f a & r . W w). M A. .m

".d .‘Irn .A9.IOW.M..H‘ .utmol).',. . jfliupjc. ... “k...- ’4 J5. -..é

... m u ..a... . IBM“... 99? n... mu W («.14. Hurt: Kubruwrtvk WW»

I!

W. a.

. u .3, 3n~~fl.nh

(K \. inf-WW»)...

HI. m a 2 5:... l n - ..

... At. «9 Hifi/M» ....n 0. Ag 1 «in. n. Du .s aw In. ugh. ,4... a

(“.39 L ' . fa .....hu #1 a» «'0‘ .V {\. . (a‘lh. . walrufiro 0.5.... 04“!

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

-. I:

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

s—1.

‘(Gv‘

.

' - J

u . .

- ' .I I.

‘ o. (I «..A ,..uC

.

pl 7 I u. t I »

~

It '0 ‘ a»

1‘ ' '- -

.‘o 'I ' -

/ v. y ‘ I

Avchf.~ IOWL u

.. 'o v1 . i

l f If k I. .

‘4 a

1,. \.«.. .. (4 ..l

.... _ _

wk' .5 ) y. I

. n ..a o. . n,

U

a..; . .n

K .Pfqr.c.... 'L

P . .

t.:y rt.» .i.. ‘...

o)

.. 4 ..J. A r .

IVs...“ 'r\ . v

‘.tn:

p—o

K.

.4

icxscaLh9345NT

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;

l

0

a 1

I‘d

;

.C

‘0

.

xa.

I.

.‘

“

..

.,

w

c

.

1|,

A

.4

.

fiquH$CT

The liquid phase isomeriZutions of methylcyclopentene,

cyclohexsne, ethyicyclopentene, 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-methylcyclopentnne 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

predominantprohhct is a six~membered ring.

t ‘-

."

“.4

I".

J

1-:

L. A

9"

h

.4

,0

1‘9

,.;

0".

a!

(.v'

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 explaincf 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

i

..-

‘J \.s.

.b

V?

s.

v.

Q

.1

..a

.

II

I_

—..

I

.c.

,.

we

.

.

II

.

r

L

nv”.

’\

O

u

t,

A).

.

I.

q

u

._

l1‘

~‘

_.

...”.

....h

..

.-

0“

sO

.0

x1

.on

_

O

..

ls.»

‘

.rJ

...\e

.

Ah

h

.

v

Dn

,e

'i

I

~

..

a

.

_-

s

e

..

..r-

..

ole

'\

s

a" .-

«\II.

n

J

I.

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

..J

w

9‘

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""

- c4— . + 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+

'7'

. ---v.

.--.

t ,u f

i. -

. a

e v A ..veA—‘

.

. . _ -

, I.

I - 1

. .J‘

.4.

1

I

-\

‘A ~.

I

,

4

1 ....

. ...7._Z> .

.ie V .

» J

, e

i J

V

. s

i

s- a.

5

.

I

—

ul N

(4‘

L

7.7.— ‘

>-

, xv .

\\

—‘

(“C

": Ni

O -

o.

J

.- s

.a \-

e ’V

'. .

. '.

- J.

- I

.

v

i .

54.r. x

K-

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)

(fl + I,“

N' i ’VMB. \

// K .

\§‘--

WI. m-

- +

3&5! 4—--—~‘ i/

..i _+ .7 ' ,L_. L_i 4/I ...—...}. ( ,-’ "" \‘g \ ,/ \\

‘ 4__* i ; “ a r :

\_w/’ 4' \_fif+‘(/\j (6)

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.

ixv ?'\Frb

.

1.

[4|

’-7

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

$4-241511'J1l \ J) + [... -.. f/ it +

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"

e

..

.l

Cn

w

\

JI

:\.

...

y

4

ol

0

o

L.

v‘\

.a

...

ro

_

n

L

......

,

4-

\.

.

h

‘u

1.

..

.

4

_v

.

.

It;

i

p‘

_z

.

O1

v

u

-

‘

I,

l

,-

w.

..

...

Iv

’'

I

v.

ua.

.e

.Ow

.

J.

'-

.

...h‘.

..

al

T'

i

u\

‘in

~,

A.

n.

‘J

.

A

._

J}

.

I‘.

ill’.

III]...

A!!!“

-.--— ...

. "II.‘

l\:k

it,

,

AT.

_

T\.\...l

‘\wl"

JT-

also explicablc on the basis of bIJOlUCJlar reactions,

1.6. (8).

'+ -k

x"\ __ ‘Y fi f /‘\/R

a.) in U

47/}: /R C.

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

._.

Ha-

..a

L.\'01

ib:

I

,f

+

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

u.

U {4" ':

.ot

-id‘ovg

VP.

7.!

' ,

L: a, e..

. .,.

3).. _J

'4.

I

..12} if!

I

. e

clad-e

.-

"t

5.7

p.

I.

1 .

st

.

f.’ " .-a

,5

«cu-fl

. 1"

es s“

'—

J- t...

A

duke:

not-

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

A

..1

J{I

f.‘

‘0‘

all.

JV

\K.

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

a.f

r.

33.‘

...

13

a.

.4

4-

:. A . he 21

J

.4 ~—

’”a.

Q25,

.rOf.

it

- 1.1, ..

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 rigures 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.

««p

e

I

\1

A

b e

.5,

b.

.

- 12 ~

The infraeredspsetra ere sheen in Figures I and II.

These show theresenoe or a_ methyl group but the absence

or‘a genedinethylcoupound.‘ A canoerison of the inrrh-red

sptotra obtained from the compound with spectre oft“:

pure dimethylcyciooentsnes both ois end trens shows that- ...:m h» ~“Mk' ‘

’ “ *

thtconpdund from theIiaonerilatlons is trans l,2 or 1,3-

dinethyldyolopehtshe or a ulXture Iof Ithe two. i

" .... .' .... ... - _ - ..

S ; .

3 a

i 1

2,. .... - L ".--—....- ‘..-- | - I

v 3 ' i

f i ‘; -..- -. ..., ,.-‘...-.A.. .V. . , .. , . . .. .. . - . _ _ -.-, . -.- .

i :

: , i ‘

8.. , --.. ..-- _ - “...-

: '2;«I ‘g

: J ' ' 4‘—— - e ..-, -- e -, _ -

‘. 1

i ' g ' f

r ~~~~~ f ~--~ ~-\~ ~ ~- - '-r_ ;

i h l 4 t

g A : g - 5: 1 E ' '

r“’“ ‘ . ’ ""“""‘ "" ’ ’." ‘ ‘ " ’I‘ "

. !

i :g i , i h

r"-* ; “*** _ '

a x

3”“: ‘7' '" ‘

; a

i r'9.--..." . -_ ..

a _ i ?

t2

re.

“a...

.I'

.“D

.o

\I

‘r

us

‘0

l'.i

.. .

t0.7--

- .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.

4

Fig.

I.

Infrared.spectrum

of

"dimethyl-

cyclopentane

".

Fromthe

reaction

of

cycloheptane.

Fig.

II.

Infrared.spectrum

of

"dimethyl-

cycloPentanel'

Franthe

reaction

ofmethyl-

cyclohexane.

J r 1 4 7

2 1 0 ppm

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

reaction of cycloheptane.

Fig. IV.

i L l2 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-

, -’ ”f ’- 1 1

O 10 20 30 10

O

temp. U. !

— . s

IV:-'L._‘-5mMEL

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 smell 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 contounds,

with variations in time, temperature and aluminum chloride

concentrations

:7}

lv-

.7.‘

ChemicalszI

Methyloxclopentane 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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’7 «I l I..." still "' O .0 "i

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Q s . e. .t T? “Au 60,4 .. . .I‘I‘I 9‘ I.)u'..s -

I! . r

O s ...: sl r I V 1 . | . 'I 1*. s. a . 1 w: e ... n t F r .3 . fl .6 'a . Poo .\ I.

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e... .1 - -. . 0 .IL; I I . L- .cssut f. IL .It.

Cycloccptane was obtained from Alcrich Chemical

Company.‘ Technical grace.

Lthylcyclopcntane was prepared from cyclopentanone and

cthyl bromiuo by a Grignard reaction, subsequent dehydration

of the alcohol and hydrogenation of the resulting 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; 48-18°/B mm.

The clerics were hydrogenated in etnrl acetate, at

atmospheric pressarc and a temperature of 50° OVcr platinum

oxide to give a qcantitativc yield of ethyl-cyclopcntuue

b.p. 101-1030/750 1a., nge 1.419J. Literature valieégb.p.

102-1060/760 mh., n§9 1. 4194.

l-coci-l-~r**V‘_iclocent~ne ma 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-Isthyloyolo-'R)

of CYOlOgfiflthSSS, 43..‘.I

u '

N

J." 10‘:‘tub W“5 ODt uin'kido Liter!-.‘5

pentanol b.p. SI-EQO/161h1.,

2:3.5 .A-'\

n-—- 1.4333.

,c0 , ,

cure Valuca, b.p. El-Eco/lu mn.,

The 1-m€JleLluntJ10l wIs trcutcd with c two-fold

excess 01 cold c;ncentrc t‘:d r.jC:;conlcric uciu solution and

iii"

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shaken intermittently for twenty minutes.' The l-chloro-

l-mcthyleyclopentane formed as an upper layer. This was

separated, 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.,'n§9 1.4465, egg .9541.

The l-chlorle-methylcyclopentane was prepared

immediately before use and was not stored for over I11

hours before use.

ghlorocclohexane was pregared 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.

(.14 moles 70%) of chlorocycloheXane was obtained. Boiling

point 142-1450/751 mn., ng- 1.4621. Literature valuei?

b.p. 142°/7ac mm., n3: 1. 46254.

l-chloro-l-methylcxclohexane 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 3. (O. 5 moleo) or

'oyclohexanol were used. Distillation yielded 36 g. (.58 0010.,

add.é%) of l-methylcyclohexanol. Boiling point 64-66°/20 an.,

n%9 1.4587. Literature value§? h.b. 67-680/21 mm.,~n§2

1.4584.’

...

v!

r'.

{4.

e r...

O b .1. .'

~awa-

I.

flz,

.‘.

a

I

F

C .

.4"

\I

or,3 f“

- 25 -

The lfmethylcyclohexanol was treated with a two-fold

excess or cold concentrated hydrochloric acid and shaken

for thirty minutes. The 1-chloro-l;methylcyclohexane that

formed was separated, dried in an air stream for thirty

minutes, and distilled in quantitative yield. Boiling

point 42-45°/20 mm., né-01.4572.t Values listed in the

literaturgf b.p. 450/20 mm., ng— 1.4579.

The l-chloro-l-methylcyclchexane was prepared

immediately berare use and was not stored for more than

six hours beiors use. _

.' Chlorocyclchectane was prepared byaLithiun Aluminum

Hydride reductionor cycloheptanone and subsequent treatment

or the alcohol with hydrochloric acid. Ten grams (.062 moles)

of cycloheptanone were treated with l. 2 g. (.051 moles) of

Lithium Aluminum.Hydride, to yield 8.6 g. (.075 moles, 85. 5%)

or cyclcheptanol. Boiling point 85-88°/15 mm., n%9 1. 4754.

Values listed in the literaturg? b.p. 87-880/15 mm., n§9.1.4757.

I The cyclcheptanol 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-1-ethylcyclopentane was prepared by a Grignard

reaction or ethyl bromide with cyclopentanone and treatment

of the resulting alcohol with concentrated hydrochloric acid.

Ii

.0 ~§n n: 0"

'3 'Q .

.P; .‘

l ’-‘

‘

"I

' a L (Jig/J. ‘-

x.4,

- 27 -‘

The l-ethylcyclopentanol was prepared in 58% yield by the

reaction or 109 g. (1 hole) of ethyl bromide and 24 g. (1 mole)

of Magnesium turnings in ether with 42 g. (0.5 moles) of

cyclopentanone. Obtained were 50 g. (.265 moles) of 1-ethyl-

cyclcpentanol, b.p. 43-44°/4 mm., n§9 1.4559.‘ Literature »

valuegz b.p.'58.5°/8 mm., n39 1.4540.

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. 52-550/55 mm., n§9 1.4525. Values listed in the

D

‘ I 23

literature, b.P. 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 Fractonetcr. The columns

used were 5-50? Silicon Oil on Celite and the temperatures

used were 65-1000. Identification of the compounds was

made by s 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.

‘uantitative determination or product percentages was

made by integration of the areas under the signals and

direct correlation of these areas to component weight.

.-

...» . . ...L!

.4

)»

J‘ u‘

:7".7! g...

4

f

r

y

,;‘4

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vb

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-28-

In the case of ethylcyclopentane a different method

was used. The product resulting from the isomerization of

ethyloyclopentane is methylcyclohexane. A good separation

or the two compounds could not be obtained by the use of

vapor phase chromotrcgraphy, so quantitative determination

was carried out by use of infra-red spectroscopy.

'The percentage composition a: the’reaction mixtures ; s

were determined by comparison of several lines in the spectra

with the spectra of mixtures offknown composition.' Th.' ‘

following lines were used:

.thyloyOIOPCntane" 8.0913131 9.5211.

methyleyclohexsne- 10.8Qn,‘11.06n, 11.48u, and 11.90u.

.L

.‘I‘h

' ‘

.ui;

SURE1.13Y

The liquid phase isomerizstion 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

methylcyclopentene, was studied under similar conditions.

No evidence was found in support or a bimoleculsr reaction

sequence, but the data do not exclude this possibility.

[petunia-arm.Dfl.tsfi.sflt.’mk.lla‘1

A.

~‘

~‘

'e

'.

v'

i. I

‘\

'9

‘V;

Three other hydrocarbons, ethylcyclopentane, methyl-

cyclohexene and cycloheptane were also isomerized under

similar conditions. No evidence was found for the occurrence

0: s bimoleculer 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.

i

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APEEHDIX

Attempted Preparation of Lthzlczclcbutane~

'It has been found that dislkyl oxalates decompose in

29

good yield to Sive olefins. It seemed interesting to try ~

the reaction on l-ethylcyclobutsnol. Therefore, the following

reaction reaction sequence was used in an attempt to prepare

ethylcyclobutane:

,: Km". 0 0 ‘”' r~

i“”“§"0 , ! i-OH H "- * f g 9' 4

i i ....1") 023551‘ ”fig?“ ' ; Cl- C- 0- Cl) MO- 0- 0"ng

1......- 2} s00 .. ’ ...... ' Q i t .;'”"" ‘‘‘‘' L....1

.~ 0 ' r'

g \\\|_ i f" /“* 32 A ;

- w 0- 6-2 6-0.:em—1 rm“ “"r/ ‘ —' PtO ’ i 'i i 1'! - i ,6 -..—...-

f 3 -——---———-5» 3a “I ‘ .

‘ x i i s ”a“ <

To 27.5 g. (1.144 moles) of magnesium,turnings in other

and 124.7 g. (1.144 moles) of ethyl bromide was ended 20 g.

(.286 moles) of cyclobutsnons. The excess Grignard reagent

was decomposed by addition of ice-cold saturated solution

of ammonium chloride. The l-ethylcyclobutenol was separated,

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

79.9%) with the following physical properties: b.p. eggse°/

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-ethylcyciobutanol was treated with oxelyl chloride

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

In the first procedure, l-ethylcyclcbutanol was dissolved

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a . : ~ 5 . .1 . . s . v, . ..,P (\ r. t .P V\ P. I s. l‘. ‘r x..ss ... .0 hls.

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- 51 -

in ether and pyridine and the oxslyl chloride was added

drop-wise. The mixture was refluxed for three hours and

then dissolved in water. The ether layer was Separated,

washed and the solvent distilled Oif. 'The resulting ester

was pyrolized at 130-21o° . ' -

The second procedure involved dissolving the alcohol

in s sixsrold excess of freshly distilled guinoline followed 3mm;

by drop-wise addition of the oxelyl chloride. The reaction gi ‘ ‘

mixture was then pyrolized directly at temperatures up tofl'r E

£350. . 5 j “

Neither method gave satisfactory results, in that,

only s 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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