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TH E815

4.5L,

MICFHCM‘Q CTATE UNWERSITY
Lip, {C/‘K RY

    

Isomerizqtion of Cycioalkanea
Under

Carbonium Ion Conditions

A Thesis

.n

submitted to the College of Natural
Science ofl.Miohigan State University
in partial fulfillment for the degree
or Master of Science in Chemistry

' ‘5
Q",

by

Edward J. Apple

(D

I

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J;

 

 

 

T LE OF CONTENTS

Page
I Acknowledgment - - - - - --------- 11
II Abstract - - - - - - - - ------- - - i
IIII Introduction ------------- - - 1-7
IV Results and Discussion - - - - ------ 8-22
V Enoerimcntsl -’ ----------- - - - 23-28
VI Summary - - - - - ------------ 29
VII “Annendix Q - - - - ------------ bO-ol

VIII deferences ---------------- bB-ob

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The author GXpresses his appreciation to Lr.
G. J. Karabatsos for his guidance and counsel throughout
the course or this investigation.

special thanxs is given to Miss F. x. Vans and
fir. n. A. Taller for help in determining the nuclear
magnetic reasonance spectra of the ccmgounds.

Grateful acknowledgment is also extended to the

Estrolcum Research Foundation for their financial

support;

 

 

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The liquid phase isomeriZutions of methylcyclopentene,
cyclohexsne, ethyicyclopenthne, methylcyclohexene and
oysloheptsne under carbonium ion conditions were studied.
The catalysts used were aluminum chloride and the
corresponding slkyl chloride or the cycloalkhne, i.e.
l-chloro-l-uethylcyclopentnne in the isomerization of
nethylcyolopentsne. The effect of time, temperature and
aluminum chloride concentration on the above hydrocarbons
... studied.

The question or whether primary oarbonium ions are
formed as reaction intermediates from the more stable
secondery and tertiary carbonium ions was examined. in
all cases where they have been postulated, the date are
also in accord with a bimoleeular process which does
not involve primer? carboniun ions. No evidence was
found in this work supporting binolecular reactions,
although the results do not exclude their occurrence.

:“Fivs; six and seven-membered rings interconvert
under the exocrinentsl conditions. In all cases the

predominantprohuct is a six~membered ring.

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IHTHODJCTItN

The isomerization of hydrocarbons and related
compounds in liquid phase reactions has been studied
for many years. These studies have included different
types of catalysts and reaction conditions. Relative to
this sort are those carried out with Fricdel-Crafts
catalysts such as aluminun chloride and aluminum bromide.

The proposed mechanisms for these reactions involve
carboniun ions as intermediates.

“Thc general concept of the intermediate formation

}'tc explain

cf carboniun ions was first stated by ahitmore
the 1.2 shifts so common in organic chemistry. Then,
followed several discoveries of importance relating to
aluminun halide induced rearrangements. Helena: reported
that in addition to aluminum halide, hydrogen halide and
water; or an alkyl halide must be present to induce
isoscrization. Pines and tackeraalsc observed that an
olefin or alkyl halide was needed in catalytic amounts to
initiate the reaction. These findings coupled with the
discovery by hartlett, Condon and Schneider’cf the rapid
hydrogen-halogen exchange between isopsraffins and alkyl'
halides under the influence of Lewis Acids firmly

established the-intermediacy of c rbcnium ions. The

 

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concepts developed therein4form the basis of much of the
modern mechanistic interpretations of liquid phase
isomerizations occurring under these conditions.

By consideration of the above observations and
concepts, one is able to rationalize the formation of
any product under liquid phase carbonium ion conditions.
However, the number of mechanistic paths able to ration-
alize a given product is usually large. This makes the
problem of singling out one specific mechanistic path
as the correct or even dominant one very difficult.

Mechanisms suggested for some of the more common
liquid phase isonerizations involve the intermediate
formation of primary carbonium ions from the more stable
secondary and tertiary carbonium ions. The following are
typical.examples:

The isomerizatlon of n-butane to isobutane?

+—
C-C-C-C... air“: ahead-+13

 

C C
v ”t A «2M6- « ‘hv VET“ h -
:+
0“

C Ii}: U
0-3-0 2:: 0-0-0... RT

6
The isomerization of methylcyclOpentane to cyclohexane.

+
I '1- R.“ 212:: l \l +HE
. + .+ , . (a)
»,H RH \
[j all t: ...... Q... a

 

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up."

The above mechanisms are consistent with the
observed results; however; ealculationsvshow that at
least 38 keel/mole of activation energy is required to
convert s tertiary carbonium ion to'a primary carbonium
ion and 22 heal/mole ofLectivation energy is required to
convert a secondary carbonlua ion to a primary carbonium
ion. These energy requirenents Justify the examination
of alternate mechanistic routes.

In all cases where primary carboniun ions have been
postulated as reaction intermediates, the data are also
in accord with binolecular reactions not involving
primary carboniun ions. The occurrence of binolecular
reactions in the isotope-position rearrangement of
t-amyl chloride with aluminum chloride has been shown?
Bimolccular reactions may be formulated for cases (1)

and (2) as follows:

4.
c-c-c-c z: c-c=-—c-s “1""
- c

4— . + N v 4/
c-c-c-c + 0-3 = and ‘2 s-c-c-c . M 3-9-6

0 c coach aeac(m

d. AJH L z +
c- c 7—4 Coo-C —————\ c-saca—o—c-c-c

aces Rims

/L: H
z, 3"“; '+ 3+,
L__...__9 ("—- ___.___‘

fl EH
.I‘W :/ ~39 >,. \< 'N..H, +x (4)
L... +' L......_.J 4“” 3 er” \ 5 4.... g

+— 1+

 

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since this work desls with cyclic hydrocarbons, the
binoleculer reaction process (4) may be.cxamined further.
It the reerrsngement is going by (4), then the possibility
or other products being torsed by rearrangement of the
intermediate oarbonium ion must be examined. Reactions

(5) and (5) appear plausible. Identification therefore of

 
 

 

(5)

 

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five and seven carbon compounds in the isonerizetion of
nethyloyclopentane would constitute evidence for the
occurrence of binolecular reactions, although it would
not rigorously prove the occurrence or (4).

The interconversion of methylcycIOpo.tanc end
cyclohcxane is reported in the literature to be an
“equilibrium process. It appeared desirable, therefore,
to study the reections of cyclohexane and methylcyclopentane

under oerboniun icn conditions.

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slut.—

Three other conpounds appeared suitable for study
under liquid phase carboniun ion conditions, namely

ethylcyolopentano, methyloyclohexane and cyclohaptane.

 

The following reactions have been reportadzlo’ll'ld’lu'l4
r/Lj No deaction
\\// L
, _ l,
/l\. “5131i 37-31 I 3 + g j
' J 80", IO nourg (trans) -*~-*——

3.5%

"'/\‘ ”K 'o " t d 7 t
#_ , n o‘» unrea e are
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OU”' 7 traces traces
X '2— car-:93:- I’L

 

 

j p
f" \3 3- 0439.3
10C ,1)

The proposed mechanisms for these reactions involve

primary oarbonium ions, 1.6. (7). However, the results are

+.

,/\\ ‘ C+ C (7)
s : Eli~
Ly} ( (5 + R J"

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also explicablc on the basis of bIJOlUCJlar reactions,

1.6. (8).
'+ -k
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a.) in U
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It can be seen that the predominant product in these
reactions is the six-membered ring, methylcyclohexane,
which is formed in preference to the five or seven-
nembersd rings. This is undoubtedly due to the greater
stability or the six-membered ring. opitzer and Huffmanls
calculated from heats of formation that cyclohexans is
l keel/mole or 532 more stable than any other cycloalkane.
Pitzer's work also leads to the sane conclusions}5

A general study of liquid ghuee isoaerizations of
theee cycloalkanes was undertaken with the following
objectives: (a) to distinguish between the postulated
primary carbonium ion processes and bimolecular reaction
sequences, and (b) to ascertain the amount of inter-
conversion between five, six and seven-membered rings

under liquid phase carbonium ion conditions.

In order to generate the desired carboniun ions under

1%:

ti 4 us-|. V

r.. J

i

conditions analogous to those dead for the isotope-
position rearrangenenc or t-anyl chloride, the alkyl
chlorida;of the cycloalkanes were used in the oreaence
or aluminua chloride.

A qualitative and quantitative study or tine,
temperature'snd aluminum chloride concentration upon the

direction and-extent or isomorization was also made.

‘
to n

c
9. ‘q ‘-

--.

w.

Results and Discussion

Reactions were run on five different hydrocarbons and
the reeulte obtained, with respect to time, temperature and
aluminum chloride concentration are shown in Thblee I-Y.‘
The reactions consisted of a volaude fraction and a brown
residue containing the alaninum chloride and polymeric ’
laterial. ‘The volmnle fraction was analyzed by vapor
phase chronotrography. .. ‘

Several points of general interest are apparent from
the results. (i) The reactions appear to stop after short
periods of time. (2) Ethyl acetate was found to inhibit
the reaction of methyl and ethylcyclopentanc. Similar *
reports or inhibition by other compounds in this type of

l‘Therefore,'de-

reaction nay'be found in the literature.
hctivation of the catalyst ...m. to be a common phenomenon

in this type of reaction.‘ Under the liduid phone reaction
‘conditione the deactivation of the catalyst is acct likely
caused by the polymer.' (3) 'Temperature-substantially
affects’the"anount of isomerinstion. (4) The qualitative
composition of the product is virtually unaffected by time,
temperature and aluminum chloride concentration. Cyclcheptane
appears to be an exception. -

' "The data given in Tables I and II summarize the results
obtained in the isomerination of aethylcyclopentene and
veyclohexane. ~It can be seen that reaction of either'compound

leads to only one product. No product was found which would

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correspond to_the occurrence of reaction (5) or (6).;
Therefore, in the case of these two compounds, there is_
no evidence for the occurrence of a bimoleculer reaction,
but the results do not rule out this possibility, because
reactioa_(4) may be occurring at a much faster rate than a
(5) or (6). Furthermore, the reaction conditions may be
such that reactions_(b) and (d) are highly unfavorable.
These reactions involve_the formation of an olefin and a

I secondary carbonium ion while (4) involves the foraation
,9: an olefin and a tertiary carboniun ion. It has been
“foundithat fission steps leading to secondary earbonium .
ions do not compete favorably with those leading to tertiary
carboniua ions. _ ‘_.

Graph I shows that the amount of interconversion.in
the nothylcyolopentane-cyclohexane systea_is highly
temperature dependent; the ratio nethylcyclOpentane/
cyclohexane increases with temperature. Graph II shows
that reaction is complete sithin a short period of time.

' .Entries (19) and (20) of Table I when contrasted
with (ll) and (15) show the effect of ethyl acetate upon
the amount of isomerization. Fran these results it must
be assumed that ethyl acetate is an effective inhibitor
for this_type of_liquid phase reaction.

Table III listed the results obtained for the.isoneri-
nation of ethyleyclopentane. Entries (l),(e) and (a) sore

 

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run sith ethylcyclopentane obtained from a hydrogenation
reaction using ethyl acetate as solvent. It is noticeable
that these reactions shoe relatively low percentages of'
rearrangement. By the use of vapor phase chroaotrography,
it was found that the ethylcyclopentene contained 21 ethyl
acetate as impurity. further purification of the ethylé‘
cyclopentane was carried out by use of the Bookmanl
negachroae before the remaining reactions were run. 'Coaplete
conversion to methylcyclohexane was obtained in all of these
reactions indicating that the ethyl acetate was responsible
for theinhibition of the earlier reactions. This agrees
with the results obtained for the nethylcyclopentane"
isoaerisation. iIt should be noted that the only product
in this reaction is the six4meabered-ring systea, aethyl-
cyclonesane, and that there is-no further ring expansion
to a seven-nenbered ring structure.‘ I ' I

Table xv .no.. that this isbalso the ease for methyl-
cyclohexane. ?here is no ring erpansion to cycloheptene,
but there is a ring contraction to a diucthylcyclopentane.
In the case of cycloheptane, as shown in Table V, the anor
product is methylcyclohexane along with small amounts of a
dinethylcyclopentane. The above results, coupled sith‘*
reports in the literature that dinethylcyclopentanes

isomerize to methylcyolohesane}aleads to the follosing’

’eonclusionsz“fhere is an equilibrium between Isthylah

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eyelcherane and dimethylcyclopentane shifted highly in
the direction of methylcyclohexane. The conversion of
cycloheptane to methylcyclohexane is not reversible, and
the methylcyclohexane formed then isomerizes to a five-
aembered ring structure. The stability of the various
ring structures must also be considered.. The conclusions
agree with the previous reportg:lin that the six-membered
ring structure is more stable than a five or seven-membered
structure. It may be further concluded that the five-
sembered structure, dimethylcyclopentane, is more stable
than the seven-nembered structure, cycloheptane.

The dimethylcyclopentane reported in the isomerization
of both aethylcyclohexane and cycloheptane was not definitely
determined, but the following evidence points to one or
both of the trans 1,8 or l,3—dimethylcyclopentanes.

The position of the signal peak for the compound in
the vapor phase chromatagraph shows it to be a seven-carbon
compound with a boiling point slightly below that of
nethylcyclohexane. a sample of the compound was separated
on the chromatograph and analyzed by n.m.r. and infra-red
spectroscopy. Figures I-IV show the spectra obtained.

The n.m.r. spectra are shown in figures III and IV.
The peak at T9.03 would correspond to the methyl groups.
The presence of tertiary hydrogens is also shown in the
spectra. This eliminates the presence of l,l-dimethyl-

cyclopentane.

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- 12 ~

The infraeredspsetra ere sheen in Figures I and II.
These show the resenoe or a_ methyl group but the absence
or‘a genedinethyl coupound.‘ A canoerison of the inrrh-red
sptotra obtained from the compound with spectre of t“:

pure dimethylcyciooentsnes both ois end trens shows that

- ...:m h» ~“Mk' ‘ ’ “ *

tht conpdund from theI iaonerilatlons is trans l,2 or 1,3-
dinethyldyolopehtshe or a ulXture Iof Ithe two. i
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3 a
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: J ' ' 4‘
—— - e ..-, -- e -, _ -
‘. 1
i ' g ' f
r ~~~~~ f ~--~ ~-\~ ~ ~- - '-r_ ;
i h l 4 t
g A : g - 5
: 1 E ' '
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0.7--

- .LS -

Table I

Isomerization of Methylcyclopentanea

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

he. H m.moles A1613 Time Temp. ER" %[:::)‘-
(min.) °C.
1 b.3h 30 -35 . 0

2 b.3h 10 0 0.9
3 h.3h I 20 o 23.0
h h.3h . 30 0 S.h
S 8.68 10 0 1.5
6 8.68 20 0 h.1
7 8.68 30 6 8.3
8 b.3h 5 26 I 8.3
9 h.3h lo 26 3h.1
10 b.3h 20 26 h3.2
11 h.3h 30 26 53.5
12 8.68 5 26 13.0
13 8.68 10 26 h0.2
1b 8.68 20 26 h9.h
15 8.68 30 26 60.?
.1 16 b.3h 10 no 26.h
17 8.68 10 ho 27.3
18 b.3h 180 30 60.5
b19 b.3h 30 26 0.8
bzo 8.68 30 26 1.0

 

 

 

 

 

 

a. hh.6 m.moles of methylcyclopentane and 1.63 m.moles of
l-chloro-l-methy1cyclopentane were used in each reaction.

b' 3.2% of ethyl acetate present.

Thble II

Isomerization of Cyclohexanea

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

No. m.moles 11013 ($112.) Tergp. IWt. % b
1 1.7 10 0 <1
2 1.7 20 0 <1
3 1.7 30 0 0.h
h 3.1: 10 0 0.9
5 3.h 20 0 1.7
6 3.1. 30 o 2.7
7 1.7 10 26 <1
8 1.7 20 26 1.9
9 1.7 30 26 - 16.9

10 3.1. 10 26 6.3

11 3.1. 20 26 11.5

12 3.h 30 26 11.6

13 1.7 180 30 8.7

lb 1.7 10 1.0 1.3

15 3.1. 10 I ho 5.9

 

 

 

 

 

3- h6.h m.moles of cyclohexane and 1.7 m.moles of chloro-
cyclohexane were used in each reaction.

 

.. 1,: ..

Table III

Isomerizstion of Ethylcy'clopentsnea

 

 

 

 

 

 

 

 

 

No. m.moles 111013 a: EtAc Time Temp. we. fl. 6
I (mim) . c. I

1 1.16 2 30 26 1h

2 1.16 0 30 26 100

3 1.16 0 5 26 I 100

h .58 2 30 ho 8

5 1.16 2 30 1.0 12

6 1.16 0 30 70 100

7 1.7L: 0 90 70 100 A

 

 

 

 

 

 

a. 15.6 m.moles of ethylcyclopentane and .58 m.moles of l-chloro-l-
ethylcyclopentane were used in each reaction

 

Isomerization of Methylcyclohexanea

Thble IV

 

 

 

 

 

 

 

 

 

 

 

 

 

No. I m.m61es 111013 (:35) Torso. wt-” 6] 7
1 1.5 30 0 0

2 3.0 30 0 0

3 1.5 30 26 0

h 3.0 30 26 0

5 ’ 1.5 180 26 0

6 1.5 30 ho 1.5
7 3.0 30 b0 h.1
8 1.5 30 70 7.5
9 3.0 30 70 10.0
10 h.5 30 70 9.h
11 3.0 60 70 9.9

 

 

 

 

 

 

8.

39.3 m.moles of methylcyclohexane and 1.5 m.moles of
1-chloro-1-methylcyclohexane were used in each reaction.

Table V

Is «urination of Cycloheptanea

 

 

 

 

 

 

 

 

 

 

 

No. m.moles A1013 (51111:) I Tera). Wt. 1Q Wt. % é’l
1 1.2 30 -15 3.1 o

2 .6 .. 30 ' 0 3.5 0

3 ’1.2 . 30 I 0 5.1 0

h .6 3o 26 5.6 0

5 1.2 30 26 37.1. 2.0

6 .6 30 ho 111.11 0

7 1.2 30 ho 52.5 2.5

8 1.2 30 70 89.7 .7.2

 

 

 

 

 

 

 

a. 16.6 m.m01es of cycloheptane and 0.6 m.moles of chlorocycloheptane
were used in each reaction.

 

 

 

.ondpmoaoaoho
mo 5.30.89. map SUE ... ognomojho
439636.. so 3.366% omega .H .wE

 

 

 

 

 

 

 

 

 

1

6:88:03?
...TEpos wo 830.8.“ ofi. 18E ...ondpscmoaobé
4355p. .8 356.8% e223 .HH .mE

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

J r 1 4 7
2 1 0 ppm

Fig. III. NMR Spectrum of "dimethylcyclopentane". From the
reaction of cycloheptane.

 

 

Fig. IV.

 

 

 

 

i L l

2 1

NMR Spectrum of "dimethylcycloPentane ".
methylcyclohemne.

 

From the reaction of

 

‘7.

 

Q

. I"
t g
H H

Graoh I

Effect of Time upon Exteat of Reaction
Temperature 26 U. ,
I'-'Lolar Ratio: AlCIB/cyclic chloride 2 fororé

 

 

 

 

 

 

 

 

2 .66 1‘0
a.
80
()0 __
[to -— /
20 _
_fi_ 1'”"” 1 1.
time (min.)
Graph II
Effect of Temperature upon Extent of Reaction
, neaction Time' 10 Minutes
Molar Ratio: AlClB/cycli chloride 2 for()
2.66 forth
3..
ho _
30 _
20 _
10 r-
, '7 ”f ’- 1 1
O 10 20 30 10

O
temp. U. !
— . s

I V:-'L._‘-5m MEL

Elf-LR I 411333! TAL

3 Apparatus:
E; The reactions were carried out in a 25 ml. round bottom

, I flask equipped with a side-arm inlet. The flask was connected
ii to 0 Vacuum system through a small column and distilling head.

RSSCILQQ Procedure:

IFive ml. of methylcyclopentane were placed in the reaction

 

flask and the flask was immersed in a pro-heated oil bath for
ten minutes. To the magnetically stirred solution was added,

through the side-arm, 0.2 ml. or lochloro-l-methylcyclopentane

 

_..__.._- _
O )U."

Lam:

v...

and .29 g. or aluminum chloride (Baker a Adamson, reagent

 

a:
g grade). After thirty minutes, the liquid portion was

é collected under vacuum, at liquid air temperature. A brown
1: residue remained in the reaction flask, presumably polymeric

1%;

material and aluminum chloride.

The above procedure was followed for the other concounds,

with variations in time, temperature and aluminum chloride

concentrations

:7} lv- .7.‘

ChemicalszI

Methyloxclopentsne was obtained from ihillips Fetrcleum

 

Company. Pure grade (99 mole % minimum purity).
Methzlozolohexane was obtained from ihillirs ietroleum

Company. Pure grade (99 mole firmininum purity).
Cyclohoxane was freshly distilled laboratory grade.

Boiling point 81-820/751 mm. Literature values}eb.p.

810‘0/760 Me. n? le4290e

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':‘ , _ -. . c .‘J‘ ‘ - 1 J_ 4“... Q.‘ ‘J '_\.

Cycloccptane was obtained from Alcrich Chemical

 

Company.‘ Technical grace.

Lthylcyclopcntane was prepared from cyclopentanone and
cthyl bromine by a Grignard reaction, subsequent dehydration
of the alcohol and hydrogenation of the'reaulting olefina.
The Grignard reaction was run with 218 g. (2 moles) of
ethyl bromide, 48 g. (2 holes) of Jagnesium turnings and
84 5. (1 mole) of oyclopentanone. The reaction mixture
was decomposed directly to the olefins with 10% hydrochloric
acid solution. Distillation gave 39 g. (.406 males, 40.6%)
of two olefiha (ethylcyclopcntcne and cthylidine cycIOpentane)
b.p. 48-48°/B mm.

The clerics were hydrogenated in ethrl acetate, at
atmospheric pressarc and a temperature of 50° OVcr platinum
oxide to give a giantitativc yield of ethyl-cyclopcntuue
b.p. 101-1030/750 1a., nge 1.419J. Literature valieégb.p.
lOB-lOéo/VSO mh., n§9 1. 4194.

l-c oci-l-~r**V‘_iclocent~ne as 3 prepared by the
Grignard reaction of nethyl iofiiic and cyclonentcnonc.

Using 569.2 3. (2.6 moles) of methyl iodide, 62.4 a.
(2.6 moles) of Magncsium turnings and 105.2 g. (1.3 moles)

(.432 miles, 37;) of i-isthyloyoio-'

1‘.)

of CYOlOgfiflthSSS, 43.

.‘.I
u '

N

J." 10‘: ‘tub W“5 ODt uinCdo Liter!-

.‘5

pentanol b.p. ci-CC0/161Ca.,

2:3.5 .A-'\
n-—- 1.4cc3.

,
c0 , ,

cure Valucn, b.p. 51-53°/iu mn.,

The l-me JleLlu ntaiol W13 trcutcd with c two-fold

excess 01 cold c;ncentrc t‘: d r.jC:;c onlcric uciu SULdtiCn and

iii"

a-
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um

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shaken intermittently for twenty minutes.' The l-chlorc-
l-methylcyclopentane formed as an upper layer. Thin was
sepcreted, dried in an air stream for thirty minutes and
dietilled in Quantitative yield. Boiling point 70-71°/
145Umm.,’n;g 1.4464. Values listed in the literatur§%b.p.
70°/145 mm., age 1.4465, egg .9541.

The l-chlorle-methylcyclopentane was prepared
immediately before use and was not stored for over I11
hours before use.

ghl oroc clchexane was pre,ared by the addition of 60 m1

 

of concentrated hydrochloric acid solution to 20 g. (.20
moles) of cyclohexanol and refluxing for one hour. After
separation, washing, drying and distillation, 15.6 g.
(. l4 moles 70%) of chlorocycloheXene was obtained. Boiling
point 142-1450/751 mn.. ng- 1.4621. Literature veluei?
b.p. 142 °/7cc mm., n3: 1. 46254.

l-chloro-l-methylcyclghexene was prepared by the Griinard
reaction of methyl iodide with cyclohexanone and treatment of
the resulting alcohol with concentrated hydrochloric acid.
In the reaction, 142 g. (1 mole) of methyl iodide, 24 g.
(1. mole} of Magnesium turnings and 49 g. (0.5 moleo) or
(cyclohexanol were used. Distillation yielded 36 g. (.58 holes,
add.é%) of l-methylcyclchexancl. Boiling point 64-66°/20 an.,
n%9 1.4587. Literature valuc§? h.b. 67-680/21 mm.,~n§2

1.4584.’

,3 f“

er

#. ...
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- 25 -

The lfmathylcyclohexanol was treated with a two-fold
excess or cold concentrated hydrochloric acid and shaken
for thirty minutes. The l-chlorc-l;methylcyclohexane that
formed was separated, dried in an air stream for thirty
minutes, and distilled in quantitative yield. Boiling
point 42-43°/20 mm., né- 01.4572.t Values listed in the
literaturgf b.p. 43 0/20 mm., ng— 1.4579.

The l-chlcro-l-methylcyclohexane was prepared
immediately before use and was not stored for more than
six hours beiore use. _
(I Chlorocxcloheotane was prepared by a Lithiun Aluminum
Hydride reduction or cycloheptanonc and subsequent treatment
or the alcohol with hydrochloric acid. Ten grams (.062 mole.)
of cycloheptanone were treated with l. 2 g. (.031 moles) of
Lithium Aluminum.Hydride, to yield 8.6 g. (.075 moles, 85. 3%)
or cycloheptanol. Bo iling point 8o-88°/15 mm., n%9 1. 4754.
Values listed in the literaturg? b.p. 87-880/15 mm., age 1.4757.

1 The cycloheptanol was treated with a three-fold excess

or concentrated hydrochloric acid and refluxed for three
hours. The chlorocycloheptane that formed was separated,
hashed, dried and distilled to give a quantitative yield.
hailing point 45-460/6 mm., nge 1.4692. Literature valueg?
b.p. 1740/760 mm., ngg not listed, D3 .9957.

l-chloro-l-ethyicyclopcntane was prepared by a Grignard

reaction or ethyl bromide with cyclopentanona and treatment

of the resulting alcohol with concentrated hydrochloric acid.

' Q
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- 27 -‘

The l-ethylcyclopentanol was prepared in befi yield by the
reaction or 109 g. (1 mole) of ethyl bromide and 24 g; (1 mole)
of Magnesium turnings in other with 42 g. (0.5 moles) of
cyclopentanone. Obtained were 50 g. (.263 moles) of l-ethyl-
cyclopentanol, b.p. 43-44°/4 mm., n§9 1.4559.‘ Literature »
valuegz b.p.'58.5°/8 mm., n39 l.4540.

The léchloro-l-ethylcyclopentane ass prepared in
quantitative yield from l-ethylcyclopentanol by treatment
with a two-fold excess of cold concentrated hydrochloric
acid, with shaking for thirty minutes. Physical properties
found, b.p. 52-530/35 mm., n§9 1.4525. Values listed in the

D

‘ I 23
literature, bepe 50.50/35 films. 11%? 104525, a? .9548.

Analysis or Prodmts:

Small amounts or the distilled reaction mixtures were
injected into, and separated to the various components by
a Perkin-Elmer Model 154 Vapor Fractoneter. The columns
used were 5-30? Silicon Oil on Celite and the temperatures
used were 65-1000. Identification of the compounds was
made by a comparison of the retention times of pure samples
of known compounds with those of the reaction products, by
separation, collection and infra-red and n.m.r. spectroscopy
on the collected samples.

duantitative determination or product percentages was

made by integration of the areas under the signals and

direct correlation of these areas to component weight.

'31

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In the case of ethylcyclopentane a different method
was used. The product resulting from the isomerization of
cthylcyclopentane is methylcyclohexane. A good separation
or the two compounds could not be obtained by the use of
vapor phase chromotrography, so quantitative determination
was carried out by use of infra-red spectroscopy.

'The percentage composition of the’reaction mixtures ; s
were determined by comparison of several lines in the spectra
with the spectra of mixtures offknown composition.' The‘ ‘

following lines were used:

 

.thyloyOIOPCntane" 8.0913131 9.5211.
methylcyclohexene- 10.8Qn,‘ll.06n, 11.48u, and 11.90u.

.L

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SUl‘dili‘ifi Y

The liquid phase isomerization of methylcyclopentane
to cyclohexane in the presence of l-chloro-l—methylcyclo-
pentane and aluminum chloride was studied with the objective

of assessing the contribution of bimolecular reactions to

a:

'1' 12-: W. ‘
.
i

the rearrangement. The reverse reaction, cyclohexane to
methylcyclcpentane, was studied under similar conditions.

No evidence was found in support or a bimolecular reaction

 

sequence, but the data do not exclude this possibility.

[petunia-as?” .Dfl.tifi.sflt.’mk.lla‘1
. . ~ ‘ ~ ‘ ' . ' . w'
(

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'9
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Three other hydrocarbons, ethylcyclopentane, methyl-
cyclohexane and cycloheptane were also isomerized under
similar conditions. No evidence was found for the occurrence
0: s bimolecular process, but as above data do not rule out
'this possibility.

. The isomerizations favor the formation of six-membered
rings over the five or seven-membered rings.

Methylcyclohexane and cycloheptane were found to yield
small amounts or a mixture or trans 1,2 and/or 1,3-dimethyl-
_cyclopentane. Identification of the structures was made by
infra-red and n.m.r. spectra. I

Ethyl acetate was found to inhibit the isomerization

of methyl and ethylcyclopentane.

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APEEHDIX

Attempted Preparation of Lthylcyclcbutane~

'It has been found that dialkyi oxalates decompose in
29
good yield to Sive olefins. it seemed interesting to try ~
the reaction on l-ethylcyclobutanol. Therefore, the following

reaction reaction sequence was used in an attempt to prepare

 

 

 

 

ethylcyclobutsne:
,. Km". 0 0 ‘”' \~
(“M“TV'O , ! i-OH H "- * f g 9' 4
i : UNI") 023551‘ ”fig?“ ' ; Cl- C- 0- Cl) MO- 0- 0"ng
1......- 2} sec .. ’ ...... ' Q é i .;
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i i 1'! - I ; -..—...-
f 3 -——---———-5» 3a “I ‘ .
‘ x i i i ”a“ <

 

To 27.5 g. (1.144 moles) of magnesium,turnings is other
and 124.7 g. (1.144 moles) of ethyl bromide was added 20 g.
(.286 moles) of cyclobutanons. The excess Grignard reagent
was decomposed by addition of ice-cold saturated solution

of ammonium chloride. The l-ethylcyclobutanol was separated,

washed, dried and distilled. The yield was 22.6 g. (.226 moles,

79.9%) with the following physical properties: b.p. §9768°/
40 mm., ngg 1.4410. neport of the compound in the literature
could not be found so verification of the structure was made
by infra-red and n.m.r. spectra.

The l-ethylcyclobutanol was treated with oxalyl chloride

to form the dioester. This was tried in two different ways.

In the first procedure, 1-ethylcyclobutanol was dissolved

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in other and pyridine and the oxalyl chloride was added
drop-wise. The mixture was refluxed for three honrs and
then dissolved in water. The other layer was Separated,
washed and the solvent distilled Oi r. 'The resulting ester
was pyrolized at lad-213° . ' -

The second procedure involved dissolving the alcohol

in . sixsrold excess of freshly distilled guinoline‘rollosed 3mm;
by drop-wise addition or the oxelyl chloride. The reaction gi ‘ ‘
mixture was then pyrolized directly at tehoeratures no tofl'r E
£350. . 5 j “

Neither method gave satisfactory results, in that,
only a small quantity of compound was recovered from the
pyrolysis. 'rhe co:apound contained a band in the infra-red
at 5. 80-5.83 corresponding to e carbonyl stretch, and had '
a boiling point of 55°/75i mm. '

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F.C. Whitmore, J. Am. Chem. $00.,‘Qi, 3274 (1932).

J.D. Heldman, J. Am. Chem. 530.,‘Qg, 17§9(1944).+

H. Fines and Escher, J. Am. Chem. 500., fig, 595 (1946).

P.T. Bartlett, F.£. Condos and A. Schneider, J. Em. Chem.
Soc.,.§g, 1531 (1944).

3.8. Bloch, H. lines and L. Schmerling, J. Am. Chem. Soc.,

pg, 153 (1946). __

H. Pines, B.M. dbarham and V.N. Ipatieff, J. Am. Chem. 300.,
19, 1742 (1948).

A.G. Evans, "The Reactions of Organic Halides in Solution".
manchester University Press, hunchester, sngland, 1946, p. 15.
J.D. Roberts, R.E. McMahon a J.H. Hine, J.A.C.S.‘zg, 4237 (1950).
Schult, H303 and Verheus, sec. trav. chim., ca, 793 (1940).
N.D. Zelinskii and co-workers, Zhur. Obshchei Khim.,.§1,
2156(1951). Chem. shun, ge, oozes (1952).

N.I. Shuikin and L.M. Feofsnova, Izvest. Abad. Nauk. 8.8.5.3.
Otdel. Khim. fiank., 1952, p. 137. Chem. Abetr.,‘gz, 1618h (1955).
H. yinee, ?.J. Pavlik and V.N. Ipatieff, J. hm. Chem. 500.,

1:3, 5738 (1351).

E. Pines, F.J. Pavlik and V.N. Ipatierf, J. Am. Chem. 500.,

23, 5544 (1952).

H. Pines, h. Aristofr and V.N. Ipatiefr, J. Am. Chem. coc.,

1;, 4055 (1950).

R. byitzer and H.M. Huffman, J. Am. Chem. Soc.,.§g, 211 (1947).
K. 5. Pitzer, Science, 191, 672 (1945).

G. J. herebatsos, F.M. Vane, Private communication.

 

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- 33 -

G.D. Hangman, "fiendbcox of Chemistry and hhyeica", 38th ed.,
Chemical nabber Fablishing 00., Cleveland, Lhic, 1956.

G. Chavanne and P. Becker, Bull. soc. chin. Belg., fig, 591
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C.H. Collins enc 3.4. ficmnend, J. erg. Chem.,.§§, 638 (1960).
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(1949).

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294 (1935).

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A.F. Plate and 1.1. Eelinkcv, Ahur. Cbechei Khim., 29 1064
(1959).

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(1936). Shem. Abstr.,.§§, 8977i (1988).

J. Sorbett, Prchte ccnnunicctien.

 

 

 

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