SOME HYDROXY DERIVATIVES 0F
CHLORDDIPHENYLMETHANE

THESIS FOR THE DEGREE OF M, S.

Philip Stanley Chen
1930 _

         

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A Thesis

Submitted to the Fe malty of the
autumn State College of Agriculture and Applied Science
. 1n mrtnl fulfillment. of the requirements for

the Demo of

Easter of Science

by

Philip Stanley Chen

Acknowledgment
To Dr. R. C. Huston. the author

expresses his thanks for generous aid and
kindly guidance in accomplishing this work.

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Page
I. Introduction 1
1!. Historian).
1. The Work of Cloison 2
2. Aluminum Chloride .a‘ Condensing Agent 9
3. Bonzylation of Phenols 11
4. The Work of Huston 13
III. The Problem Defined 17
IV. Experimental
1. Condensation by the Unison Method
1. Propamtion of 2-hydroxy-2‘cchlorodiphenfl»
netrxano 18
2. Preparation of 2-hydroxy-5,5,2'-triohloro-
diphenylnethnno ' 21.

3. Preparation of 2- ohlorobonzylphenylethor 23
4. Propontion of z-chlorobonzyl-z,t-diohloro-
phonylethor 25
B. Condensation by the Huston Method
1- Preparation of bhydroxy-Zbchlorodiphenylo

Bethune 27
2. Preporation of bhydrom~5,5.2'-triohloro-
diphanylmethnno 31
c. Eotoritication :53
V. Sun 34

'1. Scheme of Condensation 35

I. Introduction

In this thesis, two menods of condensing phenols
with ortho chlorobenxyl chloride are described. By the
Chisen method, the phenols were first mde to form a
sodium salt which was suspended in a suitable medium and
then treated with the benzyl chloride..According to former
investigations, this method gives only the or he substituted
carbon compounds or the ethers, depending upon the nature of

the medium used.

By the flueton method, the condensation was effected
by the cttslytic action of anhydrous aluminum chloride.
The products formed were generally the pars substituted
compounds, a small per cent of the ortho derivatives being

also formed in some cases.

Both these methods are discussed in detail in the

historical part or this thesis.

II. Historical

_l. The work of Claison

Clsisen (Ber.. 20,646) in 1887 published his first
serious contribution to the theory of the scetoacetio ester
synthesis. Kc explained the methauism of the process as

follows:

W on:
_- / t.
on c { sausage ...._. Ciis-C-OC2H5
3. \0C2}{5 \OC-glis
no. 2::
Giza-cfcogns I 01-13-00- 002215 ...._.. mayhem-002125
002115
I 20221531:

The formation of an addition product as indicated
above was proved by the fact that benzyl benzoete unites
with sodium nethylate and sothyl'benzoate with sodiun‘ben-

zylste to form the some addition product which can be isolated.

/0;Ie
c 1': .43) I CITVOIIa ---c5n — -ocz1

as
C -'E - [O C It 013a -—->C fl -C-OC H
Uskocng,’ 77 05 \ocfiz"

Then sodioacetoecetic ester is allowed to react with
slkyl halides, the alkyl radical of the latter replaces the
Intel in the ester..An intermediate addition product is {cried
previous to the elimination of sodium halide. The metheniel

of the substitution is represented by the following equation:

can u 93a H
onyc==c-co xi / 1—2'}: ..._.... c113.g—g;cocr.

9 1.1

_....., Guys-gown

That the substituent elkyl radi a1 attaches to the
carbon instead of to the oxygen was explained by the theory
on enol-keto teutomeriem. As soon as the sodium is removed
from the eodioecetoecetic ester by acidifying he derivative,
acetoecetic ester is liberated in the enol form, but it
rtpidly’changes until 90 per cent of the enoi is changed to
the keto form. The equilibrium between the two forms, however,
any be disturbed and one foam may be changed to the other
according to the nature of the reagent used. If a reagent
is used that acts only with the enol form, the keto form is
gradually changed to the enol by the shifting of the hydrogen
ttom from carbon to oxygen. On the other hand, if a reagent
that removes the Rate is added, the shirt occurs in the Oppo-
site direction. There are other factors besides the nature

of the reagent, that determine the shift from one form to the
other.

The enol-keto tnutomorien wan also found in many other
organic compounds and reactians. For inetence,when benzyl
chloride is condensed with phenol, the resulting product may
be phenyl benzyl other, benzyl phenol, or both, detending

upon various factors as will be discussed in later sections.

0:1 0:23

a] He -—-—‘> (:) I % H2

Olfa CIT-.201
,1 .__.__, I-éaCl / O-o—ozfichx

Phenyl benzyl other

0.1
'C“2 Q
or

Eenzyl phenol

Claisen states that while the ether is the product one
would expect to be formed, the benzyl phenol formed is the
reeult of "anomalous metal substitution", or, as be otherwise
expresses it, the result of ring slkylation.

To explain the formation of the carbon deivetive,
thnee differnont views have been advanced and were discussed
by X. Von tuners, G. Yegener, end Th. nan: (Chem. Zentr.. I,
2&47-8, 192:), namely:

(1) ”The initial fornstion of adoition products with

subsefluent splitting.

92) ”The initial formation of normal oxygen derivatives

with rearrangement of these into carbon derivatives.

(3) “The separation of the metal as metalic halide,

formation of free alkyl and enol rudicals,
-o:o<f -C-C”

"3\

-—---p
0- O

and with the sli3ht reIe tivity of the alkyl group
partial or complete arren3eaent of the enol to hate
radical, and finally union of Le radicals."
The first hgpotheeis W‘s bee d on Licheel’a theory of
the reaction between silver cyeeic.e de metI3l iodide (J. pr.

37, 488; 40, 139) which.un3'1 be represented b3' tLe following

scheme:
AI;
CeAg C<' C-
!" ICIESI—fi"I-—-—-" {A31
II II-CII:5 Z-I-Citb

It an be Been that the metL3l roadical of €231 attaches
to the nigrogon, instead of to the cerbon.ae we might expect.
A3 applied to the re e.ction 01 sodium pim cnoL eand en alk3. l

halide, the neILLLILn may be illustre ed as f0110I Is:
/I

~C-Ofia ~fiaI “3:0 ~COH
u ,1 PI -—--o- . 02.321 ---—-o- 9 ...._......, n
-c.-II -CIIII. -Clm oC-R

Thus, by the formation of en Lduition, a shift of bonds
takes place which makes possible the final formation of a com-
pound with the alkyl redicsl attached to a carbon in the ring,
instead of to the 0x339n atom, the carbon hav1IIg t‘; e position
ortho to the oxygen. nus, when elk3l or I:eLz 3'1 p3 enole ere
condensed by using Cl: ieen' e metLod, the resultiII Jproduct
is of the ortLo type, tlxat ie, in the new comgound thus formed,
the OH 3rou3: eIId the new su1)stitueht occup3 3ositione adje cent
to each other in tke ring.

The Lecord hrIotueeiu, tLat o? the rezzr Incoment from

the initial Coderivativce to the f.II 31 C derivatives, is

inadeouate, for it is incomp1eheneible why an O-derivative
should be transformed into a C-derivative in benzene more
easily timn in ether.

The third hypot11esie was pro;1osed by zieliceflue.
According to this hypotzeeie, O—derivativee should be formed
with ally'l or benzyl radicals because of. their greet reactiv-
lty, but this 18 not the case, as she n by the eXgnrimELt of
Claieen Linn., 412,210-45, 1925) on ti 1e alkylation oi pFenols.
But rather the opposite View is more provable. Since allyl and
benzyl rnflicnle are dietinguiekecl by their 8113 t veience
requirements and therefore Iold ox' on 0? lg 100:.e1;-, the;r
show a preference for combining with carton to form a stable
combimtion. 1 ever thelese the {.11 mtim oi 13-.o.ice.le and the
ieouerization of enol to keto radicals is neceeaary to explain
the reactions or this lid.

It was found that the formation or O- or C-dorivetive
depend‘ upon a n;mber of factors among which the following
ones are most important.

1. The nature of the alkjlizetinn q;ent---K. Von.Auwers
and Th. Eahr (12011.. 6113, 408-16, 1:328) state that the halides
of such radicale as are characterized by a smell affinity
oomeumption, such as 31151 and benzyl,y'ie1d chie ‘ly C-deriva-
tivee: w11ile thus alk;rla liiie etF1y1 and pregyl, favor the
formation of O-derivetives. This is also a "ueotion of satura-
tion. Claieen states that the looeer the bond between the
halosen and the alkyl radical the more smoothly the reaction
progresses. fie know that unaetuation in the elel rzzdicle on

the carbon atom.adjacent to that one bearing the halosen

results in a comvzr tlvely 103331;? 1131d 3 10 en.

3; Busch (7..Ancew. Chem. 38, 1145-0. 1925) states
that the tendency of berlzyl raulcala towurd C-alkyl3tion of
phenols 1ncr33333 3 th the ixcreuelug su bstltutlcn of the
hydro gem of mot‘m 333 33rbon with 3r r31 gzoup. T3119 it is
possible to obtain et113ra with Co rC“T 1 in nonrdissociatlrg
media, (C§ 5)QCZTC1 wields only t‘e otrboz derivatives.

2. The nature of two solvent or the medium in which

the reactio“ occ 3r3---Solver ts such as water, alcohol, and

 

other oxygen compounds, txat are characterized by a tendency
to d1330313t3, 3r3 331133 31333313t13; 33313 333, 3:33 employed,
give 3-33rivat1ves 33 the 33333333t13r products. Sn the otko“

2

hand. if 3 333-313533L3t133 333133, such 33 3332333, toluene,

\I

or other Shiatuucca 1:521:13}; 33331;»: 123 ozgpen, :13 B333, C-Czeri-
vatlvem 31 1 L3 53r33d.

Claisen and LLGtfia (Ser., 53E, QVS, 1925) found that
when alkali phenolatcs were treated 13 : w-dlssoclatl 3
media with 333:3uratefl alkyl halides, th3re 335 obtained
almost 3: tirzl; 33rbon dcriv t3 V88.

0131333, Framers, Io 3h, 13' .d Tletze (A.n3., 4 ,210-45,

25) foxmd that 311;]. bromide and 3361113: p-cx‘esolztte in

met 31 alcohol :pvo 90 5 of p—creaol :llyl 3t33r. while in
benzene tiere r3sulted 30 fl O-ullgl Karivativea 33d 80 7
C-allyl deriv.tives.

Thlle it 13 Lot 3483 L3 explain why dissociating
media yléld O-derlv3tives and 313-3L330313t3 * media yield

C-fierlv:tive3, 1t is probably true that reaction media such

as toluene exert a 1033€;31;3 3fLect on the valence bonds

between the 31331 or henzyl radical and the halogen, thus
producing tfia Carbon sunntltution.

According to Kichael (Tar., 41, 1080-1991, 1908),
there is an interaction betweun the molecules of tLe solvent
and o? the solute find this involves a coastant interchange
between the free and bound molwcules of the solVent. Thus,

for example, if the transformatien cf the comanXEs

(Kate / salvent);::;::xr(;flnfl. solvent)

is accomplished by an increase in entrogy. the solutinn in
this particular solvent will result in lscaerlzution, the .
degree of isomerimatlon deyeuuiug Upon the relative increase
in ButrOyj in any given Case. But this in turn deyenaa
Collectively upon the tutul chance suffered by he various
physical and cheminnl foroaa takiag & Bart in the trans-
formation. It is, theraforo, extremely hard to watabliuh uy
simple relationship between any given physical consta t of

a servant and its power of iwrmerlzz'ztion.

°. Aluminum Chloride as Condensang.fl3cnt

Since the discovery of the fricdsl~€rofts rooction
in 187? (Cong. roud., 84. 392~953 Ber., 10, 1180), aluminum
chloride has found wide application in organic synthesis.

It is used in slnost every type of change which involves the
elimination of hydrogen chloride, bromide, or iodide. Its
nature in effecting condensations has not been definitely
known. It is probable that its action may he explained by one
or a ccmbimzticn of the following theories:

(1) Intermediate compounds.

(2) Cotolytic action.

(3) Dfiiyc‘amticn.

The first view eve held by Ecoseken.(rec. trsv. Chim.,
19, 19-26, 1900; 20. 102-100. 19013 28, 501-014, 1903; 25,
98, 1904; 30, 148-150, 1911) who regresnnted tie ration of
eluminum.chlorido by the following season:

mom / ANY-13 —-—-—»I‘(30(‘.1,A1613

FC’}::1,A1813 { R’EI ”morning / 3:01

P-C’JIZ'JJCls ,1 x1120 --—.z:co:.‘ ,1 A1813 ,1 3:23:30
where R'H regresento an aromatic hvdrocarbon or one of its
derivatives.

The Catalytic action of aluminum ctloride was advocated
by Friedel and Crafts and supported by Cuetmvson and Stool.
Friedel and Crafts assumed the formitiou of an intermediate
compound which “sites with the halogen cougound, regenerating
aluminum chloride, as shown below:

061:6 { A12C16 “COEiBAIQCls I 2'01

10

 

cGzzszL12015 I :01 061151: I 1112016

This theory was for sometime doubted since it was

found that one amount 0: product increased when o large nu

ouantity of ainmin m coloride wee used, which showed that
aluminum chloride could not be a true cctwl3ét. “'stov on
(fier., 11, 2151, lWIS) isoloted a numb r of stable compounds
formed by the union of aluminuzn czzloride with h} dr00“rbon
and haVing t?le formulas flnClU,C~I~ and.AlgClG,GGGH6, whicl
accounts for the neseeeity of using large nuantitiee. From
this, Steele (Trans. Chem. Eoc., 1470, 1903) concludes tist

elumiaum chloride is a true catelys t, diff orh1;; from otler
catel3rets :13 in its tendency to become 11m ctiv e throurh
the iormttirn 033' Stable co wounds with Cert-11:1 suhetag-tzces
produced doting the reaction.

Norrie (Ind. Eng. Chem., 13, 184, 1924) also studied

tie catnly tic action of aluminum chloride. Tripheoyl mo‘h3l

chloride, etfiyl other and similar compounds were used in the
condenczatlcn.

The corroratiu“ actLon of alum}.num chloride is
illustrated by the work of Eerz s: d Melt}: und'slso by that
of Jaubert . I.orz a. 1d iHei h (Ber., 14, 1:7, 1881) treated
phenol with aluminum chloride and obtained oi; hour-*1 eti- zer.

Jaubert (C mt. rend. 132, 134, lQOl) prepared aniline and

p-toluidine from hydroxyl aminewhyorochloride end benzene.

11

3. Fe Izznlntion of Thexola

The work of Kollar112 and Forts from lG?l-l€?5
(7tsclu‘. Charm, 1:371, 705; ram, 5, 4-1.7; 6, 4-16) marked
some of the earliest work down on benzylation of pherola.

They prepared dialeryl kotono, using fiboapborlc nuiydrido

an dehydrating agent

(Jazz. mien. lio’llo' I, 589; II, 1.6)

synthesized bcn"3l nhenol 92d ben"vl anisol respect 1 ely by

A

the action of Lenayl chloride on phenol std 9FL1"101 in the

’0-

presenoo of 2 no turnixgs. In 18?5 ”atorno, in connection
with ?lletti (ibid., 5, LL11, used a mixture of acotic and
sulfuric roids snrboou of give, 93 tho catalytic agent. In
the prepvration of bonxylatod or sol Lcho goats later, zinc
was egoin used by Patorno 2nd Lazzarv (6332., 8. 805).

In 1981 Lfinhnnnn (39r., 15, 152) aged zinc chloriao
in lo canoe ' “ti :n of bonnyl phenol, while zinc was used
in Pater} o' s expo: 1110113111 1.81717. Izzcidontly Liehmann raised
the ouestion as to who her tLe zinc or the ziac chloride
we the 9.01.1179 catalyst, as in Paterno’a exi'orimcxtt. zinc c
Chloride could be easily formed from the zigc and the free
H01 found in bonzyl chloride. he also oLowsd from his own
observations thr=t a very small nuantity o: zix.o chloride
could catalyze t1o ram ction.

Perkins and flou;ken80n (J. 0.3., $7, 721, 1880)
prepared boozyl {tonyl acetate by treating b03231 chloride

filth phonyl acetate in the presence of aluminum chloride.

12

The to'k n 0936333.;11833 of “13;“uic alcohols with
aromatic comgounds using alleinum calor3d3 as a dehydrating

‘

.1 N: ,.., .. ‘! . .‘
a$ent was hwy LAOHH McIulfi

x—J

$13 \1303 Taste :1 and his helpers
tnfipzatucir research along this 1133, which 31311 *0 taken
up in detail in the next section. They obta1ncd i‘air y gcod
rcle ‘tn 51% mag: ?rieicl THC Crrfts (J. Chem. Scc., 41, 116.
1682) stated that their roam tlcn 13 DBL: 113 133 C3 wijle in

the presence cf congeunds w3111:2112 the 3rcup 03 or 0?.

13
4. The Iork of Huston

In 1916 Huston and Friedemann (J. A. Chem. $00.. 38,
2527) condensed.benzyl alcohol and benzene by the use or
.snhydrous aluminum chloride as a dehydrating agent. They
obtained.diphenylmsthsns as the principal condensation pro-
duct besides a certain.amount of orthotand para dibenzyl-
benzene: and other hydrocatbons among which use anthraceno.

Tao years later Huston and Friedemann (J..A. Chem.
800.. 40. 785) applied the come reaction to the secondary
aromatic slodhols, tertiary hydrocarbons being the principal
products. With benzene the reaction is as follows:

ccxzscnmz): ,l can£3 A1013, censcrmcgns I H20
They found that the yield.could be increased by using a
larger quantity of benzene and at low temperature. They
Ilse stated that the yield is better when.fi is an aryl group
then when it is a alkyl group such as methyl or ethyl. the
latter being more depressing.

In 1920 Keaton (Science. 52, 206-7) prepared p-benzyl
phenol by condensing,aromatic alcohols with phenols in the
presence of aluminum chloride at low temperature..As before
noted. benzylphenol had previously been prepared by Faterno
and his helpers, and also by Libhmann, although emuninum
chloride was not used by these investigators.

In 1924 fluston (J. A. Chem. 300.. 46, 2775) applied.
the same reaction to the condensation of henzyl alcohol sith
phenol. anieol and phonetol, and concluded that the phenolic

hydroxyl group does not interfere with the substitution of

14

the benzyl group in the benzene ring.

Two years later Huston and Sager (J. A. Chem. Soc.,

48. 1956) applied this reaction to saturated and unsaturated
aliphatic and aromatic alcohols with benzene and found that,

of the alcoholic derivatives of the aromatic InidrocarE‘vons,

only those in which the hydroxyl is on the carbon atom ad-
Jecent to the ring react. that unsaturated.aliphatic’alcchols,
and saturated aliphatic alcohols up to and including amyl
alcchol do not react. and that unsaturutiou onthc carbon.atom,
adjacent to the alcoholic group, increased the reactivity of
the hydroxyl toward the dehydrating effect of aluminum chloride.

In the some year (1926) Eluston and Bartlett prepared
P-hydrcxyl-l,l-diphenyl pentane from pheuyl butyl carbinol
and phenol dn the presence of aluminum chloride.

By the same method Huston and Strickler in 1927 con—
danced prepyl phenyl carbinol iith phenol and obtained
P-hydroxyl-l,l—diphenyl butane.

Huston, Lewis and Crotemut (J. A. Chem. 500.. 49.

1365, 1927) used phenol tnis time instead of beacons in the
condensation 0d secondary alcohols. They found that the yield
of ethylphen;l carbinol and phenol was 50.95 fl while botzhydrol
and phenol gave a 40 5 yield. This gives further evidence that
unsaturntion on the alpha carbon atom increases the reactivity
of the hydroxyl group, and conseQUontly the yield.

In the same year Huston and Swartout carried out the
benzylation of O-crescl by the use of aluminum chloride on
O-Grcsol and henzyl alcohol and obtained 2-methg1-4-benzyl

phenol along with a small amount of Somethyl-G-benzyl phenol.

15

The yield of 2-mothyl-4, 6-dibenzyl phenol was wheat 19 fl
of the theory. In order to distinguish between the two 130.
neric mono-bensyl derivatives. the investigators benzylated
o-crlool by the method of Clsisen.

In 1928 Huston and Honk benzylsted mete cresol by the
same method. Since in this phenol both ortho positions are
Open.es I811 as the pore, there is a greater possibility for
sabstitution. Three compounds were obtained from the odndenr
lotion: 3-methyl-4-benzyl phenol and 5-methyl~4.6—dibenzyl
phenol. and 5-wethy1—G-benzyl phenol.

Work on the condensation of para cresol was next
ctrried out by Huston.and Lewis in.the same year. Both
aluminum chloride and Clsieen's methods were used in their
investigation. Since in the per: crosol only the ortho posi-
tions to the hydroxyl are open, both methods should give a
Illo- and a di—benzylsted product. This was borne out by the
production of 2-benzyl-4-methyl phenol and 2.6-dibenzyl—4—
methyl phenol. It was femid that using the phenol and alcohol
in the molecular ratio of three to one increased the yield.

In 1929 Huston and flaxfield studied the effect of
varying proportions of phenol cnd.&lC13 on the yields of 0-
and P-benzyl phanol. They found that the yield of the latter
was increased by increasing the amount of phenol, but not
by increasing thetfilCls. One mol of.A1015 did not give higher
yields than.halr a mol.

In lQJO Huston.snd Eldridge obtained the ether as well
as the benzylated phenol from the condensation of 2,6-dichlor
phenol and benzyl alcohol. The ether was identified to be 2, 6

16

2,6-dichlor phony]. benzyl ether. It might be mentioned that
this was the first time that the other had been identified

in any of the previous A1013 condensations.

17

III. The Problem Defindd

The object of this problem can be stated as follows:

i. To prepare. identify. and study the preperties of
acne hydroxy derivatives of ohlorodiphenylmethsne.

2. To prepare also benzoyl derivatives or the above
00111130131115.

3. To establish definitely that O-eubstitution accom-
panies the P—substitution in condensations with Alwsinum ed
chloride.

4. To determine the positions of chlorine entering

into the following groups upon direct chlorination:

C‘lceé’b

Cl

OCHQOOH

18

IV. Experime ntal
A. Condensation by the Claieen.uethod

1. Preparation of 2-hydroxy-2’-chlorodiphenylmethane

The chlorODenzyl chloride neod.in these experiments
Ill prepared by first making ortho chlorototuene according
to the method of fiarvel and no. Elrain (Org, Syn. v01. 3,
pp. 56-35. 1923). This was then chlorinated according to
the procedure used by Erdmann LA. 272, 151. 1892). The
product. a colorleee oil, distilled over at ale-214°.

The dondeneation of chlorobezyl chloride and phenol
by the Claieen.method was carried out in the following
manner. 29.2 g. of phenol was first dissolved in 100 cc. of
totuene, to which 7 3. of finely cut sodium wee then.added.
The mixture was allowed to stand over night under a refrex
condenser..d white cheesy mass was formed. This was sodium
phenylate according to the following reaction:

06115011 I Ha ....... censor}: / e 112
To this can adddd 50 g. or Vhlorobenzylchlorlde and the
resultant mixture heated at 150° for “an. hour. while con-
nected.to a reflex condenser. This product was shaken out
lith tee portions of water to remove the salt. Difficulty to
leperatc the aqueous salt solution from the Oil product was

sometimes encountered due to the nearly equal densities of

the two. It was found that if a small quantity of water was

taken for the first portion and a rather large quantity for

19

the second portion, the difficulty could.be easily overcome.
‘After the salt had been removed from the oily product. 10
totnene use then distilled off and the residue treated with
Claisen93 alcOholic potash (A. 442, 244, 1925) union dissolves
any free hydroxyl groups. This mixture was shaken out with
petroleum ether to remove any possible others and the extract
'uee saved for further investigation. The remainder was aci—
dified. The dark red oil which separated out was extracted
Iith ether'snd this was dried over anhydrous potassium
carbonate over night. The other wes than distilled off and
the residue fractionated.

Third fractionation

Below 95° 15 mm. Phenol 8.5 3.
95-1400 3 mm. 4.5 3.
140-1500 ' ' 11.. 3.
150—2200 ” ” 4.0 g.
Residue 10.0 g.

The fraction 140-1500. boiling,at 146-151 (3mm.) was
I light green oil. It turned to deep pink on long standing.
From its method of.preperetion this compound must be 24hydrosy.
Biohlorodiphenylmethene:

Clcnzc1 O 01 n OH
Ea i.
’Q U”:

A Parr'Bomb determination for chlorine (J..i. Chem.
300.. 39, 2069, 1917) carried out on this compound gave the

20

fella! ing results 3

6 C
Sample 55 Cl detn. 5 Cl cclc. 0.1”??? ”33
.4382 6- 16.69 16.22 .22. 27‘;
.6266 16.66 16.22 02 4. é 7

The theoriticel percentage of chlorine nae calculated
for one atom of chlorine and the experimental result verifies
this statement.

5 z. of the 2-hydroxy-2‘-chlorcdiphenylmethsne was
reigned out and chlorinated according to the method given
by Reuben (Die tiethcden Der Org. Chem... Vol. III. 799.),
using chlorofm as solvent. A ten per cent excess of the
flheoreticel amount of chlorine required to form the compound
2-mon-3,5,2'—trichlorcdiphenylmetrmne

Cl OI C1 61
I 912 fig 1

It. need. The product did not solidify before it was needed
by B-hydroxy-S, 5.2'atrichlcrodiphenrlmeumne crystals obtained
from condensation of chloratenzyl chloride and 2,4-dichloro—
phenol as described beloe. The solidified product was pressed
between filter papers and recrystallized from alcohol. It
melted at 69.5-60.6°.

A Parr Bomb determination for chlorine was calculated
for three atoms of chlorine and the experimental date confirm

this statement as shown by the following results: @ C
Swen x 61 detn. 9: c1 eelc. MA“? 4’03
.1717 3. 36.64 37.01 I7, 72.

.1876 36.86 37.01 / 7.4 7

21
3. Preparation of 2-hydroxy-3,5.2‘-trlohlor0phenylmeunne

The same procedure previously employed in the
preparation of 2-hydroxy-2'~ohlorophenylmethane was used
in the «Memetlon or 2,4—dlohlorophenol and chlorobenzyl
chloride. The freotlon 147-1550 (a...) 801me to :1 11m:
grey me during e. for smoke" standing. This was pressed
between filter papers and mcryetelllxed in alcohol into
clusters of fine needle: in the form a: rosette. The
compound has e. melting point of 69.5-60.6". From 11.: method
of preparation this compound met be 2-hydroxy-3,5.2'-trl-
chlorodlphenylmethane:

C1 H C1 0 Cl Cl 0 Cl
2 £33 32
U I <3 -- 0‘ be).

CI

The compound upon quantitative analysis an the

following results for its chlorine content: 0,;
Sample 5 c1 detn. % 01 oalo. o./ A/x'“: Art";
.2172 g. 55.91 37.01 .2/. ‘22?
.1313 36.18 57.01 /g. “7

The theoretloel per cent of chlorine no calculated
for tree atom: of chlorine and the experimental result:
beer out this statement.

It 15 seen that this compound oheoh exactly with
fihydroxy- 3, 5,2’otrlohlorod1phenylmethnne obte lned by
ohlorlmtlng 2-hydroxy-2'-chlorodlphenylmotlnne. This is a
further evidence that the eubetltntlon derlutlvee formed by

cnleen‘e condensation of phenol and ertho chlorobenzyl
chloride in 2-hydroxy-2'-ohlorod1pheny1methane.

22

23
3. Preparation of z-chlorobenzylphewlether

This other as prepared by condensing ohlorobenzyl
chloride with phenol in s diseocieting medium of methyl
alcohol instead or in non-dissociating medium of toluene.

The method used see tlmoet identical sith the procedures.
employed in the previous experiments except that the con-
densed product wee frectiomted rimt after the remoml of
the salt. After two fmctiomtione a clear light green oil
distilled over at 140-1450 (2.5 mm). This compound according
to the method of premration must be B-chlorobonzylphenyl-

ether:
c1 1
angel on 00
1’ “‘00-“?- O 2

Thst the molecule contains one atom of chlorine ens

proved by the Parr Bomb determination as follows:

E a.
Sample % Cl dotn. f5 01 oelo. 0.] Ni; ”:3
.3257 g. 15.45 16.22 [4. /7
.2832 15.57 18.22 )2. 5‘ Z-

The petroleum ether extract from the preparation of
2-hydroxy—2‘-chlorodiphsnylmethene one first distilled to
remove the petroleum ether and rimlly fractionated. in oil
of the some color and some boiling point Ins obtained. A Parr
Bomb determination proved the compoind to contain also one

ston of chlorine:

c (1‘.

7“. q f/ 2
Sample 3:: c1 detn. 7; <31 celc. a/M/f; * -3
.4003 16.21 16.22 / 3' L7
.2005 16.87 16.22 7 ' 5 3

Therefore both others are identical, although the
ether formed in the non-dieeociating medium was only a small
fraction or the condensation product, thereon the other
formed in methyl alcohol use exclusively.

25

4. Preparation of Z-chlorOhenzyl-2,4—dichlor03henylether

In. he preparation of this other the following amounts
lore used:
2.4 dichlorophenol 25 g.
ohlorobonzyl chloride 25 g.
Soidum 6 a.
Methyl.slcohol 100 cc.
litter eight hours' rationing, the salt in the condenp
nation mixture was shaken out with two portions of water.
The oil solidified instantly. It was fractionated at 2 mm.
The fraction between 150-1750 is pressed‘hetseen filter
papers and recrystallized in alcohol. 19 g. of pure shite
needles was obtained) mp. 61-653". The yield was 43 x.
. The compound according to the method of preparation
mt be 2- chloratenzyl- 2, 4-diohlorophenyle ther .

Cl C1 Cl
CH C C‘fit) C1
02 model...» 235

A Parr'nonb determination for chlorine gave the

following results: CyC;
Sample :33 Cl doth. 59’ Cl Gale. SHIN/7] ”92:3
.2091 36.80 37.01 49/. 67
.2385 36.68 37.01 3‘4: 55"

The theoretical per cent of chlorine was calculated
for three atoms of chlorine and the experimental result

verifies this assumption.

The some other was obtained by froctionating the
petroleum ether extract from the premmtion of 2-hydroxy-
3,6.2’-trici'zlorodigm6nylmet}mm. It has the some crystalline
form and also melted at til-62°. A perr Bomb determination

also showed the three chlorine atoms in the molecule: 5,. 6,
Sample 55 Cl fletn. 5‘ Cl cclc. am ”’7 M93
.1975 g. 36.84 57.01 070.9 9

.1971 30.72 227.01 a? 0. 3‘?

B. Condeiwation by the Huston {ethod

1. Preparation of 4-hydroxy»!'-chlorcdiphenylmemane

The procedure used in this experiment was similar to
that previously employed by Huston in the preparation of
benxyl phenol (J. A. Chem. Soc" 46. 2775). so 3. or chloro-
benxyl chloride and 87 g. of phenol tore placed in a glass
cylinder uhich contained 200 cc. of petroleum ether. The mix-
ture was vigorously stirred by means of e meclmnical stirrer.
21 g. of freshly ground anhydrous aluminum chloride res added
in call portions. The reaction was not as violent as in
other experiments of this type. The temperature did not rise
above 27". Stirring was continued for half an hour after all
the aluminum chloride had been added. The reaction mixture
was allowed to stand until all the hydrochloric gas had been
siren off. Two layers were formed with petroleum other on
top and a pinkish my oil at the bottom. The whole mass m
decomposed by pouring on cracked ice to which some hydrochloric
acid (1:1) had been adddd. The petroleum other layer was
separated out and distilled. The water and oil portion was
extracted with other. To this extract was added the residue
obtained from distilling off the petroleum ether. The whole
as dried over potassium carbonate and allowed to stand over-
night. The ether was then distilled off and the remined frec-
tionated at Sam.

28

Third fractionation

Below 75° (phenol) 48.5 g.
75-140° 6.0 3.
140-1500 10.0 "
150.1700 15.0 "
170-25300 0.0 "
Feaidue 3.0 ”

The fraction 150-170° solidified.sfter several hours
standing. It was pressed between filter papers and recrystelp
lined from ligroin. 10 3. of clusters of white short needles
as obtained; m. p. 68-69°. A Perr Bomb deternimtion showed

thet there is one chlorine etom in the molecule: C<1
Sample of 01 «lots. 5 01 celc. emu/{774%}
.2170 15.85 16.22 9. (9%
.2213 10.04 16.22 /0. c7/

The filter papers were extracted with other. from
which 4 g. or oil boilingzet 140-1500 was obtained. This
use combined with the original.ldo-l50° fraction.end ro-
fractionstsd, giving 13 g. of a purer product which resembled
the ortho compound prepared.by the Cleison method. The above
crystallized compound, therefore, must be the pure compound,

dehydroxy-2'-chlorodiphenylsethsne:

Cl 01

011201 ,1 : on <3an

A bigger yield of the 13am timn the ntho commund
was observed in en ee~uent coedexm t13ns eh n larger quan-
tities vere used. iiuch resinous material be 3. 13.3 between 170-
2200 (333.) was 3130 obtained from the ovuuouoatLJq p1 oduct.

'30 prove theater or not the 140—1530 (3:2:3.) fraction
was the ortho 033)c*nd, a Ear: Bomb Rotcrminution was run.

it gave the follou 1*“; results. showing the compourul to con-

tain one chlorine atom la the mOIBCLle! $21. 1
‘ Sample :3 Cl data. ,“3 51 3.110. 6/M/7A";
.2923: 6.14. 16.22 /0. 5/
.3540 3.8.40 16.22 M , 3 f

For further evidence, 5 3. of the product was chlo-
rinated and the melting point determined. It melted at 59.5-
60.5° which checked exactly with that of 2-hydroxy-3,5,2'-
trichlorod iphe‘z Mime theme .

Fae structtre of the para compound was proved by the
same method The-following were the resulte of the chlorine

determination, calculated for one etl>m of chloziue.1n the

-moIecfil§?
Sample ~ -- ' :3 C1 tie-tn." 55 Cl cellos
.2170 "‘“'15.85' "”'"" 15.22
216~w0~0 - 16.04VWNM ”m«w~15.22

Theé>5 g. of the compound wee chlorinated. The pure
crystals‘x‘n'élted at 86.5-87.5": which checks with the melting
point of the precinct prepared by condensing 2,6—dichloro-
phenol oi h chlorobenzyl chloride, as described below. Thero-

tore, the chlorinated product must be 4-hydrozy-3,5,2'-tr1-

chlorodlphenylme thane :

01 01
02120011 I 012 __..... OCHZ

Q

01

1

30

OH

31

2. Preparation of 4—hydroxy- 3,5.2'otr1chlorod1pheny1methano

The procedure used uae'almilor to the one described
above. The following amounts were used:

Chlorobenzyl chloride 50 g.

2,6—dlchlorophenol 54 3.
Aluminum chloride 21 g.
Petroleum other 200 cc.

Second fractionation gave the following results at

a mu.
Below 110° Phenol 51 g.
110-160° mostly phenol 19 "
loo—200° 27 "
zoo-220° 3.5 '
Residue 51 '

The fraction loo-200° one pressed between filter papers
and recrystallized from 113mm. 15 3. of white needles molt-
1113 at 86.5-87.5° one obtained. From the method of preparation
this compound must be 4~hydroxy-5,5,2'-trlchlorophonylmethanez

c 01 01
«z: 01 1 on on
2 {Q on ........ 0 2Q).
1

A Parr Bomb deter-mimtion for chlorine mvo the

following results:

(2 C.
~ .I3_, ”’1
Sample 23 c1 detn. 5'2; 01 oalo. 0./ No“; ‘13
.2025 36.7? :57 .01 (20 . 5/ 7

02072 56.84 57.01 7/. S L}

32

The theoretical per cent of chlorine wee calculated
for three atoms of chlorine and the experimental result

bears out this statement.

c. Esterifioation

The benzoyl derivatives of (l) 2-hydroxy~2’-chloro—
diphenylnstlnne, (2) 4-hydroxy-2'-¢hlorodiphenylmothano.
(3) 8-hydroxy-3,5.8'-trichlorodiphenylmsthane. and (i)
hhydroxy- 3, 6,2'-trichlorodlphenylmethane were prepared
by dissolving 2 g. of the phenols in 5 cc. of pyridine
and adding calculated amount of benzoyl chloride. The
following esters indicate the compounds respectively formed:

(1) {:90112 9 b. p- 173-1760
co

at 2.5 mm.

1
donOgC) m. p. 64.5-65.5"

’
,/

(2)

(s) 1 c1
10ml m. p. 81-822"

CO

G) 1
( <30! C) m. p. ee—e7°

0

34

‘V. Summary

1. The tailoring compounds were prepared and

identified:
a. 2-hydroxy-2'-chlorodiphenylmethane.
b . 4-hydroxy- 2'- chlorodiphonylme them .
c. 2-hydroxy-3,5.2’-trichlorodipnenylmethane.
d. 4-hydroxy-3,5.2’-trichlorodiphenylmethane.
e. Bonzoyl derivatives of the above compounds.
f. 2-chlorobonzylphenylethor.
g. 2-chlorobenzy1-2,4-diohlor0phonylether.

2. In the aluminum chloride condensations both the
ortho and the pore compounds were formed, the bulk of Which
one the para.

3. When the following compounds were chlorinated.
chlorine was found to take the 3,5 (meta) position to
the connecting carbon in the ring containing the hydroxyl:

Cl 0H

““20

Cl

c1101:

Some Hydroxy Derivahves of
Chloro Diphcnyl Meihane

l
CficmOw , ‘
\ C.”
mp. 68-69.
6*

5900
|
Cf>w©°3©
' a . . 64.5-65.5'
C>w<:><' '"P

   

" 0*

0? "up GI 62
6|

“<3" ‘2

0’6.
x k": 0" 9C H (:00 ‘ 80 c1
. wzC) —~—~ wC>
cu Cl
Cl

Imp. 59.5-60.5. m.p. 8| ' 82'

*CI;

 

C!

' OH I
ngHsCOCI
~ .. szQ ————~ CBC
s‘ . 0
G 0 hp. I46 -|5| 3 nun.

I 3 : ' h P' I‘D-I76. 2.5mm.
9 hp. HI- I45. 2.5 mm GO Cl 0

Cl
0
(”599/4 p. 56- 57’
C' ' n /’J//

Quad» / i
CI
mp. ass-575’

Vb
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Phi'ip 5cm

 

 

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ran“ u.i.~¢n thrive. a..~ C
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