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CONDENSATION 0F PHENOL AND
ALLYL ALCDHUL EN THE PRESENCE
0F ALUMINUM CHLORmE

THESE FOR THE DEGREE D? M. S.
Prosper Fredrick Neumann

1933

 

 

 

 

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I 1 .II I .| . VIIII, 'L Vi‘lytyiil-l I'll! {:1th [I til nii rs ,0" "Int.

CONDIBJSATIGJ OF PWOL m um AIDGIOL
IN ME. PRESENCE 0? am CHLORIDE

A Thesis

Submitted to the Famxlty of Elohim State
College of Agricultm and Applied Science
in partial fulfillment 0f the r-equiramnta
for the Water of Scimoe Degree.

by

Prosper Fredrick Hermann

m 1933

mummi-

M author Him" to “pro“ hi!
o.pprooiauon to Dr. B. c. Man
for hi. mum advise and kindly
3111ch in momnshing this

Wk.

331657“

TAB“ OF GOKTEE’I‘S

Page

Historical Data. 1 - 8
Statement of the Problem 9
Expertmntal Data

Preparation of 5.1131 Phony}. Ether 10

Prepmt ion of M1111 Phenol 10

who um Chloride Condensation 12

The Effect of ”range mturo 15

Mutual. of tho Condensation Mixture 16

Samar: 51

HIS’PMIGLL MA

is on historian homeland for this thooio tho author hoo not
included tho history of oondmsotion ”actions brought shout by sash
«hints os molt. £013. 32304. 220.. to)... £1015. oto. me his-

for: of such oondsnsotims has been usply oovorod by toms: sou-hon

in this lobed-stay. for mnplo, a. Won-en, I. Davis. I. Emmathor,
and I. Ballard. m Inter tools that since this mtorial is til-ooh
snilobls in good torn. it would to hotter to give 0. our": of tho
rssoaroh that has boon dam on suoh oampounds that hon 15 direct hoor-
ing on tho problem investigated. In this survey sill ho inolmd tho
9.1171. proposal and iso-propmarl derivativos of phenol Ind anisolo that
soro cousin-rod ss poooihlo oonotitnmts of tho suction shim. In
a: mos tho phenolic factions sore outset-ted into thoir sothyi «hots.
to tho litmturo supplios much Inoro dots on tho ollyl. W. and
imp-n71 dorintivos of mink than it does of phenol.

ALI-flu rm 33mm

11111 phowl other, 0535m2033mg. was first prepared by claim
and Bislo‘o (Ann. 401, 21319153 Ann. 418, 7811918). A minim-o of phenol.
Any). bromido. potassium carbonate and oootono woro boiled for own
hours on s water both under s roflux condenser.

mo yield was vory good. Purifiootion must ho omiod out under
diminish“ pressuro booms of o. mom shioh sill tab plooo on
tho application of too much host.

111:1 phony! other is describod as an 011 with o. rather pleasant

odor. It hoso sp. a. of .986 at 20°C; boiling st 191.7% {om-r),
88°C at 19 In. It cannot ho crystallised mu on oxtromo cooling.

Gail-LII. mos

o—illyl Phenol (Cl-Choviool. l-hydron 24:11:]. bonsono) was firot
encountered by Claim (m. 401. ”£191” on domains B-ollyl
salicylic ooid by news or host. '

It is host obtained by tho general method diomored by Cloioon
(Ann. 418, 7831918) for tho conversion of the oily]. others of phenols
into their oorroopmding o-ollyl phenols.

illvl phonyl other was boiled under an oir omdmsor until tho
touporatnro no longer rooo (about six hours). i’ho groom rioo in
tomorsmro tron obont 190% to 220% was on to o mb‘blo ro~
own-augment. sawdust onslogons to that taking plooo when um oni-
liues. in tho for: of oalts, oro hootod to high tomporoturoo. m
allyl group wondered to tho o-positicm in tho honsono ring.

o-ollyl m1 is m oily ouhotamo with o camel-lik- odor.
boning at 109-110°o m o mum. at 22 a... and solidifying in
o ironing nirtnro to o mo of crystals outing at 4°C. It roduooo
M4 in on oqmons solution and produces o bluo to greenish brown
oolor with 70615. no yioll of o-ollyl phenol is olmoot mtitotiwo
whom proporod os describod ohm.

rmn. mm.

M171 Phenol (Chanel. l-hydroxy i-ollvl honsono) was first
isolated by nylon: frost tho fresh lenses of tho hotel m troo as
found in Jays (3. 82. 2736; 23, 85911890). It has also been found
in oil of boy. According to all ovoilahlo information it has hover
boon synthesised. (musical is o colorless, highly odorouo liquid
having tho follow Proportieo oooording to Eylmam- 3., 1'. 257°C.
Du 1.033. Refractiwo Index 1.644).. It produces an intenso hlno
oolor with o solution of ferric chloride. is proof of structuro and
oowposition. tho following was given: nolooular weigzt and analysis
dotornimtims checked with the onlonhtod valnos for (398100. fho
uthyl stator was proporod hy mans of potaosim hydroxido ond methyl
iodido. It is reputed by Bylaw as having o n. r. of 226°C and pro-
duced an oxidation with patsssinn pennngamto in hot or cold solu-
tion, an: said we: . melting point of 177-1va°c. on titration. this
ooid mmd to hm on oqui'mlent weigfl squeal to that of misio ooil
(p-nethory honsoio ooid) sad answerod to the dosoription of this acid
both as to ohomiool and physical prepertios.

0-3301.

o-Anol (moan! Wool. 1-4qu Murmur! been»! was 1m-
“ by Pauly and mum (in. 585, 280.1911) from salicylic eldo-
hydo ond sthyl mum iodido in o diethyl other solution. A oas-
pound, possibly (093100)” of high boiling point was reported as for--
ins slang with tho proponyl phenol. Pauly and Buttlzu- described it to
o polo yellow, sisoid oil. giving o yellow red oolor with concentrated
I‘lfln'io sold and dissolving in sodium hydroxido.

1“

4.

o-onol orystolliseo in silky noodlos fro- lia-oin. hos o molt:-
in; point of 51.8% mi boiling point at 229.2390. an odor and
tosto sro oililn' to thoso of m1.

o-onol my slso bo oomoniontly reporod by heating on on oil
both o-ollyl phenol with throo tinoo its vellum of methyl slooholio

potossiun hydroxido for o period of two hours.

HEIDI.

Hnol (WWI phenol. 1413mm bpmpwl henna!”
onsmacnosn‘m. .

We (1. SDI. 8.88) prepared this compound by hosting ton
ports of anothol and amt perto of alcoholic potassium hydroxido for
o period of twenty-four hours ot o taper-stun of 2mm°o.

It crystallisos in leafs. melting st 95°C end boiling at 850°C.
9: standing in tho light it soqniros tho oolor of s brownish oil.

fl is olso ropa'tod propored by Doha! and Eiffoneon ml. (4.),
8. 803) from p-hydroxy benssdehydo and three solooulor woigxts of
othyl ngnosim bronido.

o-xsornom PHHNOL

o-Isoproponyl Phenol (3-hydroxy l-iooproponyl Benson 1
gamma) c6341. Doha]. and i‘ioffeneou (31. (4). 8, 516) report tho
proporotion of this oompomd from the methyl ester of oalioylio acid
and throo molecular wodg1to of methyl magnesia iodido.

It is olso reported proper-ed from 2. l'dion-lu-isopropyl bonsai
by distillation at atmospheric groom. (flooring and ham. 1). R. r.
208, see; a. 1909 I. 1522).

B.

It is reported so It oolorlooo liquid having on odor resublinc
thy-oi: boiling point of 204%. no no u... m 33% at is u. it
is oonowhst solublo in wster and polymerisos easily on standing.

leidorl. Smith end nth-eel (J. in. Chen. 80¢. 53. 539031931.
ibid no. 284.1933) "Dori tho preparation of o-isoww m1
by oondonsins ellyl sloohol and phenol in tho presume of sulphm'io
Mid.

mu. m or rum max. .

methyl Ether of Hllyl mono}. (wtrwl cheriool. ostregol. iso-

onethol. p-ollyl mioolo. p-nothozy um honsohoh mgxmcagcwom.

his momdhesbeenfouodtobo s constituent ofmnyosssa-
tiol oils sueh es tarragon. miss bark. boy. fennell. estrogen. end
torpentino.

mm (B. 22, 2743) reports tho preparation of this compound
from palm phenol by heating with methyl iodido in an 3100110110
solnt ion of methyl oleohol.

i'iffonesn (a. r. 159. 482) reports that it my be prepared by
treating mthory phenyl magnesia bromide in an other solution with
ollyl bromide.

Rim-an reports this eompmmd es mung o boiling point of 226%;
however, tho more recent workers report boiling points of 213.2190.
she-218%. and 112%.

By hoot ing, for twenty-fou- hours with three to four volumes of
o saturated oolut ion of slooholio poteoe 1m hydroxide. it was charged
into methol (p-proponyl onioolo). (Grimm. 31. 3, ll. 54; mm,
B. 23. 8595 Emma, o. r. 159. 482).

0.
upon sxidstion sith potusiun permanganate in s sold soetis said
solution than was reduced Hethoxy phony]. soetis sold end snisis

“1‘. (WM. 3. 82. 2744. Bertram and “lb“. ‘1‘. 235. 183,
It was not reduced by sodium and sloohol. Images, 3. 32, 1439)

max.

mothol (isoestragol, 1-mothoxy Hum) benzene, p-propsnyl
snisols): enscmoaosn‘ocn, is tbs principsl constituent of noise,
stsrmiss. end {smell oils and has been reputed present in then
oils by nu investigators. It as first carefully studied by Oahonrs
(m. chem. phys. (a). z. :74; u. 439).

It has been synthesised in several says. urine!!! ()1. (5). 11.
as}. mom (1. 25, em report thst by boiling 9-0-1111 anisols sun
slsoholis possum: hydruids it was converted into mothel. nsll
and A. Hoff-n (I. 878. 1680) report that snothol my 1!. repel-s1 by
the distillstion of ethyl (”than phenyl) carbine]. with sulphuric
ssid. Bshsl sad riffomsn {0. r. 132. 5653 31. (4) 8, 304) report its
mtim from snisio aldehyde and ethyl magnum iodide by heating
€10 Im on s Inter bath.

Ansthol is described so an oil rith s pleasant odor or miss,
cystsllisiu in pistes true sloohol. man sslt st 21.1%, and boiline
st 233% st "1.). m.

an bro-mum it rodmood first s dibromids mung st 57%
(Bell and mm 3. to putt. (men. II. or, (1895) 198) and also s
mo sn- soothe). dibronids melting st 107-108°O.

m fusion with potassiuls hydroxide, methol farmed PMPOHFI
phenol toaster vith eons p-tvdroxy bensoio said. (ndenburg and
warns. Ann. Ohm Supl. Bd., 8. 88. and 141. 260).

7.

lnothol upon oxidation with potassium permgmate, as well
as potassiu diehromate, yielded as its ouidation prommt p-nethoxy
bonsois acid (Anieio acid). (Hansel. A. 151, 28; Gerelli. G. 20,
693).

m additional intention was obtained on this mob studied
substance; believer. since it had no direct bearing on the investiga-
tion being conducted it is not inohnded here.

mu m 0? o-I-ISOPROPEIL PHEHOI.

Hothyl Ether or o-Ioororopenyl Phenol ( l-methory z~1sapropeny1
barons): manatonslcsnpms. Banal and fineness (31., 3, 315)
report the reparation of this oanpomd by the mthylation of 0-»
“0er phenol using dimthylsulphate in an alkaline potassium
hydroxide solution. It is also reputed by the sane investigators
as being prepared trons the netbyl ester of o-Isethyory bsnsoia acid
and film mlocular wimts or methyl mansion iOdido. {0. r. 159,
1403 Bl. 4, 3, 51!). me: report it as a colorless liquid boiling
at ”8499.0. Upon oxidation with potassim permanganate in the cold
there is rednoed smother; sootophsnms (a. n. 141. 596). The me
when report that upon rednotion with sodium and alcohol o-isoproyl
anisols is terms. (31.. s. 516; c. r. 141, 597).

mu. mm 01’ P‘ISOPROPM PEEEOB

mthyl Ether of r»! sopropmyl Phenol (heathen l-isopropenyl

neurone. p-isopropsnyl anisole): Cuzc0(035)cen40083.
Behal and Eiffenean report (a. r. 132, 5613 139, 1403 ll. 4,

5. 817) obtaining this empomd as a dimer by heating on a water bath
the ethyl ester of anisio aoid and two molecular weights oi’ methyl
melts: indide. rho nononer was obtained by the distillation of the
diner st atmospherio pressure. he monomer formed crystals with en
odor resembling anothol and ostregol. melting at 52%. and boiling at
mean. images. 3. 57. 3995. sue... a. r. 132. 561). n m in.
soluble in water and soluble in ethyl alcohol.

an oxidation with potassium permanato in the sold it procbuoed
d-nethoxy eoetophenone (3.. 1.. c. r. 141. 59?. Bl. d, 3. 5181.

11pm rednotion with sodins and ethyl alcohol. p-isopropyl anisole
resulted. me diner mentioned above is reported by Behel and i'iffenoan
(a. r. 138. “13 ll. 4. 3. 320) to form odorless crystals. melting at
We end boiling at aim-215%, is no. It was depolymrised by ammo
ing ordinary pressure. It did not add bromine or decolorise potassins
W“ in the sold.

STATEMENT m M manner

To determine if phenol and ellyl alcohol
can be omdonsed by some ot lamina
dhlorids. 1'0 examine the oondmsation
nut-ureter men-«mmotparaellyl
phaol.

mama; DATA

10 e
PART 1

Preparation of A131 m1 Euler: cansomzmwnz

is preliminary work. allyl phonyl ether and e-allyl phenol
were prepared. It was felt those mounds night be obtained from
the eondensation mixture of phenol and allyl alcohol.

Allyl phenyl ether was prepared using the method described by
Ciel-an. (Ann. 401. 81: 1913).

hlar quantities of menol. ally! bromide, and potassium oar-
bonate together with 150 grams of acetone were heated for eight
hours on the water bath mder a reflux eondmser. Potassius bromide
settled out and the reaction Iixture became a thick paste. On cool-
ins the mixture was treated with water and extracted with patrolm-
ethsr. After washing the ethereal extract with sodius hydroxide
and water. it was dried over potaseim carbonate and distilled in
none. field was 120 you” boiling at 77°C) motor a pressure of lo
m. 89% of theoretical.

Preparation of Mllyl Phenol
this eonponnd was prepared using the method described by Olaisen
and Eisleb (Ann. 401. 21: 1913. 418,-. 78: 1918).
7! grams of allyl phexwl ether were boiled under an air condenser
until there was no further rise in the boiling point. rhis required

about .1: hours, the boiling point rising mm 191% to 220%. m-
rise in the boiling point was due to the rearrange-ant or the allyl

them ether (3. r. 191%) into o-allyl phenol (a. r. 221%).

11.

the rearranged product. after cooling, was dissolved in
20% aqueous eodius hydroxide and extracted with petroleum: ether
to remove any unchanged allyl phexvl emer and all amounts of
alpha nethyl somarane which say have formed. me o-allyi phenol
was liberated from: the alkaline solution by acidification with
sulphuric acid, taken up with diethyl ether, and dried over sodim
sulphate. After emcentratins the ethereal extract it was “sill-
led in none and produced an oil boiling at 92-93% at 10 la.
Yield 68 grams. iii of theoretical. It pooressed all of the proper-
ties deeoribed by Claisen.

12.
PAR! I!
m. dlmimss Chloride Condensation. (Huston's ltethod)

flterials and Quantities Used.
188 g. phenol (2 holes)
39 g. ally! alcohol (z/s mole)
.4 g. almim'ss chloride (1/: sol.)
.. 250 cc petrolens ether
ea. freshly distilled phenol .a. dissolved in in. patrols):
ether contained in a three necked flask equipped with a mechanical
stirrer, a reflux sand-user. and a sat stopper equipped with a
thermometer. Ill'hne latter served as a means of following the tenor-
atnre of the reaction mixture, and by renewing it. the materials
could be conveniently sodas. ‘ '
After thoronghly mixing. the allyl alcohol was added. followed
by the slain. chloride which was added in small ascents over a
period a: one hour. During the addition of the alumina chloride.
hydrochlcioaoidgaewasliberatedinageneronsenountandthere-
action sitters became a dark red in color. During the oondmsation

the tanperatnre never varied no. so to 35%. use: the rm: additiu
of the admin:- ehloride the mixture was stirred for about one hour

and M let stand over night.

n1. alanin- cbloride somlex molecule was then decomposed by
nsing a mixture of 150 g. of ice and co cc. of oonomtrated hydro-
chloric acid. i'hs resulting mixture was extracted with sulphuric star.

u
‘-

13.

After drying the ether extract with anhydrous sodim sulphate.
it was ooncontratod and on distillation produced the followings

 

3. P: Bongo mum's Eggnog“ composition
Up to 8| 745 an. ether
85 o 110 743 an. alLvl alcohol
70 t 80 19.20 m. WI
80 <- 150 ‘ 19-20 In. condensed product
160 .. 240 20 m. condonsed product

240 a (residue)

tron the fraction 90-80. wpon redistulation, there was obtained
109 g. of pure phenol; 73 g. having taken pert in the reaetion.

Analysis of Fraction 80-160 at 19-20 an.

This fraction included the boiling points of allyl phenyl ether.
o-allyl phenol. and p-allyl phenol. It was diseolwod in an excess of
claism'e alooholio potassium hydroxide thioh radar-ed the xhehslie
mounds soluble. |i'he nixtnre was then extracted with patrol"
ether. During his extraction great ears was taken to hop the min-
tIre cool as it is a oomn thing for allyl derivativee to change
into prowl derivatives when heated in the prosaic" or alkali.

the petrolems ether extract produoed. on oonoentration and dis-
tillation. o 3. od‘ an elhli ineolnhle material boiling at 80-65“ at
ll II. his was assmod to he allyl phenyl other. It will he on-
sidered later in this paper.

he alkaline Claieon solution. on aoidii'ioation with hydrochlorie
aoid and extraction with sulphur-is other. prodnoed 8 g. of an oily

14.

liquid distilling at loo-115° at 16 a. on. h1g1.» boiling point

tractionwas too nil tebeei'awealsequanoe.
bastion lso-uo°, which was by m: the largest or the freo-

tions. Wood 30 g. or a straw-oolored. wisoid, Ionic-solid material

that distilled for the most part at zoo-.216" at a 1-.
the final fractionation wodnoed the following:

Be Pe'Rgggg

70- 80
80'- 38
100.115
115-808
808-810
210-216
818'-

i total eight oondmeatione were oorriod out with similar pro-
oedure end results.

Pressure

19.20 lfle

l8 In.
16 In.
16 In.

6 In.

Gmoitm
Phenol

m. insol. portion
Condensed produot
or no consequence
Condensed produot
Condensed product
Torry residue

mad as described on the following pagee.

Woialt
109 as
8 Be

26 g.
3 a.
15 so

we various frootione were combined and ana-

lb.
WWW

n2. oondensationwee repeatodtonote the «feet cite-per.
atnre on the mounte of the various fractions. rhe omdensation
weeearriedout inaireeeineniztureefwator. ioe, and salt.
l tau-ram. between 0 and s°o was uintained elm-lag the tine or
addition of the aluinu dlleride. me reaction prooeded as usual.
yielding the final fractions as follows:

I. r. R& Pressure domed #comaeition Foifiat

80-10009 15-16 m. Phenol 118 g.
loo-115% 4.- 5 m. Condmoed Prod. 4 g.
zoo-210°;- 4- a m. Condensed Prod. 115.5 g.
zlo-sle°o 4- s m. Condensed ?rod. 2.: g.

216- 4- 6 m. Tar 10.0 a.

fine foregoing date cine evidenoe that the rednoed temperature
doom-wee the anomt of the high boiling point fraction as well as
the mt or tar. rt increases the mount of traotion loo-115%.
tron the amt of phenol recovered it follows mat the reduced
temperature decreases the total mount of emotion.

16.
”ISIS 0' m ”HERBAL PRACTIW

Fro- ile several omdnleatione there was obtained, by extrac— _
tin with China's alcoholic potaeeiun hydroxide. a total of 20.0 a.
or an oily poem with e boiling point or 30.83% at 12 and 58%
at 7-8 new insoluble in dilute anon-ll: soluble in sulphuric and
petroleum etheree It was armed that the fraction moor consider-
ation nee allyl phenyl omel- sinoe it answered fairly well to file
description of that eonpomd. Boiling pointe or allyl whom]. other
given in the literature are: 85% at 19 am; 191.7% at no u.

{The boiling point or the prodnot in question who not determined at
atmospheric pressure because of its rearralgment into M1131 Dime!
et mat temporatm‘e).

In attemting to confirm the aesunption the following moedure
was carried out:

h m of the supposed other were boiled under an air eon-
denser for a period od’ six hours in an attempt to bring about its
W into o-allyl nhmol. (Oleisen. m. 413. 10. 1919).
the initial toiling Point was 191.0. Ming the remaining refluxing
period it failed to rise further. {During the rearrulguent of allyl
M ether into e-allyl phenol there is always a nrhod rise in the
boiling point. free 191%. the boiling point or the ether, to 22000.
the boiling point or e-ale'l phenol. (Claim. Ann. 418. 78; this
presut thesis. page l.

he reaction mixture. after treatment with alooholio potaseim
hydroxide. was extracted with patrolman other to remove treoes of mu
ehanged ether. fro- the petroleum other there was obtained 9.! a.

17.

or the mohansed ether. 3. r. 196-198°0. i'he alkaline solution on
acidification and extraction with eulphuric other failed to yield
nothing of any conecquenoe. yet the rearrangement of the allyl
other of phenol into the e- suhetitution product is practically
quantitative according to the literature and to the work done by
the author. rhie gate evidaloe of an incorrect aeaulnption.

. the roarrengencnt was attempted again. using 20 a. of the ether
and refluxing the mixture for a period of tour-four hours. me
boiling point failed to rice appreciably and practically all or the
alkali in soluble material was recovered. it boiled sharply at 196—-

197°!) and did not poseees the odor of allyl phony]. ether as prepared
by claim's method (in. 401, 8131913).

Allyl phenyl ether is not an isolatahle product in the couldn-
sation Iixture of allyl alcohol and phenol by home of aluinm ehlor-
idle

This imestiator expects to examine further this ethereal free-
tidal. aesminc it to be alpha methyl comrane which is knoll to he
die of the tyoproducts prodllnd in the rearrangomnt of allyl phenyl
ether. Possibly the presuce of alminm chloride idlumoed the
changing Of the All}! like! into alpha methyl comm.

It is reported in the literature that o-allyl phenol changes
readily into alpha methyl mane by boiling in the presence of dry
midi” Maine (Of. 001'. pate 279,864).

13.
ANALYSIS or FRACTION loo—115° at 16 no.

iron the several condensation- there was obtained a total of
28 grams of this fraction. Distillation at atmosmerie pressure
predwed ll grail! of an almost eolorless oil dietilling at 236-
231'. I. P. 0f ”1311 Film! 237°. (Wham Bar. 4. cheat. nor.
as. 2736).

m1. phemlio substance possessed the following properties
which cheek with those given by p-alIJl phenol by Eyhaan as above;
soluble in dilute alhli. blue color with aqueous ferric ohlorlde.
sienna-libs odor.

Preparation of the Ethyl Ether
Fifteen grams of the supposed p-allyl phenol were dissolved in
a sligxt noses of 20% poteooim hydroxide, and with agitation. l! 3.
of dinethyl sulphate were added over a period of one have. A temper-
ature below fifty degrees was minteined. The reaotion mixture was
heated on a water bath for thirty nimtes to remove the excess dsmthyl
sulphate. After being mde allmline, with Iodine hydroxide. the mix-
ture was extracted with petroleum ether.
Distillation of the ether extract produced the two fractions:
200-224 5 6.
824-230 9 8.
Praotion 224-230 was emsldored as the methyl ether of p—allyl
phenol (I. r. given by urban, 226°C).

19.

Six grams or the Iothyl ether. 1. r. 224-230". were oxidised
by using neutral potassim permganste and warning on a water bat
for one hour. me oxidation was not very rigorous although there
was a rapid disooloration of the poi-magneto. The oxidation pro.
duet. after being recrystallised five titles from hot water. was a
wise. needlelihe wound with a melting point or ism - 192°.
that giver. for anisio sold is 184°.

'Bhese results check with the data given by Kyla-n (her. 1. M
Gee. 22, 2756) for the proof or structure for p-allyl phenol.

Bertram and Ialbem (Arch. d. Phan. 835,, 17731897) repm't that
by careful oxidation of methyl ohavieol in his sold. using potassi.
permanganate para nethoxy phenyl, aeetie aeid resulted (I. P. 85-86 0)

Using the nothod of Bertra- end lal‘hm, file reminder or the
methyl ether (3 grms) was shalom with two arms of potassium permano
geriate in 200 N. of water. and 8 oe. of aoetie acid. During the exi-
eation a tenperatore below rive deg-see was maintained. the reaetion
mixture after being nade alkaline with sodiue carbonate was filtered.
'rhe filtrate after beings-do acid with sulphuric aoid was extracted
with ether several tines. me other extraot failed to produce anything
of eon-aqua. the oxidation was not repeated as the supply of fie
material was emanated. Berti-en and Ialbans report using 20 grass at
the material in an oxidation.

m thebasis or internationtmishedbymMandthe above-dis-
eassed data, the eonelosion is reached, that p—ally‘l phenol is produced
in a ~11 amt byeondemins allyl eleehel and phanl in the resende
of aimin- ohloride. here is every evidmee of para substitutim.

3.0a

miners a rmonox zoo-210° at a an.

his was by for the largest or file fractions obtained. Iron
the several oonduisotions appoxi-ately 173 grains of this material

was obtained.

It possessed the following properties:

M

(b)

M
m

M
(f)

Soluble in dilute alkali. repreeipitated by
hydroohlorie acid.

Straw-solored. very viscous liquid. acquiring
a brownish eeler on standing.

bluish-brown solar with aqueous ferric ahloride.

Absorbed bromine in ohlorotorn solution without
the liberation Cf hydrobrcmio acid.

care a negative test for halogens.

Failed to crystallize from other. aloohol. benseno.
toluene. xylene. rte. it did. however. fora a
whitish amorphous powder by the evaporation of a
bensene solution over a period of sewerel days.

i seareh or we literature revealed no allyl. propenyl. or ism-

prwl derivative ed phenol that answered to this description.
especially with regeot to the boiling point.
Combustion Analysis.

 

m «am 2.2 L1! 1.2
0235 d. 79.5 7.25 13.68 toolo)
.231 e. 78.76 6.98 14.23 -
image 79.03 7.11 13.95

one. for 093100 80.3 7.45 11.9

Althougi the agreement or marinated and ooloulated data is

not a shoe one. it is at least an indioation that the substance in

21.

question. since it is not one of the allyl. propenyl. or iso-
propenyl doriwatiwes of phenol reported in the literature. is
a polymer of one or lore of the aforementioned compounds.
Seweral investigators hare reputed that in the synthesis
of at least new of the abovennantioned compounds there was a
learned tendency tonrd polymerisation, and in sane cases the pre-
duot was aotmlly obtained as a polamr. mm, howewer. in his
original article does not mention any polymerising tendency of p-
allyl phenol. '
(see Pauly am muse. in. see. 280.1911
lohal end rirrenean. Bull. see. Chen. 4. 3. 513.1900
leidorl aiith flooreal. J. Ohm. Soc. 63. 5390119511
in the liait of the reports by previous investigators. it was
seemed that the metance in question was a polymerised product.
molecular weight deteminetions by the boiling point nethod
gewe the following results:

solvent, bensene.

arena arms Observed lolsouler

351nm Moe Wu Weim found
12.64 .518 .272 403
18.64 1.2796 .68 598

calculated for cgamo. 134.
me noleoular weight found is approximtely three times that of the
monomer. flierefore the conclusion is that the substance in question
is a triner.

(The author is indebted to i. H. leeleyfor this molecular
weight determination).

23.

on standing. in a ”lotion of houses. which we. allotted to
evaporate spontaneously over a period or several weeks, the pol:-
eerieed product formed a Ihite amorphous ponder that melted to a
eat-viscous liquid owe! a tunerature range of 1.48-3.55". m cool-
ing true a hot mixture of xylene and water it formed shite, fluffy.
Mat needlelih crystals et the Jmction or the two imiscible
liquids. m. seal-crystalline substance melted over a temperature
mac or was“.

DEOIJIIERIZA‘HOH

In all eesee more compounds of the me being considered were
ebteined as ”More. the manners were secured by distillation at
atmospheric pressure.

the hundred and fifty gems of the pewter were distilled at
atmospherie pessnre. During the distillatim considerable deco-
peeition took place. no distillate weighing about no arms was
s mile. straw-colored liquid. distilling our the wide range of
loo-240‘. n was found to 1». mm. in alkali. gm on msatura-
tie. test with bromine. and prodwed a man: blue color with aqueooe
ferric chloride.

After several refrutionations were accupliehed using a fifteen-
inch fractionating calm the following fractions were obtained:

an to 195 B 8.
195.200 10 g.
zoo-no 60 8-
810-820 13 s.
220-240 18 e.

no- reeidue (tar) 7 g.

23.

liederl reports (J. “or. Chen. soc. 53, 3390; 193].) the pre-
paration of e-isc-prropenyl phmol by condensing phenol and allyl
alcohol in his presence of sulphuric acid. It was obtained as a
polynom- iexich was “polymerized by distillation at atmospheric pre-
ssure. It was felt at the tine that the large fraction zoo-e10 light
possibly be o-isopropenyl phenol on account of its boiling point. 205-
206 (Behal and l'iffenean Bull. 800. Ghana. 5.3153190”. lo other allyl.
propeuyl. or sic-propenyl derivative of phenol has a reported boiling
point within ten degrees. to reaction nodzanim, while: to the one
given by Hiederl for the formtion or c-iso-moouyl phenol. could be
worked out on the basis oi‘ aluminu- chloride as the condensing agent.

me fraction 200-210 was care-folly fractionated and the traction
208-206 collected. Yield. 48 grams.

me methyl ether was prepared by using dinothyl sulphate as des-
crfictl on page W. of this thesis.

rracticnation of the methylated wodnct produed the 2.11m.

B. P. BE Pressure m
175 e 19! 748 n. 4 c.
19! .. 800 748 II. 35 s.
200 e 210 746 III. 6 Bo

rhe boiling point given for iso-propcnyl anisole is 198-199. the
large fraction 195-200 was an indication of the presumes of ieo-propmyl
anisole.

Dehal and riftonean (a. r. ldl. 596) report that on oxidation with
potassius permanganate in thevcold, rise-prowl anisole produces 2-

nethuy acetophenone I. r. 33.

24.

Ten grams of the methyl ether were nixed with 7 gems of
potassiu permanganate dissolved in 250 cc. of water. (m standing
ever niaxt there was considerable “animation of the persona-
nate. After filtering. the filtrate on being acidified liberated
a white flaky precipitate. After being recrystallised from hot water
six times there was obtained a white, nonoclinic crystalline comm
(I. r. 183.6 l. e-isoapropeoyl snisole should yield on uidatim:

3 mother: acetophmone
0c #30

OCfiG cicAQ
C\ ‘e Pew
0/11 at

0 eQI‘T/3
edafi/

c-methcxy .
bmoie acid I. r. 90.!
me crystalline product was soluble in dilute sodium hydroxide and
rsprecipitated by hydrochloric acid. Its melting point correspmded
to that or on.“ acid. (p-nethoxy bensoic «no u. r. 184').
me oxidation was repeated with similar results. once as Just
described and again by heating he reaction mixture in n uter bath
{or two hours. he variation in twperetnre had no effect on the final
result.
Equivalmt Weigat Nomination:
more was eridmee me the onidntim product was snioic acid.

25.

fritation Data.

.1178 g. were dissolved in 50 es. of enter and 30 cc. of ethyl
alcehel in a weluotrie flack. Ehree 2! cc. wticns were titrated
using .m l. sodim hydrexide and msnolthelein as an indicator.

m J. 1.1. .131
a. 5803 ‘0” 1.98 8.00
Equivalent 'Cigl“ “as, We, ”zen
‘ Calculated for Anisie acid (083803) 168

Pound (Average) ”1.7

The promot obtained by oxidising he traction in question Inst
be anisio acid bounce of (at its melting point. [by its likeness to
misic acid. is) equivelmt weight determination.

wise-propewl phenol is not a constituent of the condensatim
.mm or phnel me am alcohol. nu.’ is positive mar or para
substitution in this alumina chloride eondusatia, a test which on»
tude the scope of Boston's mthod in synthesisioe emetic omen“.

mums a? mentors ale-220° and 220-240“

I. 3. when (her. d. Ghee. ace. 22, 273631889) reports hat the
mm ether or p-alh‘l phenol u. . boiling point of 225%. mu.
however. does not ages with data furnished by recent workers.

Grime: reports (Bull. see. Chen (Paris) 3. ll. 58) the preparation
of Estragol by repeated fractionation 1 Oil of istragcn. He gives a
boiling point or ale-316% (coo-rd. meal was proved to be the sale
as methyl chawiccl. ll 1892. some ten years before the work of Grist:

.6.

on estrsaol. schinel and 0e. (herioht d. and. cos. leer. l?)
feud that the chic! constitut of oil of estrogen was we”!
ohavioen cu met..- their dismiste,‘ hours; and saloon. (drab.
d. mare. 255. 1773189?) estimated the amount or this substance
in oil of estrogen to be 67.0%. m onidation this substance pre-
dmed the smae oxidation products as those reported by Kym,
namely. para-nethexyphenylacetic acid and anisio acid. It se-s
highly probable that new chaviool and estragol are idmtical.
{his assumption received cartirnatim by the report of hell and
dash. (Ber. d. Chou. Gas... 29. 344) who found that methyl charicol
tron estrogen oil (isomethol. they called it) gave a nonobren
dibronide castaway mummifi- Ihen treated with branine in
an other solution. an oxidation it yielded a batons having the
for-tale eBay-(cons) cowl-organ

mm. Terrace and mrton (AI. mil. Jam. 19. 846) re-
port the preparation of methyl ohawieol from oil of estrogen pur-
chased fro- l'ritssdxe Bros. may repa-t it as having a boiling point
or sm-eiz’o (mom-.3. when heated with an alcoholic solution of
castle potash they report a ran-meant into anothol (pent-0pm
aniecle). may also report the reparation ed anisie acid by 0:11»
dation. using the nthod given by members and mo. (Ann. chem.”
(lisbig), ldl, 848). an brominaticn in an sitar solution they fiend
that it roadib' absorbed one molecule or bromine) haewer, it was
impossible to inlets he dibruide. hydrobromie acid was liberated
after the addition of one mole of bromine. i'he reaction mixture pro-
duced the tri-bronide sew described by Bell and club (Ber. 4.
Glen. des. 29. 244).

2‘7.

an the umptitm that the boiling points reported by the
more recent workers are correct and that Ey‘mon had node an error
in his reported boiling points, the following procedure was
followed: -

me fractions 310-820 and 220-240 were eombined and the nethyi
ether prepared by using the method described on page hf, of this
thesis. 'rhe nethyl other was carefully fractionated and the fraction
810-216 oolleoted. 50 gram of the phmolie fractions. on methyle-
tion and frenetiomtion, yielded the relieving.

Up to 810 8 g.
210 6 216 28 8.
216 e 224 4 So
224 0 230 7 Be
230 a 235 3 Se

23! e residue. of no eonsequence.

Fifteen grams of the fraction 210-216 were heated for a period
or thirty hours with three times its volume or sahzretod methyl slee-
helie potoeeiu hydroxide. Elie treatment is reported to ones on
am may to shame into the ieornrie prowl mus. m-n methyl
diarieol is treated in this say it is manged into its isomer anathel
(we never-V1 enisole).

After the period of hosting, the mixture eas diluted with water.
extracted with petrol“ other. dried over sodim sulphate. and then
distilled with the following nations:

210 . 217 12 s.
217 - 228 1.5 g.

28.

one gm evidence that no mining or the double bmd had occurred.
for if it had me reuniting product. menthol. would hm dietilled
at 253-254.

A eeoond ottempt was made to remrmm the the mt‘fwl emai- in
question but Vith no moose. .

Hell and m (Ber. d. Gum. Gas. 29, 84431896) repat that by
bromimtien it was inpaeible to isolete the dibmide or mm
eludeol.butthwdidsueooodinobteiningambmmthylohniool
dibrmide eelting at 63.4%.

risesransoi'theuthylefiuen. Rollo-enuredissolved inad
«.ofdxloroi‘eseendefierooolinsiosnioenixtnre.tweeleset
bromine unaided inesolution of woodman-e hoppingtmul.
it first the color or the ermine «seamen-ed at mes without the
liberation of hydrogen braids” After ebont one heli’ the bromine had
been added. hydrogen bromide see libereted in e large mt.

After www.mmmtuuwuuwmm
other. dried mr «loin chloride. mutated ad distilled in
mm. yielding e light strov-eolored oil dietillim at loo-145% at
ie-eo II. he oil failed to eryetellise from petroleus other. and mold
not solidifyinemeelosnixbureofioeendeoltoret theterzmerotm'e
a! ”lid oat-hon dioxide.

several distillation tollwed by intmse cooling failed to bring
about the solidification of the on.

me brominetion no repeated end the resulting all failed to
solidify or erystallise.

39.

A sample ei‘ oil of estrogen. obtained from Fritsohe Bros"
see carefully fractionated by using a fractionatins column and the
fleetion 213-116 collected. This fraction according to walbau
and Bel-tree (Arch. d. Plum. 238, 17731897), arndorff, Terrasee
and Kortm (All. men. Journ. 19. MI). is methyl ahaviool or estra-
gol. This fraction had more of a terpene odor than did methyl
ether of the eel-”Wins fraction eelleeted by depolymerieation
of the oondmeation product.

mm grams or oil or eetreeol. obtained by the above mentioned
distillation. were divided into two partians and bronimted in a
ohloroton solution. to one portion was added one mole of bromine and
to the other two mice. on distillation in mono the former deem-
posed. The latter failed to crystalline from the several eolvente
tried and eonld not solidity in a treesing mixture. looording to the
literature (Bell and Gaab, Ber. d. 011.. Gee. 29. 5“) methyl ohaviool
obtained from oil of estrogen formed on bromination a mono bran methyl
ohavieel dibromide, which crystallised tree petroleu- ethsr and melted
at 62.45%. rut-thei- attempts are being man to bring about the crystal-
lisation of the brominated product. It was the intention to one the
crystallised bromide in seeding the broninated eondmeation prodnet.

so.
OXIDATION 0}? mm mm zen-2.30%

This ether reeeznbled semen“ the methyl ether obtained from
the phenolic fraction ”mafia from the original condensation
mixture.

8m grams of this eter fraction were heated on e water bath
for two hours together with 200 cm. of water end 5 grams of peter-
eius permanganate. Oxidation was indicated by the change in eolor
of the permanganate. . The oxidation fixture failed to yield enything

of eonsequenee.

31.

SUMMARY

fhe results or the work outlined in this finals on; be
mailed es follows:

Allyl eloohol and phenol eondused in the presume or
elmimn chloride.

the elimination mixture wowed the fellow;

le) in elhli insoluble portion Ihieh eould not be
identified es e130". W ether. this uteriel ie etill
mint!!!“-

m A phenolic auction which it we eeoept the date
endprooroi’stmetureeei‘mishedbywmnispere
e111! W1-

(03 A polymer which by mlysis end uoleouler Isiazt
detemimtione proved to be e trinee' or the moleeuln
(creole 6,3100.

Denomination see effected by distillation et etmospherie
pressure. he depolymrited prodnet hes not been definitely
idmtified. but does contain e pare eubetituted phenol.

)7 oxidation there ie definite mo! of pore substituting

the inveetigetim of thie eoMmsetion is to be entwined.

 

—v————e-
h‘ .

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