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S‘VMI C~iLkJiunLhMl J-JQ-otla‘LQI‘u—HJ £31:

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p 3’3 0-3;:‘011 34....-.31431

.A

’i‘hesi a

aubnitted to the Faculty of th
iiicl'dgan State College
of Agriculture and Apylied Science
in partial fulfillnwnt of the requirements

for the degrae of Easter of acienco

by

E46115“ d E‘rmflzlin Liaridgga

Sept. 1. 1930.

éokn owl e g 2:; ergo at

The writer wishes to, express

hie einoere appreciation to
Dr. B. O. Huston

whose guidance and helpful

suggestions made possible

the completion of this work.

381 ‘ 'G

C‘.
3v

 

Foreword

Historical

Early'work on the preparation of benzyl phenol
The Friedel Crait'e Reaction
Aluminum.ohloride as a dehydrating agent
Claisen reaction and the alkylation of phenols
Halogenation and halogen derivatives

The preparation of halogen compounds

The theory of halogen substitution

Statement of the problem
Experimental

The preparation of 3-5 diohlor 4 hydroxy
diphenyl methane

Preparation of 2-6 dichlor phenyl benzyl other
Attempts to prepare the tri-chlor derivative
ot’psra bensyl phenol .
Preparation of 3-5 dichlor 2 hydroxy diphenyl
methane

Attempts to prepare the tri-chlor derivative
of ortho bensyl phenol

Preparation of 2-4 didhlor phenyl benzyl ether

Summary of experimental work

Page

01003!“

10
10
13
16
17

23

SOL-Isl 011.023.1153 IIEiIVATIViJS CI?
9 do 6‘31112'31. PEELZIOI.

Foreword

A large amount of work has been done in this
laboratory on the condensation products of phenols
and oresols and their derivatives. Consequently the
literature on this subject has hesn reviewed end
discussed to s. considerable extent in the vsricus
theses. For this reason. it was not thought necessary
to repeat this review. but to confine the historical
portion of this thesis principally to a discussion I
of the literature dealing directly with the benzyl
phenols and their halogen derivatives.

1. Early work on the preparation of bensyl phenol.

The preparation of honey]. phenol was first re-
ported by Paterno (Gees chem. ital. 2. 1-6. 1872).
Benzyl chloride and phenol were condensed in the
presence of zinc. The resulting compound had a boil-
ing point of 175-1230" at 4-5 m. This same compound
was also prepared by benzylating anisole and treat-
ing the mixture with H1.

in a later paper (Gees. chem. ital. 5‘. 381. 1875)
Paterna and Filete report the use of a mixture of

sulphuric and acetic acids as a dehydrating agent in

the condensation of benzyl alcohol and phenol.
This time crystals and an oil were obtained. The
crystals were said to be the benzyl phenol and the
oil an isomer.

Perkins and Hodglinson (J.C.S. 724. 1880) re-
port the isolation of the benzyl phenol from.the non
solution of a mdxture of phenyl acetate and benzyl
chloride. Hip. eo-ei° and b.p. coo-323°.

Leihmann (Ber. 15. 152. 1883) need zinc chloride
as the catalyst in the condensation of benzyl_alcchcl
and phenol. The resulting product had a nap. of 84°

and b.p. 25-330°.

2. The Friedol and Crafts Reaction.

.Aluninum chloride has been found to have remark-
able condensation powers. These were first discovered
by Friedel and Crafts (Compt. read. 84. 1592-95. 1876)
while investigating the condensation of alkyl halides
and aromatic hydrocarbons. This reaction has been given
the name of the Friedel Crafts reaction and has receive
ed wide spread application in the condensation of both
aliphatic and aromatic compounds. We are proncipally
concerned with it here in the preparation of the benzyl
phenols and their derivatives.

CGHSCHQCI 9 causes .81§13 conscngcon4on o moi

There have been many theories advanced as to
the action of £101; in these condensationo. Boeoeken
(Rec. tray. chime 29. 85-112. 1910) believes that
the catalyst does not react thru the production of
intermediate products} but rather that the reaction
in a result of the change in the affinity or one etom
for another. This clunge my result either in an en-
tire elimination of the atom or group tronnthe root
or the molecule and n reacting no such. or an acti-
vation without separation from the rest of the mole-
cule. He gives an evidence of this assumption. the
(1) reaction of SOQCLB with PhCl in the presence of
A1013 when no dichlor diphenyl eulphone was obtained.
only polyehloro benzene and (2) the action of BzCL
and.0535 Where BnPh was obtained.

Later. the same author (Rec. trot; chhu. 50. 381.
1911) shows that dissociated chlorides like SOgCLg.
C3H015 and 6013630 not in the presence of A1013 like
non-dieeociated;molecu1en with activated chlorine atoms.
The reaction of 6536. 302C13 and A131; gave much.Ph303H
and 131101. but also P1130301 and 33113303. This is to be
expected from.the theory an a catalyst displaces the

eqdlibrium SOQCLQ = 302 ‘+- C1,

"'1
U

considerably to
the right.

Boeeeken finally explains the reaction (Rec. trav.
chin-1. :50, 148-50, 1911) by stating that ”in order to

secure condensation. an unsaturated compound and one

-4.

which can be ac activated that it can cowbine with
the unautureted.compound. must be brought together
in the presence of the catalyst. the reaction being
mode poeeible bth e loan of free energy'. The
fillowing reactions were given in explninationa
110001 4 A1015 . I-ZCGCl.A1613
RC0€1.A1013 ., R8?! '3 {cc-Rumors ¢ 2101
IlCOli'AlCl5 deconrpoocd with H30 3 RCOR' 9 A1013

heisenheimcr and Cooper (Ber. 543. 1655-65.1921)
liken the reaction of A1013 to that or engage-a
reagents in that the aluminum.oomfiounde are formed
with the.Al functioning on the controling aton.with.e
coordination number or 4. similar to E3 in the comp
pound Etgomq' he

ergo I‘ll-8" I

eeuand and Bettng (Ber. 553. 2245.55. 1922)
believe that the Alblg forms complexes with.double
bonde such an that with noyl chloride.L1015..(6330)o01
which reeult in a loosening of the union between the Cl
and 0. thus enabling both.to odd. They state that an
aliphatic double bond and those of the benzene ring
differ only no n.mntter of degree.

Sohaarechmidt (Z..Angewt Chem. 37. 286-8. 1924)
Offers much the some erpleinetion. He otetee that the
A1013 activates the aromatic hydrocarbon. which active»
tion is accompanied by u loosening of the bonds or the
organic helido..A complex in formed between the three

in held by eurilury valences
compounds in which the A1013

-5-

and the ad ition compound by ordinary valencee. The
stability of the comolex dopende upon the divieion of
the inner veloncee. If these are neutralized. the
"molecular course" is followed and the A1015 is not
regenerated. This calls for molecular quantities of
the metallic chloride. If a cilitting out'occure in
the complex at the point where the addition takes
place. the A1313 is regenerated end can he need again.
This involves the "catalytic couree' and.much emailer
quantities of A1013 are required. Secondary reactions
or ouhstitufients in the ring may decompose or use up

the metallic chloride. thus calling for larger amounts.

Aluminum.chloride no a dehydrating agent.

Huston (JtA.C.C. 38. 2527-33. 1916) and Friede-
men report the use of A1313 in the condensation of
hcnzyl alcohol and benzene. giving large yields of
diphenyl methane.

A1313

053;:5011‘3321 ¢ 053:6 . CcfiEfiCHgCGI’Ifi ‘ 1320
In this and in cubeeqncnt work on the condensation of
eeconfiery alcohols. phenols and cresole (JtA.C.S. 40.
785-93. lQlS; Ibid 48. 1955-9. 1938; Ibid 49. 1365-8.
1927) the reactions are dehydrating rather than cot-
elytic. oltho the line between the two olaegfie diffi-
cult to determine. '

Huston (Sci. 53. 205. 1930 and J.A.C.S. 46. 2775-9.
1924} reports the preynretion cf p-henzyl phenol by
the condensation of phenol and benzyl alcohol in the

presence of A1813. The reaction one carried out in

~66

petroleum other ouop anoion at a temperature below 30°
in which case he phenol and £1315 did not react to
give dipho wl etller as reported by'xerz end woith.
One half mol of A1013 was found to be sufficient for
the boot yields. Gmitting the petroleum ether loosened
the yield.

file methyl and ethyl esters of p-benzy l phenol
were also prepared by the A1015 condensation. eniaole
and phenotole respectively being used. In all of the
preparations the temperature was c' controlling factor.
as et tile h53“ her tomr rofiuroe ( 40° and above) a vigor-
ou 5 rec ction takes place giving a variety of products.

Bonsyl chlcrldo and phenol were also condensed in
the prepeza tion of p-benz"1 pllcnol. thus making nae of
the catalytic z.cti 0:1 of the metallic chloriue. filth
either the benzyl alcohol or bcnzyl chloride. the same
intermediate complexes ocemod to be produced and H01
was evolved in large amounts.

E.L.xexfield. in a thesis written 1929 at the Lich-
igan Sta 'to Cello 3vo. studied the effect of 73:3 .og pro-
portions of phenol cnd.AlCl3 on the yield of e and p-
honzyl phenol. fie found tl- lat by increaeing the amount of

phenol the props ortion of the o-bonzyl phenol to the para
cemgcund increased. Ono mol of A1013 did not give high-

+!

or yields w: :n L mol

Claioon reaction and Alkylation of phenols.
The v :‘hon reaction is l.mortunt 1n the pHeporctlon

of the benzyl phenols because it makes possible the

-7-

production of the ortho derivative in utmost quan-
titative amounts. The action of sodium. sodium ethozide
and oodamide in effecting the condensation between
carboxylio esters and ketones or other carboxylic esters
as given by Clesien (Ber. 20. 646-650. 1877) was later
applied by the same author to carbon alkyletion of
phenols (Z. angew. chem. 36, 478-9. 1925; Ber. 583.
275-81. 19253.Ann. 442. 210-45. 1925).

053503219. e 0635011201 - camoscesscsg 1 Heel

In this preparation, the phenol was treated with
sodium in e non-dissociating medium such as toluole
and the benzyl chloride added. The result was a
mixture of mono and di benzyl phenols and an ether.

The ether was removed by first dissolving the red
liquid in alcoholic KOH end then extracting with pet-
roleum efijer. The potassium salt of the phenol is not
soluble in petroleum.ether and is not removed by the
extraction. The ether produced by the reaction was
identified as the same compound as is obtained when the
condensation is carried out in a dissociating medium
such as ethyl alcohol.

The benzyl phenol is the result of ring alkalation.
the medium being the most important factor in the re-
action. Tith the dissociating medium the benzyl group
substitutes on the hydroxide of the phenol.

H
on.
0- C--

it

-3-

In the non-dissociating medium. ortho substitution in

the ring is obtained.
WM:

 

Clcsien. Von Auwers. Busch and others have offer-
ed cxpleinetions for the carbon nlkylstion (in the ring)
of phenols. The first author (I. angst. chem. 36. 478-9
1923) finds that the formation of the alkyl phenols
must be by direct carbon slkylation es the others do
not rearrange to produce them. The alkylation in effect-
ed by the unsaturation of the slkyls. The tendency is
still further increased by the use of alkaline phenols.
Para substitution. where the ortho position is taken.
has not been demonstrated. The ortho bensyl phenol.
prepared by the author. had 8. mp. of 21° and a. b.p.
of 312°. In 1925, however. he reports the ortho deri-
vative to exist in two forms. the unstable form melting
at 21° and the stable at 52°. Subsequent attempts to
produce the letter heve foiled.

E. von.Auwers and associates (Chem. Zentr. 1.
3547-8, 1926) advanced three possible explainstions for
the carbon elk"lation. First. the formation of sdd- -
ition products with the subsequent splitting as given
by C;eise.. Second, the formation of normal oxygen
derivatives followed by reerrnnremont. Third. the

sepe etion of the note 38 a metallic halide with the

-9-

formation of the free alkyl and anal radicals. With
the rearrangement of the enol to the hate and finally

the union of the radicals. we have this reaction:

(2’ 0H
———9 ______?

The character of the keto-snol and the alkylation agent
as well as the medium, directs the elkylization to the
oxygon‘or carbon. Setureted halides promote the forma-
tion of the oxygen derivatives while allyl and benzyl
halides favor the cnnbon. In dissociating media the
exchange between ions is stronger and for that reason
the oxygen is favored.

K. van Auwers (Ser. 613, 403-16.'1928) studied the
effect of different halides on the direction of the
alkylation. From these studies it appears that iodides
yield more carbon derivatives than bromides. Also the
methyl halides favor the carbon, while the ethyl favors
the oxygen. Ea explainetion is given for these results.

Busch (Z. anger chem. 58, 1145-6. 1925) and Busch
and Knoll (bar. 603, 2243-57. .937) state that carbon
alkyletion of phenols increases with the increasing
substitution of the methane carbon atom.'Whilo it is
possible to obtain others with benzyl chloride in non- ‘/
dissociating media. di-benzyl chloride yields only
carbon derivatives. The introduction of electronegative

groups favors other formation. Alkyl groups on the

-10-

phenol nucleus diminishes ether formation.

r. F..Short (J. Chem. Soc. 538. 1938) reports the
rearrangement of benzyllphenyl other by heating to
225°‘vith.2n012 or to 190° in a etreem.0f H01. A
mixture of phenol. o-benzyl phenol and pubenzyl phenol

was obtained.

The preparation of halogen compounds.

There has been very little work reported on the
halogenetion of benzylnted rhonole. E. Faterno and H.
Pilate (0322. Chem. ital. 3. 121-129; 251-264. 1874)
prepared e dibrom derivative by treating the benzyl
phenol in 082 with an excess of bromine..An amorphous
subetence was obtained which was soluble in CHC13 and
csg. but not in ethyl alcohol or other. n.p. 175°.

Sintenis (Ann 151. E45 ) reports the preparation
of bennyl chloroyhenyl other and bencyl bromophenyl
other. These were made by panning chlorine or bromine
into an alcoholic solution of the ether to which some
H30 had been added an a catalyst.

Perntoner and Vitnli (Sana. chin. it. . 28. 197-
240. 1838) report a ohlor benzyl phenol made by treat-

I
I

in; benzyl phenol with sulphuryl chloride. The explqln- 1
/
ation given for this reaction is that the chlorine odds

on, followed by an elimination of H01. The chlorine
supposedly enters the phenol ring in the ortho position.
Auvers (Ann 357. 85-94. 1907) prepared tri-brom

/'
\/

phenyl benzyl other, tri~chlor phenyl benzyl other and

-11-

two di-brom derivatives. In tizceo experimento the tri-
chlor or tri-brom.phenel wan dissolved in alcohol and
treated with benzyl phenol and sodium ethoxido.

L. Zincke and.W. halter (Ann 334. 367-385. 1909)
stuoied the bromine substitution in p-benzyl phenol.
The reaction gave two typeo of crystals. one nhich.wao
huneteblo and melted at 44° and.nhich changed to a rhomp

bio form with a m.p. of 57°. The formula given woo

N Br-
.-,3- -0”

The tri brcm and penta brom derivatives were also re-
ported.

The name author_(Ann 350, 369-87; Ann 363. 246-84)
states that mono. di and tri brom o-croeol can be pro-
parod by direct bromination with or without a catalyat.
The mono derivative is reported no 5 brom o-crosol end
the di no 5-5 d1 brom o-oreeol. The tri is probably 3~
4-5- tri brom o-creeol. Pseudo bromides were obtained
if the reaction was carried out at high temperatures.

Zinche has done e great deal of work on the halogen-
ntion of phenol and croeol derivatives. Diphonol methyl

methane with bromine in acetic :oid gave

m:.~c - .:ml "'1'- MM“

This compound heZted with bromine in a sealed tube at
100° gave the hexn brom derivative. E.p. 169-170°. The
hopta brom oo11pound‘wno also plepered.

Van Alphen (Rec. traw. chem. 46. 799-812. 1021)

-13-

reports the brominetion of 4 hydroxy tri phenyl methane

giving the fii-brom derivative.

. .
-.\CII.I.0H

Barv (Quant. J. Indian Chem. Soc. 3. 101-4. 1920)
prepared benzyl o-chlor phenyl other. the meta and para \//
derivatives of the sameether and benzyl 2-4 dichlor phenyl'
other..All of theee were prepared by means of the lance-
trope.

Iaxfield of this leooretory in a thesis written in
1929 reports definitely that brominetion of benzyl phenol
takes place in the phenol ring rather than in the benzyl
radical. fie found t1 .e some change in the melting point
and crystal form of dibrom p-benzyl phenol as reported
by Zinoke and Halter. The stable form has a m.p. of 56-7o.

Heedley {1&Lter‘5 thesis, L; ohi5on State College,

:33) studied the effect of the introduction of a chlo-
rine atom upon the activity of M} b<:nzy1 5roup. He
found that the activity was greatly increased. He also
est olielied the fact that chlorine enters the following
groups by first substituting in tiie ring containing the

hyUI’CX 3’10

.3? -0" ““c'-‘§~.:w’
"H i H
. - c; C Cl -C-4‘IIII.’JH
5,- m» . O
C!

-13-

The theory of the substitution of the halogen.

The directing influence of various groups attached
to the banzcno ring on entering groups or atoms. has
been the subject of considerable study. Holloman (Ber.
44. 725. 350%. 3555. 13113 J;A.C.S. 36. 2495. 1914:
and.Chem. E67} 1. 137, 1924) explains th:1t this in-
fluenco is in icated byt .o VBQCiti es of the reactions
of the groups already in the 11.5. That is . when a third
aubstifiuont C is to entcr a ui su :titutcd bong one
compound C¢X¢33. tho reaction can he prodicte d by a

“1. ,1.. . 1 . ,. 4‘ .-‘ .-
bvou of tae op’ed o1 tug erCthnu:

II

c6125; + 0 (25:14.50

H 51?. Wn
. b1;)..ll_’ ~

(_

q

(5—.
L .
4
C)

The grou‘o which infl1unco tho crtho-para cub-
stitutiou in such a roacticn are in diminishinc series
as follows:

6:1 :55“) I 31' Cl C} 3.
and the mafia position;
C331? 3x...

Kornor (3533. Chem. it 1. 4, 305, 445. 1874) states

that acid " .rou23 di.zoct a no? atom or radical to the

n-v v
\

mata position. rho halo5nno, : unJ boaic groups direct
to the ortho and para.

Pry (5.3.3.3. 36. 1335, 1911) su55cs to an electronic
explaination for the oubotitution. in which he assumes
that the hydrosono on the b enzozto rin5 are a.lteruately
positive and negatIVL. Substituonta of the same polarity

as tho group alrea&J in the ring are di1cct od to th

-14-

zeta position. while those of opposite polarity will
take the ortho or para. According to this oxplolnaticn
the halogens in the presence of a very small amount of
moisture or some other halogen carrier. produces
positive X by splitting of the X3 molecule, giving the
compound HC'Kf. The holognnotion of the bonzyl phenol

would be x ploined gooey-lin5 to th. following equation:

,, H x+
-5. Wu o-c mou-

Fry givcc as proof of the positive hnlO5cn. the fact
that‘it cannot be directly replaced by an OH‘. The
para gcsition in the above equation bcin5 occupied.
limits tiio zzJotitution to tha ortho position.

While the idea of positive and nc5ctive hydrogen
and probably halogen has boon -acriou3 y questioned and
largely dropped from tho theory. yet the effect of the
polarity tendency of the 5ronpo in the ring is still
hold. Pfciffor (Ann. 451, 132-54. 1928) explains tho
subotitt ti.on of tho bromine in th< berm one nucleus by
assuming that ouch groups no CE, 2?; etc. confer polar
proportion on the attached carbon atom. This causes
polar rearrangement or ohiftin5 thru the root of the
rin5 which is the fn.otor 5ovornin5 th coubotitution of
other atoms or radicals. Those of like polarity go to
the meta position which is the forthm from the effect-
ing group. Unlike groups subotitut c in tho ortlio and
para.

Substitution would be explained in a simi lar

manner by the Lewis-Langmuir electronic thonrv of

.15-

valence (Valance and the Structure of tho Atom.and
Holsoulcs. A. G. 8. Honcgrsph.1923). This theory sssulss
that the chemical bond is produced by s pair of electrons
shared by the two atoms. Tho position of those electrons
with reference to tbs positive nucleus of the atoms
depends upon the comparative strength of these nucleus.
With.similsr atoms. such.ss the carbons of cthans. the
pair assumes s position midway between the centers. The
other extreme is illustrated by the Ho and Cl 0! Ecol

in which the strong positive character of the 01 stolen:
entirely removes the clcctrcnipsir from the field of the
Ha atom.

In the combination of three or more atoms. the
position of tho pair of electrons between say two is
effected by the other atoms depending upon their strength
snd position in tbs molecule. Thus in bonsyl phcncl.
the position of the electrons between carbon and.csrbon
or carbon snd.hydrogcn is effected by the presence of
the hydroxide group. This group having s strong sttrco-
ticn for electrons will pull the electron pair nearer
to the oxygen stun. This pulling-effect is relayed thru
' the carbon to the carbon-carbon bond and also to the
carbon-hydrogen bond of the orthc position..As the pairs
of electrons of this politics are pulled toward tho
carbon. the carbon-hydrogen bond is weakened. directinh
substitution to that position. Thus in the preparation
of the chlorine derivativss of para bcnzyl phenol. the
chlorine will substitute in the orthc position.

.15.

STATJLLZFI‘ OF TEE-3 PLOBLkJH

The object of this problem can be divided into
three parts no follows:

1. To prepare. identify and study the propor-
tion of the chlorine derivatives of ortho and pore
benzyl phenol.

2. To prepare acme of the derivatives of these
chlor benzyl phenols.

3. To determine to what extent chlorine in sub-
etituted in the benzyl phenol by direct chlorination
and the position taken by the entering chlorine atoms.

-17.

LnSJMIL I-JJJE‘E“ 2!.‘L

A. The preparation of 3-5 dichlor 4 hydroxy diphenyl
methane.
1. By the.AlCla condensation of 2-6 dichlcr phenol
and benzyl alcohol.

CI
chin-3. -73.»!
CI

Fifty arena of benzyl alcohol and 225 grams of 2-6
dichlor phenol were euepended in about 250 cc of petro-
leum ether. The euepeneion nae mechanically etirred
while 30 grams of A1013 wee added at intervale over a
period of 1 hour. The phenol ie only elightly soluble
in the ether. Stirring was continued 30 minutes after
the addition of the 51013 and the mixture allowed to
stand over night. At no time during the reaction did the
temperature 30 above 33 degrees.

The euepeneion was decomposed with ice and.HBl and
the petroleum.ether withdrawn. The water mdxture was
extracted with ethyl ether and both eolution dried over
potassium carbonate..After dr3*ing. the eolvente were
distilled and the reeiduee combined. The recidne from
the petroleum ether was an oil while that from.the ethyl
ether solidified on cooling. The combined residues were
fractionated by distillation.

let. Fractionation.
1. 100 to 122° at 15 mm mm A ens-11 amount of oil.

mostly benzyl alcohol.

-13-

2. 133 to 155°--- A large fraction which solidi-

fied in the receiver. Kostly 3-6 dichlor phenol.

3. 155 to 204°~~- A smaller fraction which only

partially solidified.

4. Above 204° -- A large amount of charred material.

The fraction between 155 and 204° was refractionat-
ed..a small amount of 2-6 dichlor phenol was obtained
between 155 and 195°. The larger portion distilled
between 195 and 235°. From this portion. 23 grams of a
yellow oil was isolated.

This condensation was repeated using the same
materials and.proceddure as before except that 032 was
substituted for petroleum other as a solvent. Upon
fractionation of the residues obtained after drying
and removing the solvents. e.larae amount of charred
material was obtained and only 15 grams of product.

In order to obtain a better yield. a study was
made of the charred material left in the flask after
distillation. It was found to contain a large amount of
potassium undoubtedly as a result of the drying with
K3803. In subsequent preparations. therefore. the drying
use omitted. By this method. the charring was avoided.
but the yield was not greatly increased.

The yellow oil from six preparations was combined
and purified by distillation. The boiling point after
three fractionatione was 194-1960 at 15 mm.

A determination of the chlorine content of the oil
was made by the Parr bomb method (J.A.C.S. 39. 2069).

-19..

Results of the Chlorine analysis

1 2
Weicht of oil used .1840 .1889
Vol. of .1N AgHOS 1d.55 00 14.95 co
Vt. of Cl in 83mple .CSOQCB .05293
Percent Cl in sample 27.7 - 28.1
Theoretica1p01 in tue diehlor benzyl phenol-o 28.0.

since the method of rre azgtion of the oil and the LM'

analysis,0hecked with the theoretical. it was at first

1 r9 '\

sup tossed thet the compound l.’ as o-S cichlor 4 hydroxy

L

uooequant results. however. showed

0

diphenyl methane. .

'u

that this was not entirely true. as will be seen later.
2. By the chlorination of p-benzyl phenol.

.5 -01! +201 .-.- "gown/(l

Para benxyl phenol Wis fir tprepared by the A1013

3‘)

condensation method previously described. 30 grams of
phenol. 50 grams of sons 31 alcohol and 50 grams of
A1013 were used. Petroleum other was the solvent. After
fractionation a ad. r201yste 3.? zzyoron from petroleum ether.
11 grams of pure product wcs obtained.

The para benxyl phenol was chlorinated according
to the method outlined in "Hethods of Crgo nic Chemistry”.
Houhen Vol. 2. p 799. Ton grams of the phenol was sus-
pended in chloroform ins flask connected with a chlorine
generator and wash bottle of sulphuric acid. The gener-

ator consl 'steo of an Erlen3:eye1 fl: sk and separatory

funnel. The calculated amount of Khn04 (7 grams) was

-20-

plsced in the flask and 42 to 45 cc of HCl in the funnel.
.After all of the chlorine had.been swept thru the chlor-
oform solution. the solvent was distilled and a yellow
oil obtained. The oil solidified on cooling. but was
fractionated by distillation. All but e very small
amount came over at 190 to 205' at 15 an. The distillate
solidified and was separated from.sn oily substance by
pressing between filter papers. The crystalline product
was then recrystallised until pure. h.p. 58.-58.5°. B.p.
195-196° at 15 mm.

The crystalline compound.was analysed for chlorine.

Results of the chlorine analysis.

1. 2.
Weight of sample .1843 .2137
Vol. of .lB.A3303 used 14.3 co 16.8 cc
Wt. of Cl in sample .050765 .05964
Percent Cl in sample 27.6 28.1

Theoretical fl Cl in diohlor bensyl phenol 28.0

Again the analysis and method of preparation indi-
cated 3-5 dichlor 4 hydroxy diphenyl methane. but a very
different compound was obtained by the previous method.
Crystals of this compound seeded in the oil prepared
by the 51013 condensation. dissolved.

The bensoyl derivative of each of these compounds
were prepared. using the Schotte and.3sumsn reaction.
Two grams of each were dissolved in 10 cc of pyridine
and 1.2 grams of bensoyl chloride added. The mixture was

poured into water in which a small amount of KOH was

.21.

dissolved. The Ebh.preventsd the extraction of benscio
acid by the ether vhioh was next used to remove the pro-
duct of the reaction. The ether was evaporated and the
solid.shinh remained.preesed.betveen filterpepers and
recrystallised. The product obtained from the oil was in
appearance snd.mslting point (98.5-99.0°) identical with
that from.the crystalline compound obtained by direct
.chlorination.

Further studies were made in an effort to determine
which.of these apparently pure compounds was the product
desired. Previous to the chlorine analysis. it was
thought that the crystalline compound.woe the tri chlor
derivative reported by Headley. The melting point of his
compound.vas 55.0 to 57.59. which was very near that of
the crystals prepared.here. The chlorine analysis. how-
ever. shoved only two chlorines.

During the course of these studies. the solubilities
of the compounds in slkalee'sas tested and it was found
that. whereas all of the crystalline compound dissolved
in the K03. only a part of the oil was soluble. Following
this indication. 10 grams of the oil was treated with
KOH. The insoluble portion was separated and the ROM
solution acidified with.ECl. A crystalline compound was
obtained which when recrystallised gave a melting point
of 58.0-59.0' and was identical with the crystals obtain-
ed by direct chlorination of p-bensyl phenol. The infor-
mation was sufficient to prove that the crystals from

both.of these reactions. meaning the A1013 condensation

and the direct chlorination. was 3-5 dichlor 4 hydroxy

diphenyl methane.

Finding the crystafline corpound in the mixture of

oil. accounted for the honzoyl derivatives being the same.

but did not account for the similarity in boiling point

and chlorine content. Apparently the crystals are solu-

ble in the oil. thus oro

J.

however. must have the

crystals. hut can not be P phenol. no

in alkalne.
oil

n1 1
.L 4'13

a
(as 1
\—

19'30 at 15 Y‘I’Z. It "a" th
Results of

Weijht of oil used
Vol. of .13’Agfi03 used

‘mL
w b e

0f Cl in samyle
Percent cl

The snolyrio in

inos and the some molecular we

chlor benzyl phenol. “he

+1
--4

VJJI
'o ‘0 1e .4

‘ ‘5
) 1“.-

J

on

11

venting their i

molecu

tr e (".th Tit

H

‘ O

s
for

H .5
'~4L

t

He

wit

1

9+
(2.9

on. The oil.

mule as the

k~Je

not soluble

(In
54

h K03 and separ-

pructically pure. 3.p. 195-

pl-

co"@ound having

“‘s

tht

I

. . 9
area for c
5 O
icrinc anal
r‘ g
.e' 3

as thy

.t of

Illorinee

.1950
15.05 cc
.05346

27.?

two chlor-

the di-

rect likely compound. not a

phenol, with this molecular fornule is 2-6 dichlor phenyl

Cl
benzyl other.

C!

2

3° The Preparation of
:1???) £3 £3 {3‘}6L(Sz:zr 1¥KFZP'53 j!) Irt‘?':) z:

TAW,” ‘
CJLJ.1).L {0’3

and benzyl

H

(7' C-

I!

-6 dichlor phenyl henzyl ether.

;red by treating 2-6 dichlor phenol

-ohol accord-

-93-

ing to the Cl? icon method before described. 6.5 graua
of sodium was allowed to reac t with 100 cc of methyl
alcohol. The solution was cooled and 45 grams of 2-6
dichlor plienol added. This mixture was heated on the
oil bat h at 150° for 30 minutes, cooled and 35 grams

of oenzyl Chloride added. The entire mixture was allow-
ed to stand over night and thcn heated on the oil bath
for five hours. After coolinj, the oil \&S extracted
with petroleum other, the ether removed and the residue
distilled.

A very small amount of henzyl chloride “is ohtein-
ed :ebnccn 93 and 173° at 15 mm. The second free tion
all dictillod between 193 and 195°. This was purified
by further distillation. The refiultine compound was a
yellow oil, having a boiling point of 194 to 195° at 15
mm, insoluble in non and with an odor similar to the oil
obtained along with the benzyl phenol derivative in the
first A1315 condensation.

Thus in the condéncation of 2-6 dichlor phenol and

benzyl alconol, a mixture is obtained which has been

eho n to contazn t1o henzylated chlor phenol and the ether.

0. Attempt to introduce three chlorines in p-benzyl phenol.
3-5-4' tri chlor 4 hydroxy diphenyl methane had

been previously prcpt-"ed by Heudley (thesis before men-

tioned) by the A1015 condensation of 2-6 dichlor phenol

and p-chlor honxyl phenol. An attempt was here made to

introduce the three chlorinae into p-benzyl phenol by

direct clilorination.

-04-

Ton grams of the phenol were treated with the equi-
valont of thrao ohlorinco by the rerma.ganoto method. The
product obtained in we trials gave a m.p. of 58.0 to
58.”° and was identical with that from the previous chlor-
ination when two chlorinoo wore introduced. A large excess
of chlorino woo thou used. but again only t} o dichlor Z J

deriVotivc woo obtainod.

D. Proporooion of 3-5 dichlor 2 hydra:1 diphonyl methane.
1. 31/ tulle Clay-Lsen I‘ez. Gui-CY}. H
on 0
Cl H
a u m. 7;.
c1 ' 5’

Sodium (11.5 grams) was suspended in 133 cc of
toluene and Gl.§ grams of 2-4 diohlor phenol addod. This
mixture woo heated on the oil bath co 150° for 30 min-
utoa during which timo the white sodium colt was pro-
duced. Tho mi; turo loo coolod and 63.5 gram: of boncyl
chloride added. After otandir a over n1 got. it was heated
for 5 hours on the oil bath. cooled and treated with 230
0c of methyl alcoholic £03. The solution was then ex
tractod.with petroleum ether to remove the eth or produced
by tl.o loco: ion. The potrolcum other solution woo cot
aside for a later ioolation of the ethorial compound. The
methyl alcoholic colution was nouhtolizod with H31 to
again liberate the phenol and extracted with ethyl ether.
After renewinr the ozhcr. the rodidue was fractionated

by distill ation.

-25-
lot. Fractionation

l. 90 to 140° at 15 mm--- A light oil which proved
to be mostly unooaurou boa: yl chloride and 2-4 dichlor

honol.

2. 140 to 310° at 15 mm ---35 grams of material
which solidified in the receiver and which proved to be
atmoot entirely the dichlor lLoc zyl phenol.

3. 210 to 320° at 13 mm ---A heavy rod oil.

4. Above PTOO --- A tarry product from.which no
material would distill.

The fraction 143 to 210° oa.s recrystaflfizod several
times from higu toot gasoline and gave about 50 grams
of product meltin3 at 77.0 to 77.59. The chlorine analysis
gave the following results:

Results of tho chlorine analysis.

Height of 22,2319 .3000 .1895
Vol. of. 13 A3 0. used 15.0 co 14.8 co
Wt. of 01 in cam 18 .055325 .05354
Percent Cl in sample 27.5 27.7

I ,. a .. q c u. 5 ‘ I 9 ‘ 4
hecretlcml Cl 1n too QLCHLOT cerlvotLVc--- 28.03.

(W

2. By the direct ohloringticn of o-benzyl phenol.
Ortho bgnzyl phenol was prepared by t.‘1a Claiaen

reaction using 1 mol. each of sodium. phenol and benzyl

chl aria. o‘crnn ed in tolu2n2. 33 gramo of pure product
war octainoo.

The cllorination was carried out in the some manner
as before Heinz the weight of Krn04 calculated to fur-

nish two equivalento of crwl;:ine. The dark colored oil

o‘ot 3i nod v. .

tween 190

.3
I

t;on froau

N

tical with

E;lel

,.1 _
tnose

-26-

fractionated and the portion boiling be-

330° at 15 m3 333 purifi

lby re crystalli-

high toot gasoline. The cryst Ulla war a iden-

frc: tho reaction of 2-4 dichlor phenol

and benzyl chloride. H.p 77.5 to 78.L°. Bhia compound
was analyzad for chlorine.

Lofults of tin; chlorine analysis
Weight of sample .2316 .3364
'fol. of .15 A3305 used 17.0 cc 18.4 co
Wt. of Cl in sample .00035 .0650
Percent C1 in sonple 37.6; ?7. 6
Theoretical 1n the dicllor ieliVuLJVG"‘ 2%.OJ.

(It 9'14) 1).;-

was p‘+p.rc

from alcohol

E“?.O ’1. (16311 Ur'lolV-B

d.

the two products

The rozulti n; LCHVDUHQQ were reorystafldzcd
to whicn watel has been added. Needle

shaped crystals do rel '0? ad in each cace. K.p. 66.0-67.00.

the

‘0 - --.—~ fl Q I . -n.. t
(a Line-A, L; LA": 1 in}? La

each of taeoe eactionfi was the

hydroxy diphenyl

E. Attempt to ir ntro uce three chlorinos in o-ben zyl phenol.

of chlorine
01' tl;3

CPL-3 ‘3

inaticn was

F. Prepar

o-Benzyl gncncl woo Erhjocted to three equivalents

W

chlorination. hilt as in the

‘. I- I‘ 1 I \ I
I. .1 Hail; 7 89.1110}. "

para compound, no evidence of further chlor-

I. r. ' ,4-
O ‘4)tal‘i’lr’3 t.-

ntion of 2~4 liohlor gncnyl benzyl other.

C! 4”

CIH-o-g-

11.5 firafin of sodium was allows! to react with 200
cc of methyl alcohol. 35.5 5rum: f 2-4 dichlor phenol
W95 added and the mix tura heutai for 3 mirutes on the
oil bath. Then 63.3 grams of be.; 5’1 c3101 de was added
and thp Whole let stand over night. It was then heated
for 5 hours an& extractn‘ *Lth petroleum ether. After the
ether wcs-ramcvad, the 1C.*Lufl was distilled. A small
amount of bénzyl ckloride can: ever between 90 and 150°
but the Hajor portion of the oil distilled between 190
and 193° at 15 mm. The diSLillate solidified in the
receiver an; was recrm¢tallizfi f: m petroleum ether.

The gurified 3:3"t51: were prisms having a melting
point of 53.3 to 53.3°. Almost a 'anuLuaLive yield
was: obtafintzd.

In Drier to iécntify ths IUU-OLCQM enher extract set
aside from tin preovration of 3—5 dichlor 2 hydroxy

1phenyl methanfi, the Iraidae iron “la extraction was

distilled. Ta:

r1
(+-
O
H:
P‘-
‘ 1
1..-
'3
t,
k
,4.
'J
'4;
H
(7
*4
r)
H
\U
0
<‘
(I)
”a 0‘
if
8!
CD
0
:3
p
0
H

and 132° at 15 mm. The distillate was puzi iea by re-

['6‘

cryst9Jizm Jtion :99 gave the ?933 yrls'r29t 0 crystals as

firnrmrpfl rum 9 ° 9 n9 :qu O
I .§ t~.‘.’(.) leA' : vj‘vv, . ’1’.._ . ‘JV . U Swim! . .

nwr- Y\_/ ,«rn W M'W’ r '1'! 11‘? 1 «,1 1r
I.)VJ&~::AI¥:L ”.1..- uALia-J‘h..' 4.43“.) UiVa-LJ.

1. The followinv comvounfls were prepared, identified and
some of their properties date mined :(See flow sheet)

.'ulcr 4 nydroxy a1 :lenyl mc’du;rle.

Its benzéyl derivativa.

2-6 dichlor .JERHL’l bang f1 ether.

5.

~28-

5-5 dichlor 2 hydroxy diphonVl methane

Its benaoyl derivative.

3-4 dichlor phonyl bonzyl ether.
lo evidence was obtained of the substitution by
direct chlorination of more thafl two chlorinea in
either para or orth honzyl phenol.
the A1313 condensation of 2-6 dichlor phenol and
benzyl alcohol gave the other as well as the benzyl-
ated phenol. This 18 the first time that the ether
has bean identified in any of these A1013 condensa-
tions. It is possible that it is formed in all of
them and that it was only because of the difficulties
encountered in the purification of the phenol that

it was identified in this cage. It may be that the

ether is formed in all A1613 condoncations. and that
this is followed by a rearxangement to the phenol.
In the cage of the condausation here reported. the
presence of toe chlorine atoms strengthens he ether
bond and the reaxrangement ma" have been retarded.

a

$his. 01 coarse, will require for hsr study.

OR a 6!
Cl . °
cu cu Mggghf ‘W
N“ / / M-f. 37.5- ‘0‘ at: 98-9 °
W
O

\ /
.4 a:
, \ 4’ 1/
‘3 0H ’éfg on
'so {a Cl C,
‘0': 4' CI ‘7
0%- \Q \
'a
. ..

 

\ {Cg
\W’ 1 m;
\ \

iv
—- — -—-9
\ Ch 7‘”, 606/ n.2, -
H

\
’Zto/ CI Mg. 66 47"

CI
Ill/£2124
a./:'\ Na in alcohol—I.
a e {Z‘JZ.§°

CI

son: CHLOE/Alf DERIVATIVES or
O & peBE/VZVL Pfiflkfl