SOME BBOMD DERIVATIVES OF
M-CRESUL

THESIS FEB THE DEGREE OF M. 8.

james Alfred Hutchinson
1931

 
    
 
   

W"

U!
u-nmaflm"

 

SOME BROIO DERIVATIVES OF n-CRESOL

A Thesis _
Submitted to the faculty of
MICHIGAN BTA‘I‘E COLLEGE

In Pattie]. Fulfillment of the
Requiruente for the Degree
of
later of Science
Department of Chantry

By
Jane: Alfred Hutchinson

June. 1951

ACKNOWLEDGMENT _

The writer wishes to express his
appreciation to Dr. R. C. Huston, under Ihoee
guidance this work ha: been.done. But for
his timely advice and encouragement, thie

work could not have been accomplished.

331.640

HISTORICAL

Very little is known of the bromine
derivatives of upcresol. There may be two explanations
of this peculiar circumstance. Either the previously
high cost of n-toluidine or the difficulties encountered
in the preparation and proof of their structures. at
any rate the literature contains very little on the
subject. The very discouraging results which I have
obtained, has led.ln to believe that it is perhaps the
latter reason as to why more previous work has not been
done on such a common organic substance.

Neville and dinther in 1882 (Ber. 15, 2991)
prepared a Ii-bron-cresol by the diasotixation of I-bI’OI-
uptoluidine. The diasoting agent used was sodiul nitrite,
and the diasoniun salt thus formed was deco-posed with
water. They obtained a mono bron n-cresol nelting at
56-67°.

Claus and Hirsch (J. pr. chem. 2, 59, 59)
prepared 2-4-6 tribron.n~cresol by treating mpcresol with
bromine in chloroform solution. Their product melted at
84°.

2-4—6 tribroan-cresol was also prepared by
earner (Bl. Soc. Chem. 2, 46, 276). much the same method
as that described by Claus and Hirsch was used. The only

difference being that water was used as a solvent instead

of shlorcfcns. ‘They obtained a product which melted at
81-88'. -

In 1898, Bodroux (Ccnpt. rend. 126, 1282-85)
found that when.s~cresol was treated with bromine in the
presence of aluminum chloride, a tetra braIL-pcreso1
was formed which.se1ted at 194'.

Ausers and Richter (Ber. 32, 3382) prepared
2-4-6 tribrcs.necresol but the reduction of 2-4-6
tribrun a-oxy bensyl bro-idea The reduction was sscosplish-
ed by the use of sins and acetic acid.. Their product
melted at 84°, thus checking the work of Claus and
Hirsch. '

Gibbs and Robertson (J. Chem. Soc. 1914. 2. ~//”
1885) prepared a dibrols s-cresol to which they assigned
the_formu1a EZQJdibrcsMs-crescl. This was accomplished
through the diasotisation of 4-6 dibron n-toluidine'was
prepared by the broninatien cf ‘00t9fl9t0131d1fl0'1n.th.
cold. ~ The dibrcn n-cresol thus prepared salted at 55'.

One year later walther and Zipper published an
article (J. pr. Chem. 91, 364-414) in which they described
the preparation of 6—brcm m-crescl which under our systen U/
of naming would be 3:311). n—cresol. They prepared this
compound by the addition of the calculated quantity of
bromine in carbon tetra-chloride solution to n-cresol

in the same solvent at-5' to 40’. They obtained a

compound.melting at 62'. The melting point of the
bensoyl derivative is given as 83-83.6'. However,
they gave no proof of the structure of the compound
whatsoever.~

Bursa and Balada (Gas. Ceskoslarenskeko
Letarnistrs 6, 107-190, 1926) state that by bromination
of m-crescl at ordinary conditions, without the aid of
solvents or catalysts, 2-4-8 tribrom m-cresol is
formed. Thus proving that the rule valid for amino
derivatives of benzene is applicable in this case.
The abstract from which this material was taken gives no
proof for this assumption.

Hodgson and Moore (J. Chem. Soc. (1926), 2036-40)
’3:brom m-crosol from the corresponding amino compound by
dissotisation. They give as the melting point of the
cresol thus obtained 58°. The melting point of the
corresponding amino derivative is given as 46’. nothing
in the literature which I have been able to find, in
any way corresponds to these figures. They give no proof
of their structures of either the cresol or the amino
compounds.
V Bures (Chem. Listy. (1927) 21, 221-227) makes
the following rule for substitution of halogens in

m-crescl. 'Chloro or brcmo substitution products of

secresol follow the same rule as for halogen substitution

in amino or hydroxy derivatives of benzene. In
m-cresol ha10gen derivatives in the 4 and 6 positions
to the hydroxy group are most likely.“

I believe this to be a fairly thorough review
of the literature on the subject, of bromination of
m-oresol. It is very plainly seen that there is little
if any conclusive evidence as to the exact structure of
the bran m-crescls described. It will also be noted

that inmany cases the material is very conflicting.

EXPERIMENTAL

Throughout this work we will speak of the
derivatives of m-cresol as occupying one of the positions

as indicated below.

/
. 0H
6 2
5 CH3 3
4.

For the toluidines we will use a similar

method of nubering starting with the amino group.
I
NH2

4 2.
4..
This will, I hope, make it much easier for
those reading this work to understand. Since some

writers prefer to start numbering with the methyl group
rather than the hydroxyl.

MONO BROM. - META CRESOLS

One mole of m-cresol (108 gm.) was dissolved
in.chloroferm and placed in a tall-foul liter beaker,
which was fitted with a.mechanical stirrer. The beaker
was placed in a freezing mixture of salt and ice and
cooled to 0' to -lO'. This temperature was maintained
throughout the addition of bromine.

One mole of bromine (160 gm.) in chlorofcns
solution was then slowly added.from a dropping funnel.
The mixture being stirred very rapidly during the
addition to prevent local heating. 1 copious evolution
of hydro bromic acid followed. When all the bromine
was added, the mixture was stirred for half an hour
to insure complete reaction. The mixture was then
allowed to stand over night to eliminate most of the
hydrcbrcmic acid.

The brominated m-cresol was then transferred
to a distilling flash and the chloroform.removed. The
remaining oil was then.distilled in vacum (16 mm),
the following fractions collected:

below 100' ----------- liquid
100-120' ------------- liquid
120-138° ----- - ------- liquid

130-140. ------------- solid

The fourth fraction was recrystalised several
times from petrolem ether to a constant melting point
of 66-67“. The second and third fractions were com-
bined and distilled at ordinary pressure. In this
fraction was found a small quantity of unchanged
m-cresol and 26 gm. of material which had a constant
boiling point of 206-208“ at 731-. of pressure. '
This fraction, I believe, is the __6-brom m-cresol. The
proof of this coupound will be taken up later.

The 4-brcm m-crescl crystalised in long white
silky needles, which matted together when brought down
out of concentrated solutions. Petrolen ether was
found to be the best solvent for the 4-brcm m-cresol,
however it is soluble to some extent in water and may
be crystalised from hot water. ‘

Analysis by the Parr bomb method showed this

compound to be a monobrcm cresol.

wt. of cc .1! Calculated

couple Ag 103 for Br. round
. 2314 12. 61 .4278 . 4269
. 2166 ll. 71 . 4278 . 4266

As has been noted in the historical part of
this paper, flather and Zipper (J. pr. chem. (1916) 91,

364-414) prepared a brom m-cresol in much the same

manner. They assigned the formula 6-brom m-cresol.
The formula is possible by numbering from the methyl
group. However, they give as the melting point of the
o-onpoonc 52-. The compound which I obtained in almost
the same manner melts about 6° lower or 66-57.. The
melting point of the in benzoyl derivative 83-83.6°
however, checks rather closely to the one which I
obtained 82. 6-88'. There was no proof of the structure
of the compound given in the article.

To prove the structure of the 4-brom m-crescl,
I attupted its. preparation through the dissotisation
of 4-brom m-toluidine. This task was accmuplished in
the following manner.

Acet-m-toluidide was prepared according to
the procedure outlined by Gibbs and Robertson (J.
Chem. soc. 1914. a, 1886) from the preparation of 4-5
dibrom m-toluidine. Thirty grams of m-toluidine was
boiled four hours with slightly more than the
theoretical amount of acetic anhydride. ‘dater was
added to decompose the unchanged anhydride and .the
volume made up to 500 cc with glacial acetic acid.
Bromine (46 gm. 1 mole) in acetic acid solution was then
slowly added in. the cold. Upon addition of water the
coupound separated out as a white crystaline solid. The
crystals were filtered off and dried between pads of
filter paper. when recrystalised from alcohol the 4-brom

aest-m-toluidide'melted at 107-108'. ,

: For the general purposes of this experiment,
purification is not necessary. The dried 4-brom acct-m-
toluidide was boiled for two hours with the calculated
amount of 20% alcoholic potassium hydroxide to resort
the scyl group. Upon cooling the 4-brom m-toluidine seper-
ated out and was filtered off. The mother liquor was
concentrated and a second crop of crystals obtained.
After several reorystalisations from alcohol the 4-brcm
m-tcluidine melted at 79-80'.

After purification of the amine by crystalis-
ation, it was dissolved in much boiling dilute hydro-
chloric acid. Upon cooling the hydrochloride separates
as fine white needles. The calculated quantity of sodium
nitrite in water solution was than added in the cold.
The mixture was stirred constantly until all the hydro-
chloride dissolved. After about two hours standing the
diasonium chloride was decomposed by heating on the
water bath for half an hour. During this period of
heating, nitrogen was evolved and the solution took on
a reddish brown color with a layer of dark oil on the
top.

The mixture was then subjected to distillation
with steam. A yellow oil came over, which on standing
turned to a brown. The oil was salted out and extracted

with ether. The ether was removed on the water bath and

10

the resulting oil treated with dilute sodium hydroxide
to dissolve out the substituted.m-cresol. The alkaline
solution.was filtered and the filtrate acidified with
hydrochloric acid. (It is best to again salt out the
oil before extraction.with ether, as it was found that
the brom cresol was quite soluble in water).

The other was evaporated off. The remaining
oil solidified on standing. After repeated crystalisations
from petroleum other the 4-brom.m-cresol melted at
55-55-. It will be noted here that the 4-brom m-cresol
prepared in.this way has the same melting point as the
solid brom.m-cresol obtained by direct bromination.

Analysis of the 4-brom m-cresol prepared in

.this manner'showed it to be a.mono brom.m-cresol.

fit. of 0° .13 Cuculsted.

sample Ag H03 for Dr. Found
.2384 12.9 .4278 .4266
.2018 10.96 .4278 .4272

The yield was exceptionally good for this
type of reaction. Tan grams of the amine yielding two
and one half grams of the brom cresol or a 25%.yield.
Further proof that these were the same compounds
was afforded through the preparation of the benaoyl,

benzene sulfon, and the toluene sulfon esters of both

11

dompcunds. The esters were all prepared by the
Schotten-Bsumcnn.reaction.

The bensoyl esters crystafized from alcohol
in fine white fluffy needles. The melting point was
found to be 82.6-83°. Analysis gave the following

results:

Wt. of co .1! Calculated
'Sample . Ag N03 for Br. Found
.2016 6.98 .2749 .2732

The benaene sulfon esters crystalised from
alcohol in fine white needles very similar to the
benzoyl ester. The melting point of this.compound was
found to be 79-80“.

It. of‘ co. .1! Calculated
sample Ag l03 for Br. sound
. 2205 e. 84 . 2445 . 2419

The toluene sulfcn ester crystalized from
alcohol in small shinny plates which matted together.
The melting point was 84-86°.

12

its 0: ~ 0° sly Cfllculated
sample Ag 303 for Br. Found
.2113 6.23 .2346 .2326

The next task was to prepare and prove the
structure of the 6-brom.n~oresol. This proved to be a
very difficult one but I believe it has been accomplished.
Because there are so many steps to be taken in arriving
at the desired end, the yields are cut down to such an
extent that only very small quantities of the desired
products are Obtained.

p-i‘oluidine was “mm according to the
directions given by Johnson and Sandborn (Org. Syn.

Vol. 6. 8). '214 sis. of p-toluidise was boiled two hours
with 800 cc of glacial acetic acid. 0n cooling the acet-
p-toluidine separated as a crystaline mass. The

crystals were filtered off and dried between pads of
filter paper. when recrystalised from.alcohcl the
acylated toluidine melted at 146-1460. However, for our
general purpose this is not.neeessary..

The dried acet-p-teluidine was then nitrated
according to the method described by Kuhlberg (Am. l68,k/
134). 100 gas. of acet-p-toluidide was added in small
quantities (5 m) to 4.00 gm. of concentrated nitric acid
(sp. gr. l.d6). The temperature was maintained between
30 and 40 degrees during the addition. (The nitro group

13

will enter the ring in the ortho position to the amino
group since the para position is already filled by the
methyl group). The acid solution was then poured into
cold water. The e—nitre lacet-p-toluidige separated out
in fine yellow crystals. When crystalised from alsohol
the compound melted at 92-93'.

The acyl group was then removed by cooking with
alcoholic potassium hydroxide . It is very essential in
this hydolysis that only slightly more than the theoretical
amount of alkali-be used. After two hours heating, the
o-nitro p-toluidine separated as a brick-red substance.
This compound when recrystalised from alcohol melted at
114-1165

The amino group was then replaced with bromine.
This was «complished by the diascniua perbronide
reaction as described by Bulow and Schmactsnberg (Ber.
41, 2609). Sixteen and four tenths grams of nitro
toluidine was treated with 30 gms. of concentrated hydro-
ohloric acid and warned. The nitrc toluidine changed from
a brick-red color to a salmon color. The mixture was cool-
ed and 60 gaze. of ice added, and the vessel placed in
an ice bath. Ten grams of sodium nitrite in 30 cc of
water was then added with constant stirring. The
temperature being maintained at 0'.

Bromine (29.7 gm.) in a water solution of

14

17.8 gm. of potassium bromide was then.slowly added
fron.a dropping funnel. when all the bromine had'

been added the mixture was stirred for several minutes
to make certain all the bromine had reacted. The
orange-red percipitate. (diaronium perbromide), was
filtered by auction and washed with water. absolute
alcohol. and ether. Small amounts of the washing
agents being used. The diasonium perbromide was then
placed in a beaker and covered with absolute alcohol.
The alcohol was wanmed to effect decomposition of the
perbrcmide. tIt will be interesting to note that 96%
alcohol works equally as well in this decomposition).
Care must be exercised in heating that the decompisition
does not become too violent. During the decomposition,
nitrogen was evolved and the odor of east aldehyde be-
came very prominent.

When nitrogen ceased to be evolved, the
alcohol was removed by distillation and the resulting
oil distilled with steam. The p-broa.s~nitro toluene
distilled over as a very insoluble yellow oil, which
settled to the bottom. The oil was separated from the
water layer. On standing it solidified. (Chilling is
some times necessary to cause the compound to solidify).
When recrystalised from alcohol the p-brcm‘mpnitro
toluene melted at 31-32'. I found that the perbromide

15

method affords an excellent means of replacing an
eminc group with bromine. From a number of runs and ‘
average yield of 60% was obtained.

The p-brcm m-nitro toluene was then reduced
by tin and hydrochloric acid to 6-brom m-tcluidine.
The reduction.appears to take place very smoothly.
but yields were very low. Some trouble was also
encountered in causing the amine to crystallize. one
sample did crystallize and somelting point of it wasf
obtained. The.melting point 32-33’ checks very well‘ 1;
with that given by Neville and «lather (Ber. 13, 972) &/
31-32', considering the temperature at which the com:
pound melts. On other runs the 6-brcm m-toluidine *
remained as an oil and would only solidify upon
freezing. This liquid had a boiling point of 116-1180
at 16 -. wroblewsty (Ann. 168, 177) gives a melting
point of 68' for this compound but in.refuting Neville
and dinthers wort fails to give any probf of the
structure. .

The 6-brom m-toluidine was then dissolved in
such boiling dilute hydrochloric acid. Upon cooling
the hydrochloride separated as white orystaline solid.
The mixture was cooled to 0° and the calculated amount
of sodima nitrite in water solution was added with

constant stirring. After standing about two hours the

16

the diasonit- salt was decomposed by heating on the
waterbayh. During the period of heating nitrogen
was evolved and the solution tool: on s darhoclor.

f The mixture was then subjected to steam
distillation. a yellow-red oil distilled over. The
oil was salted out and extracted with ether. 'The
ether was removed on the water bath and the resulting
oil dissolved in dilute sodium hydroxide. , The alkaline
solution was filtered and the filtrate acidified with
hydrochloric acid. The oil was again salted out and
extracted with ether. The ether was removed on the
water bath and the resulting oil distilled at ordinary
conditions. It came over at 206-208. at 731 n.

Analysis by the Carina method for bromine

proved the compound to be a mono brom crescl.

dte 0: Sn- “cupid. Calculated.
sample N03 for Br. Found
(
. 2855 guess ' .4273 .4220/
- 2% 2 '7

The boiling points of the oil obtained by
direct bromination and the 6-bras m-cresol prepared in
this way gave every indication that they were the same
oylponndst
Boiling point of brom crescl from direct bromination

206-208'. Boiling point of brom crescl from amine

 

II Jill 1‘14}. I

\ Izi. ll J

17

bromination 206-208.. Both boiling points were taken on
the same day, thepressure being 731 mm.

Further proof of the two compounds was attempt-
ed by preparation of the benzoyl esters of both compounds.
Due to the quantity of the two compounds at hand very
small amounts of them were used in.preparing the esters.
leither one has solidified as yet, and the quantity of
oil is much too small to determine a boiling point.

The toluene sulfon esters were also prepared

in small quantities, and they too remain as a liquid.

18
DI BRO] META CRESOLS

Our attention next turned to the dibrom
m-cresols. It was discovered that when m-cresol was
treated with two moles of bromine in chloroform
solution, two definite dibrom m-oresols were formed.
Because one appeared to be a solid and the other a
liquid, it was decided that the solid dibrom m-cresol
had the structure 2-4 dibrom m-cresol. This left the
only probable structure of the liquid dibrcm crescl
to be 4-6 dibrcm m-eresol. .

These assumptions were made in view of the

following structures.

I H
OH OH
Br Br
CH3 CH3
Br Br
H.P. 64-66 Bore 132’135 16 me

Because formula I was more compact it was only
reasonable to believe that it was the solid ccapcund.
It will also be noted that formula II is very symetrioal.
and therefore should also be a solid compound.

19

The fonmation of dibrom.m-cresol by direct
bromination was accomplished in.much the same manner as
that described for the preparation of 4-brom m-cresol.
One mole of m-cresol was dissolved in chloroform and
cooled to 0'. Two moles of bromine in the same solvent
was slowly added with constant stirring. After evolution
of hydrobromic acid had ceased, the chloroform was re-
moved and the resulting oil fractionally distilled at

16 mm of pressure.

Fraction

below 100' ------------------------------------ liquid
lOO - 120' --------------------- ------- ------- liquid
120 - 130° ------------------------------------ liquid
130 - 140' --------------- ‘ --------------------- solid

The first three fractions were very small and
were disregarded. The fourth fraction was recrystallized
several times from.petroleum ether to a constant melting
point 64-66°. At the end of the crystallising the mother
liquor contained a quantity of oil which would not
solidify. The oil had a boiling point of 132-1362 at
16 mm of pressure.

.Anslysis of the solid compound showed it to

be a dibrom crescl:

t1.

20

wt. of cc .1] Calculated

sample Ag B03 for Br. Found
.2646 19.7 .6016 .6993
.2312 17.61 .6016 .6001

An attempt was then made to distinguish
between these two dibrcm m-cresols. Gibbs and Robertson
(J. Chem. Soc. 106, 1886) outlined a method for the
preparation of 4-6 dibrcm m-cresol. Since the two
assumptions already made, gave one of the dibrcm cresols
this structure it was decided to follow these direction
for the preparation of the compound.

Thirty grams of m-toluidine were boiled four
hours with slightly more than the theoretical of acetic
anhydride. water was added to decompose the unaltered
anhydride and the volume made up to 600 cc. with glacial
acetic acid. Two moles of bromine (90 gm.) in acetic
acid solution were then slowly added in the cold with
sonstant stirring. The temperature was maintained about
0‘ during the addition of the bromine. On addition of
water the product separated as a white crystaline solid.
Recrystallised from alcohol the 4-6 dibrcm acct-m-
toluididc melted at 167-168..

Upon cooking with alcoholic potassium hydroxide

the acyl group was removed and the 4-6 dibrcm m-toluidine

21

was obtained by distillation with steam. After several
crystallisations from alcohol the (4-6 dibrcm m-toluidine
melted at 74.6-76'. leville and flinther (Ber. 13. 972)
give 76-76“ for the melting point of this compound. The
procedure was varied slightly from that given by Gibbs
and Robertson, since they did not purify the amine before
proceeding with the diasotisation.

After purification of the amine by crystallis-
ation from alcohol. it was dissolved in much boiling
dilute hydrochloric acid. Upon cooling the hydrochloride
separates as fine white needles. The calculated quantity
of sodim nitrite in water solution was then slowly added
in the cold. After about half anchour of stirring
practically all the hydrochloride had dissolved. The
diasctised mixture was thenallowed to stand for two
hours before decomposition by heating was started- when
heated on the water bath nitrogen was evolved and the
solution became dark colored with a layer of dark oil
on the top. The mixture is then subjected to' distillation
with steam.

A yellow-red oil distills over which has a
very characteristic quinone odor. This oil was salted
out and extracted with ether. The ether was removed on
a water bath and the resulting mixture dissolved in
dilute alkali and filtered. (This separates the 4-6

22

dibrcm m-cresol from the 4 brom toluquinone). The filtered
alkaline solution was acidified with hydrochloric acid

and the oil again salted out. The 4-6 dibrcm m-cresol

was then extracted from the acid solution with ether.

Upon evaporation of the other the d-6 dibrcm.m-cresol
solidified and was pressed between pads of filter paper

to remove any oily impurities.

After several reerystalliaations from petroleum
other the 4-6 dibrcm.m-cresol.nelted at 65-66.. Gibbs
and Robertson, whose procedure was followed in preparing
this compound. gave 55' as the melting point. The first
melting point taken checked this figure very well, but
after several orystallisaticns from petroleum ether the
constant melting point was 65-66‘.

when the oil obtained from direct bromination
of m-cresol was seeded with a crystal of the 4-6 dibrcm

, m-oresol. it readily solidified. After chilling in

the ice chest, the crystals were pressed between pads of
filter paper to remove the oily impurities and recrystallised
from petroleum ether.- when pure, the crystals melted at
65-66“. This gave every dndication that the two previous
assumptions were correct.

That there are two dibrcm.m-cresols can
readily be seen in the manner in which they come down.when
crystallised from.petrcleunlether. The 2-4 dibras

85

m-cresol crystallizes in long, fine white or slightly
pink cyrstall, which mutt together. The 4-6 dibrcm
n-orescl, when crystalised from petroleus ether, comes
down in fine white crystals which cling to the sides of
the beaker. The 2-4 dibrcm m-cresol crystalline very
easily, while the 4-6 dibrcm m-crescl is very hard to
crystafiise. When the crystals of 4-6 dibrcm m-erescl
are scraped from the sides of the heater, the crystals
come down very rapidly and a pure product is hard to
obtain.

To further prove the identity of the two
compounds, the hensoyl ester of each was prepared. The
ester of the 2-4 dibrcm m-cresol. when pure melted at
30-819- The actor of the 4-6 dibrcm Is-cresol obtained
from direct bronination salted at 84-85“. as am the
ester of the 4-6 dibrcm m-oresol which was prepared
from the 4-6 dibrcm m-tcluidine.

. Further proof was also afforded by the direct
bromination of the 6-brcm m-crescl previously prepared.
In the 6-brom m-cresol, the bromine is in the ortho
position to the hydoxyl group. This leaves vacant the
para position, which should be the most reactive if
m-creecl is to be considered as‘reacting the same as
phenol. This being the case, when 6 brcfl. n-cresol
1'. treated with bromine we should have formed 4-6

24

dibrcm m-cresol. This was found to be true, as when
6 brom m-cresol was brominated, a dibrcm m-cresol was
formed which melted at 66-66“, the same as the 4-6
dibrcm m-oresol.

Following this same line of reasoning, it was
thought that when the 4-brom m-cresol was brominated,
both the 2-4 and the 4-6 dibrcm m-cresols should be
obtained. However, when the calculated quantity of
bromine was added to 4 brom m-crescl, observing the
usual precautions as to temperature, a-very unusual
result was obtained. A goodly quantity of the 4 brom
m-crssol was recovered, and a small amount of material
which melted at 83-84. was obtained. On further
investigation it was found that the material checked
very closely the melting point given in the literature
for 2-4-6 tribrom m-cresol. I will not attempt to
explain why such a reaction should take place, but may
be taken up in future investigations.

SUMMARY

It has been shown.that when m-cresol is
treated in the cold with one mole of bromine, two
definite mono brom m-creeels are formed. Namely,
4-brcm m-cresol and 6-brom m-crescl being formed. I
have attempted to prove the structure of both of these
compounds by preparing them by didactisation-of the
corresponding toluidine.

It has also been shown that when m-cresol is
treated in the cold with two moles of bromine two
definite dibrcm.m-oresols,are formed. The two dibrcm
cresols being 2-4 and 4-6 dibrcm m-crescl. I have
definitely established the formula of the 4-6 dibrcm
m-cresol by preparing it from the corresponding
toluidine. The structure of the 2-4 dibrcm m-cresol
'has also been established if the laws of substitution

\

of organic chemistry hold.

Some Bromo Deriva‘rives of m-Cresol

we. mecca, mcocw, m,
CH’COOH Br. ___ KOH
‘ ' Ale.
1 C": 0‘3 0‘:
Br Br
mp 101000 Imp. to 19°
Miguel mu 0H
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