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The reaction of styrene oxide with B-naphthol

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The reaction of styrene oxide with B-naphthol

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Content THE HEACTIOH OF SCTBME OXIDE WIfH £ -HAPHSHOL
A Sheeis
Presented to
the Faculty’ of the Graduate School
®he University of Southern California
In Partial Fulfillment
of the Eequireaents for the Degree
Master of Science
Leonard fi. Jules
Auguet 1949
UMI Number: EP41575
All rights reserved
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UMI EP41575
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C Vo 3~1*
This thesis, written by
Leonard _H,_ ..Jules
under the guidance of h..is.. Faculty Committee,
and approved by all its members, has been
presented to and accepted by the Council on
Graduate Study and Research in partial fulfill
ment of the requirements for the degree of
Master of Science
Dean
Date...August,...19.49.
Faculty Committee
Chairman
Chapter
I. Introduction
CONTENTS
II a Historical................................
r ' ~ '
III. Discussion ...................................................
A. The Acid-Catalyzed Reaction of Styrene Oxide
with ft-Naphthol .......... ........ ..........
B. The Uncatalyzed Reaction of Styrene Oxide with
/3-Naphthol. ..........................
C. The Alkali-Catalyzed Reaction of Styrene Oxide
with /^Naphthol............................ ..
D. An Unusual Reaction of an Ester.........
IV. Experimental . . i ........................ ..................
A. Preparation of Styrene Cbdde.............. ..
B. The Acid-Catalyzed Reaction of Styrene Oxide with
$-Naphthol ........... ...................
1. With Excess Naphthol: Formation of 1,2,7,8-Di-
benzo-9-Benzylxanthene, 1-Phenyl-l,2-Dihydronaphtho-
(2,l-b)furan, and 2-Phenyl~1,2-Dihydronaphtho-
( 2,l-b)furan .............................. ........
2. In the Presence of Benzene with Excess /S-Naphthol;
Formation of 1,2*7,S-Dibenzo-9-Benzylxanthene and
1-Pheny 1-1,2- Di hydronaphtho(2,1-b)furan,............
3. In the Presence of Benzene with Excess Styrene Oxide;
Formation of 1-Phenyl-1*2-Dihydronaphtho-(2,1-b)furan
and 2-(2-Hydroxy-l-Naphthyl-2-Phenylet hanol. . . . . .
Chapter
C. Preparation of the Lactone of 2-(2-Hydroxy-l-
Naphthyl)-2-Phenylethanoic Acid . . . . . . . . . . . . 23
D. Preparation of 2-(2-Hydroxy-l-Napht hyl) -2-
Phenylethanol .......... 2^
£. Preparation of 1-Phenyl-l, 2~DlhydronaphthQ-
( 2,1-b) fur a n ................ • 25
F. Preparation of Phenylacetaldehyde............. 25
/
G. Preparation of l,2,7,8-Dlbenzo-9”*BenzyIxanthene .... 26
H. The Alkali-Catalyzed Reaction of Styrene Oxide
with /3-Naphthol: Formation of 2-(2-Naphthoxy)-2-
Phenylethanol and 2-(2-Hydroxy-l-Naphthyl)-2-
Phenylethanol............ 26
1. Isolation of 2-(2-Hydroxy-l-Naphthyl)-2-
Phenylethanol as the Acid Phthalate: Formation
of 1-Phenyl-l, 2-Dihy dr onapht ho (2,1-b) f uran........ 29
2. Isolation of 2-(2-^ydroxy-l-Naphthyl)-2-
Phenylethanol as the Acetate: Formation of
1-Phenyl-l, 2-Ed. hydr onapht ho (2,1-b) fur a n .......... 30
I. Preparation of Ethyl a-Bromophenylaeetate............ 32
J. Preparation of o-( /S-Naphthoxy)-Phenylacetic Acid. . . 32
K. Preparation of a-( ^9-Naphthoxy)-Phenylacetanilide. . .
L. Preparation of 2-(2-Naphthoxy)-2-Phenylethanol. .... 3*+
M. Preparation of 2-(2-Naphthoxy)-2-Phenylethyl
4-Nitrobenzoate ....................................... 35
N. Preparation of Phenacyl Bromide.............. 35
0. Preparation of 2-Napht hoxymethyl Phenyl Ketone .... 35
Chapter
P. Preparation of 2-Naphthoxymethyi Phenyl Ketoxime . . . 36
Q. Preparation of 2,4-Dinitrophenylhy drazone of
2-Napht hoxymethyl Phenyl Ketone ............... 36
R. Preparation of Aluminum Isopropoxide ......... 35
So Preparation of 2-(2-Naphthoxy)-l-Phenylethanol .... 37
T. Preparation of 2-(2-Naphthoxy)-1-Phenylethyl
4-Nitrobenzoate ...... ............ 32
U 8 Preparation of the Acid Phthalate of 2-(2-Hydroxy-l-
Naphthyl)-2-Phenylethanol ........ .......... 35
V. The Reaction of the Acid Phthalate of 2-(2-Hydroxy-l-
Napht hyl) -2-Phenylethanol with Dilute Base: Formation
of 1-Phenyl-l32-Dihydronaphtho(2,1-b)fu ran ...... 35
W. The Uncatalyzed Reaction of Styrene Oxide with /3-
Naphthol: Formation of 2-(2-Naphthoxy)-2-
Phenylethanol. .......... ho
X. Reaction of 2-(2-Naphthoxy)-2-Phenylethanol with
£ -Naphthol in the Presence of p-Toluenesulfonic Acid. ^
Y. Reaction of 2-(2-Napht hoxy)-1-Phenylet hanol with
/9 -Naphthol in the Presence of p-Toluene sulfonic Acid. 4 . 5
V. Summary............................................... 43
Bibliography ........................ 44
CHAPTER I
INTRODUCTION
Olefin oxides are known to react with a large number of compounds
to produce materials in which the oxide ring is no longer present. Such
reactions are usually catalyzed by either acids or bases. For example,
the reaction of propylene oxide with ethyl alcohol is known to proceed
as follows:
CH3-CH-CH2 ♦ C2H50H -----> CH3-CH-CHa * CH3-CH-CH20H
OH 0C2H5 OC2H5
The relative amounts of the isomeric ether-alcohols depend in part upon
the type of catalyst used.
Acids, amines, malonic and acetoacetic esters, Grignard reagents,
phenols, and water react similarly. These reactions have been shown to
be nucleophilic displacement reactions.
The alkali-catalyzed reaction of olefin oxides with phenols appears
to proceed normally to give the expected ether-alcohols. However, the
acid-catalyzed reaction of olefin oxides with phenols, in the few studies
reported in the literature, evidently follows a different pattern, since
the ether-alcohols are not formed. Instead, alkali-soluble materials,
presumably resulting from attachment of the oxide to the nucleus of the
phenol, result. This latter mode of reaction has received very little
attention, and it was the purpose of the present work to elucidate the
oourse of the reaction and the nature of the products.
\/
0
CHAPTER II
HISTORICAL
There are but three instances reported in the literature where
the acid-catalyzed reaction of an olefin oxide with a phenol has been
studied. Price and Mueller (l), in 1944* reported a study of the re
action of cyclohexene oxide with phenol as catalyzed by boron trifluor
ide. These authors reported the reaction gave a p-substituted phenol
in very small yield as indicated below
Presumably the p-cyclohexylphenol was not the initial product but was
the end-product of a series of reactions. Anisole also reacted with
cyclohexene oxide to give nuclear-substituted anisoles.
Sexton and Britton (2) studied the reaction of propylene oxide
with phenol and reported that in the alkali-catalyzed reaction the pro
ducts were the expected isomeric ether-alcohols with the secondary alco
hol being present predominantly or exclusively. However* the acid-cataL
yzed reaction of propylene oxide with phenol gave mostly tars and only
a 6# yield of the isomeric ether-alcohols. They did not report any work
on the nature of the tarry material.
Guss (3)» in his study of the reaction of styrene oxide with
phenol, showed that the alkali-catalyzed reaction gave the expected iso
meric ether-alcohols. The acid-catalyzed reaction was reported to fora
an alkali-soluble mixture whose composition was not studied. The evi-
other
"f " products
-3~
dence would indicate,, however* that nuclear-substituted phenols were
formed o
Thus, it appears that the alkali-catalyzed reaction of olefin
oxides with phenols proceeds as might be expected, while the acid-catal
yzed reaction follows a different course to lead to substituted phenols0
CHAPTER III
DISCUSSION
The acid-catalyzed reaction of styrene oxide with phenol has been
found to give an alkali-soluble mixture (3). This mixture could, pre
sumably, be composed of all the phenols resulting from mono-, di-, and
tri-substitution at the ortho and para positions of phenol. This does
not take into account the possibility of the existence of additional iso
mers that could arise from the two directions of ring opening of the oxide
in its reaction with any given position on the nucleus of the phenol. For
this reason, it was deemed advisable to initiate the study of the course
of this reaction by choosing a phenol, such as 2,4-dimethylphenol or /9 -
naphthol, which has only one likely nuclear position available for substi
tution. While it was originally planned to use 2,4-dimethylphenol in this
work, a delay in the receipt of a shipment of this compound made it exped
ient to examine the reaction with ft -naphthol in the interim. As the in
vestigation with /3 -naphthol progressed, however, it became apparent that
this phenol should be used throughout the entire study. There was no re
turn to 2,4-dimethylphenol.
A. The Acid-Catalyzed Reaction of Styrene Oxide with /?-Naphthol.
From the reaction of styrene oxide with y3 -naphthol, in the pre
sence of a catalytic amount of p-toluenesulfonic acid, l,2,7,8-dibenzo-9-
benzylxanthene (I), 1-phenyl-1,2-dihydronaphtho(2,1-b)furan (II), and
2-(2-hydroxy-l-naphthyl)-2-phenylethanol (III) were Isolated and identified.
Another compound, which by carbon and hydrogen analyses corresponded to
2-pheny1-1,2-dihydronaphtho(2,1-b)furan (IV), was also isolated, but the
-5-
structure of this compound was not definitely ascertained
CH
CH-CH
I
~h
IV
III
Since alkali-soluble products had been obtained from the acid-
catalyzed reaction of styrene oxide with phenol (3)» it was somewhat
surprising to find that the acid-catalyzed reaction of styrene oxide with
%
/3 -naphthol produced, largely, alkali-insoluble products. It was first
thought that this alkali-insoluble mixture, from which three pure com
pounds were eventually isolated, might contain the isomeric ether-alcohols
V and VI, since the normal reaction of olefin oxides with alcohols takes
this course.
/ ^ CH-CH*
HCTs
The designation, HOTs, will be hereafter
used to indicate p-toluenesulfonic
acid monohydrate.
+
°"CH2 -°H0H
VI ^
However, carbon and hydrogen analyses showed this conclusion to be un
tenable* Furthermore, the isomeric ether-alcohols V and VI were subse
quently prepared for another purpose by unequivocal methods and demon
strated to be unlike the compounds isolated from the aforementioned
alkali-insoluble mixture* In addition, these ether-alcohols were not
converted to any compound found in the mixture when subjected to the con
ditions of the reaction, eliminating the possibility that they could
have been intermediates of any sort. This possibility was explored be
cause Kitchen (4) found that acid catalysts effected the rearrangement
of isobomyi 2 , 4-d im ethylphenyl ether to 2,4-dimethyl-6-isobomyl phenol*
He found that isobomyi phenyl ether, bomyl 2,4-dimethyl-phenyl ether,
and isobomyi p-cresyl ether would likewise rearrange to give phenols 0
van Alphen (5) also found that acid catalysts effected the rearrangement
of triphenylmethyl phenyl ether to p-hydroxytetraphenylmethane and tri-
phenylmethyl o-tolyl ether to a-2-hydroxyphenyl- ft , , /9 -triphenyl-
ethane0
the postulation of a ring-opening reaction of the oxide involving the
alpha position of the ^0-naphthol, The isomeric phenol-alcohols III and
The only alternative conclusion that was apparent consisted in
/ \_CH-CH
\ /
These would be expected to be alkali-soluble, however, so the compounds
in question could not have their structures. If these phenol-alcohols
should undergo a cylcodehydration to the furans II and IV under the
conditions of the reaction, then alkali-insoluble products ought to
be found in the reaction mixture.
HOTs
III
II
CH2-CHOH
mQ*m
The carbon and hydrogen analyses were in harmony with this deduction, and
positive identification of II was made by comparison with the authentic
compound independently synthesized,, The structure of IV was inferred
from the carbon and hydrogen analysis and from the presence of II.
reaction, two were thus identified as II and probably IV. The third com
pound was found to possess a molecular weight and a carbon and hydrogen
content consistent with the empirical formula C28H2O0o Furthermore, the
compound was unreactive and did not appear to be readily cleaved by
boiling 55-58# hydriodic acid. Such behavior indicated a very stable
ether linkage was present and excluded a furan structure as a consequence.
This naturally led to the conclusion that a xanthene was a possibility
since styrene oxide is known to be isomerized by acid to phenylacetalde-
hyde (6), and the latter is reported (?) to react with 0 -naphthol to give
the xanthene I0 The necessary confirmatory evidence showed the third
alkali-insoluble compound from the reaction mixture to have the structure I.
From the.alkali-soluble portion of the reaction mixture some of
the phenol^alcohol III was isolated but none of its isomer, VII, was ever
detected. Only when styrene oxide was used in excess could III be found
Of the three alkali-insoluble products isolated from the above
in the reaction mixture, although it might have been present in other
instances* It was shown that III was converted into II under the con
ditions of the reaction* This is very good evidence that III is the im
mediate precursor in the formation of II in the reaction of the oxide
with ft -naphthol.
The structures of 1-phenyl-l,2-dihydronaphtho(2,1-b)furan (II)
and 2-(2-hydroxy-l-naphthyl)-2-phenylethanol (III) were determined by
comparison with the products from the following reaction sequence*
CK— 0 0
CH-COOH
VIII
Li A1H,
HOTs
OH
III
Prom the reaction of ft -naphthol with mandelic acid, the lactone
(VIII) of 2-(2-hydro xy-l-naphthyl)-2-phenylethanoic acid was formed® The
reduction of this lactone with lithium aluminum hydride gave 2-(2-hydroxy-
1-naphthyl)-2-phenylethanol (III), and by refluxing a benzene solution
of III with a catalytic amount of p-toluenesulfonic acid, the furan II
was produced®
The structure of 1,2,7,8-dibenzo-9-benzylxanthene (I) was deter
mined by independent synthesis® It is a known compound and was prepared
by the reaction of phenylacetonitrile with stannous chloride and anhydrous
.10-
hydrogen chloride to give phenylacetaldehyde, followed by the reaction
of the aldehyde with j3-naphthol and anhydrous hydrogen chloride (7)»
By varying the solvent and porportions of reactants used in the
acid-catalyzed reaction of styrene oxide with -naphthol, varying a-
mounts of the foregoing products were obtained, - With excess y9“naPhthol
and no solvent, the isolated products consisted of a 21„5% yield of the
xanthene I, 39% yield of the furan II, and a minor amount of IV; with
excess ^-naphthol and benzene as a solvent, the yields of isolated pro
ducts was 1,5% of the xanthene I and 44ol% of the furan II; with excess
styrene oxide and benzene as a solvent, no xanthene was isolated but a
27o2% yield of the furan II and a small amount of the phenol-alcohol III
were found,, Seme of the postulated furan IV could have been present in
every instance, but it was not isolated as such except as noted above,,
Swem (8) observed from the acid-catalyzed reaction of styrene
oxide with allyl alcohol the formation of only the secondary ether-alco-
holo With this formation as a guide, Swem postulated a mechanism for
the oxide ring-opening under the influence of an acid catalyst. The mech
anism for the opening of the oxide ring, as formulated by Swem, is as
followss
SriCl
-11-
CH-CH
V ‘J
> C6H5~CH— CHa
OH OC3Hs
H
It was reasoned that the electron deficiency around the non-term
inal carbon atom makes the non-terminal carbon-oxygen bond stronger than
the terminal carbon-oxygen bond. The weakness of the latter bond was
considered to direct the opening of the rlng0 It is significant to note
that the mechanism of the oxide ring-opening as proposed by Swem does
not explain the formation of the products observed in this study of the
acid-catalyzed reaction of styrene oxide with $ -naphthol.
The occurrence of the nuclear substituted ^Q-naphthols in the
acid-catalyzed reaction of styrene oxide with ^-naphthol suggests, but
does not prove, that the prevailing mechanism is like that obtaining
when olefin oxides react with aromatic hydrocarbons in the presence of
aluminum chloride (9)«
Be The Uncatalyzed Reaction of Styrene Oxide with B -Naphthol0
The reaction of styrene oxide with -naphthol was repeated with
out an acid-catalyst. The only product isolated was 2-(2-naphthoxy)-2-
phenylethanol (v) 0 Since 92% of the $ -naphthol was recovered, this ex
periment shows that p-toluenesulfonic acid does exert a catalytic effect
on the reaction and also probably affects the course of the reaction,,
C„ The Alkali-Catalyzed Reaction of Styrene Oxide with ff-Naphthola
From the base-catalyzed reaction of styrene oxide with excess
-12-
fi -naphthol, 2-(2-naphthoxy)-2-phenylethanol (V) and 2-(2-hydroxy-l-
naphthyl)-2-phenylethanol (ill) were isolated and identified,.
The product isolated from the alkali-catalyzed reaction of styrene
oxide with phenol consisted of a mixture of primary and secondary ether-
alcohols in 85% yield (3)<. Since only 12.1% pure V was isolated from
the base-catalyzed reaction of styrene oxide with yQ -naphthol, the alka
li-soluble material was inspected for a reaction product. Fractional
crystallization of a base-soluble material from a benzene-petroleum ether
mixture yielded a crystalline compound in 53«2% yield melting at 122°,
the melting point of y0 -naphthol. However, a mixture of this product
and /3 -naphthol melted over a 30° range, while the melting point of a
mixture of the compound and authentic 2-(2-hydroxy-l-naphthyl)-2-phenyl-
\
ethanol (III) was not depressed. This is the same compound that was
isolated as a product from the acid-catalyzed reaction of styrene oxide
with yQ -naphthol.
Compound V was prepared by a Williamson type of reaction of sodium
/3 -naphthoxide with ethyl a -bromophenylacetate to give the sodium salt
of a -( yS -naphthoxy)-phenylacetic acid (IX), followed by the reduction
of the acid with lithium aluminum hydride.
% ^ 0 -CH -ch2 oh
NaOH
CH-CH
-13-
f X X / A T'0Mn
N COOC2H5 p
4. ^ CH-CH.J
X = / Br
/ \ / ^ v / 0~CH~CQ0H
G j a *
X X
IX
O-CH-COONa
CH-C“0
CH-COONfl
O-CH-COOH
1.L1A1H*
2*HaO, H+
Another product, other than IX, was isolated from the reaction of sodium
ft -naphthoxide vdth ethyl a-bromophenylacetate* This compound was
identified by a mixed melting point with authentic lactone (VIII) of 2-
(2-hydroxy-l-naphthyl)-2-phenyiethanoic acido Lactonization probably
occurred during the isolation process,, It is noteworthy that the alpha
position of the /?-naphthol has entered into this reaction*
Compound VI was prepared by the reaction of sodivun J3 -naphthoxide
with phenacyl bromide and subsequent reduction of the ketone with alum
inum isopropoxide0
ONa
+
+
OCH,~C
A C-CH^Br
VI
O-CH, -CH A s. /
!, Al(OC3H7 }3
2, H^O, H+
-14-
This secondary ether-alcohol VI was not isolated from the base-catalyzed
reaction of styrene oxide with ft -naphthol„
The p-nitrobenzoic acid esters of V and VI and the anilide of IX
were also prepared0
The activity of the alpha position of 0 -naphthol is well known.
One recent example to illustrate this point is the experiments conducted
by Tryon, Brown and Kharasch (10). These authors used deutero-ethanol
to compare the rates of exchange of the nuclear hydrogen atoms of various
phenols and phenol-ethers® They found that 0 -naphthol exchanged two
hydrogen atoms, the ethyl ether of £ -naphthol exchanged one hydrogen
atom, while the a-methyl- /9 -naphthyl ethyl ether exhibited no exchange
of hydrogen for deutero atoms under comparable conditions0
Another example is the work of Hardman (ll) who obtained 3-(2-
hydroxy-1-naphthy1)-propionitrile
from the reaction of acrylonitrile with -naphthol in the presence of
sodium hydroxideo However, when benzyltrimethylammonium hydroxide was
used as the base-catalyst, 3-(2-naphthoxy)-propionitrile was formed (12)„
Although alkali-catalyzed substitutions at the alpha position of
yg— naphthol occurred in the reaction of styrene oxide with jQ-naphthol
as reported in this work, Boyd and Marie (13) found that the base-catal
yzed reaction of ethylene oxide and propylene oxide with 0 -naphthol
gave maximum yields of 95 01% and 94°2? 6, respectively, of alkali-insoluble
material* They did not report the finding of any alkali—soluble products0
■15-
These results seem to indicate that not all olefin oxides react toward
(3 -naphthol in the same manner as does styrene oxide0
Do An Unusual Reaction of an Ester»
In an effort to separate III from $ -naphthol more readily than
was possible by fractional crystallization, the phenol-alcohol XII, while
still in the presence of the (3-naphthol, was converted into its acid
phthalate X« It was planned to separate the half-ester X from the
naphthol by extracting X from an ether solution of the mixture with dilute
aqueous sodium bicarbonate and then to regenerate the phenol-alcohol III
by hydrolyzing the acid phthalate X with dilute base0 However, when di
lute sodium hydroxide was added to the bicarbonate extract of X, a solid
separatedo This alkali-insoluble material was shown to be the furan II
by the. lack of a depression in melting point of a mixture of it with
authentic IIo
CH-CHgOd'y^
CH-CH20H
Dioxane
It was definitely determined that the acid phthalate X was not
hydrolyzed prior to the formation of the furan II „ This was shown by
recovering the phenol-alcohol III unchanged after refluxing it with dilute
alkali for one hour0 Furthermore, the ester structure need not be &
phthalate, for the acetate of III was also prepared and hydrolyzed to
IIo By boiling a bicarbonate solution of X, II was precipitated,,
Apparently the bicarbonate was decomposed by heat to the carbonate,
which was a strong enough base to convert the phenolic hydroxyl group
into its anion and cause the reaction to occur,, The conversion of
X to II was demonstrated to be quantitative, since a pure sample of X
prepared from the pure phenol-alcohol III, was hydrolyzed with dilute
base to give a 99% yield of II„
The reaction of the acid phthalate X with alkali to produce the
furan II is pictured as follows:
This is considered to be a nucleophilic displacement reaction, the
carboxylate group of the ester being displaced from the alpha alkoxy car
bon atom by attacking base, which, in the present case, is the anionic
oxygen of the naphthoxy group. The ease which which the furan II is formed
from the acid phthalate X marks the reaction as an outstanding example
among reactions of this typee The spatial configuration of the ester X
0 COO"
y^yCOQ~
X > c o o ’
“17“
is undoubtedly very favorable for cyclization®
Hauser (14) in a paper which considered the various inodes of
reaction of esters with bases, cites the following instances in which
attack by the base on the alpha carbon atom of the alkoxy group occurs0
Adickes (15) obtained dimethyl ether and sodium benzoate by
o
heating a mixture of methyl benzoate and dry sodium methoxide at 175
for twelve hours„ The yield of the ether was 37%o Magnani and McElvain
(16) verified this reaction but were not able to isolate any alkyl ethers
from benzoic acid esters of alcohols higher than methanolo Another re
action of the same type was carried out by King and Wright (l7)o They
o
found by heating the potassium salt of phenol at 190-200 with dimethyl,
diethyl, or dibutyl phthalate that anisole (75#)* phenetole (66%)s or
phenyl butyl ether (76%) was formed, respectively, along with the potas
sium salt of the acido The potassium salt of guaiacol, likewise, reacted
with dialkyl phthalates to give guaiacol ethers0 Wallingford and Jones
(18) reported that various mono-substituted malonic esters were alkylated
by heating their metal derivatives to 125-175° with alkyl carbonates to
form di-substituted malonic esters«
R* 1 R-0 R, R-Q
";c(coor)2 m ♦ '00 > ^c(coor)2 ♦ \>o
R-0 R M-0
The yields of products from seventeen different reactions varied from
less than 10% to 83% 0 Hammet and Pfluger (19) studied the reactions of
several esters with trimethylamine. They found that trimethylamine was
o
methylated slowly at 100 by methyl esters to produce the tetramethyl-
ammonium ion0
R-COOCH3 * (CH3)3N: > R-COCf ♦ (CH3)^N+
It has been suggested (19) that the esters of strong acids, such as
arylsulfonic and sulfuric acid, react in an analogous manner when ser
ving as alkylating agents0
CHAPTER IV
EXPERIMENTAL (20)
A® Preparation of Styrene Oxide.
Styrene Oxide was prepared in 69. yield from styrene, bromine,
and water by the method of Alquist and Guss (2). The crude material
was distilled at 50°/2 ram., n^° 1®533S®
B. The Acid-Catalyzed Reaction of Styrene Oxide with 8 -Naphthol,
1® With Excess B -Naphthol: Formation of 1.2.7.8-Dibenzo~9-
Benzylxanthene (I). 1-Phenyl-l.2-Dihydronaphtho(2«1-b) furan
(II). and 2-Pheayl-1.2-Dihydronaphtho(2,l-b)furan (IV)®'— In a
100 ml® conical-bottom three-neck flask, equipped with a mechanical
stirrer, reflux condenser, and dropping funnel, were placed 21.6 g®
(0.15 mole) of /3-naphthol and 0 .1 g® of p-toluenesulfonic acid®
To the molten, stirred material, at an oil bath temperature of 140-
145°, was added 6*0 g. (0.05 mole) of styrene o9Bi.de over a twenty-
minute period® The solution, which turned dark red and frothed
slightly, was heated and stirred for an additional forty minutes®
The reaction mixture was then cooled, dissolved in 150 ml® of ben-
i 0
zene, and the resulting solution extracted with 150 ml. of sodium
hydroxide. The basic solution was then extracted with 100 ml® of
benzene. The dark-orange benzene solutions were combined and dried,
first with anhydrous sodium sulfate and then with 30 g. of silica
gel. The dried solution was passed through a glass tube, 1 x 90 cm.,
filled with activated alumina. The benzene from the yellowish solu
tion was evaporated under reduced pressure, leaving a yellow solid®
*•20 —
(The yellow solid was digested with hoi ling 80# ethanol (by
volume) until the solid existed as a fine yellow powder. The boiling
mixture was filtered by suction, and the solid was washed with boiling
80# ethanol. This solid was crystallized as eolorlees plates from
glaeial- acetic acid; yield, h.O g. (21.5#)» ®*P* 177-17®°* The melting
point after recxystallization from glacial acetic acid was 178-178.5*.
The melting point of a mixture of this compound and authentic 1,2,7*®-
dibenzo-9-benzylxanthene (I) (7), a.p. 178-178*5°, was not depressed*
This compound was unaffected by boiling for three hours with 55-58#
hydriodio acid*
Analysis* Oaleulated for C28H200: 0, 90.28} H, 5*^3*
mol. wt., 372. Found; C, 90.31. H, 5*75f ®ol. wt. (Beokznann method
in benzene), 35®*
On cooling the afore-described 80# ethanol filtrate to room
temperature, a white solid precipitated. This solid was collected
and, after crystallization from 95# ethanol, 3*5 g. of material
melting at 9^—95° was obtained. The glacial acetic acid filtrate
from the first xanthane crystallization was diluted with water until
no more solid separated. The solid was collected, and a hot 95#
ethanol solution of the solid was treated with charcoal. On cooling,
colorless needles, weighing 1 .8 g. and melting at 93-9^°» separated.
The total weight was thus 5*3 g* (39#)* The solid melting
at 9h-95° was dissolved in hot absolute ethanol, and the
solution was treated with charcoal. On gradual cooling,
colorless needles having a violet fluorescence separated, m*p. 55-
-21,
95o5°o THe melting point of a : mixture of this compound and authen
tic 1-phenyl-l,2-dihydronaphtho( 2, X-b)furan (II), mep0 95-95«5°#
was not depressed0
Analysis: Calculated for CigHg^O: C, 87o78j H, 5<>72o
Found: C, 88„01j H, 5*89°
The ethanol filtrates from II were obtained and diluted
with water until no more solid precipitated. By fractional crys
tallization of a portion of the solid from dilute ethanol, a color
less crystalline material melting at 81-81«,5° was obtainedo
Analysis: Calculated for CjgHj^O: C, 87.78; H, 5»72o
Found: C, 87.95; H, 5.94.
This is presumably the isomeric furan, 2-phenyl-l,2-dihydro-
naphtho(2,1~b)furan (IV;, but no structure proof was undertaken.
2o In the Presence of Benzene with Excess 13 -Naphthol: Formation
of 1.2.7b8-Dibenzo-9~Benzylxanthene (i) and 1-Phenyl-1«2-Di-
hydronaphtho(2,I-b)furan (II). — A solution of 2106 g„ (0o15
mole) of £ -naphthol and 0*1 of p-toluenesulfonic acid in 25 mlc
of anhydrous benzene was stirred and refluxed in a 100 ml. conical-
bottom three-neck flask, equipped with a dropping funnel, mechan
ical stirrer, and reflux condenser, while 6.0 g. (0.05 mole) of
styrene oxide was added over a twenty-minute period0 The solution,
which turned red, was heated and stirred for a total period of one
hour® The reaction mixture was cooled, diluted with 100 ml. of
benzene, and the solution then extracted with 150 ml. of 1$ sodium
hydroxide to remove excess £ -naphthol.
-22-
The benzene solution was dried with anhydrous sodium sulfate
and the benzene evaporated* The brown* liquid residue was dissol
ved in 100 ml. of absolute ethanol* the solution heated to boiling,
and water added until a solid separated* The boiling mixture was
filtered, and the solid was washed with hot dilute ethanol: weight
0.28 g0 (1.15$), m.p« 174-176°o The solid, after being crystallized
from glacial acetic acid, melted at 178-178.5°o The melting point
of a mixture of this compound and authentic 1,2,7,8-dibenzo-9-
benzylxanthene (i), m.p. 178-178.5°, was not depressedo
On cooling of the aforementioned ethanol filtrate to room
temperature, a white crystalline solid, weighing 6.0 g0 (44.1$) and
melting at 90-93°, separated. The melting point of a mixture of a
purified sample of this compound and authentic 1-phenyl-l,2-dihydro-
naph tho(2,1-b)furan (II), m.p. 95-95o5°, was not depressed.
3. In the Presence of Benzene with Excess Styrene Oxide: Formation
of 1-Phenyl-1,2H-)lhydronaphtho (2» 1-b)furan (il) and 2-(2-hydroxy-
l-Naphthyl)-2-Phenylethanol (III). — A solution of 7.2 g„
(0.05 mole) of /3 -naphthol and 0.1 g. of p-toluenesulfonic acid in
25 ml. of anhydrous benzene was stirred and refluxed in a 100 ml.
conical-bottom three-neck flask, equipped with a condenser, mechan
ical stirrer, and dropping funnel, while 6 .1 g. (0.051 mole) of
styrene oxide was added over a twenty-minute period. The solution,
which first turned pink and then pale brown, was heated and stirred
for a total of one hour. The solution was cooled, diluted with
carbon tetrachloride, and extracted with an excess of 10$ sodium
-23-
hydroxide. The solvent was evaporated, leaving a brown, viscous
oil. The oil was dissolved in hot absolute ethanol, and on cooling,
a white amorphous solid precipitated; weight, 3«7 g® (27o2%), m,p.
90-92°. The melting point of a mixture of a purified sample of this
compound and authentic 1-phenyl-l,2-dihydronaphtho(2,1-b)furan (ll),
o
m0po 95-95 < > 5 , was not depressed0
The previously mentioned alkaline extract was acidified with
hydrochloric acid, and the mixture was extracted with carbon tetra
chloride. The carbon tetrachloride was evaporated, leaving a brown
solid. This solid was dissolved in a small amount of hot carbon
tetrachloride, and, on cooling, gray crystals separated. A mixed
melting point identified the crystals as 0 -naphthol. Evaporation
of the solvent left a small amount of solid, from which, by frac
tional crystallization from dilute isopropyl alcohol, needles,
melting at 120-122°, were obtained. The melting point of a mixture
of this compound and authentic 2-(2-hydroxy-l-naphthyl)-2-phenyl-
ethanol (III), m.p. 121.5-122°, was not depressed.
C.. Preparation of the Lactone (VIII) of 2-(2-Hydroxy-l-Naphthyl-2-
Phenylethanoic Acid.
This lactone was prepared by a method similar to the one employed
by Arventi (22). A mixture of 35 g® (0,246 mole) of 0 -naphthol and
25 go (0.164 mole) of mandelic acid was heated in a ten-inch pyrex test
tube at 190-195° for one hour. The reaction mixture was cooled until
solidification just started, and then 50 ml. of 95% ethanol was added
with stirring. The insoluble white lactone was collected, washed with
-24-
ethanol » and dried| weight, 27<>1 go (63,6$), m.p. 180-185°*. Recrystal
lization from glacial acetic acid gave colorless needles melting at 186-
187°o The melting point reported by both Bistrzycki and Flatau (23),
who used 73$ sulfuric acid as the condensing agent, and by Arventi (22)
was 185-187°•
The method of synthesis of the lactone constitutes the only evi
dence for its assumed structureo
D . . o Preparation of 2-(2-Hydroxy-I-Naphthyl)-2-Phenyleth anol (III)»
Five grams (0,0192 mole) of the lactone (VIII) of 2-(2-hydroxy-1-
naphthyl)-2-phenylethanoic acid was placed in the thimble of a Soxhlet
extractor, and 1 06 g, (0 o0423 mole) of lithium aluminum hydride and 500
ml, of anhydrous ether were placed in the 1000 ml, round-bottom flask.
The ether was refluxed until all the lactone in the thimble had dissolved.
The mixture was then chilled in an ice bath, the Soxhlet apparatus re
moved, and a condenser was attached to the flask. Ten milliliters of
water was slowly poured through the condenser to decompose the excess
hydride. Two hundred milliliters of 10% hydrochloric acid was added,
and the mixture was warmed until all of the complex was decomposed. The
two layers were separated, and the ether solution was dried with anhy
drous sodium sulfate® The ether was evaporated, leaving a brovm, vis
cous oil. This oil was dissolved in hot isopropyl alcohol, and the
solution was treated with charcoal. By diluting the hot, yellowish solu
tion with water and allowing it to cool slowly, a pale brown, crystalline
solid separated! weight, 4,8 g, (95$), m,p, 121-121.5°, A hot chloro
form solution of the solid was treated with charcoal, diluted with five
-25-
volumes of carbon tetrachloride, and on cooling, fine colorless needles
separated, m.p. 121.5-122°.
This compound was used in a mixed melting point determination
to identify a product from the reaction of styrene oxide with 0 -naphthol.
J[» Preparation of 1-Phenyl-1,2-Dlhydronaphtho(2,1-b)furan (II) 0
In a 200 ml. round-bottom flask, fitted with a reflux condenser
with a take-off tube (24), were placed 2 .0 g0 (0 o00756 mole) of 2-
(2-hydroxy-l-naphthyl)-2-phenylethanol (III), 0.1 g. of p-toluenesul
fonic acid, and 100 ml. of anhydrous benzene. The solution was refluxed
for one hour, during which time 50 ml. of benzene was distilled off to
remove water formed during the reaction. The solution was then cooled
in an ice bath and filtered to remove the sulfonic acid. The benzene
was evaporated from the solution, leaving a brownish solid. The solid
crystallized as long colorless needles from dilute ethanolj weight,
1.5 g. (80.5*), m.p. 95-95.5°.
This compound was used in a mixed melting point determination
to identify a product from the reaction of styrene oxide with 0 -naphthol.
(See page 20 for analysis) 0
The above cyclodehydration was repeated in the absence of p-tol
uenesulfonic acid. From the solid residue left after evaporation of the
benzene, only a trace of alkali-insoluble furan was obtained. The remain
der of the residue proved to be starting material.
F. Preparation of Phenylacetaldehyde.
Phenylacet&ldehyde was prepared in the manner described by Williams
-26-
(25) from 32 g. (0.272 mole) of phenylacetonitrile, 114 g. (0 .3 mole)
of anhydrous stannous chloride, and anhydrous hydrogen chloride. The
weight of wet, impure product was 8 .2 g.
Go Preparat ion of 1.2.7.8-Dibenzo-9-fienzylxanthene (I).
The xanthene was prepared by the method of Dilthey and Biebert
(7). Anydrous hydrogen chloride was passed into a 500 rale round-bottom
flask containing a solution of 802 g. (0.068 mole) of the crude phenyl-
acetaldehyde and 19.7 g. (0.137 mole) of £ -naphthol in 70 ml. of
glacial acetic acid. At the end of three hours colorless platlets
formed. The solid was collected, washed with acetic acid, and dried;
weight, 1.0 g. (3o95%)» m.p. 177-178°. The melting point after recrys
tallization from glacial acetic acid was 178-178.5°. The melting point
reported by Dilthey and Giebert was 177-178°e
This compound was used in a mixed melting point determination
to identify a product from the reaction of styrene oxide with ft -naph
thol .
The Alkali-Catalyzed Reaction of Styrene Oxide with -Naphtholt
Formation of 2-(2-Naphthoxy)-2-Phenylethanol (V) and 2-(2-Hydroxy-
l-Naphthyl)-2-Phenylethanol (III).
In a 100 ml. conical-bottom three-neck flask, equipped with a
mechanical stirrer, reflux condenser, and dropping funnel, were placed
6.0 g. (0.15 mole) of sodium hydroxide, 21.6 g. (0.15 mole) of -naph
thol, and 25 ml. of water. While the stirred solution was heated on a
boiling water bath, 6 .0 g. (0.05 mole) of styrene oxide was added over
a twenty-minute period. The brown solution was heated and stirred for
-27-
an additional forty minutes, and then cooled to room temperature and
poured into a separatory funnel* The solution, which became opaque
when diluted with 150 ml* of water, was extracted with two 100 ml*
portions of carbon tetrachloride* Ether was not used for extraction
because of the known solubility of sodium /3 -naphthoxide in this
solvent (26)o
The carbon tetrachloride extract was dried with anhydrous sod
ium sulfate, and the solvent was evaporated under reduced pressure
leaving a brown, gummy residue weighing 3«7 go A hot, glacial acetic
acid solution of the residue was treated with charcoal, and when the
solution was diluted with water and cooled, colorless needles weighing
1*5 go and melting at 99-103° separated* An orange oil separated when
the yellow filtrate was warmed, diluted with water, and cooled* The
solution was decanted from the oil, heated to boiling, diluted with
water, and allowed to cool slowly* A gummy, pink solid weighing 1*0 g*
precipitated* The total weight of crude material was thus 2.5 g*
(18,9^)o A hot heptane solution of the combined crude product was
treated with charcoal, and on gradual cooling, colorless needles sep
arated; weight, 1*6 g* (12,1%), m.p, 106-107°* After another recrys-
tallization from heptane, the compound melted at 107-108°, This was
identified as 2-(2-naphthoxy)-2-phenylethanol (V) by analysis and by
virtue of a lack of depression in its melting point when mixed with a
sample of material known to have, the structure indicated*
Analysis; Calculated forCjgHj^Oa: C, 81*79; H, 6.10
Found; C, 81*81; H, 6*30»
-28" -
The basic solution from the carbon tetrachloride extraction was
acidified with hydrochloric acid, and the precipitate was collected by
filtration and washed with water until the filtrate was neutral to
Congo Red0 The solid was steam distilled until y 8-naphthol no longer
came over in th« distillate» The volume of residual water was reduced
to 200 ml0 by distillation, 5&o5 g° (l»0 mole) of sodium chloride was
added to the residue, and the steam distillation resumed until again
0 -naphthol no longer came over in the distillate„ The brown, oily
residue was dissolved in dilute sodium hydroxide, and the solution was
filtered and acidified,, A brown oil separated which solidified on
standing; weight, 8.9 go This solid was dissolved in a minimum volume
of boiling benzene, and about five volumes of petroleum ether was added
while the hot solution was being agitated,. This mixture was cooled to
room temperature, and the clear solution was decanted from the oil which
had separatedo The oil was treated repeatedly in the same manner until
only a tarry residue remained. The combined, decanted solutions were
chilled in an ice bath, thereby precipitating a gummy, brown solido
This material was fractionally crystallized from benzene and petroleum
ether in the same manner described above. The yield of pale-brown, crys
talline solid was 6.7 g. (53®2$), m.p. 119-1210.
A hot chloroform solution of the solid was treated with charcoal
and diluted with ten volumes of carbon tetrachloride. A white solid
separated during cooling. Fine colorless needles were obtained by dis
solving the solid in hot chloroform, diluting the solution with five
volumes of carbon tetrachloride, and cooling, m.p. 122-12205°<> The
-29-
melting point of a mixture of this compound and authentic 2-(2-hydroxy-
l-naphthyl)-2-phenylethanol (III), m.p. 121.5-122°, was not depressed.
Analysisi Calculated for C|8H^6C>2: C, 81.79? H, 6,10*
Found: C, 81.93? H, 6.26.
1. Isolation of 2-(2-Hydroxy-l-Naphthyl)-2-Phenylethanol as the
Acid Phthalate: Formation of 1-Phenyl-l, 2-Dihydronaphtho-
(2»l-b)furan (II). — A repetition of the above reaction be
tween styrene oxide and -naphthol was carried to the point where
the basic solution remained after the carbon tetrachloride extrac
tion. This basic solution was acidified with hydrochloric acid,
and the mixture was shaken with two 100 ml. portions of ether. The
ether solution was dried with anhydrous sodium sulfate, and, after
evaporation of the ether, a brown solid remained. This solid,
together with 7*9 g. ( 0 .1 mole) of anhydrous pyridine and U .8 g.
( 0 .1 mole) of phthalic anhydride, were dissolved in 75 ml. of
dioxane, and the solution was allowed to remain at room temperature
for seventy-two hours. The solution was then poured into a separ
atory funnel and diluted with 400 ml. if ether. This solution was
washed with three 100 ml. portions of 10$ hydrochloric acid to re
move pyridine, washed with 50 ml. of water, and then extracted
with six 100 ml. portions of 5$ aqueous sodium bicarbonate. By
this procedure the phenol-alcohol was removed from the -naphthol
in the form of the sodium salt of its acid phthalate.
The bicarbonate extract was warmed to remove dissolved ether,
and to the warm solution was added 100 ml. of 10$ aqueous sodium
hydroxide to effect hydrolysis of the ester. A solid separated.
Precipitation ofethe solid also occurred after prolonged
boiling of a similar bicarbonate extract or at room tempera
ture, on standing for several hours, after the addition of the
alkali to the bicarbonate extract. The solid material was
filtered off and crystallized from 95$ ethanol to give 6 .2 g.
(50.4$, based on the 0.05 mole of styrene oxide used) if pro
duct, m.p. 94-95°« A hot 95$ ethanol solution of this solid
was treated with charcoal, and colorless needles were obtained
on cooling, m.p. 95-95*5°. The melting point of a mixture of
this product and authentic 1-phenyl-l,2-dihydronaphtho(2,1-b)
furan (II), m.p.95-95*5° was not depressed. It is apparentf
therefore, that ring closure occurred in preference to hydrol
ysis of the ester. These results might also be taken to,in
dicate that none of VII, an isomer of III, was present in the
reaction mixture.
When the free alcohol III (1.0 g.) was treated with 10$
sodium hydroxide (50 ml.) for one hour, the alcohol was re
covered unchanged. This proves that only the ester of the
phenol-alcohol III cyclizes easily, and the hydrolysis of the
ester to the alcohol can not be an intermediate step in the
cyclization reaction.
2. Isolation of 2-(2-Hydroxy-l-Naphthyl)-2-Phenylethanol as
the Acetate; Formation of 1-Phenyl-l,2-Dihydronaphtho(2.
1-b)-furan (II). — The basic solution from an analogous
, -31-
reaction of styrene oxide with -naphthol, after extraction
with carbon tetrachloride, was acidified with hydrochloric
acid, and the mixture was extracted with two 100 ml. portions
of ether. The ether solution was dried with anhydrous sodium
sulfate. Evaporation of the ether left a brown solid. This
solid was dissolved in 75 nil. of dioxane, and 7 .9 g. ( 0 ,1 mole)
of anhydrous pyridine and 10.2 g. ( 0 .1 mole) of acetic anhy
dride were added to the solution. This solution was allowed
to set at room temperature for twenty-four hours. The mixture
was then poured into a separatory funnel, diluted with 400 ml.
of ether and then washed with two 100 ml. portions of dilute
hydrochloric acid and with two 100 ml. portions of water. The
ether was distilled from the solution, and the ester, mixed
with £ -naphthol, was saponified by boiling with 20$ aqueous
sodium hydroxide for twelve houra. This reaction mixture was
extracted with 150 ml. of carbon tetrachloride, and, after
evaporation of the solvent, a brown solid remained. This solid
was dissolved in hot 05$ ethanol, and, with cooling of the
solution, pale-brown needles melting at 94-95° separated.
These weighed 1.2 g, (9.8$, based on the 0.05 mole of styrene
oxide used). A hot 95$ ethanol solution of this brown mater
ial was treated with charcoal, and colorless needles were ob-
o
tained on cooling, m.p. 95-95.5 • The melting point of a mix
ture of this product and authentic 1-phenyl-l,2—dihydronaphtho
(2,l-b)furan (II), m.p. 95-95.5°, was not depressed.
•32-.
This experiment shows that the acetate also can undergo
ring closure to the furan« It is realized that the conditions
of the esterification step could result in reaction of the
acetic anhydride with the phenolic hydroxyl as well as with
the alcoholic hydroxyl. Any formation of di-ester, or of
phenolic ester alone, would be expected to reduce the yield
of furan since the conditions for ring closure would then be
less probable or absent.
I. Preparation of Ethyl g-Bromophenylacetate.
Ethyl a-bromophenylacetate was prepared from 54 g. (0.397
mole) of phenylacetic acid, 3 .0 g. ( 0.097 mole) of red phosphorous,
104 g. (0.65 mole) of bromine, and 46 g. (1.0 mole) of absolute
ethanol according to the method of Anschutz (27). The crude pro
duct was distilled at 126-127°/3 mm., n ^ 1.5375 (literature (28)
20
nD 1.5375). The yield of colorless product was 67 g. (69.4$).
£• Preparation of q-( i9-Kaphthoxy)-Phenylacetlc Acid (IX).
To a refluxing solution of 16.4 g. (0.1 mole) of sodium
$ -naphthoxide and 60 ml. of absolute ethanol in a 200 ml. round-
bottom three-neck flask, fitted with a mechanical stirrer, reflu*
condenser, and separatory funnel, was added a solution of 12.2 g.
( 0.05 mole) of ethyl a-bromophenylacetate and 10 ml. of absolute
ethanol over a period of forty-five minutes. A thick, brown pre
cipitate formed after about half the ester was added. The mixture
was stirred and refluxed for a total period of three hours. Since
-33-
reactions of this type often give the sodium salt of the acid in
stead of the ester (29), the following procedure was used to iso
late the product* The reaction mixture was cooled to room temper
ature, filtered, and the greenish solid washed with absolute ethan
ol. The solid was then dissolved in 150 ml* of water. The color
of the solution was red, and with the addition of solid carbon
dioxide a flocculent precipitate was observed, which dissolved
when the solution warmed to room temperature. A red, gummy mass
precipitated when the solution was acidified with hydrochloric
acid. This material solidified when the mixture was warmed. The
solid was collected, washed with water, and air dried, m.p, 149-
152°, yield, 6.0 g. (43*2$ based on the ester). This 3olid acid
was treated with Nuchar and crystallized from dilute ethanol. It
was recrystallized from heptane to give colorless needles, m.p.
155-155*5°. The neutral equivalent was 278, which is the molec
ular weight of the expected monobasic acid IX.
Analysis ; Calculated for Cj gH^Oj; C, 77*68; H, 5*07.
Founds C, 77.69; H, 5*23.
The ethanol filtrate from t he above reaction mixture was di
luted with 300 ml. of water and extracted with ether* This ether
extract might have contained some of the ethyl ester of the ct~( J3~
naphthoxy)-phenylacetic acid, but no attempt was made to isolate it.
The aqueous solution was treated with solid carbon dioxide, and the
precipitated )§-naphthol was removed by filtration. The filtrate
.taas acidified, and the yellow oil which separated solidified on
-34-
standing j weight, 2.4 g.* m.p. 121-160°. This solid crystallized
as colorless needles from glacial acetic acid, m.p. 186-187°. The
melting point of a mixture of this compound and authentic lactone
(VIII) of 2- (2-hiydroxy-l-naphthyl)i-2-phenylet hanoic acid, m.p. 186-
187°, was not depressed.
K, Preparation of g-(jS-Naphthoxy)-Phenylacetanilide.
The anilide of a -($-naphthoxy)-phenylacetic acid (IX) was
prepared by the usual procedure (30). The crude product was dis
solved in hot absolute ethanol, and the solution was decolorized
with charcoal. On diluting the hot solution with water and cooling,
the anilide crystallized in the form of a cream-colored powder, m.p.
177-178°.
Analysis« Calculated for C2*Hi902Nj C, 81.56) H, 5.42.
Found? C, 81.71) H, 5.51.
L. Preparation of 2-(2-Naphthoxy)-2-Phenyiethanol (V).
This primary ether-alcohol was prepared by reducing 2.0 g.
( 0.0072 mole) of a~(£-naphthoxy)-phenylacetic acid with 0 .3 8 g.
( 0 .01 mole) of lithium aluminum hydride according to the procedure
of Brown and JUystrom (31). The crude solid was dissolved in hot
glacial acetic acid, and the solution was decolorized with char
coal and diluted with water. On cooling, fine colorless needles
formed. The needles were collected by filtration, washed with di
lute acetic acid, and dried) m.p. 104-106°, weight, 1.3 g. (68. 4%).
The compound, after being recrystallized from heptane, melted at
This product was used in mixed melting point determinations
to identify a compound from the reaction of styrene oxide with fi -
naphthol. (See page 27 for analysis)
M. Preparation of 2-(2-Naphthoxy)-2-Phenylethyl 4-Nitrobenzoate.
The p-nitrobeneoic acid ester of 2-(2-naphthoxy)-2-phenyl-
ethanol (v) was prepared by the usual procedure (32)® The crude
ester was recrystallized in the form of cream-colored needles from
95$ ethanol, m.p. 117-117•5°•
Analysis t Calculated for ^25^19O5N; C, 72.63; H, 44.63.
Found: C, 72.83; H, 44.83.
N. Preparation of Phenacyl Bromide.
Phenacyl bromide was prepared by the procedure of Cowper
and Dhvidson (33). The yield of crude product was 76 g. (91$);
m.p. 45-50°.
0. Preparation of 2-Naphthoxymethyl Phenyl Ketone.
This ketone was prepared by a method similar to that of
Fritz (34). A mixture of 14.4 g. (0.1 mole) of /3-naphthol, 75 ml.
of water, 4 .0 g. (o.l mole) of sodium hydroxide, 150 ml. of 95$
ethanol, and 19*4 g* ( 0 .1 mole) of the crude phenacyl bromide was
refluxed in a 500 ml. round-bottom flask for three hours. At the
end of this time the orange mixture was cooled to room temperature
and diluted with 1000 ml. of water. A brown oil separated and
solidified on standing. The solid was filtered off, washed with
-36-
water, and dried by suction. The yield was 15 g. (57%)* An alcohol
solution of the solid was not appreciably decolorized by charcoal;
however, the ketone was readily adsorbed by the charcoal. A white
product melting at 102-104° (m.p. 104-106° reported in the litera
ture (34)), was obtained by leaching out the ketone from the char
coal with boiling 95% ethanol.
P. Preparation of 2-Naphthoxymethyl Phenyl Ket oxime.
The oxime of 2-naphthoxymethyl phenyl ketone was made by the
usual procedure (35). The crude white solid melted at 136-140°.
The compound crystallized in the form of fine colorless needles
from dilute ethanol, m.p. 139-141°. Recrystalliaation from benzene
and petroleum ether gave long white needles melting at 143-144°.
The melting point of the oxime reported in the literature (34) is
144-145°.
Q. Preparation of 2.4-Dinitrophenylhydrazone of 2-Naphthoxymethyl
Phenyl Ketone.
The dinitrophenylhydrazone was prepared by the usual proced
ure (36). About 0.1 g, of the orange-red solid was dissolved in
250 ml. of boiling ethyl acetate, and on gradual cooling, fine
bright-orange needles formed, m.p. 228.5-229°.
Analysis: Calculated for gN^05: C, 65.15; H, 4.10.
Found: C, 65.04; H, 4.16.
R» Preparation of Aluminum Isopropoxide.
Aluminum isopropoxide was prepared by the procedure in
-37-
Organic Reactions (37)• The crude product was distilled at 134-
144°/7 nun® with an oil bath temperature of 190-198°. The yield of
the colorless, viscous liquid was 186 g. (91$).
S. Preparation of 2-(2-Naphthoxy)-1-Phenylethanol (VI).
In a 200 ml. round-bottom flask, fitted with a reflux con
denser with a take-off tube (24), were placed in 2.0 g. (0.0076 mole)
of 2-naphthoxymethyl phenyl ketone, 23 ml. (0.023 mole) of one molar
aluminum isopropoxide in.isopropyl alcohol, and 50 ml. of anhydrous
isopropyl alcohol. The solution was heated on a steam bath until
the reflux, which was taken off slowly, gave a negative test for
acetone (38). A total of 3) ml* of reflux was taken off before the
test was negative. The liquid residue was heated on the steam bath
under reduced pressure until almost all of the isopropyl alcohol wa3
removed. The solid residue was then hydrolyzed by agitating it with
warmed, dilute hydrochloric acid. The mixture became cloudy and a
yellow oil separated. By first cooling in an ice-salt freezing mix
ture and then warming on a steam bath, the oil solidified into a
white solid. The solid was collected, washed with water, and dis
solved in hot dilute acetic acid. On cooling overnight, a white
granular solid precipitated; m.p. 84-86°, yield, 1.76 g. (87*5$).
A sample of the product was treated with charcoal and recrys-
O
tallized from heptane as fine colorless needles melting at 86.5-87 .
Analysist Calculated for CteH, 602t C, 81.79j H, 6,10.
Found: C, 81.70; H, 6.16
-38 -;
T. Preparation of 2-(2-Maphthoxy)-l-Phenylethyl 4-Nitrobenzoate»
A mixture of 0.1 g. of 2-(2-naphthoxy)-l-phenylethanol (VI),
0.2 g. of p-nitrobenzoyl chloride, and 2 ml. of anhydrous pyridine
was warmed until the solids dissolved. The solution was then
allowed to remain at room temperature for twnety-four hours, during
which time a crystalline solid separated. This solid was washed
by decantation with 20 ml. of 10% hydrochloric acid, 10 ml. of water,
and 10 ml. of aqueous 5% sodium carbonate, respectively. The yellow
solid was first crystallized from dilute ethanol. A hot heptane
solution of the solid was then treated with charcoal, and on cooling,
yellow needles separated, m.p. 104-105°.
Analysis; Calculated for C23H19N05s C, 72.63j H, 4.63.
Founds C, 72.72; H, 4.75.
U. Preparation of the Acid Phthalate (X) of 2-(2-Hydroxy-l-Naphthyl)-
2-Phenyle t hanol.
N.
One gram (0.0038 mole) of 2-(2-hydroxy-l-naphthyl)-2-phenyl-
ethanol (III), 2.2 g. (0.015 mole) of phthalio anhydride, and 1.2 g.
(0.015 mole) of anhydrous pyridine were dissolved in 25 ml. of
dioxane, and the solution was allowed to stand at room temperature
for seventy-two hours. This solution was then poured into a separ
atory funnel, diluted with 200 ml. of ether, and the ether solution
washed with two 100 ml. portions of 10% hydrochloric acid and with
50 ml. of water, respectively. Finally, the ether solution was
extracted with three 100 ml. portions of aqueous 5% sodium bicar
bonate. The combined aqueous bicarbonate solutions were acidified
-39-
wit h dilute hydrochloric acid, and the mixture was extracted with
two 100 mls portions of ether* This ether extract was dried with
anhydrous sodium sulfate and the ether evaporated under reduced
pressure. Chloroform was added to the residue, and the mixture
was heated to boiling, cooled,and filtered. Evaporation of the
solvent from the filtrate left a brown, viscous oil which did not
crystallize on cooling. The oil was dissolved in boiling benzene
o
and on cooling, brown crystals separated, m.p. 114-120 . These
crystals were dissolved in boiling, anhydrous benzene and the sol
ution treated with charcoal. On cooling to room temperature,
white crystals separated which sintered at 114° and melted at 119-
o
120 . It was noted from the carbon and hydrogen analyses of this
compound that each molecule apparently contained one molecule of
benzene of crystallization.
Analysis; Calculated for C32H2605: C, 78.35$ H, 5.34.
Found: C, 78.37$ H, 5.41*
V. The Reaction of the Acid Phthalate (X) of 2-(2-Hydroxy-l-Naphthyl)-
2-Phenylethanol with Dilute Base? Formation of 1-Phenyl-l.2-Di-
hydronaphtho(2tl-b)furan (II).
To a solution of 0.1081 g. (0.000220 mole) of the solvated
acid phthalate of 2-(2~hydroxy-l-naphthyl)-2-phenylethanol in 20 ml«
of aqueous 5$ sodium bicarbonate was added sal, of 10$ sodium hy
droxide. Although the solution became cloudy within two minutes,
hydrolysis was hastened by warming. The white precipitate was col
lected, washed with water, and dried; weight, 0.0525 g. (99.0$),
-40-
n.p. 94-95°.
The melting point of a mixture of the product and authentic
1-phenyl-l,2-dihydronaphtho(2,1-b)furan. (II), m.p. 95-95.5°s was
not depressed.
W, The Uncatalyzed Reaction of Styrene Oxide with /Q-Naphtholi
Formation of 2-(2~Na phthoxy)-2-Phenvie t ha nol (V).
A solution of 21.6 g. (0.15 mole) of -naphthol in 25 ml.
of anhydrous benzene was stirred and refluxed in a 100 ml. conical-
bottom three-neck flask, equipped with a dropping funnel, mechan
ical stirrer, and reflux condenser, while 6.0 g. (0.05 mole) of
styrene oxide was added over a twenty-minute period. The solution,
which remained pale-brown, was heated and stirred for a total period
of one hour. The reaction mixture was then cooled and diluted with
100 ml. of benzene, and the solution extracted with 150 ml. of k%
sodium hydroxide.
The alkaline solution was acidified, and the precipitated ^Q-
naphthol was collected and driedj weight, 19.9 g« (0.138 mole), 92%
recovery.
Evaporation of the solvent from the benzene solution left a
brown liquid having the distinct odor of styrene oxide, later was
added to the residue, and the mixture was refluxed to convert the
oxide to the water soluble glycol. The resulting mixture was ex
tracted with ether, and the ether solution was dried with silica
gel. Evaporation of the ether left a brown liquid which solidified
on standing overnight. A portion of the solid was dissolved In hot
95$ ethanolg and the solution was treated with charcoal, diluted
with water, and cooled. A yellow powder melting at 98-104° sep
arated. This material was decolorized with charcoal and crystal
lized from heptane as colorless needles, m.p. 106-107°. A mixture
of this compound and authentic 2-(2-naphthoxy)-2-phenylethanol (V),
o
m.p. 107-107.5 , was not depressed.
X. Reaction of 2-(2-Naphthoxy)-2-Phenylethanol (V) with B -Naphthol
in the Presence of p-Toluenesulfonic Acid.
A solution of 1.0 g. (0.0038 mole) of the ether-alcohol 7,
1.1 g. (0.0076 mole) of /3-naphthol, and 0.1 g. of p-toluenesulfonic
acid in 50 ml. of anhydrous benzene was heated at reflux for one
hour. The solution was then cooled and extracted with two 50 ml.
portions of 10^ sodium hydroxide and washed with 50 ml. of water.
The benzene solution was dried with anhydrous sodium sulfate, and
the benzene evaporated under reduced pressure, leaving a white solid
o
melting at 93-98 . The solid was fractionally-crystallized' from
heptane, giving, for the most part, the ether-alcohol V, m.p, 106-
o 0
107 , and a very small amount of solid, m.p. 165-170 , which was
obtained by evaporation of the solvent after removal of the ether-
alcohol .
Acidification of the basic solution gave 1.1 g. of ^-naphthol
melting at 118-120°.
This experiment was carried out to show that 2-(2-naphthotxy)-
2-phenylethanol (V) did not rearrange to give 2-(2-hydrosxy-l-naphthyl)-
2-phenylethanol (III) under the conditions used in the acid-catalyzed
-42“
reaction of styrene oxide with ^9-naphthol. Some phenolic ethers
are known to rearrange to give nuclear-substituted phenols when
heated with sulfonic acids (A).
Y. Reaction of 2-(2-Naphthoxy)-1-Phe’ nylet hanol (VI) with /3-Naphthol
in the Presence of p-Toluenesulfonic Acid.
A solution of 0.2 g. of the ether-alcohol VI, 0*2 g. of /3-
naphthol, and 0.05 g. of p-toluenesulfonic acid in 15 ml* of anhydrous
benzene was heated at reflux for one hour. The solution was then
cooled, extracted with dilute sodium hydroxide, and the benzene evap
orated under minimized pressure. The glassy, viscous residue was
crystallized from dilute ethanol, giving pinkish solid melting at
o
155-165 * This material was not identified but is possibly the sul
fonic acid ester of the ether-alcohol.
This experiment was conducted to demonstrate that 2-(2-naph-
thoxy)-1-phenylethanol (VI) is not an intermediate in the acid-cat
alyzed reaction of styrene oxide with -naphthol.
CHAPTER V
SUMMARY
The reaction of styrene oxide with /3-naphthol, in the pre
sence of acidic and basic catalysts, has been studied. From the
acid-catalyzed reaction, l,2,7,8-dibenzo-9-benzylxanthene (I), 1-
phenyl-1,2-dihydronaphtho(2, 1-b)furan (II), and 2-(2-hydroxy-l-
naphthyl)-2-phenylethanol (III) were isolated and identified by
comparison with authentic compounds. The isomeric furan, 2-phenyl-
1.2-dihydronaphtho(2,3-b)furan (IV), was also isolated, but its
structure was only inferred. The formation of these compounds was
suggested to be due to direct nuclear attack and demonstrated not
to be due to the rearrangement of the ether-alcohols V or VI.
From the base-catalyzed reaction, the primary ether-alcohol,
2-(2-naphthoxy)-2-phenylethanol (V), and the nuclear-substituted
phenol-alcohol, 2-(2-hydroxy-l-naphthyl)-2-phenylethanol (III),
were isolated and identified. Both of the two isomeric ether-alco
hols, 2-(2-napht hoxy)-2-phenyle t hanol (V) and 2-(2-naphthoxy) -1-
phenylethanol (VI), were synthesized independently.
An unusual reaction of the acid phthalate X of 2-(2-hydroxy-
l-napht hyl)-2-phenylethanol (III) with dilute base to give 1-phenyl-
1.2-dihydronaphtho(2,1-b)furan(II) was observed. This reaction was
distinguished by the relative ease with which it proceeded. It was
shown that hydrolysis of the ester was not an intermediate step in
the formation of the furan II.
BIBLIOGRAPHY
Price and Mueller, Am, Chem. Soc». 66, 629 (1944) •
Sexton and Britton, J®_ Am.. Chem. Soc.» 70 . 3606 (1948)•
Guss, J_a_ Am. Chem. Soc. (1949) In Press,
Kitchen, J_j_ Am. Chem. Soc.. 70 . 3608 (1948).
van Alphen, Rec. Trav. Chlm.« 46, 287 (1927).
Herzog, L., unpublished Master(s thesis, The University of
Southern California, Los Angeles, 1949, p. 10.
Dilthey and Giebert, Bar., 76B, 1086 (1943).
Swern, Billen and Knight, J. Am. Chem. Soc.» 71. 1152 (1949)«
Smith and Natelson, vN Am. Chem. Soc.. « 3476 (1931).
Tryon, Brovai and Kharasch, Am. Chem.Soc., 2003 (1948).
Hardman, Am. Chem. Soc.. 70. 2119 (1948).
Bachman and Levine, J_. Am. Chem. Soc., 69» 2341 (1947).
Boyd and Marie, Chem. Soc., 105. 2117 (1914)•
Hauser, Shivers and Skell, Am. Chem. Soc.» 67, 409 (1945).
Adiekes, Ber»„ 66, 1904 (1933).
Magnani and McElvain, Am. Chem. Soc.. 60. 813 (1938).
King and Wright, Chem. Soc.. 1168 (1939).
Wallingford and Jones, Am. Chem. Soc.. 64. 578 (1942).
Hammet and Pfluger, J_» Am, Chan. Soc., 55* 4079 (1933).
Melting points are uncorrected| microanalyses for carbon and
hydrogen were performed in the Microchemical Laboratories of
the California Institute of Technology, Pasadena, California,
-45-
by G. A. Swinehart, and in the Elek Micro Analytical laboratories,
4763 West Adams Blvd., Los Angeles, California, by S. Elek.
(21) Alquist and Guss, U. S. Patent 2,237,284 (April 8, 1941).
(22) Arventi, Ann, Scl. Univ. Jassy. Pfc. I, 2£, 344-55 (1937).
Am. Chem. Soc. Abstracts. 32. 5339 (1938).
(23) Bistrzycki and Flatau, Ber.. 30. 130 (1897).
( 24) Fieser, Experiments in Organic Chemistry, Second editionj New
York; D. C. Heath and Company, 1941, p. 323.
(25) Williams, J*. Am*. Chem. Soc.. 61. 2248 (1939).
(26) Handbook of Chemistry and Physics. Hodgeman, editor-in-chief,
thirtieth edition; Cleveland: Chemical Rubber Publishing Com
pany, 1948, p. 546.
(27) Anschutz, Ann.. 354. 12? (1927).
(28) Marvel, Prill and De Tar, £4 Am. Chem. Soc.. 6g. 57 (1947).
(29) Fuson and Rachlln, J. Am. Chem. Soc.. 64. 1567 (1942).
(30) Shriner and Fuson, The Systematic Identification of Organic
/
Compounds. Second edition; New York: John Wiley and Sons,
Inc., 1940, p. 132.
(31) Brown and Mystrom, £. Am. Chem. Soc.. 69. 2548 (1947).
(32) Ref. 30, p. 137.
(33) Cowper and Davidson, Organic Syntheses. Coll. Vol. II. Blatt,
editor, second edition; New York: John Wiley and Sons, Inc.,
1940, p. 480.
(34) Fritz, Ber.. 28, 3031 (1895).
(35) Ref. 30, P. 167.
-46-
( 36) Ref. 30, p.143.
(37) Wilds, Organic Reactions» Vol. II. Adams, editor-in-chief,
New York: John Wiley and Sons, Inc., 1944* p. 198.
(38) Wilds, ibid., p. 200.
of S o u t t e r a CaMfcrmia UDeos";

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Creator Jules, Leonard H (author)

Core Title The reaction of styrene oxide with B-naphthol

Degree Master of Science

Degree Program Chemistry

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