and a solution of trieyelopropylearbinol (22*8 g., 0.15 mole)
in 60 ml. benzene was slowly added with vigorous stirring over a period
of one hour, during which time the temperature rose to 1*0°* After all
the carbinol had been added, practically all of the potassium had been
consumed and a clear yellow solution resulted.

The solution was refluxed

for 30 minutes to cause the last few particles of potassium which had
adhered to the sides of the flask to react*

A solution of p-nitrobenzoyl

chloride (29 g*, 0*15 mole) in 250 ml. of benzene was slowly added with
vigorous stirring while the temperature was maintained between 10° and
20°.

Stirring was continued for an additional five hours*

The mixture

was then filtered and the benzene was removed in vacuo. Ho ester could
be Isolated but p-nitrobenzoic acid and p-nitrobenzoio anhydride were
Identified by infra-red spectra.
c) From the lithium salt of trieyelopropylearbinol and p-nitro­
benzoic anhydride*
The lithium salt of trieyelopropylearbinol was prepared as previously
described from cyolopropyl chloride (38.3 g*» 0*5 mole), lithium (7 g*,

39

1 mole), and dioycXopropyl keton© ($$ g., 0.5 mole),

A suspension of

IS© g* <0,5 mole) of p^filtrobmaole isfcydride (21*) In 1*00 ml, of other
was slowly added with stirring and allowed to stand, with stirring, for
twelve hours,
in vaoup.
d)

The mixture mas filtered and the filtrate evaporated

Mo eater could b© obtained from the viscous residue,
%

the method of Brewster and Ciottl (21).

g a p ^ nitrobanaoio aoid (2.5 g*, 0,05 mole) was dissolved ia 50 ml*
of warm pyridine,

The solution was cooled and

(5*3 g*, 0*03 mole) was added,

The

benzenesulfonyi chloride

solution was cooled to 0° in an

ice bath and trieyelopropylearbinol (2,3 g,, 0.015 mole) was added.
The solution was stored at 0° with frequent shaking for four hours.
A fairly large amount of crystals had formed which was collected on a
filter and was reerystallised by dissolving in acetone and them adding
petroleum ether to precipitate the solid.

A sharp welting point could

not be obtained because of Wintering*, but the solid melted at around
ISO0 , The infra-red Spectrum (mull in mineral oil) was identical with
that of p~nitrobensoio anhydride*

The original filtrate was poured

into a mixture of Ice and water and was filtered yielding a small amount
of p~nitrobensoie acid, sup, 21*0° (lit. value 238° (25)).
The experiment was repeated with the same result®,

m another

experiment, 0,015 mole instead of 0.0J mole of benaenesulfonyl chloride
was used but only p-niirobensoic acid was isolated.

Structure proof of l^l«<iieyclonr©iffil*k^chloro^l^buten©j
oxidation with
tm .r r n T i •nmrw
i - r i w - : - - ...............
A mixture of 31,6 g, (0.2 mole) of potassium permanganate, hOO ml.
of water, and 1? g. (0.1 mole) of 1,l-^dicjrclopropyl-U-chloro-l-butene

UO

(obtained from the reaction of the lithium salt of tricyclopropyleazbinel idth p~»tirbbeasoyl chloride) m s $ U m d for tee hours at 0°
and for m

hour® at room tei^eratare*

filtrate extracted tuith fire

the mixture w * filtered and the

portions of ether*

The extracts

vers combined, dried ever anhydrous magnesium sulfate and the solvent
removed*

There remained k g* (UQ$) of c&cyclopropyl ketone, b*p* 65°

at IB sea*, the infrared spectrum of which m s identical with that of
authentic material*
The aqueous solution which remained .after the ether extraction m s
acidified with dilute hydrochloric acid aid extracted with five 7£Vial*
portions of ether * The eoa&ined extracts were dried over anhydrous
magnesium sulfate and the ether removed in. v^eno* The oil tditch remained
ms

up in ligroin (b*p* 66*75°), filtered while hot and then

cooled in crushed dry ice * The solid which separated m s collected on
a filter*

There was obtained 3 g* (30$) of $ -chloropropionic acid,

sup. 3$~39& (lit* value 39® (S5>)»

Its infrared spectrum m s identical

i&ih that of an authentic eanpl©*

A test tube containing 10 ml* of concentrated hydrochloric acid
m s cooled in an ice bath and $ g» (0.033 mole) of trieyelopropylearbinol
m s added* The test tub© m s shaken frequently over a period of 30
minutes, the temperature being maintained at 0°. The organic layer m s
separated and the aqueous layer extracted with three 5-sO. portions of
ether* the organic layer and the extracts wore combined and dried over

u.

anhydrous potassium carbonate. After the solvent was removed there was
obtained k*$ g* (30$) of l^l-dicyolopropyl-U^chloro-l-buten©, b.p.
l&g*425° at Ik m»** n^ X*h990# The infrared spectrum mas identical
with that of the l#l^eyolopro|^l-h^h3oro-l*bnt«ae obtained from the
reaction of the lithium salt of tricyoloprt^ylearbinol with p«*nitro~
bensoyl chloride*

l#l*Xacyclopropyl-l4*-chloro^l^butene (3k g», 0.2 mole) and 20© ml.
of 10# aqueous potassium carbonate solution mere refluxed with stirring
for

hours» After cooling, the organic layer mas separated and the

aqueous layer extracted with four £$*&&» portions of ether. The combined
organic layer and ether extracts were dried over anhydrous magnesium
sulfate. After the solvent was removed, there was obtained 2? g* (&?#)
of trieyelopropylearbinol, b.p. 71° at k mm., the infrared spectrum of
which was identical with that of authentic carbinol.

fh© procedure was simile to that used by Bartlett, Friedman and
Stiles (13). A solution of 0.3 mole of IsopropylHthium in 200 ml. of
pentana was cooled to -70° and U00 ml. of precooled ethyl ether was
added to the mixture. The helium source was removed and ethylene gas
was bubbled into the mixture over a period of six hours, the temperature
being maintained between ~7Q° and -60°. The mixture was then stirred
for two hours at -60°. Without allowing the tei^peratur© to rise above
*& q° 9 carbon dioxide gas was bubbled into the mixture for three hours

1*2

•ad the mixture was allowed t© stand ever night at *60° * the taraperature
m s then aliened to v ie * to 0° and JO© ml* of W hydrochloric acid was
slowly added* the organic phase m e separated and the aqueous layer
extracted with four 70~ial+ portions of ether which were coatoined with
the organic phase and extracted with $00 ml* of 28 sodium hydroxide.
Woe remaining ethereal solution m s dried over anhydrous aagaesium

selfate* the alkaline extract m s acidified with hydrochloric add and
the resulting organic phase m e separated* the aqueous phase m s
extracted ulth ether m d the ooisbined extracts and organic phase were
dried over magnesium Sulfate* After removal of the solvent there was
a

so

obtained 12 g« 05$) of iseeaproic acid* b*p* 9$ at 8 mm* ^
©

(literature values* b*p* 91~9% at 9 m *$

80

X*M1*3

1*1*114 (25))* The infra­

red spectrum m s identical with that of authentic isocaproic add*

The

ethereal solution which remained after the alkali extraction was dis­
tilled, but m ditmswrl ketone could be isolated (18)*
Attempts to bring about the addition of lscpropyllithium to ethylene
in pure psntane solvent were unsuccessful*
Th* AttWBPtta Aaaitloo of qyiqoproBymtWBB.tp gthylafra
the procedure was analogous to that described for the addition of
lscpropyllithium to ethylene* The only product isolated m s cycle*
propaneearboaylio acid* Ta another experiment, the ethylene m s passed
into the solution at -b©° instead of -60° but again the only substance
Isolated was cyclopropanecarboxylic acid, identified by its infrared
spectrum*

U3

B* Solvolysie Studies
isasgsg,
The dioxane used nap purified by Fieaer*e procadnre (26)*
Carbon dioxlde-fre® distilled water was employed for making up
solvent wtsctuyes and reagents*
Tbs methanol was purified by distillation over magnesium methoxide.
the kinetic studies and product analyses were carried eat In water*
dioxane solvents of several weight per cent compositions. Product analy*
ses for several kinetic conditions were also carried oat In methanoldioxane solvents of several weight per cent eoiBpositions *

the sodium hydroxide was made up in aqueous dioxane solution to
approximately 0*01 normal concentration and was standardized immediately
before each nan against Bureau of Standards benzoic acid in an aqueous
dioxane solution using phenalphthaXein indicator*

If a nan lasted

longer than one day, the base was standardized each day.
Ei^Lc fmiMtm

Approximately 0.01 molar solutions of ester were employed and the
reaction was followed by titrating the liberated p-nitrobenzoic acid
with standard sodium hydroxide* the reactions were conducted in a
constant temperature bath maintained at - 0.1° of the desired tempera­
ture.

kh

The aqueous dloxane solvent was equilibrated in the constant
tamperatora bath before each run was started, Appro:>dj»ate3y 0,001 mole
of the ester mas accurately weighed Into a dry 100 ml, volumetric flask,
At sere Mzae* 100 ml, of the equilibrated solvent was pipetted into the
flask containing the ester and the solution was thoroughly mixed. At
various time intervals, & 5*w&» aliquot was removed* quenched by freeslag In an ic©~oalt bath and inmediately titrated with the standard base
using ph«no2yhthalein as the indicator, tonally 10 to 15 points were
taken for each run and at least two m m were made for each set of
conditions«
Another method Involved the addition of cocoes* base in small lucre*
wants ***<1 recording the time at which the phenol

n indicator

changed color* This method was only used for a few m m and was abandoned
in favor of the aliquot method in which the end point© were easier to
observe* The two methods agreed when applied to the same compound under
the same conditions (compare the rate constants in Tables $6 and 5?
with those In Tables §0 to 55),
Tables containing the experimental results of the kinetic essperiiae»ts are given in the Appendix which appears at the ©nd of this thesis,
product Analysis
(a) Solvolysis of dicyclopropylisopropylcarbiryl p-nitrobenzo&te
in 80# d±oxane~20# water at 25°»
Dicyclopropylisopropylcfarbinyl p-nitrobenao&t© (12,U g,, O.GUOP
mole) was dissolved in 300 ml, of 80# d±oxane~20# water and maintained
at 25° for 1*8 hours. The solution was poured into TOO ml, of water,

us
alight^ alkaline ulth sodium hydroxide, ami extracted with eight
100*na* portions of petrolawm ether* The confined extracts were washed
with tea $QQ~ral. portions of water to remove diox&ne and were dried
m m

Brieriie* After the solvent was removed, there was obtained 6*0

g* (9$$) of dAeywS^c^Usepro^^

b*p* 6h° at k an*, a^5°

l*k61*!>* ■ (of* fable.
.2 )« The infrared epeetrum of the liquid m e
identical with that of authentic dleyolopropylieopr^^Xoarbinoli
la another experiment, 3*72 g* (0*0122 mole) of dicyelopropyX**
laopropylearbinyl p-*nitroben«oate m e dieaolved la 100 ml* of 80#
dioxana^&Q# water ami stored at 25° for six hours* The mixture wee
worked up m described above except that the liquid rmaining after
th© petroleum ether was removed was not distilled* An infrared spectrum
of the liquid (l*£h g*, §3# yield) was identical with that of authentic
c^cycJxiprcpyxxeopropyicarDxiiioj-*

b) Solvolysie of Bicyclopropy-lleopropylcaijbinyl p^nttrobeaaoat© in
80$ Bioxane«*20# Methanol at 2S° #
Th a preliminary experiment, 0.31*81 g* (O.QOlli*? mole) of the ester
m e weighed into a 100 ml, volumetric flask and brought up to volume
with 80# diQxan©~20$ methanol solvent* At various Intervals, a &*blU
aliquot was titrated with O«O0pl37H sodium hydroxide in 80# dloxane**
20# methanol* After 1? hours, the theoretical acid titer m s obtained
indicating that the solvolysis had gone to completion.
In another experiment, dicyelopropylisopropylcarbinyl p**nitrobenssote
(10.0 g*# 0*033 mole) was dissolved in 100 ml* of 80# dioxane-20#
methanol solvent and th© solution was maintained at 25° for 18 hours.

The •elation m * poured late 500 «&• of water, node slightly alkaline
i&Ah sodium hydroxide, end extracted with seven 100-ml. portions ©f
petroleum ether. The corabined extracts sure washed ulth eight 100-ml.
portion of water and dried ever Driertte* After th© solvent uas
removed there mm obtained 4*5 g* (815) of lfl'^c^lopre|^i^l^»©thoxy^
a^iethylpropaaa©, b.p. 61° at 4 mm*, aj^ 1.4566* Th© infrared spectrum
contained a w y intense ether hood (9*2u)* The region® characteristic
of hydroxyl absorption (2*?*3*tyx) and of carbon-carbon doable tend
sbsorpiien (5«SMU3n) were devoid of bunds.
■feiol. Oolo*!. for %*H*©0*

G, 78.51# H, 11*98

Found* 0, ?0*55# 78*44# S, 11498, 11*97
o) Solvolysis of ^ooproj^lc^lioi^p^lcoihinjrl p-nitrobeneoate in
705 Bicxane-lO# looter at 60° *
Mieoproprl^folopropyloofbihfl p-sdirobenaoat© (6J*t g*# 0.0210
mole) mm dissolved in 200 ml* of ?0# dloxam-3$5 eater and the solution
maintained at 60° for It hours* After cooling, the solution m s poured
into 3@0 a!. of water, made slightly alkaline ulth sodium Igrdrexid'* &&d
extracted with eight 7G-*nI. portions of petroleum ether. The eonfcined
extracts ear© washed ulth eight S00-mA. portiona of eater end dried over
Merits*

After the solvent teas removed, there remained 3*0 g. of a

liquid, the infra-red spectrum of which shewed a hydroxyl peak (2.85u)
and a ©arbosyl peak (5*B»)* live ml* of petroleum ether m e added and
the solution placed in crushed dry lee, whereupon crystallisation
occurred* The crystals (shout 50-100 mg.) which sere removed by fil­
tration, melted at 46-48°* The infra-red spectrum indicated that the

hi

substance was a p^nitrdbenaoai© bat distinctly different from the
starting eater* It m m wtomqpm&y *to&m to bo Mtsoprepg^^ethjO*
JM m b m v I ^aitrdbeasBoato.
The filtrate from which the solid nos separated mm distilled and
1*3 t*'(W) of dttsojatt^leycl^^^
^

b*p* 6o*6l0 at h m.,

l*k516, mm obtained. The li^aid mm identified through its infra*

rod Spestrnja*
d) Solvolyeis of Biieopro|)^e^lopr<^yle«rbii^rl pHnltrobeneoate
in Boiling 70# Bloxano*30f water*
MiSeppeps^^

p*nitr©bemsoate (0.2971 gty 0*000973

mole) was weighed into a 2£SQ-ml* roand^bottomed flask*. Sbcaotly 100 ml.
of 70# dlswaaMNdQ# water was pipetted into the flask at 25°* The flask
was fitted with a reflux condenser and th# eolation was reflnxsd for
26 hoars* The solution was cooled to 25° and several aliquots were
titrated ulth standard sodium hydroxide. Only 93*5# of the theoretical
add titer was oDsaxswsu
HL

d L i f j i h ^ k ja w

MMM A

it^Sliw«Sk

J

t

'

'

#) 3olv©lysis of diisoprcpsrlcyclopropylcarbinyl p-nltrdbensoate la
90# Moxane*10# ittiter at 6o°*
Misoin^o^lcyolopropylearbinarl p***nitrGb®moate (10*1*3 g*, 0*031*1
nolo) was dissolved in 250 sk* of 90# dioxane^lQ# water gad stored at
60° for 1*8 hews*

After cooling, the eolation was poured into on# liter

of water, wade slightly alkaline with sodium l^drcodLde, and extracted
with eight IflOwwflU portions of petroleum ether* The couhined extracts
wars washed With fourteen 50CMal» portions of water and dried over
Brierlte.

U8

Sh« drlad 8«0atlon m e concontrated to about 100 nl. and coolsd in
<an**h8d

lea to indae* crystallisation, Th« eolid wus colleetod on

* filter and there waa obtained 6.U g. <63)6) ©f h-ieoprojgrl-^mstbyl3~haoconjrl p-aitrobenaoate, m.p. US-IkB0,
CalcM. for C^B^O.*!

C, 66.86j H, f ,59# K# U.58

f«asd» C, 66.91, 67,0k* H, 7.30, ?»t2| H, U.b9, U.U5
The filtrate tram ahioh the eater had separated ana distilled,
b.p* 60° at h m,, and there m e obtained 0,7 g. (1350 of diiaopropylcyclopropylearfelaol, identified by its infrared epootrua,
f)

SolTolyalB of Xttiaopropj^^loproi^loarbinyl p-nitrobsnsoate

in Refluscing Methanol*
In. a p#mteMm&yr

a solution G.OQ9523 molar in eater

was prepared by dissolving 0*2908 g# of the ester in 100 ml* of anhydrous
methanol* The solution was refluxad for 10 hours, coolad and a 5-ml.
aliquot testa titrated with 0*009137$ sodium hydroxide In 60$ dioxane~
20$ methanol* The theoretical acid titer w s obtained indicating that
100$ solvolyeis had taken place*
Eu another experiment 6*57 g# (0*0215 mole) of the ester was dis­
solved in 300 ml* of anhydrous methanol and the solution was refluxed
for 12hours* Th® cooled solution was poured Into one liter of water
and made sli^itly alkaline ulth sodium hydroxide* The mixture use
extracted with eight 100-ml* portions of petroleum ether* The combined
extracts were washed with eight SOO-ml* portions of water and dried
over Drierite* After the solvit was removed, there was obtained 3*2 g*
(81$) of 3~cy©lopropyl-3-meth©xy~2^^dimethylpentane, b*p* 56° si U mm..

k9

1.U338*

The infrared Spectrum contained a Tesy intense ether

(8,5^) twit no hpitresarl band (2,?~3,fk) *»* no carbon-carbon
double bond band (5«pw&,j*)*-

|p & -« CWte*A* for %ila#0t
found*
g)

C, ?7*58j H, 13.02

G, 78.21, ?8.29f B, 13.03, 13.08

Solvolyaie of DiiaoproiylGyeloprojylciujbinyl p-nltrobensoate

in 7«W di©3eane*3C$ Methanol at 60°.
la a p^alisdiiary experiment, 0.3281 g, (0.0010?^ mole) ©f the ester
we* weighed ini© a 100-ml, volumetric flask, brought up to volume with

10% di©xane~30# methanol and placed la a 80° bath. At various intervals,
a 5-ial. aliQdot m& titrated with 0.GO9317H sodium hydroxide la 8C#
dloxan©-2C$ methanol. After 18*23 hears, 3b$ o f the acid titer was
obtained and remained at 3h% after 37.5 houre, which indicate that
solvelysis had ceased,
Ih another eacperimeiit, 3.71 g» (0,0187 mole) of the ester was
dissolved in 100 ml, of 10% dioxane-JO# methanol end the solution stored
at 60° for 38 hoars, The cooled solution was poured into 300 ml, of
water and made sl±$itly alkaline with sodium hydroxide. The mixture
was extracted with eight IQO-ml. portions of petroleum ether, The com­
bined extracts were washed with eight 500-ml, portions of water and
dried over Brierite. The solution was concentrated to about 50 ml,,
cooled in crushed dry Ice and filtered. There was obtained 3,5 g. (61$)
©f h^isopropyl^S^methyl-l-henesiyl p-nitrobenaoat©, m.p. U6~U8° which
was identified by its infrared spectrum.

50

Wm filtrate m u distilled and there m s obtained 0*7 g. (222) of

b«p# 570 at b mu, which
m e algo identified by its infrared spectrum*
Proof of JEt^ct^c^of i

p^trobensoate

a) Eeductton with Lithium Borohydrlde.
A 500-isl. three-hooked round-bottomed flask equipped with stirrer,
condenser, dropping funnel, and a gas inlet tube was charged, in a
nitrogen atmosphere, with 2.2 g* (0.1 mole) of lithium borohydride and
100 ml * of tetr&hydrofuran (dried by distillation over sodium) * 1 aolulion of 8.0 g. (0.026 mole) of U~iaopropyl-f^:methyl-3~heKei$yl p-nitrobensoate in 50 ml* of tetrahydrofuran m s slowly added with stirring
to the lithium borohydrid© solution* Ho heat m s evolved during the
addition* The solution m s sltrrod at room temperature for 12 hours*
The mixture m s cooled in an lee bath and 300 ml* of mter was slowly
added* The solution m s extracted with five 100~ml. portions of ether
and the combined extracts dried over Brtarlie* The solution m s
evaporated to dryness in vaotia* Tha residue m s taken up in petroleum
ether and filtered, yielding 3*2 g. (81$) of p^trcbausyl alcohol,
».,» 91*93° (lit. valu# 93® (25)).
The filtrate m s distilled and there m s Obtained 3.0 g. (7U$) of
Jfc©

b-ieopr©)^l$5-ffie1foyl-3~hexsttol, b*p* S30 at 5 ®su, n^ 1.U505. the
infrared spmtrum contained a broad intense hydroxyl band (3.0u) and a
weak carbon-carbon double bond band (6.Oja.) characteristic of trisubstltuted ethylenes.

51

C, 76.661 n, 12*90
Found! 0 , 76*96, 76.911 H, 12.87* X2*7b
b) Oxidation ©f lHynppei^^

With Neutral Fotaseium

Permanganate.
A mixture ©f 1 g# (0*006h ©ole) of th© uns&iurated alcohol, k g-

(0.0^5 wele) of potassium penaanganate and 100 ml* of water was stirred
for four hours at room toiaparatur©. The mixture had th© strong character*
iirfcic odor of dllaopropyl ketone* Th© mixture was filtered, 4h« filtrate
extracted with fire 20*®!. portions of ether and the ©oafcined extracts
dried over Drierite. Th© ether was removed and an infrared speotrum of
the residual liquid {about 0.7 nl*) showed a strong carbonyl hand (5.8&0
but also a hydroayl hand (2*8<^i). Comparison of this spectrum with that
©f authentic diiscpropyl ketone showed that the wavelength of each
carbonyl hand was identical.
In m attempt to distil th© mixture, decoj^osition took place.
In another ©3q?eriment, about SO ag* of the unsaturated alcohol was
shaken i&th 20 ml* of aqueous potassium permanganate for on© hour, th©
mixture was filtered and the filtrate was extracted with four 5-al.
portions of ether* The coshined extracts were dried over Brierite.
Th© dried ether solution was concentrated to about 1 ml. The presence
of diisopropyl ketone in the solution was then ascertained by vapor
phase ©hr©mattography. This was accomplished by passing an ethereal solu­
tion of authentic dtisopropyl ketone through th© Vapor Fractometar and
Obtaining a record of th© band due to diisopropyl ketone, Then a sample
of the unknown solution was passed through the Vapor Fraciometer and the
Identical band corresponding to diisopropyl ketone was obtained*

SGLVGLTSIS SE&BXfS

52

SQLTOLISXS RESULTS
A. The Hates
The rates of solvolysis of the esters sere measured In dioxane
containing various weight percentages of water at several temperatures $
the reactions were followed by titrating th® liberated p-nitrobenzoic
acid with standard sodium hydroxide*

Th® rates were unaffected by added

hydroxide Ion (Compare th© rate constants in Tables 25 and 26 with those
in Tables 27 and 28, and cojspar© the k values In Tables 6U and 65 with
those In Tables 66 and 6?)*
In most cases the ester was completely aolvolyzed to an alcohol and
p-nitrobenzoic acid, but in certain instances, solvolysis appeared to
be incomplete* that is, th© theoretical amount of p-nitrobenzoic acid
was not liberated*

Each of these two alternatives required separate

kinetic treatment*
For the case of complete solvolysis, the reaction may be expressed
by th® general equation
Ester
(a

x)

■MM"!)* Alcohol 4- A d d
<*)

M

where
a * initial ester concentration in moles/liter
x * concentration of alcohol or acid at time t
a-x * concentration of ester at time t

(1)

53

According to the usual treatment of a ftrst«*ord®r reaction,
log (a-x) m m

t

♦

log a

(2)

Th® measured quantity mas
V * volume (ml.) of standard sodium hydroxide required to
neutralise th© p-nitrobenzoic acid found at time t
(in a 5 ml* aliquot).
If

* volume (ml.) of standard sodium hydroxide required to
neutralise th® theoretical quantity of p-nitrobenzoic
acid (in a $ ml, aliquot),

then
(a-x) Is proportional to (?^-V)
and

(a) is proportional to Vg

whence
log (VfV) -

-23

t ♦

log Vf

(3)

Note that
-sgsa
where

N * normality of th® sodium hydroxide.

From aquation (3) we see that a plot of log (Vf-V) vs. t should
be linear, and th® slop® of this line allows one to calculate the
specific first order rate constant k (for a typical plot, see Figure 12),
In some oases it was observed that th© reaction did not follow the
first order rat© law described by equation (3),
lated value of

furthermore, th® calcu­

was always significantly greater than the observed

value of Vf. A typical plot of log (F^-V) versus t for one of these
reactions is shown in Figure 13.

It was found that if the observed

value of Ff, called F*f, was used in place of the calculated value of Vf,
a plot of log (?£*-?) versus t gave a straight line (Figure lit).

5U

Firur© 1?. I-lot of log (V^. — V) versus t for tie Solvolysis of
0.009^f0 I ol^r L *oyo3opropylisojropylc^ro?’nyl p-Fj 1rc benzo*te
in SOfo Pi oxen© — <0f Peter.

O.S

0 ./,

0.0

-

0.8
jfcokpo

x itr2

55

Figure 13. H o t of lor (V^-. - V) versus U for ti e Oolvolysis
of 0.0115£ ?--;olpr Diisopropylcyclopropylcrrtunyl t-PitTO*
benzor.te 5n 80f Pioxoue— fOf "ater.

0.7

lC

(V

0.6

0.5

<r>

o

A

ciccroc x ic-2

12

56

Fifiare 1/,. 1-lot of lop (V^1 — V) vereus t for the
Solvolysis of 0.01156 Toler Diisopropylc.yclopropy} —
c?rfc5nyl ]>-Nitroben?;oete in 60/’ Di oxere— 205' r eter.

0.0

12

A
3KC0KDS x 10“ ?

57

This indicated that the amount of ester represented by V^* solvolysed
to give p-nitrobenasolc acid by a first order process*
ester represented by

The quantity of

) must have been converted to some product

■which did not liberate p-nitrobenssoic acid,

The conclusion, later

verified by product analysis, was that the original ester had undergone
solvolysis to alcohol and acid and rearrangement to a new ester . Since
the total theoretical acid titer was never obtained, neither under the
kinetic reaction conditions nor under forcing conditions (i.e., refluxIng solvent for an extended period of time), it was obvious that the
rearranged ester m s quite unreactive, The process may be represented
by
Ester

—

k

Alcohol ♦

S

Acid +

A

Hew ester

A

(U)

E*

A somewhat more detailed representation is
ks

^

Acid

*

A

-s*>

Alcohol
A

(5)

Hew Ester
1*

where
kp

(5a)

and
ks
kr
E
A
E*

* specific rat©
* specific rate
*» concentration
■* concentration
- concentration

constant for solvolysis
constant for rearrangement
of original ester at time t
of alcohol or acid at time t
of new ester at time i.

58

St

B* ■<* ld t io l eeaaonfcrotion o f o rig in a l « ite r
4 * » fin a l o o ro an tratio n o f a lo o ljo l o r a d d
W | * f l a i l <wmeentra,tlon -of now e a to r -

them

Ktfyl

Bo *

B * ■4

B'f »

*«■ * Af

*

B*
(7)

fh# rat* of dleappe*ranoe of estor is glr«n tgr
* ’“H** *

k» (B>

*

k*. (B)

* k (B)
and

log

E •

(?)

«

♦ l«g S#

Sinoo
S*

**f
4f

■sj

it is easily shown that
B

KB

4k'

wfaareupm ©quation (10) beeomee
lOg < % * A»

S0) «B.

-w

i

#

lag

(53)

Using the previous definitions of ?, % m d ?*£# equation

rodncos

to
i»s O f * frr vf ) »

k
■
'*«

t ♦

log %

where ¥ and Vf v are experimentally determinM and %
the original amount of eater taken*

(Ik)
la calculated. from

1 plot of log (Y^ ** |r-j V|0 vs*

t gare straight lines (aee figure 15 far & typical plot) from the
slope of which k mas calculated.

59

3?'.iyuro 15* H o t of log; (V^ — V
versus t for the
Solvolysis of 0.01X58 folpr Di isopropylcyclopropylc^rbinyl
p-Nitrobenzoate in 80$ Dioxpne-20/' ?ster .

LOG (A)f - V

)

0.8

0.0

-

0.8

12
SIC Of'OS x X0“*2

60

Sines
k, *

|£ k

»

|jf 'k"

(15)

end

kF end ks sen be wiOnated from k and the ratio of solvolysis to
renrriutijzcmenb oroduct*
The values of k, k»> m i \

obtained for the reactions of the

esters tinder various conditions are listed to Tables k* 5 , 6, 7, end 6#
too value of toe specific rate constant listed at a given t^er&ture

to toe arithmetic moan of all toe rate constants obtained at that
temperature*

The standard deviation {56} from each m m value is also

given.
toe energy of activation, & a5 m s determined to toe usual manner
from the Arrhenius equation

to|k*

*|5jrJ

+

z

O?)

Th« H i m * plot, of log K versus # for the various reactions appear in
Figures 22 to 36 to the Appendix,

to each case, toe slope m s obtained

lay the method of least squares (2?,56) and %

m s obtained from the

equation

toere

En *

2 3 t (* slope)

E

1.58? calories degree"*3, m©le~X.

«

(18)

toe enthalpy of activation, ^ if, m s calculated from toe
equation

61

Table h
Specific Eat© Constants for the Solvolysis of Dicyclopropyliso-*
propylcaxbinyl p-Nitrobenssoate in Aqueous Bioxane
4
*•!
10 k *11©e© *.,.!
Weight Per Gent Dioxane

°c

95

90

85

8o

7

1.53*0.01

16

U.90*0.11

25

1*6010*01

hO

6*69*0*09

13.3 *0.2

16.8 *0.1

50
60

5.It?*0.05

k

5,69*006

k8

5.21*0 *12

kr

GJU50io*o]ii5

kg/ky

38.9*

11 *6

^Calculated from th© Arrhenius equation

m *

62

Table 5
Specific Hate Constants for the Solvolysis of Di~(2-methylcyclopropyl)~
isopropylcarbinyl p~N±brobett2oaie In Aqueous Dioxane

10*k, sec.»i
°c

Weight far Cast Dioxane
90
1c

k8

80

kr.

k

7
16 2.80±0.09

2.5840.0?

0.21740.017

n.9

25

6.5340.06

0.567*0.020

11.5

7.0940.0?

35 18.3±0.3
60 156*

8.0540.0U

16.540.03

136*

1.81440.11

21.14*

^Calculated from the Arrhenius equation*

9.0
6.31

63

table 6

Specific Hate Conetaats for the Solvolyels of Piiscspropylcyiclopropyleerbii^rl p^itrobenBoat© la Aqueous Btoxaae
.',.l
vj,ll"V:i.iuii-uanuiij.iui!i,rfr,-,tt4itraiw.,m.ygsnMssaaaswca:
jewkiffaw.iie«a’
**3»
.10 k. sec*
Gent Dloxane
Of»
.....

90

85

80

1.6140,03
1.5k40,03
0.065k40.0065
23.5

k_
V^r
*°k
ks
kr
k-A»*
6°k
k#
^3? .
k^Asf
70^
fc«
h**
JtsAv
8^

ka
kr
k#Ar

70

5.1240.09
k.8940.10
0.22940.001
21.k
0*73940.06
0.20840,001
0.53240,006
0,391

2.0940.0k
0.838*0.012
1*2540.02
0.670

U.69±0.28
3.Oil40.16
1,6540.15
1.8U

5.7U40.05
2 .3340,01
3.U240.05
0.681

11*940.2
7.6940.12
il.1340.Ok
1.86

lk,840,1
5.6240.19
9.1040.Oil
0.618

29.640.5
19.0±0.k
10.510.2
1*81

lk.710.2
13,940.3
0.83110.016
16.7

614

Wble 7
Specific Hate Constants for the Solvolysis of Bicyclopropylcarbinyl
p-Nitrobezizoate in Aqueous Bioxane
*
10 kf sept
Weight Per Cent Bio&ans

°n
85

80

60

1.16$G.G6

70

2.92*0.06

80

2*6810.06

7*06*0.01

65

table 8
Specific Rate Constants for the Solvolysis of Triisopropylcarbinyl
p-Witrobenzoate in Aqueous Dioxane
10 k, sec

■«.*&

Wejgfrt Per Cent Bioxane

oq

80

70

60

1.91 £0*09

7.5210.03

70

6.8210.01

80

27.1 10.6

25*5 £0.5
81.5 41.7

66

• at

(19)

The entropy of activation, z^g*$ m e calculated from the %rlng
(t$) ©qa&tion
k ,

8 -*H*A*

{20J

or

■^s* * ao r xog (-fe|-) *

(ax)

where
h m Planck *s constant, 6.623 x 10
and

kg

m

erg second

BoXtssmaira ©octant* 1*380 * lcT*6 erg d©gre©^2‘
molecul©"‘1

The values of AH* and
listed in Table 9*

obtained for the various reactions are

The value of a s # listed for a given compound is the

arithmetic we*** of *11 the A S # values calculated from equation (21)
for each k obtained for that ©©impound.

The standard deviation from

each mean value is also given*
B« The Products
Solvolysis of (^.cyolopropylisoprojylcarbinyl p^nltrobenso&te in
80$ dioxane^SO^ water at 25° yielded dlcyclopropylioopropylcarbinol
which m s identified by Its physical properties and infrared spectrum,
the yield of Isolated product m s as high as 9$%* and there m e no
evidence of alefinformation * Replacement of the water with methanol
gars 1,l^cyclopropyl^l-methoscy-S^aethsrlpropane * Although the structure
of this product was not conclusively demonstrated! the elemental analysis
and infrared spectrum (Figure 16} were consistent with this assignment.

\©
H

8

8 ?.
S♦
o\ q xr\

£ sI
<1 ©

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67

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68

ftitt formation of the other from mibanol d#momtr«tos that solvolyaie
of diagpt&Agm^

p^nitrobonaso&t© proceeded by alkyl~

oxygen fiootom* This criterion has boon m$il&smd in m m w m z other

GH,
:m
0%

80# dioxtme%<$ H*Q

CE
o-c%
GHs

69

c

I
cu
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c- n

£

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Is
a
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cd

r.

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uo-yes'Eiagwajci gjjso Jt0ct

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CVi

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?0

p^tYObwwo*%* la 7€# diox*ne3038 nnt$r at 60° gave £6# dliaopropyleyclopropyl^

mini 1$

I^laoiaropf^^-^tbyl^^^K:©^! p^nitrdbmsoat©* la 9Qf M,m ^ 1 0 8 water,
also at 60°, tit© y&©M© of tH#e« aaaoe product© were 28# and 72#,
respectively*

fbes© yield© are m % based on isolated product, but rather

©a the kinetic results*

However, the products were isolated, and there

was no evidence fo r aaasr e th e r TorGdueis*

OIU

S%

'fls

[>

aqueous dloxane

GH

/ \

CHs

OHa

C =0H -C H *C H »-0-C
as

/ \
3Ha OHa

/\

CHa

CHa

70? diox*ns-30? H,0« 96?

U?

90? aL*xK*H,
tU3? HgOX 28?

72?

o
H

\D

c-S
ef

o

u
8
t!

O

o

to
uo-geeTiasxiaaij * ti©0

72

the mam eater* In raflsa&ng methanol yielded esccXueivaXy 3~eyele~
but in 70$ f$lom m *3Q $ methanol

fropyl^SNwebh^^

at 60®, only a 3h# yield of the ether waa obtained, and 66# of the
outer had iaoraeriaed to U^iao^ropyX^S-^othfX^heK^yX p^nitrobenaoate,

Tim Infrared spectrum (Figure 18) and elemental aaalyeie of the ether
Here eonaieteut Htth the aeetgned »truotare»

It ie again eledl that

eolvolyeis inroXvod aXlgrl-oagrgen fieeion*

Wi|

[ \

I
> — a*—
I
m

o — an*

/ \

/ \0 %

0%

0%

G%0H

I—

o

100#

7©# diemae*30# 0Ba0H

3W

OH*

—

no2

73

CJ

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fS
8
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P

r~l
If
&
fc-i
t
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<\T
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53
C
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6

<15

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H
ft

o
r
~t
Ph

\0

taO-i

■ofr*
CJ
Pi
m
P
u
cl-«
w
rp

a
CJ
;r*
o
o
r-J

O3
1

O
\D
TXOf&Bp3Str3.t£ 5.1X0 0 4tG,J

O
CNi

o

t—
4

the unr©activity of the rearranged ester, U*-dsopropyl-*5-methyl3-'h0E3c©nyl p-nitrobenaoate, was demonstrated by the fact that even after
prolonged boiling (26 hours) of the original ester in 7055 dioxane-30^
water, the theoretical titer of p~nitrobenzoic acid was not obtained,
nor was it increased from that obtained in the kinetic experiments*
The structure of U~i«Qpropyl~5~m©tfayl**3-hexenyl p-nitrobenzoate was
proved by redaction with lithium borohydride to li~isopropyl~5~methyl~'
3-hexenol and p~n±trobenzyl alcohol*

The U~ieopropyl«*5~m0thyl-3-

hexenol gave diisopropyl ketone when oxidised with neutral potassium
permanganate*

CH

ch 3

O

GH—— 0

CH-GHjg-GHjj-O-

»>*

ch 3
l ±bh 4

OH

G = C H - G H 3GHa0H *

CH3

KH eiO^
11

HO-CH*

N0a

75

H d * fires the position of the double bond as shomn, hot the ester
function might hears been at % or % *

Carbon atom 2 is eliminated m

the basis that the ester mould then hare been alOyOle, and easily
solvolysod under the reaction conditions.

of

VO,

O
\o

uQ^ss'pnGire^ q.TiCQ

o
3 G p r o p y l - iethyl-3-lianono 1 (neat)

-P

Infrared Spectrun

•H

I'i.pure 19*

76

rH

O
r-*

DISCUSSION OF THE StS.70I.TSIS STUDIES

77

DISCUSSION OF THE 30LV0LTSIS STUDIES
In order to place the results of the present investigation In
proper perspective, it w i n be necessary first to discuss certain applic­
able phenomena in the general area of solvolysis mechanisms. This will
be followed by a brief review of previous studies on cyclopropylcarbinyl
systems, after which the present results will be examined in some detail.
A. Recent Concepts in Solvolysis Mechanisms
A comprehensive and elegant review article on solvolyti© displace­
ment reactions at saturated carbon atoms by Streitwieser (9) considers
at length and in detail the various nuances in solvolysis mechanisms.
For this reason, a detailed review w3-ll not be attempted here.

Sine©

the ester solvolyses reported in this thesis are all of the Sul (9,29b)
type, discussion is limited to this type of mechanism*
By the tern £%1 is meant a unimolecular nucleophilic substitution
which usually occurs by a rate-detensining ionisation to a carbonium ion,
followed by rapid reaction of this ion with a mcleophilic species.
This general definition describes the gross features of the process,
but omits many of the details! in particular, one is concerned with the
mechanism of the ionization process Itself, and also with the ultimate
combination of species to form covalent product.

Details about the

ionisation step were derived from stereochemical and kinetic studies.
The usual stereochemical consequence of an S^l reaction would b©
raceraization at the carbonium carbon atom, because a completely solvated

78

planar carbonlm ion eon not be asymmetric*

In certain systems, this

is found to bo the ease (eolvolysis o£ ooters of p^Brethoagftenslydrol
(30) «od of certain aryl^thylcarbinols (31}). Bat in most instances,
racosiaaticwa is aroco^axxted by a small s m m t of inversion ($%}*
FarfeloaXarly remarkable is the 60f inversion observed in tho aethanolysis
of hydrogen ^#l^iinotbylhf^X^ phthalate (32)*
CH3
CHg— CH

1

CB,

CHjj

60# inversion
In order to account for tho small amount

of inversion in many % 1

solvolyaae, Hughes and Ingold (33,3b) suggested preferential *shielding*
of tho carbonium ion daring solvolysies in order to account for varying
amounts of inversion depending on the structure ȣ tho substrate, tho
concept of ‘‘lifetime* of the carbenium ion sas introduced*

Jhdiciouo

combination of ^shialding*1 and ^lifetime11 could qualitatively explain
differing degrees of stereochemical imvereioa, bat a quantitative
treatment m s ispossXble*

Furthermore, the concept was confusing (35)*

Shielding by the leaving group m s placed on a sounder conceptual
basis by Hammett she suggested that the product of the ionisation step
is m

ion*pair (36), He implied that reaction sith solvent before

79

dissociation of* the tm pair would occur with inversion* Haawett1#
Interpretation r#<pitr«a tmt M m #

to t # m t for several

recently observed phmmmm discussed belw*
Soaring sad Zeia* (32) were led to « somewhat different, sad
structurally nor# detailed hypothesis, from their observation of con­
siderable inversion in the methanolysls of hydrogen 2,b-dl®etbylhexyl-ii
phthalabe. their arguiftent has been amplified by Stretbwiesor (£)* the
transition state in the iontaation process is represented by

I

in which the S*X bond is Intermediate between sp3 (in the original
raolecule) and p (as it would be if X sere associated with a planar
earfoonium ion)*
m

the central carbon will be. electronically deficient to

eacteni which depends upon the degree of solvation of X and the nature

of the groups attached to 0.

The greater the ability of the system to

internally diapers* this positive charge, the closer to. tetrahedral will
the structure of the transition state be#
A mcleophilic reagent H can help accoaaaoclat© the developing positive
charge by overlapping with the •tail* of the reaction orbital as in

or

N

the better the internal ©oapensation, the less the need for rearward
pameipationj the greater the moleophilicity of N the greater the
Importance of such participation*

80

In the tertiary carbinyl system in a highly ionizing medium the
transition state I will lead directly to an intermediate

I

or

C ***X

XU

which, if X is an anion, can be referred to as an ion—pair (or more
precisely, an intimate ion-*pair (37,38)),

Reaction with solvent to form

S

I?

and subsequently

**•*

$

will be rapid| the stereochemical consequence will be raeemizatioru
If the solvent is strongly mcleophilic, the transition state is best
represented by II, leading to an intermediate which has a good deal of
covalent character to the N ~ C bond
X

|

VI

X then departs, the net stereochemical result being inversion.
On© notable virtue of this mechanistic picture is that it can
accommodate the broad spectrum of displacement results, from classical
SN1 to classical S$j2* The stereochemical outcome will be determined
by the relative rate constants in the following summarizing scheme*

81

\

\
7

t r . ert,

0

l\
1st inierm.

0 ***• c **** x
tr* state

3

2nd. intern

produet (inverted)

3 «•*• 0 »**# 0
l|
3rd intern*

/
lUSSBa^.^— 0 * 3— q
7
\v
product (racen&c)

The mechanism depicted thus far does not allow for reversibility
which had to he introduced to explain certain results in allyl, norbornyl
and other systems.

The acetolysis of <x, <x-Klimethylallyl chloride (VH)

was accompanied by a first order isomerization
0%
CHg * CH ~ C ~ 01
I
OH*
ra

* c

CHa
I
Cl

?in

tor,r-dimethylallyl chloride (Till) (39) * The rate of isomerization
was Independent of added chloride ion, hut sensitive to the ionising
power of the medium, being favored by polar solvents*

The results were

interpreted in terms of an ion-palr which could go on to solvolysis
products or return to original or isomerized halide*

0

The phenomenon is

VII

VIII

SOH
SGfi

solvolysis products
known as “internal return,1* The partition of the intermediate between
*return* and further solvolytic reactions will be a function of solvent
nucleophilicity and ionising powerj this is shown in Table 10.
Table 10
Solvolysis of 0L,a* andY Yf ^Bimethylallyl Chloride
VII

.ki

-»>

VHI

P
Solvolysis products

see.
Rate Constant
ki
kt
k
P

Acetic Acid

.1
15% Ethanol

Ethanol

ii.O

l80

0.

1.5

380

1.8

0.22

115

0.65

S3

A stereochemical consequence of internal return in halides showed
up in the investigations of (Soaring, et al. 3 (U)) on the 3-chloro~5~
methylcyclohexene system.
Cl

IX

Cl

X

In the acetolysis and ethanolysis of optically active IX and X the
rate of racemization (formation of ion-pair) was greater in acetic acid
than in absolute ethanol, whereas the rate of solvolysis was actually
less in acetic acid than in ethanol*

For both geometric isomers in

either acetic acid ©r ethanol, the rat© of racemization was greater than
the rate of solvolysis and m s unaffected by added chloride ion*
Racemization occurred without cis^trans isomerization. Racemised chloride
recovered before solvolysis was ©oaklet©, m s not geometrically Isomerized,
The first ion-pair intermediates involved in each case, XI and XII are
symmetrical! they are incapable of sustaining optical activity.

XI

X II

these structures represent lampairs which are diff©rent fro® the
classical Debye~HtieJk©X type of loia-pair*

Their structure is geometrically

mere precise* the ions are not separately solvated and free to rotate
with respect to one another*

this allows retention of geometrical

parity* yet parasite raeea&Baiion*

Xa a sore detailed analysis of ionic

intermediates, Winstein and co-workers (37,38) hare been able to die*
tinguish kinetieelly between an *intimate* ion-pair* a *solvent~6©par«fc ed*
X©n~pair# classical ion^p&irs and free ions*
The ethanolysis and acetolysis products frosi IX and X contained the
seme ratio of ole/trans isomers*

fremm&hly these products arose from

a di«*solvated iatermediat© XIII*

In © very similar rfeadf# internal return was investigated in the
reactions of optically active j|g and t r a n s ^ iaethyloyQlohexen^l-yl
p-nitrobenaoate (10.)* Solvolysis in 99$ aqueous acetone proceeded by
aXlyl*oaygem cleavage*

For each isomer, the rate of racemXaaiion was

greater than the rate of solvolysis*
eis-trans isomerization*

Saeh ester raoemised without

The intermediate (for the cis oonpound) Is

probably beet formulated as XIVi

8$

I

i

1* Previsa* Ifcveatigaiiona ©f the

8y»b«Bte

Althea# m m very eareihl end elegant investigation* of the eyele*
j ^ l g ^ e s M n y l syetsm have been performed, a ©oa^Xetely consistent
mechanistic picture of the reactions hue not yet evolved*

In aertain

instances, reiorcaogement products predominate, Kerens in otters, no
rearrangement of the carbon skeleton is observed* seats ratiomlisations
are possible, bat they are not always oonsXstent, and it 1st still
difficult to predict shat products might be expected under a given set
of experimental conditions * Previous work was concerned with primary
and secondary eyelopropylcarbinyl systems, whereas the work described
In thie thesis deals mainly with tertiary systems*
The unusual reactivity' of the cycloproi^ylcayblnyl system in
solvolysis reactions has already been referred to in the introduction to
this thesis*
products*

This section will focus attention on the solvolysis

Tartlal hydrolysis of cyclopropylearblnyl chloride yielded

a mixture of ©arbinole consisting of U8$ cyclopropylcarbinol, hl%
cyclobutanol and %% allylcarbinol and a mixture of unreacted chlorides
which contained both cyclobutyl chloride and allylcarbinyl chloride (8)*
&bdsf the conditions used, the isomeric chlorides would not have solvolysed significantly* The rearranged earbinols are, therefor®,
derived from cyclopropylcarbinyl chloride,

hydrolysis of cyclobutyl

86

dalorl&o gilded m

idoafcieiil n&xtare of oartaiools (6)#

tfe* di&aotis&ation ©f e^l©|^pyioarbiz^^

Farihorniore,

or e^labutylamine also

g»re tlao a m i oorfcdjacrl intxfcar© (8)*
On th# othor h m & $ wvtolp*!* of oycl&bvLt&X p^toXuommjLifomt© (U2)
or cgrolopropgrloarM^rl chlortd® {8} r««alt«d in a difforent ratio of
Oolvolyoio products* eycXopro^leaarbloyl and c^rolobutyl acetate® wore
formed la a ratio of' about 2*8 to X*

*
i

As abora,

1

01
0H*,*0X

.os
♦

QHjgOOK^Ha-eH^OH

hl%

NH,
GHa-KHa

87

rearranged starting material m a also M

ehich tallies internal

return from ion~pair intermediates,
the reactions vere interpreted (8) by assuming an intereonvereiom
of the cyolopropylcarbiEQrl carbonium ion and the cyclobutyl carbonluia
ten sibh a slow end essentially irreversible reaction to allylcarbinyl
derivatives,

For exaijpl®, treatment of eycXopropylcarbinyi* cyclobutyl

or lOlyloarbinyl chlorides idth nine chloride and hydrochloric acid gave
essentially pore aHylcarbinyl chloride (8)*

the folloieihg scheme was

proponed (8) for explaining the various reactions**

*>

CHj^OR-OH^CHa

The stability of the eyclopropylearbinyl oarboninm ion has been
attributed (7*8) to resonance of the following type*

88

An alternative explanation, involving a “non-classical" carbonium
ion, was suggested by Roberts and Maasur (1+3) to account for the results
obtained when cyclopropylcarbinylamine-l-G14 m s treated with nitrous
acid.
CH
m
GHj

Ha0

CH
GHa«CH-CHa-CHs-OH

CH
#CH:
km

hl%

The CX4 m s distributed statistically between the three methylene
carbon atoms in the cyclobut&nol. A carbonium ion of the type shown in
the scheme would explain this result, the two methylene groups of the
cyclopropane ring becoming equivalent with the exocyclic methylene
group*

However, in the cyelopropylc&rbinol formed, an excess of the C14

(k$% rather than 33*3%) over that predicted by the non-classical inter­
mediate was found at the carbinol carbon atom, and only $k% (rather
than 66.7$) was found in the ring.
mechanism is operative.

This implies that more than on®

The results can also be explained by assuming

facile interconversion of the cations

89

It 1# perhaps worth noting that although the cyclobutane ring and
especially the cyclopropane ring are 11strained#M in terms of tetrahedral
(sp®) bonding, these rings do not always relieve this strain when the
opportunity arises (i.e., by exclusively forming op©n~chain allylearbinyl
product)#

This suggests that the bonding in these rings is somewhat

different than sp3. Furthermore, although secondary earbonium ions are
generally more stable than primary earbonium ions (29b), the primary
cyclopropylcarbinyl earbonium ion is apparently at least as stable as
the secondary cyclobutyl earbonium Ion#

The situation is somewhat

analogous to the comparable stability of benzyl ions*
Two striking cases have been reported, one primary and the other
secondary, in which no ring opening or rearrangement occurs during
solvolysis*

Bergstrom and Siegel (7) found that cyclopropylcarbinyl

benzenesulfonate in absolute ethanol gave cyclopropylcarbinyl ethyl ether
in a first order process*

It was also observed -that the benzeneeulfonat©

rearranged rapidly in chloroform to allylearbinyl benzenasulfonate and
a small amount of the cyclobutyl isomer*

90

CH^O-OHaCH3

<3H9~G-S0a-G6Hs

CHa»GH-CHa^3Ha-O*SOa-CeH0

/

O-SO^C^Hg
small amount

The absence of any significant amount of oyclobutyl ethyl ether in the
solvolysis product is striking, especially since cyclopropylcarbinyl
chloride in 50% aqueous ethanol yielded equal amounts of cyclobutanol
and cyclopropylcarbinol. The results may be explained in terms of the
structural concept for $^1 mechanisms of Dosring, Eeiss, and Streitwieserj
the transition state has a structure ©lose to spB in which the "tail” of
the reaction orbital is fairly large#

This, combined with the email

degree of steric hindrance, makes orbital overlap with the highly
nucleophilic ethanol important and ether is irreversibly produced without
rearrangement#
return

The situation is reminiscent of the lack of internal

in the solvolysis of d , d -dimethylallyl chloride in absolute

ethanol#
Pearson and hanger (UU) found that in the presence of toluenesulfonic
acid, cyclopropylmethylearbinol in methanol gave the methyl ether without
rearrangement. The methyl ether, in ethanol under similar conditions,
was solvolyssed to the ethyl ether, also without rearrangement.

Only on

91

pvoleagtd (6 d a j*) re flu x ,

m* angr •lly le a rto ia jrl nrtinyl athar forosd.

H

C8«CH#
2 fcra, reflux
OOHa

ch 3o h ,

ar

Q»HBOH,

h*

2 hr8* reflux

CH*CHa

fkmme results m m similar to those of Wlnsteln and Adams (k$) with the
i^eteroide*
Results very closely related to the present work were reported
by Kosover end Einstein (11) after the experimental work described In
this thesis was completed* Because of direst bearing m

the present

results, their work will ho- outlined in some detail*
For the sake of brevity, derivatives of 3,5^cyQloeholesian-*6~ol
(XVI) will be referred to as 0 (cycle) and those of cholesterol (X?)
will be referred to as A (allylearbinyl). Although this yetll. not
always lead to precise names, the meaning will be clear, and extensive
repetition of lengthy m m m will be avoided*

HO
OH
XV

XVI

92

Solvolysis of Q trichloroacetate la 80$ metban©l~20$ chloroform
«**• $9% of 0 methyl ether, 1% of A methyl ether and it# of A (cholesterol);
hot A tetohXoroaoatato under the same conditions gov© 1GQ# A,

fa the

o«ao solvent* A ^toXmonowaXfcmato, instead of the tzlcbloroaeatate,
gave 88$ of 8 methyl ether and 12# of A methyl ether* prodncta almost
Identical to those obtained from 0 iricKioroaceiate* except that the email
<|a*atity of cholesterol eae absent*

#•
KO
1%

HD

80$ OH,
G0Hs
88#

12%

It la therefore clear that A trlchloroacetate solvolysed eith acyl*
oxygen fission, whereas 0 trichloroacetat© and A p-toluenesulfonat©
oolvolysed with alkyl~oxygen cleavage*

The small airaoimt of cholesterol

formed daring the methandlysis of 0 trichloroacetato Indicates internal

23

return to A trichloroacet&te, followed by aoyl-oxygen cleavage of the
latter to yield cholesterol*

Sinco both C trichloroacstate and A

p~toluenasulfonata yielded Identical ethers in about the same proportions,
the solvolysis of these confounds must have proceeded through a common
Intermediate*

Hh® formation of more A methyl ether from A p-toluene-

sulfon&te than from G triohloroacetate Indicates that the p~toluenesulfonate returned internally to the oholesteryl derivative which further
solvolysed to the ether * fhe results may be depleted as

CC1*C00

follows*

GG!«COG
GGI3GOG
ch 3g h

ion-palr

GKsOH.

|gh 3o h

GH«0
OGH.CH30H

gh 3oh
OH saGH

0-S02-C6H4-CH3-p
p—CHg—CqH4-SOgO
ion-pair

91*

SelTrolyeia of © i^chloroaGet&te in 90% a<jaeous dioxane yielded
k9$ of Q (3#5^^1o©fealeetaa^^l}# 23# of A, and U*# of A trichloroacetate*

©holeatarol did m b react aj^raoiafcly m t h trichloroacetic

a d d under the eolvolyeis conditional hence the A trichloroacetate
isolated from the solvolybic reaction represented a direct solvolysis
product.

Addition of lithlura trichloroaceiate to the solvolysis mixture

did not effect the composition of the alcohol product hat markedly
decreased the amount of A iriehloroaoet&te produced*

the results

strongly indicate an ion^pair mechanisms

HG
OH
m

Solvolysis of 0 chloride (10) in 90% aqueous dioacane (containing
excess lithium acetate) yielded f # of C, 20# of A chloride, and B%
of A.

the

lithium acetate, which was need to prevent the solution

from b«eondng acid, did not react with the A chloride under the

95

aolvolyais c©»dttto*ie* Apparently, Internal return m s mere important
during solvolysis of the chloride thou the irichloroaeatate* C chloride
^ reported to edlih&lyee about 10® time factor than A chloride in 90%
aqueous dioxane (9a,10),

•a

ca

ion**pair

HO

mnotein»a results with the 3,5-^syolooholestan-6-yl derivatives
dejnonstr&te again the remarkable reactivity of the cyclopropylcarbinyl
system*

the secondary qyclopropyloarbinyl earbonium ion is apparently

the major contributing form to the resonance hybrid, since predominantly
cyclopropylcarbinyl, rather than allylcarfeinyl derivatives n w

the

major solvolysis products*
C* the Present investigation
X* The Nature of the Reaction
Carboxylic eeters nay solvolyae by acyl^oxygen or by alkyl-oxygen

96

fission (29c), and this solvolysis m y be catalysed by acids or bases*
All the evidence accumulated in the present work is consistent with
unlmolecular alkyl**o:xygen fission of the cyclopropylcarbinyl p-nitrobenzoates» This conclusion is supported by the observations that the
kinetics were first order and independent of added hydroxide ion;
furthermore, there was no catalytic effect of the p-nitrobonzoic acid
produced during the solvolysis*

The product of methanolysis in

methanolic dioxane was the alkyl methyl ether} since there is no evidence
for the existence of a methyl earbonium ion in solution (U6), this
constitutes support for alkyl-oxygen fission of the ester*

Finally, the

rate of solvolysis was greatly increased by increasing the ionising
power of the solvent*

For exasple, the rate constants for hydrolysis of

dicyclopropylisopFopylcarbinyl p-nltrobenzoate at 25° were found to be
1.60, 5*1+9 and 13*3 x 1Q~4 see.-** in 90, 05 and 80 percent aqueous
dioxane respectively*

This behavior is precisely what would be expected

from a reaction in which the rate~determ±ning step involves ionisation
of a neutral molecule (29d) •
2* Effect of Structure on the Rates
the rates of solvolysis reported here are truly remarkable for
carboxylic esters.

For example* the half-life of dlcyclopropyliso~

propylc&rbinyl p-nitrobenzoate at 25° in 80$ dioxane«*20$ water was only
nine minutes, and this was not the fastest ester studied.

That the

cyelopropy! groups must be responsible for this unusual behavior is
clear from the following observed decreasing order of reactivity?

97

GHa

GH3

xvn

X7HI
X

XU
OOC

That each additional cyclopropyl group help® to stabilise th®
earbonium ion formed in solvolysis is apparent from a detailed exami­
nation of the data in Table 11*
Replacement of on©

isopropyl group of triisopropyle&rbinyl

p-nitrobansoate with a cyclopropyl group increased the rate of reaction
by a factor of 21*6* Replacement of a second isopropyl group with a
cyclopropyl group further increased the rate 96-fold * Mien the rates
are compared in terms of solvolysis only (i.e. neglecting rearrangement)
these factors become 159 and 11*7 respectively*

It is highly likely

that a third cyclopropyl group would increase the rate by several more
powers of ten.

This may well be th© reason why the numerous attempts

to prepare tricyclopropylcaTbinyl p-nitrobenaoate failed*
Steric acceleration of % 1 solvolyses is now reasonably well
established (1*7) * Th© cyclopropyl group probably has a smaller steric
requirement than an isopropyl group, and certainly than a t-butyl group.

n

99

Clearly then, the ©l©ebr©n**rel@&8ing effect of the cyclopropyl group
mast override

steric plus electron!*? effect of the isopropyl group*

from the umeoolly fast rot© observed for th© jHaftrobensoate of th©
aeeondary alcohol, <5llcyclopropylcarbinolf one m m say that one cyolopropyl group la about equivalent to two isopropyl groupsf (On this basis,
m m would predict that «^lopropyllaopro|^rlcarbiriyl p-nitrobenao&te
ghould solvolya© at about th© 9 m m rat© as th© trUsopropyloarbii^l
ester}*
th© solvolysis in aqueous dioasan© of th© p*naltr6b«n»oate© of all
th© possible tertiary oarbinols with alkyls either isopropyl or t-*butyl

v&8 studied by Bartlett and Stiles (U8), Acceleration by t~butyl m s
marked (9-fold, for replacement of too isopropyl groups by t-butgrl
groups), but relatively snail than compared with th© 23,500**fold increase
for a similar substitution of cyclopropyl groups.

The ©lectronie influence

ef the cyclopropyl group is of tremendous magnitude when coireparod with
steric effects, or with electronic effects- of simple alkyl groups,
the alB&larity between the oyelopropyl group and th© phenyl group

&i electronic influence on reaction rates is striking* Although not
©non# data are available to make «Bdj©nsive quantitative comparisons,
th© indications are that the cyclopropyl group is at least as effective
as th© phenyl group towards stabilization of earbonium ions*

Cyclopropyl*

mxtetetf1 chloride in go# aqueous ethanol at 50° oolvolyzed ten times
faster than beasyl chloride (8,b9) and both of these are several powers
of ten faster than a primary saturated chloride*

This is th© only case

where a direct cos^arison is possible# The rates of solvolysis of

100

6
X
cyclopropylcarbinyl and bensyl p-toluenesulfonates arc 7*6 x 10*" «ec.~

(calculated from the benzsnesulfonate (?)) and £*33 x lef »ec*~
respectively in absolute ethanol at

(UU)

* Again, this is many posers

of tea faster than similar esters of primary aliphatic alcohols*
Somewhat more indirect comparisons are possible which admittedly are
not quantitative, but Indicate strongly that the cyclopropyl and phenyl
groups are similar, and that the cyclopropyl group is very different
from a saturated alkyl or larger cycloalkyl group*

Some data of this

type is given in the chart*

ch3

CH3

^ gh 3

\

h

^CHa

CH — C — <3H^

CH
CH*

I

XXIX

CH*

V

\

CH
I
Cl

/

\\

XXIII

XXI
When X * 01, the relative rate of XXXl/XXHI is 11 in 90% aqueous acetone

at 25° (50,33).
Mien X • OOC

^>— N0a, the relative rate of XXI/XXH is 61 in 8C$

aqueous dioxane at 60° (see fable 11).
3* The Driving Force
The unsaturated character of cyclopropane was explained by Walsh
(£1) in th® following way.

He considers each of the three carbon atoms

101

to be In a state of sp* hybridisation analogous to ethylente carbon
atoms*

The thro® carbon atoms or® at the corners of on equilateral

triangl© with to© hydrogen atoms lying in th® plan® bisecting each
angle*

The bydrogen^Niib©^

practically th® non® as in ethylene*

bond angle 1® 1%B& ($t) which 1®
the bonds between the three

carbon atoms are fomod by overly of th® three p orbital® whose axes
H o in the plane of the ring and by overlap of th® three sp* orbitals
(whoso axes also li®. in the plan® of th© ring) to fora a three~centcr
bond*

The overlap is shown in figure 20*

fh® six sp» carbon hydrogen

bond orbitals have been omitted for clarity and are merely represented
by .lines* Walsh offers physical and chemical evidence for this
structure,

The disposition of the electrons in the cyclopropane ring

Is somewhat similar to that In th® bsasens ring.

In the latter, the

overlap of two sp* bonds for each carbon atom result® in strong carbon**
carbon bonds and the six p electrons are: completely delocalised,

the

sp* thre©*-cent©r bond in cyclopropane renders this carbon skeleton much
less stable than that of benssene, and even somewhat less stable than
sp3 carbon*carbon bends in acyclic compounds.

Although the p electrons

are net completely delocalised, a cyclopropylcajpbinyl earbonium ion
Should be stabilised to a considerable extent through overlap of
p orbitals to foam a non~l®caliaed v orbital (see figure 21),

This

stabilisation of the earbonium ion should provide a driving fore® for
solvolysis reactions of th® cyclopropylcarbinyl system* Sine® four
p-orbibals are involved in the delocaliaation of the cyclopropylcarbinyl
earbonium ion, it should be more stable than the allyl earbonium ion
in idiich only three p orbitals are involved.

102

H
Figure 20. Molecular Orbital Structure for
Cyclopropane.

Figure 2l„ Ioleculer Orbital Structure for
Gyclopropylearbinyl Carbonium Ion,

103

t% M

observed ia the present investigation that a second egrclo-

prolyl group fiirtber enhanced the reactivity of the <^leprepylcajfo±nyl
toward eolvolysis to a considerable degree (hot® the sisdlarlty
of benssyX versus boiaol^di^rl)* this muay he ascribed to the additional
contributing structures which a second cyelopropyl group son provide.

i
R

o

f ho increase in reactivity oheerrod when a methyl group is at the
Exposition of the ring might be dee to its ability to transmit its
electrical effects through the cyclopropane ring as well as the stsric
acceleration it m & afford.
H
0H3

[> h

etc*

the driving force for reactions of cyelopropyl systems has seme*
tines been ascribed to a m o d for releasing the strain energy in the
three^sit&ered ring (S3,l±5,8)*
to be entirely clear.

The situation, however* does not seem

For example, in the present eases (as will be

discussed h e l m in detail) the fastest rates ware net necessarily
associated with ring gening*
Facile ring closure under shat might be considered surprising
conditions further support the contention that ring-opening Is not a
necessary feature in the driving force*
Bijsethyloyclopropjrlcarbinol, uith hydrochloric acid, gave 5**ehloro~
&^tJurl*2*peatene which upon treatnsnt with aqueous potassium carbonate
reversed the process (5h)*
my

OE
owse

OH
Similarly* it m s observed in the present investigation that treatment
of trte^lopiropylGarbinol with concentrated hydrochloric acid or
treatment of the lithium salt of trioyclopx*opylcarbinol -with p-nitro~
benaoyl chloride yielded l^l^cycloprcpyl^h^hloro-l-butene which,
upon treatment with aqueous potassium carbonate again yielded tricyclo-*
propylcarbinol.

105

15*® inter©©nrerslon between earbinol and unsatarated chloride meet
Mfci&ar proceed® through a common earbonium im intermediate*

OK]

B*e controlling and conflicting factors appear to he the stability
of the earbciitnin ion (tertiary > secondary > primary), the stability of
the product (allylcarbii^l > cyelcproj^learbinyl) and the reaction
medium (mcleophiHclty of the reagent}*
U* the Internal Rearrangement
IHisopropyl^lcprcpylcarbiJ^l, di*(2»met^loyeloparopyl )ieoproKjrl-*
oaTbinyl, and dt©y©l©p©p^^
airaaltaneously with aclvolysis.

p*niir©bensoat@e rearranged
Rearrangement m s a function ©f the

water content ©f the solvent, as shoisi in table If*

Rearrangement of Several p-Hitrobenzoates in Aqueons Dioxane
As a Function of the ^fetter Contest of the Solved

106

107

9te £*#ili1sjr w ith Which rearr*ngam oat occurred d e e r w w d 1b the
WlST

which Is <$iite different from- th© order of aolvolysie rates (see fable H }*
fhere seems to be mo direct correlation between the reactivity of
the estors and their tendency to rearrange*

in the other hand* rearrange**

miwrii ap3pears to be favored in those eonpotinds which contained bulky
grot^>s attached to the rs&etiire canter* Methyl substituents on the
eyclopropene ring® favored reaxrongement, as did replacement -of a oyelopropyl with an isopropyl group*
fhat tester (and presumably ionisation) is essential to rearrangement
is shown by m

in Which diisopropylcycloptroi^lca^inyl p~nitro~

bensoate did not rearrange in anhydrous dioxana even after five days at
60° (Gompar© the rate constants in fable® 51 and 55 with those in fables
JO, 51, 5b, 55, 5$ and 5?}#

fhe conclusion was that the rearrangement

was not a separate reaction but was intimately involved with the solvolysis.

108

These observations, tog©thar with the fact that m increase in
wfcer content decreased th® amount of rearrangement, strongly indicated
an ioo>*palr internal return pharamianon* it was also observed that for
the reaction of dliacpropylcyeloprcjyl^

p^nibrefoemoate in

various abacus dioxari© ndjeiures, hath k and % increased uniformly as
the |sap ©ant of water Increasad sdiersas

increased as the percentage

of water was raised from 10't© IS to 20$, hot decreased again in
dtoxane containing 30# water {see Table 6)« This phenomenon can best
be saqplained in terms of an lon-pair intermediate iMoh can either
solvolyse or revert to rearranged ester# This phenomenon cannot be
readily interpreted in terms of two non^related reaction paths*
%■* Mechanism

All of tl» avidenea praaantad thus £ » Buggeats that th« oyolopropylcayblijyl aatow) Btudiad Bolrolytsa vlg an iojv-palr intermediate.
This may ha minsarisod fcy the Idnetio schaaa
j*
'

S .

A#

3C

Mi.IQiiliiiO ln T Wei1

J
t
f
j)
:
d
s
v

I

J

ioa-pair

Iil.i |-.HI|I|,|.|| n l'ililH o ii

E# *
dissociated
ions

&'* OH
Garbinol

E* * X
rearranged

ester
or for the solvolysls of dlisc^ropyXcyolopr^ie^iJEiyl p-nitrbbenaoate
In aqueous dicssane,

109

0=0

/

r oh

qh 3

CH,

,CH

./ \0 %

CH*

CH,

OH,

\CH/

or
GH-

■CHs

\

CH

CH,
U

V

GHa

110

Increasing the water conient of the solvent facilitates ionization
and hence increase* the overfall rate of reaction (k)* Since both the
rate ©£ solvolysis (ks) an© rate of rearrangement (kp) depend ©a the
concentration ©£ the ioa*pa±r, the observed rate constants, k, kc and
kr* d l l be increased as the water content increases (see fable 6)»
Furthermore, a higher eater content sill shift the equilibrium away
from lon~p&irs toward dissociated ions making replacement of the p-nitrobensoats ion with water (to yield the earbincl) the favored reaction
path,

the rate of rearrangement to new ester sill be enhanced as the

concentration of ion*palrs becomes larger, but If the water content is
made too great, the rearrangement cannot compete with dissociation, and
conqplet© solvolyais occurs,

fh© result is that as the ionising power of

the solvent Is increased, k, ke, and kr all increase! but ks Increases
more rapidly than kg*, the consequence being that ultimately no rearrange*
ment occurs, and carbinol is the only reaction product.
Methanol is not as good an Ionising solvent as water (55).

It would

be expected, then, if the proposed iompair mechanism is correct, that
substitution of methanol for water would favor internal rearrangement
over solvolysis.

this was indeed found to be the case.

When diisopropyl~

cyclopropylcarbinyl p~niiroben«o&te was solvolyaed in JQ% methanolic
dioxane, 66% of rearranged ester was formed,

this is t© be contrasted

with only k% of rearrangement in 70% aqueous dloxan®,
The observation that bulky groups appear to favor the rearrangement
Is also consistent with the proposed mechanism.

Such groups would

decrease the susceptibility of the ion*pair to attack by solvent and

Ill

also decrease the amount of diasooiation to free iona.
The proposed mechanism gives only the broad outline of the
reaction path*

For example, ks represents the sum of all rate con*

stents leading to earbinol and p-nitrobenzoic acidj it includes ioni­
zation to ion-pairs, dissociation of the latter ( possibly in several
discrete steps (37*38)), and reaction i&th the solvent*

Similarly, kr

includes ionisation to ion-pairs (of varying degrees of solvation)
followed by some unspecified rearrangement mechanism*

Additional

kinetic work, including a study of salt effects, would be required to
better define these mechanistic details*

Other experiments which

might further elaborate the mechanism could involve the stereochemistry
(using an optically active tertiary ester) and the disposition of the
oxygen in the rearranged ester (using, say, carboxyl 0

^labelled

p*nitrob«nsoats®)*
6. The Energetics
The enthalpies and entropies of activation obtained in the present
investigation are listed in Table 9*

Several generalizations can be

made from the data, and interpreted in a fashion consistent with the
proposed mechanism*
In a given solvent (say SG$ dioxane) the energies of activation
are relatively insensitive to variations in th© structure of the cyclo­
propylcarbinyl esters*

The observed differences in rate can be ascribed

largely to entropy differences*
In each case (triisopropylcarbinyl p-nitrobenzoate excepted| there
is no evidence that ion*paire are important her® (JU.8)) the entropy of

112

a o ttv a tto n la n e g a tl**.

ism, 8i»0a ionic

Shis is eorudatent wit]h an ionts&tion mechan­

ion-patr intermediates will require greater orien­

tation of m m tm nM m , solvent molecules than would the original neutral
ester* Several eases permit a detailed interpretation*
fh* isq^ortaht structural change in going from the <&cyulopr©pyX~
oarbinyl to the dtcyeloprc^lisopropylearbinyl ester is a change from
a secondary to a tertiary oarhinyl group* In the latter, because of
starlc requirements of the greap* the number of degrees of freedom is
less than in the secondary ester* But in the ion-paira derived from
each ester, charge .would be approadiaately equally dispersed (each ester
has two ©yclopropyl groups), requiring similar orientation of the
solvent* therefore, in going from reactant to transition state, the
tertiary ester iwfflifl require lass change in degress of freedom then,the
secondary ester and would have the more positive A S*#
On the other hand, &t©ycXopro$yliaop:ro^

and diisopropyl-

eyclopropylcarfeinyl p-nitrobensoates have roughly equivalent sterio
requirements restricting atomic motions in the ester* But in the former,
the presence of two cyeloprepyl groups permits a greater dispersion of
charge (because of mors contributing structures to the resonance hybrid)
in the transition state* this greater charge dispersion will not only
result in a lower A Si* (about 1 *$ kcal* difference was observed) but
yni also require less restriction of solvent orientationj hence A S
yfll b« more positive for the ester with two eyolopropyl groups.
For each case in Which simultaneous solvolysis and rearrangement
occurred, A 8* for rearrangement was more positive than A 3* for

113

solvolysis,

This is consistent with the proposed mechanismj the inter­

mediate 'which furnishes the rearranged ester is not as polar as that
■which proceeds to yield the earbinol and p-nitrobenzoic acid.

This

less polar intermediate will therefor© not require as constrained an
orientation of solvent molecules in the transition state and will have
a more positive entropy of activation*
e
The decrease in A S with decreasing water content that becomes
apparent in 90% aqueous dioxane reflects the increased restriction in
degrees of freedom in the transition state required for solvent orien­
tation in this relatively poorly ionizing solvent.
It was also observed that A H * for rearrangement m s greater than
A

h

for solvolysis for each case in which simultaneous rearrangement

and solvolysis occurred.

This is consistent with the mechanism because

rearrangement of the original ester to a new ester requires more bonds
to be broken than does solvolysis of the original ester to the original
earbinol*

114

SUMMARY
1* Cyclopropyllithium was prepared In good yield from the chloride
and finely divided lithium in refloating pentane.

Cyclopropyllithium,

and certain cyelopropyl-containing ketones -Mere used as the sources of
cyclopropyl groups to prepare the following new carbinols f tricyclopropyl, dicyclapropylisopropyl, di»(2~methylcyclopropyl) isopropyl,
dicyelopropylmethyl, and diisopropylcyclopropyl,
2m Tricyelopropylc&rbinol failed to give a p~nitrobenzoat@ by a
variety of methods; th© lithium salt, with p-nitrobenzoyl chloride (and
the earbinol with concentrated hydrochloric acid) gave 1,1-dlcyclopropylU-^chloro-l-butene, th© structure of which was proved by oxidation to
dicyclopropyl ketone and 3~chloropropionic acid,

The ehloroolefin, with

aqueous carbonate, was converted back to the earbinol#
3* The p~nitrobenzoates of th© remaining carbinols (except dicyclopropylmethyl) were prepared, as were those of dicyclopropylcarbinol and
triisopropylcarbinol. Their rates of solvolysis in aqueous dioxane were
studied, variants being the per cent of water and the temperature.

All

the esters solvolyaed with first-order kinetics and alkyl-oxygen
fission; the rates were th© fastest recorded for earboxylic esters of
aliphatic alcohols. Hydroxide ion was without effect on the rates.

The

products from solvolysis in aqueous dioxane were the original carbinols
from which the esters had been prepared; i,e,, there was no opening of
the cyclopropane rings.

Similarly, solvolysis in methanolic dioxane

US

gave methyl ethers of the original

two cyclopropyl groups on

th* earbinol carbon atom ware appreciably more effective than one such
cyclopropyl group in facilitating solvolysis*

The parallel effects of

cyclopropyl and p&enyl groups on reaction rates ware noted t
la certain cases, solvolysis to earbinol and p-nitrobenzolc acid was
incomplete! examination showed that solvolysis m s accompanied by rearrangement Involving opening of a cyclopropane ring*

The rearrangement

products were allylcarbinyl ester*! for sample, dileopropylcyclopropyl*
oarbinyl p-nitrobenaioate gave ii-ieopropyl-5j-m@thyl-3-h«3cei^rl p~nitro~
bensoate*
h* The rates, solvent effects, entropies and energies of activation,
and products are all consistent with a mechanism involving ionization
of the ester to ion-paire or dissociated ions, rearranged ester being
formed via internal return from the former and solvolysis products being
formed from the latter or both*

116

LITERATURE CITED

1* S. H. Rodd, "Ch@ad.stry of Carbon Compounds*w Elsevier, New York,
1953, Vol. XU, p. 23-39.
2. M. E. Royals, "Advanced Organic Chemistry,* Prentice-Hail, New York,
195U, p. 210-222*
3* R* A* Qgg, Jr. and W. J. Priest, J. Am* Chem, Soc., 60, 217 (1938)*
h. J* R* Lacher, B. Malden, &. R* Lea and J*D.Parker, J, Am* Chem* Soc,,
M * 331 (1950)*
5* M* T* Rogers, J. Am* Chem* Soc.,

25hh (19U7).

6. I. M, Riots, J* Am* Cham* Soo., 66, 88 (19kh).
7* C* 0*Bergstrom and S. Siegel,

J. Am* Ohm. Soc*,

2k* 1U5 (1952).

8. J. B,Roberts and E* H* Maaur,

J. Am* Chem* Soc*,

73* 2509 (1951).

9* A* Streitwieser, Jr*, Cham. Revs*, j>6, 571 (1956)* (a) p* 72?,
(b) p* 631-632*
10. E* M.Kosower and S* Winsteln, J* Am* Chem. Soc*, 28, U35U (1956).
11. E. M*Kosower and S* Winstein, J. Am. Chem. Soc*, 2§# U3U7 (1956).
12. 0. E.Curtis, Jr., Ph. D* Thesis, Michigan State University, 1955.
13* H. Hart and 0* 1. Curtis, Jr., J* Am* Chem. Soc*,

2§> H2, (1956).

lh* J. D.Roberts and V. G* Chambers, J* Am* Chem* Soc,, 21# 31?6 (1951).
15. J. D.Roberts and F. H* Dirstine, J* Am* Chem. Soo,, 6£, 1281 (19h5).
16. V* A* Slabey, J* Am* Chem* Soc,, 7U* h928 (1952),
17* P. D. Bartlett and E. B. Lelferts, J. Am* Cham. Soc.,

280h (1955).

18. P. D, Bartlett, S. Friedman and M* Stiles, J. Am* Chem* Soc*, jy>,
1771 (1953)*
19* H* Gilman, W, Langham and F. M, Moore, J, Am. Chem* Soc*, 62* 2327
(19UQ).

117

#6* R . V# S idg «lo kj "Th* C h *a le «l Tl —

and T h .tr Compound*,*

Ctaftaw* Freea, Clarewtes, 1950, Tel, 1, p. 81**
1 :3 ^ **°***** * *

(1955)#

° * J* Clettt, *>,, J, Am, Ch«m, flee** 77, 621U

22* Mm X. Shriner
G. Faison* *Yhe Systematic Identification of
Organic Compounds,* Third Edition, John Wiley and Sons, Wsw York,
19X8, p* l?!*
23* fit* lari and J* Hi Saradri, Chemistry and Industry, 1011* (1956)*
H u S* Berliner and 1* a* Altechul, J* Am* Ghera* $©o*,

XXXO (1952)*

■25* X* Heilbron, ^Dictionary of Organic Compounds," Cbeford University
Frees, louden, 1953*
16* X* F* Fieeer, wl«gperim«nta in Organic Ohamisiry,* Second Sdiiion,
B* 0* Heath, Boston, 19X1, p. 368.
27* F* Daniels, J* H. Mathews, ©t al*, "S^rimentaX Physical C^saalstry,19
Fourth Edition,
Co., New York, 19k9, p. 370.
28* $* Glasstone, K. J. Latdler and' H. %ring, "Theoryof Hats Frocesses,®
McGraw-Hill Book CO., Isa York, 19kO, p. 196.
29. C. K* Xhgpld, "Structure and Mechanism in Organic Chemistry,*
Cornell Diversity Free®, Ithaca, K. Y., 1953# (a) p. 763-7&X,
(b) Chap* m , M p. 752-782, (d) p. 3X5-355*
30* M* F* BaXYs, H* A* Doughty, J* Kenyon, and a* Poplett, J.Chem.
Bos., 600 (19U2).
31* M. P. Balfs, A* Am Brans, J. Kenyon, and K* 1* Hand!, J. Chem. Soo.,
803 {19X6}*
32. W. von B» D o lin g and 1 . 1* Z e ie s, J . Am* Gfcraa* S ee*, J g , X733
(1 9 5 3 ).

33. X. C. Bateman, H. g, Church, I. D. Hughes, 0* K* Ingold, and 1. A*
Taber, J* Chora* Soc*, 979 (19X0)*
3X. M* J# Bird, I. D. Hughes, and 0. K. Xagold, J* Chem. Soc., 63X
(195X)*
35* ft* mrasfcsim, J* As. Ohara* Sac*, J|, 1635 (1939)*
36* X. P. Hammett, "physical Organic Ches&srtry," McGraw-Hill Book Go*,

Weir York, 19X0, p* 52*

118

37* ft*
S , C llp p in g er, A. H. Fetoberg, 8 , Heck and 0 . 0 ,
JtoMjaeon, J* A *, She*. S e e ., 78, 388 (19S 6),
38* * « .H» .

2?B0

39.

«ad ft. W bw teln, J* Aa. Cham, S e e ., 78, 2763, 2767,

*

ft, mnateln, (rad K. X,. (Jewing, jr. to , Chain. See,, JJ,

kQ. H. L , (Jeering, I , D, N e r itt, (rad K. F . S llv e ra a ith , J . Am, Chem.
S e e ., ??. 5>0* g

J. P . Blanchard, end E. F* SilTrerrasUsh, J. to. (Sim,
See*, jg, 51i09 <19Si().

la . B. L. Searing,

U2* J* D. Robert© and 7* 0* Ghan&era, J* Am* Chem* Soc.,
Ii3* «J# 0* Roberts and R. H. H a w , J*. Am*

Uk*

503k (1751).

Soc*, JJ, 35k2

R* 0., Fearson and S* H* Laager, J * Am* Cham* to o *, Jfg, 1065

1(5* 8* toateln and R. Adame, J* A®. Chem. Soc., jg, 638 (191$).
U6, 1* 0* Brow* and H. J b a # , J* Am* Chem* S o c , J J , 558k (1755)♦

k7* H* G* Broun and H. L* Bemais, J* Am* Cham, Soc*, 22* 1° (1753)*
1*8* F* P* Bartlett and M* SMloa, J* Am* Ghemu Soc.,
1*7. 8* MLmieln, S* Orunmld, and H* ¥. Jooea, J* Am* Chem* Soc*, 73.
2700 (1751)*
50. F*

Bartlett and M* 8* tMtia* J* Am* Oban* Soc*, |J, 2801 (1755)*

51. A* D* Which, franc* far* See*, J$g, 177 (19147).
52. W* S* OAHo^f and 8* F* Barker, J* Chem* Fhys*, 30, 68 (19U2).
53* E« K. Kosovar, Frivate communication,
5k. f * A , Favorekaya and S* A, Fridman. J* M u Cheat* (B.S.8.R.), 3^,
2*21 (19k5). C* A *, kO, k655 (191*6).
55. E. Grunv&ld and S« WineteAa# J* Am* Chem* See*, 70. 8U6 (19U8),
56. A. 0* Worthing and J* Gaffner, “treatment of Experimental Data,11
John M X ey and Sons, M r Fork, 19143.

AFPERDIX

119

th© Data Obtained from the Solvolysis Rate Measurements
the following tables contain the data obtained from the rate
measurements»
t

a tlm© in seconds

7

m volume (ml.) of standard sodium hydroxide required to neu­
tralise a 5 ml. aliquot of the reacting solution*
m volume (ml*) of standard sodium hydroxiderequired toneutralise
th® theoretical amount of p-nitrobenzoicacid in a £-ml* aliquot
obtainable from the weight of ester used in the run*
volume (ml.) of standard sodium hydroxide required to neutralise
the total amount of p-nitrobensoic acid liberated in a £~mi,
aliquot when this amount was significantly less than the theo­
retical.

Plots of log (Vf-V) versus t or log

) versus t were linear

and the specific rate constants were calculated from the slopes of these
lines.
k

* ks ♦ kr

ks • rate constant for solvolysis
kr * rate constant for rearrangement
where
WlltS* “

'■
«ih
i M

kr

.
.
.
j,

120

Table 13
Solvolysis of 0+007005 Molar Btcyclopropyliaopropylcarbinyl
p**Nitrobenasoate in 9S% Dioxane - $% Water at 60
frra.llliLJIIl'ii.iaHtBlMBfltaitteBBltBteglff'Hlliii

t
see.
156
388
528
701
851*
1060
1350
1507
1708
1973
2351*
2807
321*1
3761
1*831*
5831*
6832
IOI89
51*275

j!u_j«l wii 1—

v
ml.
0 .1*1*
0.86
1.02
1.28
1.1*1*
1.70
2.05
2.20
2.31*
2.50
2.75
3.00
3.11*
3.28
3,1*6
3.56
3.62
3.61*
3.68

1|
.

iu
ji iij i . W n iiiy i t n
u
n
im
—
w
n
w

v Vf/?f»
ml.

vf - v vfAf'
ml.

0,1*8
0.91*
1.11
1,1*0
1.57
1.86
2.21*
2.1*0
2.56
2.73
3.00
3.28
3.1*3
3.58
3.78
3.89
3.95
3.98
i*.02

3,51*
3.08
2.91
2.62
2.1*5
2.16
1.78
1,62
1.1*6
1,29
1.02
0.71*
0.59
O.ltl*
0.21*
0.13
0.07
0.01*
0.0

TltrantJ 0.008?l6H H«0H
Vf/Vt* • 1*.02 ml./3.68 ml. * 1.09
k * 5.81* x 10"* sec."1
kB - $.35 x 10“* sec."1
kj. - 0.1*91* x 10"* aao."1

321

Male Ik

Solvolyaia
.y«i« of 0*006185 Molar Dieyclopropyliaopropylcarbinyl
j^Hltroboaaoate in $$% M wm m * 3$ Water at 60
3E

*s
t
»©o«
212
box
m
978

W 1£.

ml.
0 1*9

.

0.53

3.02

0.76

0.88
1.12

2.1*3

1.01*
1.22

1*1*1*

1133

1,60

1320
1603
1788

3U9S

1973
232*6

2392
255®

V*j&»
ntlV

mi*

1.77
2.12
2.21
2,32
2 1*1
2.50

.

2.68

3832*

2.90

1*902

3.06

691*9
20103
63593

3.22
3.23
3.®

TitrantJ

2.73

1.32
1.55
1.73
1.91
2.31*
2.29
2.38
2.50

2.23

8.00
1,82
1.61*
1,21

1.17
1,05
0,95
0,85

2.60
2*70

0.66

2.®9
3.13
3.30
3.1*7
3.1*1*
3.55
0 . 008715 ®

.

0 1*2

0.25
0.08

0.06
0.0
HaOH

V * A f * * 3.55 blU/3.29 nl.
k m 5*5, i* 10"'* B8C.“*
k_ • 5,1 :x 10"* m o .**
k_ » 0.
X 10** MB.**

1,08

i2a

Tafel®

IS

Solvolysis of 0*Gil2U Molar 3Hoyelo|^Oijyli«0|^|3ylca^i^vl
I^SitrObo»aoat« in f&$ M .vm m * M% T&tter at 25®
i
sac*
230
71*0
980
3180
1390
2280
3913
2t82®
8090
7800
8730
31782

V
Wit f

o,Si
0.60
1.02
1.3*
1.32
1.89
2.8S
3.18
3.70
U.28
k .$ 0

*.38
fltrantt 0.0096868 H*0H
V*
r m $.80 ml. „
'•♦'I
k * 1*61 at 10 sac* 1

Vf * V
mi.
5*29
5*00
U ? 8

u#6a
IwW
3*91
2*95
2*68
2*10
1*52
1*30
0*6B

123

Table 16

Solvolysis o f 0,0l8c8 K ola* Dic^lopropyliBopropylcarbiHjyl
p-JRl-faPobaiaiattte &a 903? B ie x s a e - lio# V ater a t 25°C
V
m l.
1^6
510

0.U2
0 .9 5

Vf - V
«a.

8.91
8.38

1:11
8.03

l.&L
lt*0O

tm

U.28

3952

1**81*
6*20

6*38

7.60

iol*$o

3*25

Tltranti
%

0.009686s s$m

* 9.3,

ic «* 1.5.\ **10"* see."1

5'.«

3.86
3.13
2.1,5
1*73
1.08

12k

table 1?
SSolvolyeis of 0»0095k9 Molar Dieyeloprcpjrlisoproiqrloarbinijrl
p-SiiiMibaiiBeate in 905 Diojosuae- w% Water at kOTS
s ± a a tta B a s g a a te M * e s 3 B ^ ^

v i M « a t e a « a M a m u' ■-w in i»„. i» i

t
sec,

7
*&,
m
»
i—
a
n
a
iw
e
iw
n

M
$$a
m

919
1107
1*67

itos

1682
283k

2683

f t - . . ,... jif ■^ y io afijL;,n ^ fr^ ,

iiiia'iW
W
ii'W
i^^iie^e
iiia
iiiiia
iiH
in
i
e
iia
iW
'i'ia
*
!1
' »i»
e
»
i*
*
W
a
w
*iv
>
iiW
)
it
iiH
M
iii
>
i
in
m
e
iiiri Iliu
m
' ir
e
n

0.6k
1.22
1.68
8.36
2.73
2.9k
3.16
3.50
3.7k
3*9k
li.25
k.50
k.70
1, O
M.S’
$ .M

6k800

Vf » V
ml,

5.U
nti 0,0093k9H NaOH
5.11 al.
k » 6.60 x 10** see,"1

k,k7
3.89
3,k3
•an/*
J>fW
2,75
2,38
2*1?
1,95
1.61
1.3?
1*1?
0.86
0.61
0,11
#v it£
0*01
#♦0

125

Table 18
Solvolysie of 0*008258 Molar Dicyolopropyltsopropyicarbinyl
p~Nitrobenaoat© in 90% Dioxan© ** 10% Water at 1*0°C
aatm
t
sec.
11*1
1*71*
61*1
605
972
11*26
16?2
1856
2028
2661
3231*
1*132
5259
6310
7903
12095
61200

7
ml.
0,60
1.33
1.65
1.92
2.20
2.78
3.02
3.20
3.35
3.66
3.91*
l*,ll*
U.22
1*.30
1**36
l*.l*o
l*.i*2
Titrant* 0.0093U9H NaOH
Vf » 1*.1*2 ml.
k - 6.77 x 10”4 sec."1

7f-V
ml.
3,82
3,09
2,77
2,50
2,22
1,61*
1.1*0
1,22
1,07
0.71*
0.1*8
0.28
0.20
0.12
0.06
0.02
0.0

126

Table 19

Soltolyili of 0*008175 Molar Dicyclopropylioopropylcarbinyl
p-Nitrobenaoate In 90$ Dloxane - 10$ Vfeter at 50°C
t
890,
79
236
I4O3
5itU
689
822
951
1108
1300
11*58
I608
2178
21*71
3515
1*821

V
ml.
0.75
1.52
2.16
2.66
3.00
3.28
3.51
3.72
3.92
3.98
ii.03
1*.21»
1*,26
h.32
kt33
TitrantJ 0.0093UM NaOH
Vr * 1*»39 ml. .
k * 16.7 x llT* sec."1

Vf-V
ral?
3f61*
2 t87
2f23
1+73
1+39
1.11
0.85
0+67
o.hr
O.Iil
0.36
0.l£
0.13
0.07
0.06

127

table 20

Solvolysis of 0*008159 Molar Dicyclopropyllsopropylcarbinyl
p-Nltrobenzoate in 90JS Dioxane - 1056 Water at 50 G
t
seo.
72
279
1*29
591
790
969
1169
1360
1539
1729
1898
2117
2373
2868
93U3

7
ml.

VfV
ml.

0.65
1.60
2.25
2.76
3.25
3.52
3.76
3.89
lt.03
il.12
1*,19
1*.23
1*.25
U.25
1*.28

3.73
2.78
2.13
1.62
1.13
0,86
0,62
0.1*9
0,35
0.26
0.19
0.15
0.13
0.13
0.0

Titrantl 0.009311N HaOH
Vf m U.38 ml.
k * 16,8 x lO"4 seo.”1

128

Table 21
Solvolysis of 0,01255 Molar Bicyclopropylisopropylcarbinyl
p-N±trobenzoate in 85$ Bioxane * 15$ Water at 2frC
t
eeo,
21*0
1*111
605
?85
955
1U5
1295
1560
1700
1895
2175
2350
2570
2895
3220
5300

?
ml*
0.91
1.1)0
1.92
2.33
2.71)
3.01
3.38
3.80
1*.06
It. 28
1*.60
1**76
I*.98
5.38
5.66
6.1*2
Tltranti 0.009l*56H KaOH
*• 6.61* ml.

Yf*V
ml.
5.73
5,21*
1*.72
It.31
3,90
3.63
3.26
2.81*
2.58
2.36
2.01*
1.88
1.66
1.26
0.98
0.22

m

Table 22
SolTeljnsls of 0,007038 Helsx1Blaye
p-HitrebeBw&abe In 65# Max*

i & A m at 25>°0

W*fei!BWp|*a8t*W^
V
aa© *
- 1*01*
6l*0
81*0
101*0
1225

11)10

1612
1870
2025
2255
21*70
27101
1*1*15

V
?il.n
0,81*
1.16
1.1*0
1.66
1.86
2.01*
2.18
2.38
2.1*8
2.62
2.77
2»?2
3.38

Tttraat* 0.009l*56S NaQH
tf * 3,72 ol.
k • 5 ^ 7 at 10"“ see,*1

Vf-v
ml *
2.88
2,56
2,32
2,01*
1,86
1.68
1*51*
1,31*
1,21*
1.10
0.25
0.80
0.31*

130

Table S3
8 e lv o ly a l* o f 0.008261* M alar O lcgrelcqpvoti^aepra^learblR yl
p -H ltro b «n *o *ite In 80Jf Diorama * 20j< Vkt« r « * 7®C

%
SOG.

91*8
1506
2U7
3682
3302
Ul*30
5501

Vf-f?
wl.

0.92
1.21*
1.53
1.72
2.02
2.36
**71

10386

3192
3.12
3.22
3;i*3
3.1®

128?3

3.86

sm
7253
7993
QfV*.

s m

Tltranfc* 0.QQ9290H RaOH
7. *' l*.t*5 ai.
kx * 1.52 * lcr* sac.-i

3#f>3
3*fcl
2.?3
2.73
2.U3
8*09

1.7U
1.53
1.33
1.23
1.02
0.87
0;71
0.59

131

S o lv o ly a t# o f 0*01012 H & lor ___
p^NItrotM m fcoate la 80# Oloxana * W $ W otor a t f WC
rawTwwaitmv
w m mm
mnmistuw
¥
ml.

916

wv»

II

1.22
1,1*8
l.®7
2.20
2.52
2.95
3.31*
3.55
3.80
3.97
U.22

8713
3U79
ysi
5518
6205
TSB27
7962
9200
K31&5
ll2tl»5
12973

k .k z

1*•63
lt.78
Titranti

0.0092908 BaOH

V# * 5,1*5 ffll.
k * 1.5U * I®*4 mhs,**

vc
*
ml*

It,23
I’
M

3,85
8*93
2,50
8.11
1,90
1.65
1.1*8
1.83
1,03
6.82

O.67

•i!SUStSiSSSSSfPf\

132

fable t%
Solvoljaie ef 0*009522 Molar Bloyelopropyiisoproi^rleaa-binjrl
P^Kltrobeaaoate ia 80# M m m m <* 20£ Water at 16°C

t

mmm

.
e
a
w
w
-'a
r

261*
513
691*
89?
nie

li*6?
16?5
187?
2151*
2388
2595
2978
3U26
UUU6

7
A ,

0,p8
1.W*
1.71*
2.06
2.36
a.76
3*02
3.20
3.1*1*
3.59
3.76
3.98
1*.U*
l*.3l*
I*.1*8
Titrantl 0.009561H NaDH
TV • I1.98 ml,
Jt » 5.01 at lCT* aee.“*-

T£ f
A f

h.00

3.21*
2.92
2.62
2.20
1.96
l.?8
l.Sh

1.39
1.22
1.00
0,81*
0.61*
0.50

133

table 26
Solvolysl© of 0*01019 Molar Dic^rclopropyliaopropylcarbinyi
p-Nitr©benzoate In 80$ Diojcane - 20% Water at 16 C

t
sac.

V
ml.
1.U*
1,1*5
1,80
2.06
2,31*
2.53
2.82
3.06
3.20
3.38
3.55
3.71*
3.93
U.15
!*.1*0
1*.5U
2*.65
5.30

312*
501*
681
81*6
1012
1201
11*13
1605

1778
191*1*
2139
231*8
2631
3036
31*70
3962
1*1*60
10000

Tltranti

0,00956m MaOH
5.33 ml.
1*,78 x 10~* sec."1

Vf-V
ml.
1*.19
3.88
3.53
3,27
2.99
2.80
2.51
2.27
2.13
1.95
1.78
1,59
1.1*0
1.18
0.93
0.79
0.68
0.03

13U

Table 27
Solvolyeis of 0.009368 Molar Bicyclopropylisopropylcarbinyl
p-Nitrobenzoate In 80* Blcucaae - 20* Mater 0.009525 '
Normal In Sodium Hydroxide at 16°C
t
••0.

V
ml.

228
las
720

Ii.l7
3*87
3*1(5
3.09
2.78
2.5i»
2.33 ■
2.01
1.61
1.U9
1.29
1.09
0.89
0.71*
0.58
0.36

1130
1390
1632
1921*
21(38
2601
2989
3389
3887
1(383
1(933
5976

TitrantJ 0.009525H HOI
V- * 0,08 ai.
kf » U.55 x 10-» aao.*1

¥ * ¥f
ml,
U.09
3.79
3.37
3.01
2,70
2.1(6
2.25
1.93
1,53
1.U1
1.21
1.01
0.81
0.66
0.50
0.28

135

?*bl* 28

Solvelyais of 0.0088U5 Molar Bic^Xopropylisopropylcarbinyl
p-Nitrobenaoate in 8C$ Dioxane - 20% Water 0*009525
Normal in Sodiom Hydroxide at 16°C
t
sec.
361
$62
766
972
1181*
11*32
1680
1980
2339
2831
311?
1*21*9
5267
5505
6600
7637

V
ml.
3.96
3.62
3.30
3.08
2.7?
2.1*8
2.30
1.96
1.77
1.51*
1.1*0
6.61*
0.68
0.63
0.1*8
0.1*6
Titrant* 0.009$2$S H01
Vf * 0.36 ml.
k * 1*.73 x 10”4 eao."1

7 - 7.
Ml,
3*60
3.26
2.91*
a.72
2.1*1
2.12
1.9li
1.60
1.1*1
1,18
1.01*
0.1*8
0.32
0.27
0.12
0.10

136

Tabla 29
S o lro ly a la o f 0.0323$ M olar B ieyeloprepg^sepropgftcarbligrl
p -H itro b «n eo *t« In 60$ Olonem * top >fater a t 23*0

%
IMmi*

t
al*

ifUfiiiiir iiiiwi i i>nfnnjiii i iiiwiMa^MtMiniwiaiioi ii ■nn iin*nM>»^n*«n»»«4>»w»ifiwiixi^ii)*^^ ii!aiif»>i 11—i

163
350
501
619
740
8146
956
1105
1255
1437
1610
1790
2033
2355
2764
6?O0

%*v
^OLf.
mwh.ihm w im iw i.

n

1.7 8
2.?8
3.52
3.9 4
4.4o

24.68
i«»92
5.22i
5,4 3
5,724
5.9 0
6,0 2
6.1 5
6.286.4 0
6.52
Tltranti O.OD92$QB HaOH
Vg <m 6,62' nl.
k * .13*2 x V T * aae.~*

(f jii mi ji<iiiw<»«iawyii ii»^ »vii i«m

4.90
3.90
3,1 6
2.74
2.28
2,00

1.76
1.44
1.23
0.94
0.78
0.66
0.33
0,40
0,28
0.16

137

Tsbla 30
S©lv®l3f«to **£ 0 #0O9?2 Molar
p*$atr©fee9^soat« In 00# Btaaom* - 20# m t e r at 2$*Q

t

?

rUTWT, .

lb3
325
U67
5n
?b3
888
ita o
3133
1268

\i$r}'

1577
170?
1878
1999
227?
86b9

& ■ a

miT

l.bO
2.22
2f72
3*18
3.5b
3.82
b*06
b.26
b*Ut
U.63
b.72
U.SO
i*.?0
b»98
5.11
5*30

3.92
3.10
2.60
2,1b
1.78
1.30
1.26
1,06
0.90
0.69
0,60
0,52
0,bi
0.3b
0,21
0.02

0.0091308 m m
5.32 *a ,
■
2 3 * 0 k 10 * s e c *

mramfc*

Vf •

a&*

138

Table 31
Solvolysis of 0.009305 Molar Bicyelopropylisopropylcarbinyl
p-Nttrobenzoat© in 80# Dioxan© - 20% Water at 25°C
t
see.

?
ml.
1.3 0 '
1.82
2.22
2.63
2,98
3.32
3.56
3.80
1*.00
1*.12
1**21
1*.38
1*.1*7
1*.50
1*.71
lt.75
U.86

159
283
385
SOI
625
71*1*
875
992
ml;
1219
1328
11*61*
1609
1776
1951
2108
21*50

Tltranti 0,00925® KaOH
7? * 5*03
k

* 13-5 x IQ**4 sec.'*1

Vf-V

3,73
3,21
2.81
2,1*0
2.05
1.71
1.1*7
1.23
1.03
0.91
0.82
0.65
0.56
0.1*5
0.32
0.28
0.17

139

•Sable 32

Solvolysis of 0.00^022 Molar DicyclopropyUsopropylcjpblnjrl
p-Nltrobanaoate In 80$ Dioxane • 2C Water at 2JrC

%

t
sec.
135
205
26U
332
1*27
5U*
583
637
710
78lt
875
961*
1027
1107
7287

V
ail.
1.53
1.71*
2.01
2.1*2
2,?2
2.98
3.22
3.1*1
3.57
3.83
3.99
1*.16
it.23
l*.l*o
5.1*0
Tltrantt 0.008182N HaOH
Vf * 5.51 ral.
k * 13.5 x 10~* see.

Vj-V
ml*
3*9®
3*77
3.50
3.0?
2.79
2.53
2.2?
2.00
1.91*
1.68
1.52
1.35
1.28
l.ll
0.11

11*0

Table 33
Solvolysis of 0.005£22 Molar Di-»(2<-methgrlcyclopropy'llisoprow-lcarbinyl p-»M±trob©nzoate in 90% Dioxane - 10$ Vfeiter at 16 C

b
see.
li*6
337
678
1098
1586
1981
3198
1*809
32310*

7
ml.
0.1*0
0.$6
0.83
1.16
1.1*1*
1.62
2.16
2.66
3.5U

w»
51.
0.1*3
0,60
0.90
1.25
1.55
1.75
2.33
2.87
3.82

vf * vl£
ml.
3,39
3.22
2.92
2.57
2.27
2.07
1.1*9
0.95
0.0

Titrant* 0.007223H NaOH
Vf/Vt* • 3.82 ral./3.£l* aO.. » 1.08
k * 2,71 x 10** see.*1
kg • 2.51 x 10-* sec,-1
kr ■ 0*199 x 10“* see.”1

11*1

Table 31*
Solvolysls of Q.0051*98 Molar B±-( S-methylcyclopropylJisopropylcarbiiijrl
p-Nitrobensoat® in 90% Dioxane - XO% Water at 16°C

t
see.

376
077
1278
2071*
3302
1*913
6632
9372
32321*

v
ml.

ml.

0.57
0.95
1*23
1.72
2.21*
2.68
3.01*
3.26
3.50

0.62
1.03
1.31*
1.87
2.1*1*
2.92
3.31
3.55
3.81

7f
vfl
ml.

3,19
2,78
2.1*7
1.91*
1,37
0,89
0,50
0.26
0,0

Titranti O.OQ7223H HaOH
V>Af* » 3.81 »l./3o0 ml. » 1.09
k * 2.88 x 10-“ see."*
k_ - 2.65 x 10"“ sec."*
k" - 0.231* x 10"“ see."1

11*2

Table 35
Bolvelysla of 0,006240 Molar
jMSitrobenaoate In ?0f Bieaane «
t
80C*

f
b1*

If*
1(QL#

m

0.64
1.06
1
2.06
2*57
3.04
3.51
3.84

0.60
*
*. e*

IS

1333
18230
882(0
458o
3383®

km

1.85
2.23
2.70
3.3?
3#«1
4.16
iu36

Mater at

*£$■
3.67
3.21
2.51
2.13
1.57
1,06
0.55
0,20
0 ,0

Titranti 0*00715®* B*0H
VfAr* * 4.38 nl.A.02 «flu * 1.0?
tc • 7*02 « 1 # * eee,** •
k* * 6,47 * H P * «ee.*»
ky ■ 0.547 * 30** e e c . 1

12*3

fable 36
Stelvol^a of 0*OO6S£k Molar Di
p^Kltrob<maoat© in 90$

Mbbar at 25°C

?
ml*

nl.

0*66

19$
1*13
1.63

601

a .lit

981*
1339
1880
8858

i*

28598

u.ou

Sitn-wst*

1*?8
8*33

8.81
3.29
3.83
1**80

0*OOfl58H RaOH

V ^ 1* kJW aauArfk «i* * 1.

k

*>'7.1& x 1©** (we.**1

k* • 6.58 x HT* whs .""*
ky * 0*586 x 10"* o*«, *
Hthmm

3.7U
3.17

2,68

1.59

1*11
0.57
007
0.0

1UU

Table 3?
Solvolysis of Q,GO£97f> Molar Di-*(S-methjrlcyclopropyl)isopropylcarbinyl
p-Nltrobeazoate in 9Q% Dioxane * 10# Water at 35°C
t
sec*
86
2i*5
$Q$
6U5
895
1190
190U
86UO0

vr

7
ml.

nit

0.87
1*58
2*1*6
2*72
3*12
3.38
3#6U
3.79

0.96
1.7U
8.71
3.00
3.W*
3.73
a.01
it.18

Titranti
KaOH
m ^*18 ffll./3*79 s&. * i a o
k * 17*8 x K5*4 sec .~1
ks * 16,2 x IQ1**4 see*-*1
kr *» 1*67 3E IQ*"4 sec,*"1

vf -1
nil.
3.22
2 «l(li
1 .U7
1.18
0.7U
0.1*5
0.17
0.0

Table 38
Solvolysl©
0*006258 Molar £i~(2-methylcyclopropyl)isopropylcarbinyl
p-Kltrobenaoate in 90$ Bioxan© - 10$ ^feter at 35°C

sec.
80
261
1*05
607
87$
1182
171*1*
9)[11
72000

ml*

ml*

ml.

0.82
1.71*
2.21
2.75
3.22
3-51
3.81
3.50
3.92

0.92
1.9U
2.1*7
3.07
3,60
3.92
U.26
U.36
1*.38

3,1*6
2.1*1*
1.91
1.31
O.78
0.1*6
0.12
0,02
0.0

Tttrant* 0.0071U6N NaOH
VfAf*' * U.38 ml./3.92 ml. * 1,12
k » 18.U x 10“* osc."1
ks , 16,5 x 10“* t o o ,-1

11*6

T a b le 39
Solvoiyeie o£ 0.006952 ilolar Dt«*(gHEnethylcjrclopropy'lJisopropyleax'bisorl
p^Hltrobenasoate in 9Qg Dioxane - 1C$ Kaier at 35°C

vff*

t
®S0,
82
220
358
553
778
958
1580
2i*67
93600

V

?
ml.

ral.

ml,

0.88
1,68
2.28
2.92
3.U6

0.98
1.67
2.5b
3.25
3.86
U.09
U.59
1**77
U.86

3,88
2,99
2.32
1.61
1.00
0.7?
0*2?
0.09
0.0

3.67
U.12
U.28
U.36

Tltrants 0.0071U6N HaOII
VfA f * « U.86 itl.A.36 ml. * 1.12
k - 18.6 x 10-* sec."*
k- • 16.7 X 10"* BBC."1
kr » 1.91 x 10"* soe."x

Uff

table 1»0
Solrelysis at 0,005085 Molar Bl*{2^thyl<^elbwe|^l)lsoprop7^axbl»7l
p^itaredseaeoata ta 80$ Bloxsaa - 20jfMftft*r aft ?°C

........

ft

T

Me.

mi.

159

1.22
1.51)
1.90
*#13
2.1)0
2.7*
3.00
3*38
3.83

m
m

6&3
890
WOk

180®
£608
79200

tftfttfaaft* O.OG73O£0 N a m

Vr * 3.85 ml.
ft* • 8.01 x 10** Me.-*

7frff
ffll,
a.<a
2.29
3*4^3
1.70
1.1»3
1,11
0,83
0.1)5
o.m

XUS

tfafcla la

Solvol^rsis &t 0*006059 Molar Bi*(
in 805 M m & m -

at

;r£a^f;yl
l
y%g5gaB!

%

sec*

* f
1&»

®3U
■*#«

m
n
n
u
w

pn>'11. m II

X.06
i.52
X»8S
2.2i»
M b

3
«*o*

.^*40

0.?u

3»80
i*,Xlt

W.ta?aat» 0.0073062 HaOH
T# * U.X5 rax.
k ■* 8.09 * lcr* **c."'1

2,26
1*50
x,xo
0.34

0.01

11(9

Tattle 1*2
SolvoJysta of 0,008950 Molar BilaoiBr^l®yolop*N^earbli«rl
p-Httrofcewsoale in 905 Bloxana * 105 Watar at 6o»C
ssawsswasa;

t
'see.

m

910
2762
8678
6U

?
ad.

asli

0.20

0.71

0t&U
0*te

&M

1*56
tM

U.2U
3,53
2,1*0

o*M

XM
33538
73008

Hite

18997U

i*te
x«te

81*813

vM
% *

ktX l
It*■
i
,<>Z*9

k*70
5,09
5*©9
5.09
5,o?
n »o i

% A f # •* s*os>
«&* * s.;
k *0,733 3E 10** ******
It* * 0*JH37 M .I T * *** . ^
kr *
ac 10** a**#*"*1

0,98
A#*J>
SfT
*7
V
0*30
0.0
0*0
04
0.0

050

t m & U3

0*Q0£31? $fo&ar B iis o p r^ ^ lc s n ^ p rc ^ lo a x b lx ^ rl
iM £©$ I&ossa&ft * W
ftSSBfjSSjSi

b

39H&
vV f

%

M
ufti*
»«W»#

(jfrdftra*i

333©l

72319
m m
is m s

W A g # fci 60°C

vHK

ml*

nl.

0.23
0.26

0.79

4,51

V«J

1.32

0,8
©.s
1.5
i .j

2.94

2,36

4.23

1.
li

ax*
Wk>'"fa

1.48
1.48

G.93

4.80
JM»

m

0,50
0,89
0,0

S.30

1.48
1.48

SlteaaM . O.OOS791H H*0H
7*ff|» • 5,30 *a.A.48 ail, - 3.38
k * 0.745 x 10-* #•»,***
k« » 0.2G8 k 10*** we, *
1%. * 0.537 * 10s* •»,**

0^0
«4

151

fable kk
Solvolysis of 0.01021* Molar Diisopropylcyolopropylearbinyl
p-Nitrobenzoat© la B$% Dioxane * X$% Water at

vl£

t

see.
261*
7U8
1359
2519
2907
3lt53
1*223
1*86?
5533
6751
8025
1021*3
13791*
191*83
287WL

7

WZt
?
?

vf - vli

Yt'
Tf1

ml.

ml.

ml.

0.35
0.50
0.6?
1,03
1.15
1.30
1.1*1*
1.53
1.6?
1.82
1.91*
2.08
2.26
2.35
2.35

O .87
1.25
1.67
2.57
2.87
3.25
3.60
3.82
l*.17
1*.55
lj.85
5.20
5.65
5.87
5.8?

5.00
i*;62
i*.2o
3,30
3,00
2,62
2.2?
2,05
1.70
1.32
1,02
0,6?
0.22
0.0
0.0

Tltrant: 0.00871&J HaOH
Vf0£* " 5-87 ral./2.3S ral. • 2.SO
k - 2.12 x 10~* nee.*1
k~ - 0.850 :: 10** wo,*1
kr «• 1,27 x 1CT4 see.*1

152

Table 1*5

SolvolyalB of 0.008655 Molar Dlisaprojiylcyclopropylcarblnorl
p-Hitrobenzoata In 85% Dioxana - 15sS water at 60°C

aec.
277
681
1229
22*82
2891
3389
1*21*1*
1*81*0
51*60
661*5
7701
10191*
13761
191*1*0
28666

ml.

ml.

nil.

0.25
0.1*1
0.58
0.89
0.91*
1,05
1.21*
1.32
1.1*3
1.52
1.61
1.80
1.90
2.00
2.00

0.62
1.02
1.1*1*
2.21
2.31*
2.61
3.08
3.28
3.55
3.78
U.00
1*.1*7
U.72
1**97
1*.97

1*.35
3.95
3.53
2.76
2.63
2.36
1.89
1.69
1.1*2
1.19
0.97
0.50
0.25
0.0
0.0

Titranti 0.008716N NaOH
Vf/Vf' - U.97 ml./2.00 mL. - 2.1*9
k • 2.05 x 10-* aec.-1
k. • 0.826 x 10-* sec.”1
kr » 1.23 x 10-* sao.-1

153

Table 1*6
Solvolyate of 0*00921*2 Molar Dilsopropylcyclopropylcarbinyl
p-Nitrobenzoate In % % Dioxana * 1$% Water at 7Q°C

t
see.
286
1*1*9
710
853
1125
1267
1390
1672
1889
2185
21*50
2825
3320
1*1*30
5803
7818
11753
501*1*3
8933U

V
ml.

ral*

0.36
0.50
0.70
0.82
O.98
1.06
1.13
1.28
1.36
1.1*3
1.52
1.61*
1.70
1.82
1.89
1.91
1.92
1.98
2.00

0*88
1*23
1.72
2*01
2*1*0
2*60
2*7T
3*11*
3.33
3.50
3.72
1**02
1**17
it*1*6
1**63
1**68
1**70
U.85
k*90

Titranti 0.009i*l*2H NaOH
Vrftr' m I1.90 ml./2.00 ml. • 2.1*5
k « 5.69 x 10*“* sac*-*1
kg - 2.32 x 10-* seo.“i
kr - 3.37 x 10"* sac.-1

Vf-V?f
n*
ml.
1*.02
3,67
3.18
2t89
2.50
2,30
2.13
1,76
1,57
1,1*0
1,18
0.88
0.73
0.1*1*
0.27
0.22
0.20
0.05
0.0

15k

Tabla it?
S o lvo lysia of 0.01096 M olar DiiaojH'Q pyleyBlopropylcM 'fclnyl
p-Kirrobem s#ate ia 85* W awwa * 15* W atar a t 70*c
smsgssssasgasssssasBsas:

t
»«e.

7
isI •

4**
*
ail.

105

0.2U
0.it6
0.58
1.02
1.15
1.27
1.50
1.70
1.82
1.96
2.02
2.18
2.22
2.22
2.28
2.3U
2.3U

0.60
l.llt
1,1*1*
2.53
2.86
3*15
3.72
U.22
lt.52
U.87
5.02
5»kl
5.51
5.51
5.66
5.81
5*81

m

1*67
941

1115
1365
1758
216?
25?3
311U
361tl
U?02
5823
7166
13037
51693
87372

V ^ «

Titranti 0.Q09ltk2H K&OH
Vr/Vf* * 5*81 ral./2.3k ml. • 2,.1*8
k * 5.79 x IQ"*4 »«.“*
ka » 8.33 * I®** ooe."*
kr » 3.1*6 * ic r * ooo.*x

Ml.

5,21
M7
i*,37
3,27
2,95
2,66
2.09
1,59
1*29
0,9k
0,79
0.1t0
0.30
0.30
0.15
0.0
0.0

155

Tcbla 46
3 o lvo lyala o f 0*006793 Molar D ilaopropjrleyolojpropylearbinyl
p-M lrrob«nao*ta la 85)6 Bloxana - l$f tfe ta r a t 90°0

i

T

nm *

n l.

102
232
343
464
ATI,

736
863
1033
1197
1363
2183
8956
3775
78221

0.40
0.56
0.73
0.99
1.10
1.21
1.28
1.37
1.44
1.46
1.61
1.72
1.74
1.74

*

7f*vl£

ral*

®1.

1*0?
x*S©
1*96
2.66
2.95
3.23
3.44
3.68
3.86
3.92
4.32
4.6a
4.67
4.67

3.60
3,17
2,71
2,01
1.72
1,42
1,23
0,99
0.81
0,75
0.35
0.G5
0.0
0.0

ntraat* 0.009397S KaOH
* I*.67 nl.A-74 nl. * 2.68
k » 34*6 * lo -* a o c .-i
km » 5.43 * 10-* 890,“i
kj. <* 9.14 * ‘1®**

156

Table 49

toton&gtlie

« f O.OO0U02 M olar D lla o p ro p rli^ c ^ ro p y lc a rb ln y l
p-H lrrobenaoate la 855 Dloxaae - 158 Water a t 80°C

*
<WM>t

268
322
53?

728
1850
1862
3181*
771*2

ir

*
»&*

0.39
0.62
0,80
0 .8 0
0,99
1*10
1*26
1*86
1.33
1.1*0
1,1*2
1,1*8
l*6l*
1.61*
1.66
1.68
1.68
1.73
1.78
1,75
1.76

1,00
1*89
2,05
2.05
8.51*
2.82
3.23
3.23
3.1*1
3.89
3.79
3.79
4.20
4*20
4.28
1**31
4.31
4.43
4.48
4.48
4.81

fitr a n ti O.QG9397N Ba08
* 1**31 s^l. aI . 75 ®*L* * 2.56
k • 14.9 * 10“* w m , - 1
k. • 5.80 * 10** w m .**
kr * 9,06 x 10"* »«*.**

Ml,

.

I;

2*1*6

1*6?
i,i
1,10
0*?2
0,31
0
0*20

0.08
0.03
0.0

15?

Table 50
Solvolysis of 0,007015 Molar Oiisopropylcyolopropylxjarbinyl
p-Nitrobenssoate In 80$ Bioxane * 20$ Water at 6o°C

vff.

t
see.

V
ral.

ml.

172
to.?
652
871*
1582
2016
2562
2823
3051
325?
3653
1*325
1*617
1*91*5
681*1*

0,26
0,147
0,66
O.90
1*31
1*53
1.79
1.85
1.96
2*00
2,08
2,214
2,27
2.33
2*148

0.1*0
0.73
1.02
1.39
2.02
2.37
S.77
2.86
3.03
3.09
3.22
3.1*6
3.51
3.60
3.83

Titrant? 0.OO9151H HaOH
« 3,83 ml*/2.U8 ml* m 1.514
k * 5.00 x 10~* aec,**!
ks * 3.2I4 x 10”* sec."1
kr * X.?6 x 10”* see.”1

Vf-vli
9f*
ml.
3*U3
3.10
2*81
2.J4I4
1,81
I.I46
ifo6
0*97
0*86
0,?l4
0,61
0,37
0,32
0.23
0.0

158

Table 51

Solvolyala of 0,006933 Molar Diisopropylcyolopropylcarblnyl
p-Nltrobenzoate in 80)6 Dioxane - 20)6 Water at 60 0

V

Vf-vl£
r Vf»

t
800.

ml.

ml.

187
U20
601*
788
1230
1U82
1757
2580
2817
3060
3323
3855
5225
7U75

0,29
0.53
0.69
0.83
1.15
1,32
1.U6
1.83
1.89
1.95
2.01
2.16
2.38
2.5J+

o.k5
0.82
1.0?
1.29
1.78
2.03
2.26
2.84
2.93
3.02

3fh9
3.12
2,8?
2,65
2.16

3.H

0*83

3.35
3.69
3.9U

0.59
0.25
O.G

%

Titrantt 0.003805N NaOH
VfAf* * 3.9k ml./2.5k ml. ♦ 1.55
k » 1*.65 x 10“* see."1
ka •> 3.00 x 10-* oeo,—*
kj. » 1.65 x 10“* aec.-1

1,91
1.68
1.10
1.01

0.92

159

Table 52
Solvolysia of 0,007637 Molar Diisopropylcyolopropylearbiiiyl
p-Nitrobensoat© in 80$ Bioxane - 20$ Water at 60©C

v vlf.
t
a«c.
102
332
619
8U1
1032
1235
17U0
2327
326ii
1;6UQ
6102
8220
16527

V
ml.

ml.

ml.

0.31
0.58
0,83
0.98
1.17
1.33
1.66
2.05
2.32
2.62
2.77
2,914
3.00

0.1*6
0.86
1.23
l.iiS
1,73
1*97
2.I46
3,03
3.UI4
3.88
li.10
li.35
l*.l*3

3*97
3.57
3.20
2*98
2*70
2*46
1*97
1.40
0*99
0*55
0*33
0*09
0*00

Titrant!

0.00862(3? flaOH

VfAf* - lwli3 IH1./3.00 ml. *» 1*48

k * lt.W x 10“* asc.*1
kH * 3.03 X 10”* OOC.”1
kr ■ l.Wt X 10“* 69C."*^

o
Th© ester m s dissolved in anhydrous dioxane and stored at 60
for three days after which time sufficient water was added to
make the solution 80$ dioxane * 20$ water and measurement of
the rate was begun immediately.

160

Table $3
S o lvolysia of 0.OU9U M olar m il
p-W itrobenaoate la 80J* Diexane

T*S
t
aac*

?
jnl.

nl.

m
1*79
731

1.00

1.60

1.35
1.72

2.16

100U

lias
3765
1017

Tf-Ts^.
Vf»
ELLt

5.88

2.01
2.36
261t0
2986

'0*

Water

3.11
3.31
3 .1'
3.70

2.7 5
3.22
3.78
u«61i
ii.9 6
5.57
5.7 6

5.92

5.32
k.76
M t
3*70
3.U *
2,28
1.1.35

1.16

1.00
0,1»8

6.60
6.92
6.92

7027

12200

26267

0.00662CW HaOH
6.92
ml,A.33 ml.
VfAf* 5
*
I©
*4 see.”*
k * lt.6
W « 2.91 X KT* see."1
k. » l»7k x lor* see,
«**-“>•
Titraabi

0.32
0.00

1.60

th e e s te r see dissolved la anhjrdroua diexaae and stored a t 60
fo r a r e days a fte r which tim e s u ffic ie n t w ater was added to
make th e eo latio n 805 dioxane - 205 water and measurement o f
the ra te was begun Im m ediately.

161

UbX* $k

SoXvolyat* of 0*0091+81 Molar
^miwt«a*waat® in 80# Dioxan© *■ 20# Watar at 60®G

t
aao*

l+£6

831
1743
1597
191*3

2333
3251
3512
1*81*0
981*0
11373

*s » %

7
nil*
0.30
0.69
1.11*
1*1*9
1.83
2.32
2.30
2.79
2.99
3*19
3*51
3.51

"If
0.1*7
1.08
1*79
2.31*
2*98
3*33
3 *81
1**32
U.70
5.01
5.50
5*50

TXtvaxA* 0.00862C® JHaOH
■m f*fO & * / » • &

if «fj*39 ae itf** §*#*p*
ka * 3*2# x iO**4 sao»
k~ * 1.81+ X 10~4 0©©*~*

5,03
l*,i*2
3*fl
3,16

2*52
2.1?
1.89
1*12
0,80
0,1*9
0*0
0,0

* 1.5?

162

Sable 55

3olw»ly»ia a* 0.01123 Molar m«opr9^lG7alopropyl®ar1>ij97l
p-Blti>ob«n*e«t* to 805 Bieocane * 203 Mater at 6060
.......................... —

T ~ ~ " l

I"

I I I 111 l i r iH l I I I H I I

v
Ml.

313

0. 5?

o.«?

2500

■ .'v

o^f
\ *
el.

%

■a00

;' III1 1 ) I

0*91*
1*21*
1*1*8
1.98
2*1*8
2.95
3.10
3.37
3.55
3*72
3.91*
i*«13
fitvrafei

5*89
5,1*0
i*y86
2*.2*1
2*,01
3.28
2.52

6.01
6.30

0.29
0,0

5.67

0. 008918N

s»m

k * li.tr * IS*4«we**&
kr •

<f jJft
W*
ad.

0.1*1
0.90
1.10*
1.89
2.29
3*02
3.78
2**50
2**73
5.15
5.2*2

7f/? 4*6.30 bI.A.13 nl. **1.'

kB •

i ; u m » a . 1 1u i » m m . M t e g a K

2.80 x 10*4 ae*.“»
1-U7 * I®*4 eee.*1

1*80
1.57
1.15
0.88

0.63

s

163

fable 56
Solvolysle of 0.001*06? Molar Dilsopropylcyclnpropylcarbinyl
p-Hltrobanaoato in 60J6 Dioxane - 20% Water at 60®C

t
see.
39k
600
830
1350
1830
22?0
2751*
3385
1*278
5500
55275

7
nl.
0.1*0
0.62
0.82
1.22
1.52
l.?2
1.92
2.12
2.32
2.52
2.72

7Vf
Vf*
ml.

ff-v||,

0.61
0.95
1.25
1.66
2.32
2.62
2.93
3.23
3.51*
3.81*
U.15

ml*
3*Sh
3f20
Zf90
2 .$9
1.83
1.53
1.22
0.92
0*61
0.31
0.0

Titranti 0.098101 HaOH
7fA f * - 1*.15 na./2.?2 ml. • 1.53
k « 1*.1*9 x 10"* sec."1
ks - 2.93 x 10"* sec."*
kr * 1.56 x 10“* see.”1

*Tbe rate in this ran was followed by adding excess standard
HaOH in small increments and recording the times at which
the phenolphthalein indicator changed color.

16U

fa b le ST

Solvolysis of 0*00579 Molar Diisopropyleyclopropylcarbinyl
p~Witrobenao&t© In 80$ Dioxane * 20$ Water at 60 C*
vli

Vf-Vg,

■b
Me.

V
ml.

V
ml.

al,

332
638
938
1368
1800
2325
3025
3970
5k35

0.61
1.01
l.kl
1.83
2.13
2.53
2.93
3.33
3.7k

0.96
1.59
2.21
2.87
3.3k
3.97
U.60
5.23
5.8?

k,91
k.28
3,66
3.00
2.53
1.90
1.27
0.6k
0.0

Titranti O.09869H HaOH
VfAf* - 5.87 ml./3.7k ml. - 1.57
k • k.90 x 10“* sec.*1
ka * 3.12 x 10“* see.”1
kr “ 1.78 x 10“* sec,”1

*fhe rat® in this run was followed by adding excess standard
KaOH in small increments and recording the times at which
the phenolphthalein indicator changed color.

165

Table 58
Solvolysis of 0,008570 Molar Biisopropylcyclopropylcarbinjrl
p^Mltrobenzoate in 80$ Dioxane * 20$ Water at ?0°C

v

*

sec.
132
293
1*85
6?6
833
1001
1179
1377
1731
2319
2910
5295
1*8720

ml.

ml.

ad.

0.39
0.75

0.60
1.15
1.75
2.22
2.56
2.88
3.13
3.30
3.62
3.88
3.91*
i».09

3,51*
2,99
2,39
1.92
1.58
1.26
1,01
0.61*
0.52
0.26
0.20
0.05
0,0

l.U*
1.1*5
1.6?
1*88
2.Oh
2.15
2.36
2.53
2.57
2.67
2.?0

1*.H*

Titranti
■

0.01031(1? HaOH
* u.ll* ml./ 2.70 ml. ** 1.53

k » 12.0 x 10—4 aec.”1
k« - 7.80 x 10”4 aec. -1
kr » U.20 x 10”4 aec.”1

166

Tatole 59
8o lv o ly *ie o f 0,008626 Holer D ila o p rt^ le ^ lc p iT jjy lc e rb in jrl
p^ritrabeniKsate in 80)6 Dioxano - 20)6 W kter a t 70°0

t
PW t

It ©

551
831

98b
t ill

1311
lbJS7
1591
19b9
& 56
3177
5US2
87390

a il*

n l.

mX9

0.32
0.92
1.27
1.6 5
1.82
1.95
2.10
8 ,2 0
2,25
2.38
2*50
2.59
2,65
2,65

Q.b?
l.b 2
1.96
8.5b
2.80
3.0 0
3.23
3.39
3*b6
3.6 6
3.83
3.99
b.00
U.06

3.5?
8,66
2 fl2
M b
1,28
1,08
0,85
0.69
0.62
0.b2
0,23
0.09
0 .0
0 .0

m r e n ti 0.01057H 1 M
V f/V f* - U.Q6 ra l./2 .6 5 n
k » 11*7' * 10“ * M 0 .” 1
ktt » 7.57 * 10“ * 800. “ 1
kv * b.13 x 10“ * m o . * 1

l* »

1.5b

167

Table 60
Solvelyaia of 0.01015 Molar IMlaopropylo^loprogylcaAinBrl
p^Jitrobaaae&te la 80g Dioxane - W Water at 80%
g-

*55

nl.

nl.

al*

0.86
1.09
1.1#
1.79
8.15
2.Ill
8*60
2.82
8.99
3.13
3.30
3.35
3.
3.57
3.61
3.66

1.33
1.#
8.31
3*78
3.31*
3.78
U.03
u.38
1**61*
1**86
5.18
3*20
5.31*
5.5U
3*60
5.66

U.3S
3*99
3,37
8*90
2*31*
1,91*
1,65
1,30
1*01*
0*82
0,56
0*1*8
0.31*
0,11*
0*08
0.0

titranti 0.008932S HaOH
I V / M * 5.68 sa./3,66 nl. * 1,55

k1 **30.8 x 10~* a®e."i
ke * lS *k X 10“* «»»**
kg, * 10*8 z 10** aec, 1

168

Table 61
SolrolyalB of 0.01158 Molar rttloo|»r<^ l<^lepretarleart>layl
P^ll%roben*®a1>« la SQJt Dioxane * 20g Hatter at 80°0
■Jte

t
mo*

net
IS®
210
a?6
388
kS6
k9U
m

601
663
w
981
1088
1222
?98k

T
m.

a&%

l.lit
1,1*2
1.79
2.23
2.7U
3.«a
3.21
3.^)1
3.55
3.73
3.86
3*96
l*«0i*
U.U
1**12
U.30

1*76
£.20
2.78
3*Sk
1**25
lt.67
1**98
5.29
5.51
5.79
5.99
6»3i
6.27
6.33
6.39
6.67

Titrant*

0.008689H HaOH

VeArr * <5.67 ml.A,3Q *1. » 1,55
k * 28.9 * 10"» *««.■ *
k* - 18.6 X 10“*. « M V *
Jtj. m 10.3 x 10“* see,**1

4-4f*
nl*
U.91
U,U7
3.89
3.13
8.1(2
2.00
1.69
1.38
1**6
0,88
0*68
0.53
0,1*0
0*29
0.28
0.0

16?

Table 62
Solvolyeis of ©,008986 Molar Dlisopropylcyclopropylcarbinyl
p-Nltrobenzoate in 70S? Dioxane - 3056 Water at UO°C

t
seo.

319
803

12)41
2077

3075
37U1
1*30?
5293
6256
7061*
8839
10639
12609
11*652
17325
19738
22398
861*00

7
ml.

ml.

ml.

0.1*0
0.68
1.01
1*1*3
1*91*
2.20
2.1*0
2*73
3.d
3.18
3.5U
3*82
l*.ol*
U.22
1**30
1*.1*0
1*«1*1*
It.60

0.1*2
0.71
1.06
1*50
2.03
2.30
2.51
2.85
3.15
3.33
3*70
3.99
U.22
U.l*l
U.50
U .60
ll.61*
1*.81

U,39
1**10
3*75
3*31
2*78
2,51
2,30
1.96
1.66
1+1*8
1,11
0,82
0.59
0.U0

0.0093U9H NaOH
7f/7f* * 1*«81 nl./l*,60 ml. » 1.05
k » 1.61* x Hr* sec.-1
k« * 1.57 * 10"* see."1
Titranti

- 0,0718 x 10"* sec.

0.31
0.21
0.17
0,0

170

T able 63

Solvolysis of 0.009U35 Molar DHaopropylcyxslopropylcarbliQrl
p-MItrobenzoate in ?0# Dioxane * 30% Water at kO 0

t
see.
Tl|)*
1*21*

730
1223
151*0
2307
2965
3555
1(1*82
5376
6389
731a

81*65
9571*
11267
13579
19120
26693
861*00

7
ml.
0.314
0,52
0,71*
1.08
1.22
1.61*
1.95
4*
2.57

2.86

3.17

3*iiQ
3*6&
3*at
iieO?
U.28
It*58

k«?0
h M

Vf-vl£
£ Vf*

ml.

ml*

0.35
0.5k
0*77
i.ia
1.27
1*70
2.03
2.32
2*6?
2.97
3*29
3.53
3.76
3.97
k*23
U.k5
U*7k
k.88
5.05

1**7°
It.51
iu28
3.93
3,78
3,35
3,02
2,7|
2.38
2.08
1.76
1.52
1.29

Tltrants 0#.0Q93k9®r HaOH
w
» 5*05 ml*/Iu86 ml. •» 1.01*
k -1*57 x 10~* sec.-1
k- ** 1*51 x 10*"4 sec/"1
k® * 0*05^9 x 10-4 sec.-1

1.08

0,82
0.60
0.31
0.17
0.0

171

Tabl* 6k
of 0*068528 Molar Btiaoj^pgrleyelo^^
^Lto^oniiooto tm 7€» M w w m + 30%
at 5O°0

%

?

aeo*

»&«

sl»

vULf

**wi

0,88
1020

1.1*2
1*85

2288

2*1*8
2.78
3*0%

2691
3092

3,<
1.91
i*

2*:

1,6
1*
1*15
0,91*
0*#
0 ,1*9
0*38
0.30
0*23

3*89
i».0?

5250

14.02
MS>
li,!6

6936
saat

1**23
!*.31

79800

1**38

1**36

2,30

3.18
3.1*3
3 oOlkt

3*72

2*65

k M
1**35
%«l*t

%»5l
U.56
1*.58

Wtoaatt 0.0093US SaOH
% / V » 1**58 tiWb.38 *1. * 1*05
k «* 5.21 * 10** see.*1
to. • U.98 * 10"* see,*1
kj. » 0.228 x 10** sec.*1

0.16
0.07
0.02

0*0

172

Selvoljrttla

0*0089140 M U r 0iia©pr©3py:i£y«l©|^©j^^
in 70* M m m m » 3^6 Watar at 50*G
ttasass

%

7
ml*

a«c%

0.66
l.Uo
1.92
2.21*
2.62
2.88
3.19
3.1*5
3.6U
3.83
i*,©8
1$#18
1.4*H3
i%
.
*
U
j,*U
gf2
ft
1*.S6
U.38

&n
m
m k
1578
1872

1*68?
5162

T1 ?
»a.

ml,

kfXX

0.69

l.U?
2.01
2*35
2.75
3.02
3.3U
3.61
3.81
it.Ol
U.21
ii.38
J
I.*Ut*
ff9
i*
U
it.63
1**78
It*80

***K
X|({6
iiia
0*99
0,79
0*59

o*i*2
0*31
f
Ut
rn*.?
0*17
WfW
0,08
0.0

ntr«R t>
^
k
k*
kr

0,00931^8 HaOH
?#* a ii«So
*58 ml
• 5,02 * 1£T* sac,-*
• S»,?9 * 10** awt**1
• 0.230 * I©** aec,-1

3*33
^*79

«

1*<

173

Table 66

Solvolysls of 0*009296 Molar Mlaop2*o|^lc^l©pr©py3^arbli3yl
p-Mltrobesaoate in ?0# Dioxane ^ 30$ W&t&r Q+Q09U10
■WanmX in Sodi-ura Hydroxide a t £0*0

'

i

tm .
M

m

1*33
at?

ns

1059
119%

i&n
ms
ms
2S81
3311*
1*1*93
5558
7582
12393
7*000

r
s&«
iu?X
E*l$2

bO*

3.92
3.30
Wt*
susa
2.33
2.19
1*91
1*60
1.19
G„8U
0.62
A
i4iXA
v •*
3
0*37
0*26
0*12
Titranti O.0G952£M HOI
ifjp 0*12 ®a*
k m u*5'8 * K T 4 see.***

t e-fj
■mlf

UfS9

U.30
U.d
3,80
3,18
3,00
*♦7®
2,21
2,07
1,79
1,1*8

x*o?

0,7*
0.50
Of *k
WtJii
0,25
0.11*
0.0

X7k

table 6?
Sblvolysda of 0,009068 Molar Oilsopropylcyolopropylcarbinyl
p-Hitrobenaoat© in 70$ Dioxane .*• 30% Water 0,009itl0
Kormal in Soditos J^'drosd.cle at 50°C
t
©00*.
..., ..................

...

,

V
ml*

r* %
naf

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

350
316
567
7k$

976

ate
11*62
1859
2301
*?ai*
3186
3578
1*077
$lSk
m 1
7789
1*3800

i*.68
U.Ui
3*93
3.60
3*30
3.02
2.65
2.2U
1.3U
1.59
1,28
1.11
0.95
0.69
G.58
0.37
0.22
Titwaat* 0.009525S HOI
Vf * 0.18 ml.
k » U.66 x 10"* «ee,“»

l*.5o
U.26
3.75
3*1*8
3*3#
2*81*
3*1*7
2.06
1*66
1.1*1
1*10
0.93
0.77
0.51
0.1*0
0*19
0.01*

17$

fttbld 68

Solv&iyaia of O.OO8832 Molar OilaopropylcjrclopropylcapbiiQrl
|>^ltr©b«i!*»oat© la fQg Dtoxma * 3Qg Water at 60°C
oi^rifwn",
t
■•00*

7
ntiU
k"
.
H
fc
.

92
833

hOk

553
603
030
969
11.
3a
3316
1U7?
168k
380k
2k55
8730
3833
k230
33303
97*00

£f
7<r«

rr v|*

0.63
3.88
8.0k
2.55
2.88
3.83
3.53
3.78
k.Ok
k.ia
k.87
k.33
k»k2
k.50
k.52
k.59
k.63
k.63
k.63

k.00
3.35
2.59
2.33
1,75
l.kO
1.12
0.85
0.59

m
n
a
B
y
M
f
c
K
x
m
K
in
iii
p
m
M
m
.n
^
m

0.39
3.83
1.92
a.ke
2.71
3.0k
3.31
3.56
3.80
3.80
k*08
k*o8
ii.36
k»2k
k.26

U.32

U.36
U.36
k.36

titrmti o . W 9 $ m m m
Vf/Vf* *» k*63 rai*A *36 *aX* * 1*06
k * Ik *5 x lO^eec,-*1
ks • 13 *T x K T * sec****
k*» * 0*Sk7 x 10**4 aa©#**

o .S l

0.36
0.30
0.81
0,13
0.31
0.0k
0.0
0.0
0.0

176

Table 69
Solvolyels of 0*009320 Molar Biisopropylc^lxjpropylcarbiiiy-l
p-Nitrobenzoate in 70# Bioxane - 30% Water at 60°C
xr^f
%
see.

V
nd.

90
228
U03
51*5
685
877
1025
1X85
13k6
15U3
172It
1925
2135
235tt
2585
3U28
7292

0.6U
lr23
1.98
2.ii6
2.9U
3.32
3.57
3.75
it.Ql
J7.16
U.26
it.3U
u.uu
l*»lt6
U.58
U.o2

v^vZj
r Vf'

ml.

ml.

0.66
1.30
2.10
2.60
3.11
3.51
3.78
3.97
U.2U
It.ltO
U.51
lt.59
It.70
it.72
U.7U
it.85
It.89

It.21
3,59
2,79
2,29
1.78
1^38
1,11
0.92
0,65
O.ltii
0,38
0.30
0.19
Q.17
0.15
G.Olt
0.0

Titrants 0.00951*1$ $aOH
* U*89 ml.A.68 ml. * 1.06
kr « lli.8 x 10~4 sec*"1
ks » 1U.0 x 10~4 sec."1
k^ * 0.815 x 10*4 sec."1

177

table 70
Solvolyets of 0#006235 Bolar Dicyolopropylcarblnyl p-Nitro
benzoate in 8gg Dioxane - l$% Water at 0Q°C
t
sec.
257
526
816
1130
1553
2017
231*3
282U
3213
3857
1*353
5127
6200
6992
8082
9723
1331U

V
ml.
0.50
0.65
0.89
1.09
1.38
1.67
1.80
2,11
2.29
2.50
2.66
2.92
3.22
3.38
3.1(8
3.72
3.81*
Titrant: 0.008093H NaOH
V*. » 3.85 ml.
k * 2.62 x 10-* see.”1

Vf •> V
ml.
3.35
3.20
2.96
2,76
2.1*7
2.18
2,05
1,71*
1.56
1.35
1.19
0.93
O.63
0.1*7
0.37
0.13
0.01

178

Table 71
Solvolysls of 0*006897 Molar Dieyelopropylcarbinyl p-Nitrobsnzoate
in 85$ Qioxane - X5% Water at 80°C

t
300*

7
ml*

330
612
9th
it*<K
1701*
21x8
210-2
2926
33U1
3963
1*10*5
5251
6321*
7090
8216
9895

0,57
0.80
1.02
1.29
1,61
1.89
2,05
2.35
2.52
2.86
3.01
3.25
3.53
3-7U
3.91
1*.19
Titraat* O.OGS093N HaOH
7g * i**26 ml.
k » 2*73 ac ID*’4 m o ^ % -

7g^7
ml*
3.69
3,1*6
3.21*
2.97
2,65
2.37
2.21
1.91
1.7U
1.1*0
1.25
1.01
0.73
0.52
0.35
O.07

179

fa b le 72

of 0,

Bieyel<^©p^lcarbi*$ri p^itrbbenEoete

in 80% Biocane # 20% Water at 6G°G

t
as©#

*
nl*

Vf-T
ml*
m
iH
P
i

108
350
831*
1310
188$
t m
3i«a
ssm
6S-SU
6290
9it95
10670
123o 6
11(021
18959

0.21*
0(31
0.58
0,79
0.99
I.36
1.65
1.96
2 *36
2.72
3*03
3*2?
3.51*
3il8
3.98
U.i*5
Titrantl 0.007123® HaOB
Vf * 5,04* «a. _
__
k » 1.10 * 10
we.**

i».80
U.73
U.l*6
t*.2S
It*05
3.68
3.39
3i0®
8.68
2.32
2.01
1.77
1.50
1.26
1.06
0.59

180

fa b le 73

Solmiyeis of O*OO£806 Molar m e m 1
in 80# Oloasaae *

icarb
ter at

?
n&<r
0,15
O.itO
0.55
OifiU

1 p-NItrobenssoat©
~0

VfT

U.l*5

1.05
lOifc

1.80

3.89

t*»2.52
2 .8ii

t.TO

1.89

8867
9561
10687

8.57
2.25

3I: ’
3-

U.08

15U26
n t r s n t i O .609& 8* NaOH
V f » 5.09 s£L.
k - 1.21 x 10** s«c.~*

1.59
1.89
1.07
0.55

181

T a b le ?i*

Solvolyets of 0,008038 Molar

p^itroboaaoate

la 80g Bloocaae * fC$ m t e r at 70°0

7
80**
w*Mrt^8(»iiir»it<i(nfir;iirt~r

290
625

. y a w mli* j

11
1ximkipwlini n -ni*ftiiii»|fc8>i

)■"<*’

0.1*0
6.6?

3.5*
3,

1.3?

2#

1.00

1080

1*80

2918

ticXS
2*55

13072

«!#

1.67
1.37

2,(0

1*02

3.5*
3.9*

0*56
0,1(0
0*0

?Uara»t» 0.Q1G25M HaOH
f# * 3.92 sau
k m 2*86 x 10”* saa.*1

182

Xabla 75
Solvolyals of 0.00731*1 Molar Dloyclopropylcarblnyl p-Hitrobeneoate
in 80£ Dloxane » 2C# Water at 70°0

t
800.
31*9
7U1*
1092
11*91
1807
2133
2652
321*7
1*126
5765
7067
11171*

V
ml.
0.1*5
0.83
1.13
1.35
1.57
1.71
1.99
2.25
2.62
3.10
3.25
3.58
Titrant* 0.01025N HaOH
Vf - 3.58 ml.
k » 2.98 x 1G"4 see."1

Vf-7
ml.
i

3.13
2.75
2,1*5
2.23
2.01
1.87
1,59
1.33
0.96
0.1*8
0.33
0.0

183

Table 76
Solvolyals of 0,01063 Molar Dicyclopropylcarbii^rl p-Nitrobenaoate
in 80$ Dioxane - 20% Water at 80°C

t
sec.

V
nil.

ml.

96
162
2^6
353
509
602
751*
8ia
100k
1133
1208
11*55
1723
1911
2273
7750

0.71*
0.86
1.16
1.1*5
1.93
2.22
2.60
2.81
3.15
3.1*2
3.58
3.96
1*.1*0
h.78
5.02
6.22

5.1*8
5,36
5,06
U.77
1*,29
1*,00
3.62
3.1*1
3.07
2,86
2.61*
2.26
1.82
l.kl*
1.20
0.0

Titrant* 0.00887i*H NaOH
Vf * 6.22 ml.
k - 7.06 x 10-* sec."1

181*

Table 77
Solvolysis o£ 0*007900 Molar Dicyclopropylcarblnyl p~Nitrobenzoate
in 80$ Dloxane • 20j£ Water at 80°C

7

t
sec.

ral*

72
1UG
2U6
3U5
505
623
730
902
1010
m)i
127U
XU7ii
1687
1921
21U5
k9$l

0*63
0.69
0*92
1.11*
1.53
1.79
1.98
2.29
2.50
2.62
2*85
3.12
3.35
3.55
3.72
U.68

Tltrants O.GO887I
4N NaOH
7f * U.68 ml.
k * 7.0ijx 10** MO.*4

V^-V
ml.
it.os
3.99
3.76
3.51*
3,1s
2.89
2,70
2.39
2.18
2.06
1.83
1.56
1.33
1.13
0.96
0.0

185

Cable 78
Solvolysis o f 0.008U72 Molar Trliaopropylcai'binjrl p^KLtrobeosoate
la 80JS d e n s e * 20J6 Hater a* 6cPc

t
jr
i
f
e
BWC?*

T
ml.

100
)!~jlj

0.21
0.21
0.25
0.26
0.27

*rT
nl.

im
^
ia
w
w
.n1

918

1968
5182
26637
79668
1073U5
1670U0
197280
258U80

0.W

0.98

1.10
1.1|6

1.60
2.12
Eitraati 0.00851SB MaOH
ft * 4*98 al,
k m 1.99 x 10“® aao.”1

M7
U.77
U.tfc
I*.73

U.72
fc.S2
b.06

3.88
3.52
3.38
2.86

166

Table 79
Solvolysis of 0.010^6 Molar Trlisopropylcarbinyl p-Nitrobenzoate
in 80$ Dioxan© - 20$ ^iater at 60°C

t
sec.
96
81*8
U026
25639
78752
106355
161*712
19U952
256152

7
ml.
0.26
0.26
0.28
0.52
1.06
1.25
1.77
1.93
2.5U
Titrant! 0.008512N HaOH
7f * 6.20 nO.*
k * 1,82 x 10“« see.-1

Vjj-V
ml.
5.91*
5.9U
5.92
5.62
5.1It
lt.95
U.U3
lt.27
3.66

X8?

Table 80
Solvolysie of 0*009548 Molar Triiaopropylcai’
birjy'l p-HitrobenBoate
in 80$ Dioxane <- 20% Water at

t

sec*

23225
3 W
Jt7tl
89253
94398
1160&1

ml#

ml.

0.20
0.25

U.k6
k .a
U.32

0.3k
o
.0n
1
.
5
1.9 k
2.12
2
.23
2 *29
2.82

Tltranti 0*01025^ H&0H
a 4*86 »CU
k * 6*82 x 10*6 *ee*~*

3.09

3,61
2.72
2.5k

2
.
1
*7
3
2
.
3
1.8U

188

Table 81
Solvolysis o£ 0.01099 Molar Triisopropylcarbinyl p-Nitrobenzoate
in 80$ Dioxane - 20$ Water at 70°C
L ^ , PJ.

t
sec.
688
1701*
6660
22382*
31262*
76269
83007
89637
91*682
116227

I,U|JII»,..

n

',11.

. .,M » ........ ■■■■,„

.^

lli,,, I.*.,,,

?
ml.
0.19
0 .21*
0.36
0.89
1.15
2.21
2.1*1
2.56
2.61
3.13
Titrantl 0.Q1025N NaOH
V> • 5.36 ml.
k - 6.81 x 10*8 tao.”1

I

M

Vf-rV
ml.
it

5.17
5.12
5t00
1*.1*7
It.21
3.15
2.95
2.80
2.75
2.23

189

Table 82
SolvolyalB of 0.008338 Molar Trilsopropylcaibingrl p-Sltrobenaoate
In 80jl Dloxane - 20# Water at 80°C

t
aeo.

335
685
2359
7419
9566
11655
14906
18145
21715
21*669
28335
32812
938OO

V
ml.

0.37
0.1*0
0.60
1.08

1.23
1.43
1.72
1.90

2.17
2.36
2.56
2.83

4.41
Titrantl 0.009253U HaOH
Vf * 4.51 ml.
k •>27.7 x 10-e sec.-1

Vf-V
ml.

4.14
U.n
3,91
3.43
3.28
3.08

2.79
2.61
2.34
2.15
1.95
1.68
0.10

190

Table 63
Solvolysla of 0.01020 Molar Triiaopropylcarbinyl p-Hitrobenaoata
la 8096 Diaxane - 20$ Water at 80°C

t
Sec.
382
73*
2791
7507
97U5
11735
15075
18301
21856
21*776
2851*6
32910
91*087

V
ml.
0.1*2
0.1*5
0.70
1.21*
1.1*3
1.67
1.99
2.28
2.52
2.72
3.05
3.1*0
5.35
Titrantl 0.009251N BaOH
Vf * 5.52 ml,
k • 26.5 * 10 ® see.’'1

7f»7
ml.
5.io
5.07
1*.S2
It.28
1*.09
3.85
3,53
3.22*
3.00
2.80
2.1*7
2.12
0,1?

191

Table 8k
Solwlyala oS 0,009809 Molar TrU.aapxopylGaxtoljig-1 p-HHwobewsoat*
la 7QJt doguuM * 30jfWater at 60^0
sBmsssasswM?#
'2
SS & & .

ml*

ail.

0«2k
0*88

o,U7

5,3k
5.30
5,11

0.62

k,96

m m
30W U

1.01
1.26

k*78
k,5?
k»32

?5*ia

1.39
2,52

U.19
3*06

2.81

2*77
2,62

m

108it8

872*7
97107

xmm

2.96
3.06

110629

3.2k

131958

3.58
Titrantl Q.0Q8791H NaOH
T* * 5.58 nl«
k '* 7.55 * 10”® boo.”1

2.3k
2.00

m

Table 8#
Solvolyaie of 0*008576 Molar Trllscspropylcapbiayl jH-Hitrcbensaoat©

itt ?Q£ Bloxano ~ 30* *fet«r at 60°C

7
al.

t
e+m'fir
OTOt

j ©

1005
5195

1097S
16210
22585
3m s
3S7S3
75369
88180
9716?
102232
110731
131912

'

0,21*

0.26
0 ,1*0
0,59
0.73
0.89
1,12
1.28
2.21*
2.1*3
2.61*
2.68
2.81*
3.13
Titrantl O.OO879IH HaOH
T. •* !*.88 *1.
k * 7.1*9 x X0~a Me.**

Tf*r
ml,

1**61*
1*,62
U.U8
1*,29
1».1S
3.99
3.76
3*60
2.61*
2.1*5
2.21*
2.20
2.01*
1*7?

193

Table 66
Solvolysls of 0,007870 Molar TrltsopropyloarfeljaQrl p-Nitrobenaaate
In 70* Dloxana - 30* Water at 70°0

t
see.
m
101*0
2376
700lt
9427
11396
15266
52860
55948
&*2©1*
69178
@9965

7
nl.
0.28
0.32
0.38
0.7 8
1.01*
1.1 0
1.1*2
3.1 0

3.34
3 ,3 6

3I88
Titrants 0,009W»2» K»0H
r* » I* .17 nl.
k « 25.0 x 10“ ° s e e .*1

vt f
SUL-f

3.89
3.8 5
3 ,7 9
3,3 9
3,13
3,07
2.75
1.07
1.03
0.81
0 .7 1
0,29

Table 8?
Solvolysis of 0*008670 Molar Triisopropylcarbli^l p-Hitrobenzoate
In 70% Dioxane - 30% better at 70®G

t
830

*

5U6
1167
2liOO
7088
951(8
Ult68
15378
5305U
56053
6U3UO
69368
90118

V
TOl*
0,26
0,33
0.U2
0*08
1,10
1*22
1#52
3.1*6
3.50
3.7U
3.86
l*.28

Titrantl 0.Q09ll(2H NaOH
Tff » ll.59 sO-«
k » 25.9 x 10*® sec.-1

Vf-V
ml.
U.33
U.26
U.17
3.71
3.1(9
3,37
3.07
1.13
1.09
0.85
0.73
0.31

195

fable 88
Solvolyels of 0#007^85 Molar Triieopropyicarbinyl p-Hitrobenasoate
in 10% Bioxaros * 30% Water at BO^C

t
see.

V
nil.

21*2
601
1192
1821*
3268
1*373
3312
6331
7611*
9276
1028?
11276
11*115
25038
30929

0.28
0.33
0.52
0,72
1.12
1.36
1.66
1.80
2.01*
2.36
2.50
2*68
2.9k
3.86
U.06
Titrantl O.OQ9353N MaOH
Vf * 1*.25 “I.
k « 83.2 x 10"* sec."1

Vf-r
ml.
3.97
3.92
3.73
3.53
3,13
2.89
2.59
2.1*5
2.21
1.69
1.75
1.57
1.31
0.39
0.19

196

Table 09
SolvolyBt* of 0.01079 Molar Triiiepr^leaAiaarl p^atnAwOMato
la ?<# Dioacane - 306 Water a t 80&0

t
«oc.

V
nil.

3b3

0,3b
0.52
0.72
0*91
1.1*6
1,?8
8.15
2.b3
2.76
3.12
3.33
3.52
b.09
5.17

no

129b
1915
3bS6
bb76
5678
6671
776b
91*09
101*28
33425
1I(»1Q
25229
31092

5 .1*1*

Titrant* O.OD9353M HaOH
Vf » 5.77 ad.
k

* 79.8 x 10*» boo.**’

Tf-V
ml,
5.1*3
5,25
5*05
b.86
b«31
3,99
3,62
3.3b
3.01
2,65
2.bb
2.25
1.68
0.60
0.33

197

Figure
Plot of log k versus 1/T for the Soivolysis of
Dicyclopropylisopropylcarbinyl p-Nitrobonzoete in 90% Dioxano105& +*€rter.

1S.0 kcal./mole

3.1

3.2

3.3
l/T x 103

Finire 2 } 4 1lot of log k versus l/T for tie Solvolysis of
JjByf-**0Pror^liGc>propylerirhlnyl p-Mitrofccnaoete in oQ?.» Diaxracsw'etor.

— »o
« 19.8 kcal./uole

-3.0

-3.6

3.3

1/t x ie3

1 99

I*lot of lop k versus 1/T for the Solvolj’oin of
'~*!ne^^ylcy cl0l:ropyl) isopropylcarhlnyl p-Nitroberzorte
in 90% Dloxane - 10% Yiater,

\
'
a « 17.5 kcal./xaole
.c>

-3.0

3.2

3.3

200

e
Fl0t
versus l/T f’or the Uolvolysis of
M-(2-raethylcyclopropyl)isopropylcarbinyl p-NitrobenaoFta in
90> Dioxane — 10 S's"ter*

Sa = 17.2 kcal./mole

-3.0

to

3.3
1/T x 10

201

26, Flot of log kT versus l/T for the Rearrangement of
ul-v ^-methylcyolopropyl)1aopropyloarblny1 p-Nitrobenzoat© In
90% P ia x tm e - 1CJ. »oter.

fey

=*20.0 kc^l./:,cle

3.3

202

Fipro 27,
?^

I-lot of log k versus l/T for the Solvolysis of

^ r ° ^ c'/doprop-y 1o p rbiny 1 p-Nitrobemzosrte in 85^ Dioxane.

15> barter.

-2

zs

3.0

-3,2

-3.4

-3.0

2.9

,
l A x 103

3.0

203
Figure 2#^ plot, of log kg versus 2/T for the Solvolvsis of
Diisopropylcyclopropylcprblnyl x-Mitrobenzosto in 85^ Dioxsne15% ^stor.

E0 » 22.3 keel./mole

-3.6

.M
hO

-3.8

2.8

2
**. /

3.0

20k
£ igure 29<>

Flot of log k_ versus l/T for the I eerrangorent of
Diiaopropylcyclopropyloartinyl p-Nitrobenzoate in 85f> Dioxamo15/y Vister*

Log 1:

3.0

2.9

3.0

205
^
50* 1 loij of lor f versns l/T for the Solve!ys's of
Di isopropyleyclopropylc 9rbj ny1 r-Mitrober.zo.9 te in eh- Dioxeno 205 V.gter.

21.5 Ircal./nole

a

-3*0

3.0

2.9
1/T x 103

206
Figure
i lot of lop kg vornup l/T for the Tjolvolyp.i s of
Dil« opropy leyclopropylearbinyl P-b'itrobenzonte in OOP Dioxsne—
20$ A'ater.

%eg k

Ia as 21*^ kcal./nolc

2.8

3.0
j/ r x io 3

207
I 1'Tum 38♦

I lot of log kj* versus l/T for the Reerrsn':- err.ont of
? “■3°r-'j'°pyl^ clopron/ic^r-hin.vl p-ritrobonsosts in 20,7~!>ioxenc%0/o ’ pter*

-3.4

-

3.8

28

3-0

2-9
[/ T X IQ3

£ igure 33, ♦lot of log k versus l/T for the Solvolysio of
Dlls op roj_:/lcyclofropylcarbinyl p-Nitrobenzoete in 70£ Di oxor-n30& Water.

= 21.3 .:cal* / io1

-

3.8

3.0

3.1
l/T x IO3

209

Figure 34* M o t of log k versus l/T for tho Solvolysjs of
DiisopropylcyclopropylcttrSinyl p-Nitro*ensoate in 70/j Dioxsne30^ V>ater.

LOG

F0 ~ 21.2 kcol./molw

-

3-4

3 .6

- 3.8

3-1

3.0
l / T X IO-;

.2

210
Figurfc 35* 1 lot of lop kp ^eraua l/T for the Rearrangement of
•
‘^lisopy opj IcyclopropylcaToinyl p-Nitrobenzonto in VO/ Oioxano—
30^’
f-grter.

Log 1
-

£e w 24.6 keel./mole

5.0

3.0

3.1
l/T x 10-

3.2

211

Firuro
Flot of lor k versus l/T for the Sclvolysis
of Dicyclopropylcsrbinyl p-Kltroben*oate in SOf Dioxane20/'.> hater.

= 21.2 heal, /molo

5

-3.6

o
l/T x 103

212

*lot of log k versus l/T ^or toe Sclvolysis of
TriisoproyyIce rbiny 1 p-Nitrobenzo©te -r. 8c£ Dioxano - 20,1
f:S.tGT‘*

“

4 .6

3.0

213 '
Fifurc 36* -lot. 01 lor V. ve rsus l/T for th< jo] volys is
of Trii 3 o j . . rory 1ce rb5n,y1 }-litrobenzo<n te in
Pioxane -

30/

ter.

.2

'A.A

*

n
l/T x 1C-3

3.0