Ir"— »V V \x

F

t \

 

{CNDENSATZ'ON OF TERT-BUTYL -
ALCOHOL WITH PHENOLE‘N THE
‘JFESENCE OF ANHYDROUS ZINC
CHLORELE UNDER THIRTY. DEGREES
TEMPERATURE

T333515 for the, Degree of M. S.
MECHEGAN STATE. COLLEGE
Albert H Agett

I938

k...

W!

 

' "a"
Eu"; 7 M
1.. I R M 12 y

n
1»/M(‘11:-7).W;S!a.2 g

University

 

 

 

 

 

 

 

 

 

 

CONDENBATION OF TERT‘BUTXL

ALCOHOL WITH PHENOL IN THE
PRESENCE OF ANHYDROUS ZINC
GHEORIDE UNDER THIRTY DEGREES

TEMPERATURE

THESIS
Submitted to the Faculty of
Michigan State College in
partial fulfilment of the
ffeguirements for the gegree

Master of Science

by
Albert H Agett
Organic chemistry

1938

 

 

 

 

 

Lat? ‘ >5}!

AQKHOWLEDGMERT
The writter takes this opportunity to express
his aineere appreciation for the assistance and guid-
ance given by Dr.R.c.Huatan.

331595

-1-

INTRODUCTION
In 1916 Huston and Freedman (l) condensed benzyl
alcohol and benzene by useing anhydrous aluminum chloride
as the condensing agent.

In 1920 (2) henzyl alcohol and phenol were condensed
by the same method.

In 1929 (3) benzyl alcohol and parapcresol were also
condensed by the use of anhydrous aluminum chloride as the
condensing agent.

In 1934 Huston and Fox (4) condensed tert—butyl and
tert-amyl alcohols with benzene.(same method)

In 1936 tert—butyl and tert-amyl alcohols were con-
densed with phenol.(5).

To investigate the use of zinc chloride as a conden-
sing agent below thirty degrees temperature the author has
attempted to condense tertiary butyl alcohol with phenol.

 

I.
II.
III.
IV.

fiBLa OF GDNTLfiTS

Introduction

Historical

Discussion

Experimental

A.

C.

:ertiery butyl alcohol with phenol
in the presence of zinc chloride
and aluminum chloride mixture 9

Bare tertiary butyl phenol with
zinc chloride and aluminum chloride

Tertiary butyl alcohol with para bromo
phenol in the presence of zinc
chloride and aluminum chloride

Tertiary butyl alcohol and para tertiary
chenol.in the presence of zinc and
aluminum chlorides.

Tertiary butyl alcohol and phenol in
presence of zinc chloride

Tertiary butyl alcohol and phenol in
presence of aluminum chloride

Para Tertiary butyl phenol on the
pres nce of aluminum chloride.

Tertiary butyl alcohol with para hromo
phenol in the presence of anhydrous
aluminum chloride.

Tertiary butyl alcohol with care tertiary
buLVl phenol with aluminum chloride

Pare tertiary butyl phenol with tertiary
butyl alcohol with zinz chloride.

 

ll.
12.
12.

12.
13.
14.
14.

15.

15.

‘I’ '

V1.
VII.

TABLE OF CONTEfiTS
cont.

3. lertiary butyl alcohol 71th phenol in
pr n:nce of ghosphcric acid.

‘2‘.

L. I roiary butyl alcohol Wluu yore brom
phenol with phosphoric acid.

‘f‘fia '.‘.ir~1°;; 131151 bro-.1101; and oil-ens]. in
presence of metallic sodium.

5. cromination of para tuft-butyl PhSnOl.

u. cromiuation of ortho t rt.bu1yi phenol.

Tables of Results

 

15-

16.

16.
17.
18.

20.
23.
25.

 

 

 

 

-2-

11 HISTORICAL

Previous workers have used anhydrous ginc
chloride as a condensing agent and as a catalyst in
many instancec.In all cases that were investigated on
eleVated temperature was required to bring about the
desired reaction.

Liebnann (6) condensed benzyl alcohol with phenol
in the presence of anhydrous zinc ohloride.The reaction
took place rapidly and with a fair yield.

Kippernberg (7) brought about the condensation of
an alcohol and an aminc.herc again an elevated temper-
ature was requireato bring about the reaction in the
presence of anhydrous zinc chloride.

Fisher and Roser (8) (9) condensed alcohols with
aromatic bases.rhis reaction took place only at elevated
temperatures and required a long period of time.

Liebermann(10) condensed butyl,benzyl and amyl al-
cohols with phenol.Finding also that the higher homolo-
guea of phenol failed to give the ferric chloride tests.
An elevated temperature was required to initiate the re-

action.

 

-3-

here and Weith (11) also produced diphenyf other
by the action of anhydrous zinc chloride at 110° on
phenol.

Auer (12) prepared ethyl phenol by heating absol-
ute alcohol (ethyl) and phenol in the presence of an-
hydrous zinc chloride.

In the crotonizetion of aldehydee and ketoned
Perkins (13) discOVered that in a liquid medium acet-
aldehyde was converted into crotonaldehyde Iith zinc
chloride at a temperatzre of 97°.

Prieb (14) condensed benzaldehyde with nitro—
methane in the presence of anhydrous zinc chloride
to give the nitro derriVativee of phenyl ethylene.

Frank and Kohn (15) found that hot parscalde-
hyde was converted into mono-molecular aldehydes at
1309.

Knownagin (16) acetylsted aldehydes in the presen-
ce of anhydrous zinc cholride at a very high temperar
ture.

Sabateir and Msilhe 917) used zinc chloride as
a dehydrating agent,especially in the dehydration of

alcohols to give ethers and unsaturated (usuallyo

 

 

 

 

 

-_4_

hydrocarbone.lt was also found that it was impossible
to use zinc chloride to dehydrate methyl alcohol to"
give di—nethyl other as gaseous products are produced
through a very complicated reaction and a certain our
out of hexanethylhenzene is also formed.

The author use mobile to find any references
in which anhydrous zinc chloride had been used suc-
ceesfiull: as a condensing agent at reduced temperatures.

 

 

 

--50
DISCUSSION

The candensation of tertiany butyl with whenel
was attempted by the sauna: (19).no alkylated phanel
'88 isolated by this method.nnny diffltenz methods
were uaod to bring about this reaction a} the~desired
temperature but they were all unnuacessrul.1t raI
fbund,houavar,tnai by the addition or a small quaaimy
of anhydrous aluminum ehlaride to tan reaction mixturo
that the zinl ahloride was activated'gnd the reactiah
took place.Tbe percent yield of the para isomer oom-
pares favorably with that at the aluminum chloride
condensationa with less gummy material being formed.
Upon purifying the para 18639? it was noticed that
there was a 10! and a high boiling fraation that could
net be any or the original reactants.nuring tbs course
of tho investigation these traction: were prcven to
be the crib» and the dialkylated phenols rhich apparb
eniiy exist in equilihrun with the para iaamer,but in
very small quanitieo.Atten§ts were made to produce the
ortho and the dialkylated isomer: by heating the para
iconar in the preoence of the aluminum chloride zinc

chloride mixture (same amounts as used in condensationa}

 

but only the ortho~tertiary butyl phenol was iso—

latcd.in very small quanities.The dialkylated pro-
duct was not obtained in this procedure although it
was found in small amounts when tert-butyl alcohol
and phenol were condensed in the presence of the
zinc chloride aluminum chloride mixture.When the
same method was used with aluminum chloride alone
(20) both the art? and the dialkylated phenols were
isolated in small quanities (see tables).When the
ortho isomer was treated with aluminum chloride only
the para tertiary bytyl phenol oculd be isolatod.The
same procedure was also followed uaeing anhydrous
zinc chloride as the equilibrum producing agent,but
no ortho or dialkylated phenols were. isolated.With
phosphoric acid as the equilibrmm producing agent
no oriho or dialkylated phenols were ioolated.flow—
ever when tertiary butyl alcohol and phenol were
condensed in the presence of phosphoric acid (21)
a small yield 08 ortho tertiary butyl phenol was
found but no dialkylated isomer was isolated .

The structure of the alkylated phenols
were provcn by comparison with thooe produced by

Perkins,Dietzler,and Lundquiot(20).1n addition

 

 

 

-7-

Souszoe (22) condensedortho bromo phenol with tert-
butyl alcohol useing the aluminum chloride methodtTho
author upon the brominetion of the t-tertiary butyl
phenol found that the product formed was identicli in
melting Point and Boiling Point to that of Swayzea’s
above.A mixed melting point was run with no depression.
A bromine determination was made (23) (see tables) on
both compounds and close agreement with the theoretical
were obtained.0ne atom of bromine being attached to the
ring.

A carbon and hydrogen determination (24) was run
on the ortho alkylated phenol and the calculated results
agree favorably with the theoretical (see tables).The
orhto terti ry butyl phenol was then bromine determination
made (23).It was also found to have only one atom of Br
attached to the ring.51nce the melting point and the
boiling point of this compound does not agree with that
of 2-bromo 4—terttary butyl phenol and since there are
no other likely poesibiltieo it can be safely stated
that it is 2-tertiary butyl phenol.Also when the ortho
tertiay butyl phenol was treated with aluminum chloride
it rearranged almost quantitively to the 4-tertiary
butyl phenol.

Carbon and hydrogen determinetions(24) were made on
the 2,4 ditertiery butyl phenol and tho calculated re—

sults were in agreement with the theoretical (see tables)

 

 

 

.itulw‘il‘ii {1.1111

 

-8-

who author also attempted to alkylate para-
broso phenol with tertiary butyl alchhol in the
presence of anhydrous aluminum chloride,anhydrous
zinc chloride and aluminum chloride mixture,and
in the presence of phosphoric acid.I n all three
cases no alkylated phenols were recovered.Apparently
~the ortho position under these conditions is not
receptive to alkylation.

Tertiary butyl bromide and phenol were condensed
in the presence of metallic Sodium (25).The only
alkalyated phenol that was isolated was the para
leaner and no ortho or dialkalyated were abstained.

In order to fiiilitate the separation of the ortho
isomer from the para isomer it was found that it was
very conveinient to use a 5% solution of KOH.The para
tertiary hutyl phenol being soluble and the ortho
tertiary butyl phenol insoluble in this solution (see
tables).

 

A.

 

EXPERIMEHTAL

Condensation of Tertiary Butyl Alcohol with Phenol.
in the Presence of Zinc Chloride and Aluminum

Chloride Under Thirty Degrees Temperature.

Eighteen and five-tenths grams (.25 mole) of
Tertiary butyl alcohol and 23.5 grams {8.25 mole) of
phenol were treated with 80 ml. of petroleum ether in
a five hundred ml. round bottomed three necked flask
equipted with mecury sealed mechanical stirrer,and a
condenser which carries both a therometer Which reaches
into the reaction mixture and a bent tub. for the
outlet of H01 gas.This apparatus was placed in the
hood.Thsn seventeen grams (.135 male) of Zinc chloride
was added to the mixture and stirred for one half an
hour.Then to this mixture was added three grams of
anhydrous aluminum chloride.No rise in temperature was
noted.£rter the addition of the aluminum chloride the
stirring was continued for four or five hours.During
this time only a very little amount of HCl gas was
given off.The contents became a slight pink in color and
upon standing overnight became quite dark. at which
time it was decomposed with ice water and HCl.The

hydrolyzed product was then extracted three times with

 

 

ether and dried over 03012.The ether was removed by
distillation and the residue fractionated.The first
fraction was collected from 90°-120° @ l4 mm.pressure
and was found to be mostly unchanged phenol and
ortho tertiary butyl phenol.The second fraction was
collected at 1200-1350 e 14 mm. pressure and was
found to be almost pure para tort-buyyl phenol.The
third fraction was collected at 135°-150° t loom.
pressure and was found to be mostly 2,4 ditertiany
butyl phenol.fhese three fractions were purified

by fractional distillation.The para tertiary butyl
phenol was recrystallized from petroleum ether and
was to be a 38% yield .M.P.97.5°;B.P.l2$:122° e 14
mm. pressure.The ortho tertiary butyl phenol was
found to be a slightly yellow colored liquid upon
purification.Yield 1.5%;B.P.115°-117° e 23 mm pres-
sure.Ehe 2,4 ditertiery butyl phenol was purified by
fractionation.lt crysatllized as a white solid with
M.P. 53° and B.P. 1430-1450 e 23 mm pressure.Less than

15 yield was obtained.

 

 

 

 

-11-

Reaction of Para Tertiary Butyl Phenol with Zinc

Chloride and Aluminum Chloride.

Seventy-five grams (.5 mole) of pure tert
hutyl phenol (para isomer) were placed in a 500ml.
modified Clathen flask fitted with a capillary,
thermometer,and a condensing flask.Thirty-four‘
grams of of anhydrous zinc chloride and six grass
of anhydrous aluminum chloride was added cautiously
to the warmed para tertiary butyl phenol.l small
amount of HCl was given off at this time and some
iso-butylene.ghe r;»ction was carried out under
reduced pressure,water pump,and the mixture was
heatsd for three hours at 35 mm pressure.At the end
of the three hour period the heat was gradually in-
creased and about twenty grams of phenol was distil-
led fraotionally from the mixture.s solution made up
of five m1. of distilled water and eleven grave of
scales carbonate was then added to the residue and
filtered immediately,wnile hot.Upon purification
by fractional distillation obtained 54.5 grams~{73%)
yield of para tertiary butyl phenol MgP. 97°.One and
five tenths grams {2%) of 2,4 ditertiary butyl phenol
was obtained M.P.54°.

D.

 

-12-

Condensation of Tertiary Butyl Alcohol with Para
Bromo Phenol in the Presence of Anhydrous Zinc
Chloride and Aluminua Chloride.

{he procedure the same as in A above and
upon purifiaction obtained 35.5 grams (82%) of para
bromo phenol and 5 grams {3%) of an unidentified

compound.B.P. 1250-127O ol4mmm pressure.

Condensztion of tertiary Butyl Alcohol and Para
Tertiary Butyl Ehenol in the Presence Of Zinc
Chloride and Aluminum Chloride.

The procedure the some as in A above.Upon‘
purification recovered thirty grams (EOiO of para
tertiary butyl phenol.No other alkalyated phenol was
isolated.

Condensation of Tertiary Butyl Alcohol and Phenol
in the Presence of Anhydrous Zino Chloride Under

Thirty Degrees Pemperature.

 

-13.

The procedure the same as in A abOVe with the
exception that 17 grams of anhydrous (fused) Zinc
Chloride was used as the condensing agent.No
alkolyated phenols were isolatgd.Ninety % (21 grams)

of para teritary butyl phenol was recovered.

Condensation of Tertiary Butyl Alcohol with Phenol
in the Presence of Anhydrous Aluminum Chloride.

The procedure the same as in A above. Upon
purification a 41% yield oi para tertiary butyl
phenol was obsained.9.'-..P.97.5°; B.P.12-J°-122° o
14 mm. pressure.The ortho tertiary butyl phenol
upon purification was 1.52 yield of a slight
yeloow liquid with a U.P.115°-117° L23 mm. prea-
sure.The 2,4 dibertiary butyl phenol was purified
by fractional dbstillation and crystallized as a
white solid with a 2.5.2. 53. 5° and B.9.143°—145°
@23 mm pressure.A 5 % yield of the pure product

was obtained.

v ‘ tit! ISI‘ . 0 A 4. . .nlrh .4 .‘ . I n In I 11“,..bv
,nclfll. ‘ ‘yl ‘ ,... y 5.0:» : I
.1. r . u! )I l ‘

y I ‘ ‘ I r' 1' . . l ‘ ‘ . ‘ I'll-D! ‘ Ii; ‘ A “1%. v v r ‘ l . ‘ I‘ ‘ ‘
l ’1 Alf p l 1‘ l ‘ ‘ Ill: III I l ‘ ... y 5‘3!!! ‘ III I , l ‘ ‘ II ,'.' ‘. 5- v I

.
[I . AM-I ‘

 

G.

H.

 

314-

Reaction of Para Tertiary Butyl Phenol in the

Presence of Anhydrous Aluminum Chloride.

The procedure the same as in B above.
Thirty-four grams of anhydrous aluminum Chloride
was added.d great deal of H01 Was evolved at this
time.The filtrate was fractionated and obtained
58% (43.5 grams) of para tertiary butyl phenol,
five grams (6.6%) of 2,# ditertiary butyl phenol,

two grams (2.6;) of ortho tertiary butyl phenol.

Reaction of Tertiary Butyl Alcohol with Para
Bromo Phenol in the Presence of Anhydrous

Aluminum Chloride.

Eighteen and fiveotenthe grams of(.25tnle)
tertiary butyl alcohol and 43.5 grams (.25 mole)
of para bromo phenol was treated with 80 m1. of
petroleum ether in a 500 m1. round bottomed three
necked flask.fhe procedure th same as in A above.
Upon hydrolysis.extraction,and purification obtain-
ed 39 grams of para bromo phenol and no alkalyated

product was identified.

 

-15-

Condensation of Tertiary Butyl Alcohol and Para
Tertiary Butyl Phenol with Anhydrous Aluminum

Chloride.

The procedure is identical to that in A
above.Upon hydrolysis,extraction and purification
twenty grams (80%) of para tertiary butyl ph n01
were recovered.Five grams (1.5%) Of 2,4 ditert—

iary butyl phenol were obtained m.1>.53. 5°.

Reaction of Pare Tertiary Butyl Phenol with Tort.
Butyl Alcohol in the presence of Anhydrous Zinc

Chloride.

The procedure the come as in A above .25 mole
of the reactants being used.No dialkalyated phenols
were iaolated.Twenty-two grams (92%) of para tertiary

butyl phenol recovered.

CondenSation of Tertiary Butyl Alcohol with Phenol
in the Presence of Phosphoric Acid. (26)

Eighteen and fiVentenths grams (.25 mole) of
tertiary butyl alcohol and 23.5 grams (.25 mole) of
phenol and 200 grams of phosphoric acid were placed

n a ?00 m1. roung bottomed flask fitted with a
ecur

 

 

 

-16..

mecury sealed mechanical stirrer and reflux con-
denser.The flask was then placed on the steam hath
and heated for eight hours at lOO° with constant
stirring.At the end of this period the phosphoric
acid was siphoned off and tie residue was fraction-
ally distilled.0btained 19 grams (83%0 of para
tertiary butyl phenol,H.P. 95°; .5 grams (2%) of
2,# ditertiary butyl phenol,m.P.53.5°.

Condensation of Tertiary Butyi Alcohol with Fara

bromo Phenol in the Bresence of Phosphoric Acid

The procedure the same as in K above.
Fourty-three grams of para bromo phenol (.25 mole)
was used.Upon purification 95% (41.5 grams) or
para bromo phenob was recOVered.mo alkalyated

phenol was obtained.

Reaction of Tertiary Butyl Bromide and Phenol in

the Presence of Metallic Sodium.

Tleven and fiveatenths grams of (.5 mole)
metallic sodium w as suspended in one hundred mls.

of toluene in 500ml. round bottomed three necked flask

 

 

 

fl.

 

-17-

fitted with a mecury sealed mechanical stirrer and
reflux condenser.Fourty-seven grams (.Smole) of
phenol were rdded carefully and the mixture
stirrered until the r?action was completed.Then
68.5 grams &.5 mole) of tertiary butyl bromide
added slowly by means of a separatcry funnel.The
reaction mixture was stirred for six hours and
allow d to stand ovornight.Jpon purification 42.5;
(20 grams) of para tertiary butyl phenol were
isolat~o,i.r. J7.5°.No other alkalyated phenoh

was obtained.

Brominetion of Sara Tertiary hutyl Phenol

?wenty-thre' grams (.25 mole) of para-
tfrticry butyl nbcnol was displvcd in sixty file
of c r:on uttrn chloride in a two hundred ml.
ro*nd bottomed three necked flask,t~ which was
fitted a mecury see #1 mechanical stirrer,reflux
condens:r fitted with a tharometir reaching
below fhv surface .0“ the liq1‘£,and a ecprrotory
funn:l.fiourty grams (.25 mole) of Bromine was
adicd by use of the separatory funnel.During the
addition-of the Bromine the mixturv was cooled with
an ice and salt mixture ~nd kept around 10°.The
mixture was tgen allowed to come to room t m; raturc

21th stirriun for four ho rs aft r the “remine W’s

 

0.

 

-18-

added.It was allowed to stand overnight and then
it was purified by fractional distillation und r
reduces p;rs:ure.0btained a white crystalline

solid, .3. 121-1230 L l6mm/prossure and £.P.

Bromination of Ortho Tertiary Uunyl Phenol

xhe procedure indcticol to that of fl above.
Upon purificati;n a waits colorluss solid H.P. 55-

- o a , w _, _
56 sum 2 J.:.145-i48° o 14mm. pressure was obtainou.

 

 

 

 

 

 

 

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m W
1
p-brumo 0¢tartabu$yl phenol insoluble
Ortho tert.buty1 phenol . insoluble .
fif’ ' , . ‘éa
bbrm" risen .butyl phenol - soluble ' '
‘ Pita tert,buty1 phenol 1 soluble
PIECE-1T CARBogef an mismsmz
7'3 0 73 C % 3 £1 E
+ comm ammo. 031.04 % cm, ,
P~tert.buty1 phenol 30.00 '1 79.85 9.233 10.250
O~tertobuty1 phenol | 80.00 78.55 9.33 10.305
L
2,4 d11ert,tertabutyl

 

 

 

 

 

 

PERGENT BROMINE

 

 

 

 

Cale. imam;

0015mm) * % B}; % Br
2 bromo 4 tert.butyl ‘ “E .
34.93

phenol am. 36.36

 

2 tert.bubyl 4 bromo
91181101 MoP'o 35.85 34.93

 

 

 

 

 

 

 

 

 

-23-

SUMMARY

1. Tartiery butyl alcohol will not condense in
the presence of zinc chloride at or below 30° as

with aluminum chloride.

2. Tertiary butyl alcohol and phenol will con-
dense in the presence of zinc chloride and alum-
inum chloride mixture to give para tertiary butyl
phonol,ortho t rtiary butyl phonol,and 2,4 ditertu

lary butyl phenol.

3. Ortho and 2,4 ditartlanybunyl phenol apparant~
1y axial in aquilibrum with para tortiary butyl
phenol when in the presence of zinc chloride and
aluminum chloride mixturc.It is possible to isolate

them from tfiig reaction mixture.

4. Ortho tertiary butyl phenol 1n the presence of
aluminum chloride rearranges almost quanitatively to

give para tertiary buflyl phenol.

5. Para bromo phenol will not condense with tertiary
butyl alcohol in the proacnce of aluminum chloride,
zinc chloride,21nc chloride and aluminum chloride

mixture,or 1n the presence of ghosphoric acid.

 

 

 

m

-24-

SUMMARY Cont.

6. Appare ntly the para position is ctr ngly
favored whcn both tho ortho and para positions are

Open for alkalyation.

7. 1h; ortho alkalyat.d ph;nolo are ins lubl: in
5; ion whilc the para alkalyated loomiro are oolubla

1n bhie solution.

 

 

VII

(1)
(2)
(3)
(4)

(5)

(6)
(7)
(8)
(9)

 

 

 

 

 

 

 

-25.
BIBLIOGRAPHY

Huston and Friednmanp J.A.O.S.‘3§,2527 (1916)
Huston and Science _§g_. 206 (1930)
Huston and Lewis- J.A.C.S. 51 2379 (1931)
Huston and For» Masters Thesis Michigan State
College (1934)
Huston and Iiseih- J.A.O.3. 2; 439 (1936‘)
Huston,Lowia and Grotemut-J.A.C.S. $2,1365 (1927)
Huston and Goodomoot-J.A.C.S. 56' 2434. (1931;)
Huston and Bindergggggggig.zgg§;§,Michigan
State College (1935)

Huston and Anderson— Masters Thesis Michigan
State College (1936)

Huston and Hedrickanoctgrs ghesis Michigan
State College (1937) -

Huston and Petty- master's Thesis nichigan
State College (1937)

Liebmann~ Ber. 15 152 (1888)

Kippernborg- car. 19 1140 (1897)

Fisher «and Racer- Ann 11.}. (1880‘)

Fisher ind Roser- Ber l3 674 (1879)

(10) Lieberman Ber. lg 1842 (1881)

(ll) Merz and weith. Bar. 187 (1881)

(12) Ausr Ber. ;Z_ 669 (1889)

(13) Perkins Ber. ;5_2804 (1882)

 

 

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Eri-bs Annalin (1884)

3.3125 3:25

frank and Kohn monatcsh Chem. 12_ 354 (1889)

Inoswn gone Annnlin 402 111 (1913)

Sabaticr and noelhe Bull. 500. Chem. 411 524 (1907)

(1835)
College (1935)

Dumas and Beligot ann.chcm.phys. (a) 58 19

8.5. Thesis Lichigan fitsts

Author-
P"rkins; Di tzi:r and Lundquost- C.§. g§ 6532 (1935)

U.:. 1,972,599

Tchitchibabinn- Comptcs Esnuuss 1:5 1239 91934}

hull.d& La boc. Uhom de franc" 59 oar. 23b1

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Collqgs
(1936)

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laid
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