close

Вход

Забыли?

вход по аккаунту

?

The oxidation of dioxene and related compounds by mercuric acetate

код для вставкиСкачать
Northwestern
University
Manuscript
Library
The se s
CJnpublished t h e s e s s u b m i t t e d for the M a s t e r ' s and
D o c t o r ' s d e c r e e s a n d d e p o s i t e d in the N o r t h w e s t e r n U n i v e r s i t y
L i b r a r y a r e o p e n f o r i n s p e c t i o n , b u t a r e to be u s e d o n l y w i t h
d u e r e g a r d to t h e r i g h t s of t h e a u t h o r s .
Bibliographical
r e f e r e n c e s m a y be n o t e d , b u t p a s s a g e s m a y be c o p i e d o n l y w i t h
t h e p e r m i s s i o n o f t h e a u t h o r s , a n d p r o p e r c r e d i t m u s t be
g i v e n in s u b s e q u e n t w r i t t e n o r p u b l i s h e d w o r k .
Extensive
c o p y i n g o r p u b l i c a t i o n of t h e t h e s i s in w h o l e o r in p a r t
r e q u i r e s also the c o n s e n t of the D e a n of the G r a d u a t e S c h o o l
of N o r t h w e s t e r n U n i v e r s i t y .
This t hesis by .
h a s b e e n u s e d b y the f o l l o w i n g / p e r s o n s , w h o s e s i g n a t u r e s
a t t e s t t h e i r a c c e p t a n c e o f t he a b o v e r e s t r i c t i o n s .
its
A
patrons
L ibrary which borrows
is e x p e c t e d to s e c u r e
NAME
AND
ADDRESS
.
t h i s t h e s i s f o r u s e by
the s i g n a t u r e of e a c h u s e r .
DATE
NORTHWESTERN UNIVERSITY
THE OXIDATION OP DIOXENE AND RELATED COMPOUNDS
BY MERCURIC ACETATE
A DISSERTATION
SUBMITTED TO THE GRADUATE SCHOOL
IN PARTIAL FULFILLMENT OF THE REQUIREMENTS
for tlie degree
DOCTOR OF PHILOSOPHY
DEPARTMENT OF CHEMISTRY
BY
GEORGE HERBERT KALB
EVANSTON,
ILLINOIS
AUGUST, 1940
P ro Q u e s t N u m b e r: 10101570
All rights re s e rv e d
INFO RM A TIO N TO ALL USERS
T he q u a lity o f this re p ro d u c tio n is d e p e n d e n t u p o n th e q u a lity o f th e c o p y s u b m itte d .
In th e unlikely e v e n t th a t th e a u th o r d id n o t s e n d a c o m p le te m a n u sc rip t
a n d th e r e a re missing p a g e s , th e s e will b e n o te d . Also, if m a te ria l h a d to b e re m o v e d ,
a n o te will in d ic a te th e d e le tio n .
uest
P ro Q u est 10101570
P ublished b y P ro Q u e s t LLC (2016). C o p y rig h t o f t h e Dissertation is h e ld by th e A utho r.
All rights re s e rv e d .
This w o rk is p r o te c te d a g a in s t u n a u th o rize d c o p y in g u n d e r Title 17, U n ited S tates C o d e
M ic ro fo rm Edition © P ro Q u e s t LLC.
P ro Q u es t LLC.
789 East E isenhow er P a rk w a y
P.O. Box 1346
A n n Arbor, Ml 48106 - 1346
ACKNOWLEDGMENT
The author wishes to express his
appreciation to Dr. R. K. Summerbell for
his constant guidance, his valuable sug­
gestions and his encouragement during the
course of this investigation.
PREFACE
This investigation is a study of the reactions of
vinyl-type ethers with mercuric acetate, silver acetate and
cupric acetate.
These ethers are unique In their ability
to reduce mercuric acetate and silver acetate in aqueous
and non-aqueous solvents.
In addition an attempt will be made to correlate the
reactions studied in this Investigation with similar reac­
tions recorded in the literature.
Throughout this discussion dioxane will be used to
designate 1,4-dioxane.
The hexagon will be used to denote
the benzene ring, unless otherwise noted.
TABLE OF CONTENTS
page
I.
HISTORICAL
1.
2.
3.
4.
II.
Reactions of Olefinic C o m p o u n d s .....
1
Reactions of
Aromatic Compounds . . . . .
Reactions of
Heterocyclic Compounds . . .
Miscellaneous Oxidizing Reactions of
Mercury Salts on Organic Compounds
. .
19
DISCUSSION OF RESULTS
A.
Reactions of Dioxene
1*
2.
B.
C.
D.
E.
F.
G.
III.
15
16
Reactions in W a t e r ..................
Reactions in Various Solvents . . . .
Reaction of
Reaction of
Reactions of
Reactions of
Reaction of
Reaction of
26
31
Vinyl E t h e r .............
42
<? -Ethylvinyl n-Butyl Ether .
42
Isomeric Propenylanisoles
•
44
(A>-Ethoxystyrene . . . . . .
47
Phenyl D i o x a n e ...... .... .
49
D i o x a d i e n e ..............
50
EXPERIMENTAL
A.
Reactions of Dioxene
1.
2.
Preparation of D i o x e n e ..............
51
Reaction of Dioxene with Mercuric
Acetate (mol for mol) In water
. .
51
3. Reaction of Dioxene with Mercuric
Acetate (one mol of dioxene to two
53
mols of salt) In W a t e r .......
4. Reaction of Dioxene with Mercuric
Acetate in M e t h a n o l ......... .... .
54
5. Reaction of Dioxene with Mercuric
Acetate in Benzene
.
...........
55
6 . Reaction of Dioxene with Mercuric
Acetate without Solvent ...........
57
7. Reactions of Silver Acetate with
Dioxene
..................
58
8 . Reactions of Cupric Acetate with
D i o x e n e .........................
59
B.
Reactions with Vinyl E t h e r .........
C.
Reactions with # -Ethylvinyl n-Butyl Ether
1.
2.
3.
59
Preparation of the E t h e r ...........
60
Reactions with Mercuric Acetate in
Methanol and W a t e r ............
62
Reaction with Silver Acetate in Benzene
62
ii.
D.
Reaction with. o-Propenylanisole
1.
2.
E.
IV.
V.
65
Preparation of m-Propenylanisole
. *
Reaction of m-Propenylanisole with
Aqvieous Mercuric Acetate
. . . . .
66
70
Reaction with p-Propenylanisole . . . . .
Reaction with Eugenol Methyl Ether
...
Reaction with Isoeugenol Methyl Ether . .
Reactions with
-Ethoxystyrene
71
72
73
1.
2.
73
Preparation of
-Ethoxystyrene . . .
Mercuriation of tv -Ethoxystyrene
with Mercuric Acetate (mol for mol)
Mercuriation of w -Ethoxystyrene
with Mercuric Acetate (two mols of
salt to one mol of the styrene)
75
Reaction of Phenyldioxene ...............
Reaction of D i o x a d i e n e ..................
75
76
3.
J.
K.
63
Reaction with m-Propenylanisole
1.
2.
F.
G-.
H.
I.
Preparation of o-Propenylanisole
. .
Reaction of o-Propenylanisole with
Mercuric Acetate and Silver Acetate
74
S U M M A R Y .................................
78
V I T A ...........................................
80
j
i
I
i
I
(
i
HISTORICAL
Reactions of Olefinic Compounds with Mercuric Salts
i
As early as 1898, Deniges
showed that certain olefins,
for example, hutylene, react with mercuric sulfate in acid
solutions to give mercury-containing compounds.
These mer-
curials were described as yellow solids which react with
8
mineral acids to regenerate the olefin.
Deniges found that
unsaturated hydrocarbons in general react to form mercuria3.s.
Aromatic compounds,
including benzene and thiophene, were
also shown to react with mercuric salts.
Hofmann, et al, carried on an exhaustive investigation
on the reaction of several simpler olefins with mercuric salts.
They found that five distinct types of mercury-containing coms
pounds could be prepared from ethylene.
When ethylene is
passed into a saturated solution of mercuric chloride, 2-chloro
mercuri-1-ethanol (I) is obtained.
CHa
CHS
HgCl
OH
I
When ethylene is bubbled into a nearly neutral solution of
mercuric sulfate,
formed.
a compound,
C 6H 10(S04 )gO^Hg^ (II),
is
When this substance is reacted with a solution of
potassium chloride,
2-chloromercuriethyl ether (III), is
1 . Deniges, Compt. rend. 126,
2. Deniges, Compt. rend. 1 2 6 ,
3. Hofmann and Sand, Ber. 33,
(1900).
1145 (1898).
1808 (1898).
1340 (1900);
Ibid 55, 2696
obtained.
ClHg-CHa-CHa^
j:o
C IHg- C H a -CH
III
Treatment of compound (II) with potassium bromide solution
gives the corresponding bromomercurial.
These authors
found
that this bromide forms 3-oxopentamethylene mercury (IV) on
treatment with an alkaline stannite solution,
Hg
.CHg-CHa.
>
xC H a-CHa
C H a=CH-HgI
V
IV
If ethylene is bubbled into a solution of mercuric ni ­
trate, maintained just at the point of precipitation of mer­
curic oxide by addition of potassium hydroxide in portions
during the reaction,
a mercurial Is formed.
Treating this
mercurial with potassium iodide precipitates I odomer cur I ethyl­
ene (V).
4s j 5 ^6
W i t h propylene, Sand, et al,
was able to show that
two distinct compounds can be formed with mercuric salts.
Typical structures of these compounds are shown by 1-chloromercuri-2-propanol (VI) and 2-bromomercuriisopropyl ether (VII).
C H s-CH-CHa
| |
OH HgCl
CHS
CH3
I
H G ------0 ----- C
I
|
CHa-HgBr
C H aHgBr
VI
VII
4.
5.
6.
Hofmann and Sand, Ber. 33, 1354 (1900).
Sand and Singer, Ber. 5 5 , 3172 (1902).
Sand and Genssler, Ber. 36, 3704 (1903).
Using alcohol instead of* water as the solvent introduces
j
j;
1S
the alkoxy group instead of the hydroxy group.
i Schrauth and Esser
showed that
Thus Schoeller,
/S-ace toxymer curie thy 1 methyl
‘ ether (VIII) is formed when ethylene is passed into a solution
j
of mercuric acetate in dry methanol.
CHg—
*HgC
OCHa
VIII
The structures of the aforementioned types of compound
have "been the subject of much debate.
Hofmann, Sand, et al,
s ,3 ,
assigned definite structures to the addition compounds, imply­
ing that the linkage was the type usually encountered in
ordinary organic compounds.
3
Manchot and Klug criticized Hofmann*s formulae on the
basis of certain general reactions of these mercurials.
One
of these reactions was the immediate regeneration of the ole­
fin when mercurials were treated with concentrated mineral
acids.
These authors preferred to write the organo-mercuri
compounds as simple addition compounds where the mercury is
held in much the same way as water of crystallization by inor­
ganic salts.
They believed the addition formulation would
better account for the rapid reaction with mineral acids.
©, 10
Adams and coworkers
prepared a series of benzofuran
mercurials that are stable toward acids.
7.
8.
9.
10.
Treating o-allyl-
Schoeller, Schrauth and Esser, Ber. 46,
Manchot and Klug, Ann. 420, 170 (1920T.
Adams, Roman and Sperry, J. Amer. Chem.
Mills and Adams, I b i d . 45, 1842 (1933).
2864 (1913).
S o c . 44, 1781 (1922)
phenol with solutions of mercuric salts containing excess
acid results in the formation of 2-halomercurimethyldihydrobenzofuran (IX) according to the reaction:
/ - C H sHgX
0 — CH
\pH a
IX
It is to be noted that the addition follows Markownikoff *s
rule.
Thus, these authors demonstrated that not all mercur­
ials are sensitive to mineral acids.
Hugel and Hibon,
working with higher olefins, were able
to advance an hypothesis for the formation of mercury addition
compounds.
The olefins were found to react faster in methanol
than in water.
Compounds of the type,
CnHsn(OCHs )HgCsH sOs ,
were obtained using methanol as the solvent.
These authors
state that the fixation of mercury is essentially related to
solvolysis and that In eases where mineral acid salts of
mercury are used,
it Is more expedient to neutralize the acid
as It is formed in the reaction rather than allow the acidity
to Increase as the reaction proceeds.
Mercuric salts that
show no tendency to liberate free acid by solvolysis, for
example, mercuric cyanide or mercuric thiocyanates, show no
tendency to react.
Treating olefIn-mercury complexes with
potassium cyanide or potassium thiocyanate results in rapid
11.
Hugel and Hibon, Chem. Abstracts 23, 3898 (1929);
Chimie et Industrie, 1929, 296.
5*
decomposition of the complex into the olefin, mercuric cyanide
and the potassium salt of the mineral acid.
hypothesis further,
To test this
these authors allowed 1-hexadecene to
react with mercuric acetate using glacial acetic acid as the
solvent.
On careful treatment of the reaction mixture with
water an oil separated.
This oil crystallized readily and on
analysis was found to conform to the expected
C 16H Bf3Hg(C2H sO s )s .
Mercuric chloroacetate in chloroacetic acid and mercuric
propionate in propionic acid were found to react analogously.
Mercuric mineral acid salts do not react in this manner.
Mercuric iodoacetate does not react d.irectly with olefin but
must be obtained by reacting an organomercuri salt with
potassium iodide.
The purely inorganic salts must be prepared
in a similar manner,
and show a remarkable tendency for de­
composition into mercuric halide and the olefin.
Hugel and Hibon found that one of the two acetate groups
in the addition compound of mercuric
is quite different from the other.
acetate and hexadecene
It is possible to titrate
one acetate group with standard alkali while the other remains
fixed.
These authors suggest that the structures and reactions
of mercurials be written as follows:
CieHsa
C 16^38
CiqH82
AcO
+
Hg
OAc
NaCl----•‘Cl
NaOAc
Hg
OAc
where AcO indicates the acetate grouping.
xa
Marvel, et al,
were successfxil in isolating optical
12.
Griffith and Marvel, J. Amer. Chem. S o c . 53, 789 (1931);
Sandborn and Marvel, I b i d . 4 8 , 1409 (1926jT
isomers when mercuric salts were added to cinnamic esters.
Thus two isomers of
i’-menth.yl
^S-methoxy- ^-bromomercuri-hydro
cinnamate (X) were isolated.
OCH0
HgBr
■CH----- CH-COOC10H 10
X
j Theoretically four isomers
are possible.
It is not unusual to
j find only two isomers, however, as other reactions are known
'!
!
j that do not give all possible optical isomers.
Isolation of
!isomers by these authors seems to break down Manchot*s idea of
i
jcomplex formation.
It does not, however, detract from the idea
!
IS
}of Piccard (special communication to Marvel et al
) who sug1 gested the compounds be written as follows:
i
1
H
0
i
Xx
J H II
/Hg
!fc=6-C-0-CloH 18
C H a-Cr
!
X
/
i
;where
is the coordination center of the molecule.
It is to
Ibe noted that two optical isomers are possible here.
i
le
Lucas, Hepner and Winstein
postulate a “mercurinium
i
icomplex” as intermediate to the formation of mercurials as
iformulated by Hofmann et al.
Their theory is based on kinetic
]
!studies on the rate of reaction of cyclohexene in carbon tetraIchloride with mercuric nitrate in aqueous nitric acid.
!13.
|
Lucas, Hepner and Winstein,
(1939).
The
J. Amer. Chem. S o c . 61, 3102
data Indicate that two rapid reactions occur,
(a) C eH 10
+
Hg++
(to) C s H 1o
+
Kg++
The structure of the
CeH 10Hg++
+
H a0 = :
and
C sH loHg0H+
+
intermediate they assume
H+.
iscomposed of
the following resonance isomers:
H
C
H
,C+
H
Hg +
Hg ++
CXH
4-H-e
Hg+
G+
H
(a)
c4
*:h 0
o4
a-h
Lj-e
c
H
,C
(*)
Hg
H
C
H
(c)
(d)
++
These isomers then react to form compounds of the type
described by Hofmann.
This theory, therefore, correlates the
theories of Manchot (loc. cit.) and Hofmann,for essentially
there is an equilibrium between the hydrocarbon, Manchot* s type
of addition compound,
and Hofmann*3 type.
Substituting a phenyl group for one hydrogen on ethylene
apparently does not affect the ability to react with mercury
14
salts.
Thus, Manchot
obtained a mercurial by shaking styrene
with a saturated solution of mercuric acetate.
On pouring the
reaction mixture into saturated sodium chloride solution,
a
crystalline compound, 3C8H e •3HgOHCl•HgGls , was precipitated.
16
Nesmeyanov and Freidlind
of styrene.
isolated several mercurials
With one mole of mercuric acetate for each mol
of styrene, 2-acetoxymercuri-l-phenyl-ethanol (XI) was obtained
The mereurl chloride (m.p. 95-96°)
14.
15.
and the mercuri bromide
Manchot, Ann. 4 2 0 , 316 (1920).
Nesmeyanov and Freidlind, Chem. Abstracts 32, 2912 (1938);
J. Gen. Chem. (U.S.S.R.) 7, 2748
(1937).
(m.p. 102-105°) were also prepared.
The acetate (XI) on
reduction with sodium amalgam gave 1-phenylethanol.
OH
H g C sH 30 2
/ ' N A h 4
\ /
OH
h
CH.
1HgC1.
\/
m.p. 77-79°
XI
i
HgCl
XII
With excess mercuric chloride on styrene, compound (XII) was
i!
j obtained.
j
is
ji
Manchot, Haas and Mahrlein
investigated the mercuration
j
j of u> -ethoxystyrene.
It was found that mercuration with
J
;,i
Imercuric acetate was complete in three hours if the reaction
j mixture
was maintained at 50°.
On pouring the mixture into
|sodium chloride a substance, C 6H 5-CB=CH0H*2HgC10H, was found
I
jto separate.
j compound
Nesmeyanov and Freidlind
16
suggest that Manchot*s
was actually of the type shown below.
/v;
CH-0-CsH e
■CH-
The effect of a conjugated carbonyl group was Investigated
1 $ 18 j 10
by Schoeller, Schrauth and Struensee,
who isolated two
types of mercurials from cinnamic esters, namely,
<
16.
17.
18.
19.
^
^y-CH-CH-COOR1
—
<!
)P HgCsH
_TT_n_
)R
sO s
find
\ ....
\CH-CK-C=0
or
FFe:-0
OR Hg-0
Manchot, Haas and Mahrlein, Ann. 417, 93 (1918).
Schoeller, Schrauth and Struensee, Ber. 43, 695 (1910).
Schoeller, Schrauth and Struensee, Ibid. 44, 1432 (1911)
Schoeller, Schrauth and Struensee, Ibid. 4 4 , 1048 (1911)
9.
ij where R may be H or an alkyl radical depending on the solvent
i
i
ij used.
3
This work was recently verified by Matejka,
so
who also
used ethylene glycol as a solvent in addition to a number of
| simpler alcohols.
In the case of the glycol, however, it was
'j
I found that mercurous acetate was formed.
|
The reactions of aliphatic double bonds with mercuric
ij salts, that have been cited thus far,
apparently follow certain
j
j regularities, i.e., the elements of -HgX and -OR (where R is
1
ij hydrogen or an alkyl radical) add across the oleflnic double
|
I bond.
j
This is the typical reaction for a large number of
molecules containing an olefinic double bond.
Some molecules,
| which seem to have the same type of bond, react anomolously
j with mercuric acetate reducing mercuric salts to mercurous
! salts while they,
themselves are oxidized to glycols.
This
investigation deals primarily with these anomolous reactions
i
j so they will be discussed in some detail.
!
!
Balbiano, Paolini and coworkers reported on several
compounds that caused reduction of mercuric acetate to free
i mercury in cold aqueous solution.
Since their work is closely
j allied to the investigations pursued in this dissertation,
■|
I their work will be reported In some detail.
j
81,38
|
These authors found
that,f-pinen& (XIII)
reacted
j with the strichiometricly equivalent quantity of mercuric
!
; acetate to form 2 - h y d r o x y - 6-keto-1-menthene (XIV).
20.
Matejka, Ber. 69B, 274 (1936).
I 21. Balbiano, Paolini et al, Ber. 35, 2994 (1902); Atti. R.
I
Accad. Lincei
V, ii, 65 (1902); J.Chem. S o c . 82i,
|
808 (1902).
| 22. Balbiano, Paolini et al, Ber. 36, 3575 (1903).
XIII
0
XIV
Camphene (XV) on the other hand reacts to form an addition
co m p o u n d .
CHS
CH
l
CHa
C=CH,8
CH,
CH-
C-CHS
I
chb
XV
Balbiano and Paolini with Nardacci
allowed anethol
(XVI) to react with aqueous mercuric acetate for one week.
They obtained as products free mercury and two isomeric
as ,
1 - (p-anisyl)-l,2 propanediols (m.p. 62° and 114-115°)
(XVI).
'CH
CH=CH-CH
V C H - CHl l
OH OH
XVI
XVII
Methylchavicol
88
(XVIII), on the other hand, reacts with
mercuric
acetate to form a mercurial soluble in water and
alcohol,
especially when warmed.
25.
The mercurial is actually
See also Balbiano, Paolini and de Conno, Atti. R. Accad.
Lincei 16, V, i, 477 (1907);, J. Chem. S o c . 9 4 i , 901 (1908)
Kolokoloff, Chem. Cent.
1897 , I, 915.
a mixture of two isomers which can "be separated by prefer­
ential solubility of one isomer in absolute ethanol.
The
ethanol-soluble isomer melts at 81-82°, whereas the insoluble
isomer gives an indefinite melting point at about 55°.
Re­
duction of either isomer with zinc and aqueous sodium hydroxide
gives methylchavicol.
The structures of the two isomeric mer­
curials are assumed to be 3 - (p-anisyl)-2-chloromercuri-l-propanol (XIX) and 1- (p-anisyl)-3-chloromercuri-2 propanol (XX).
/V
V
och3
C H S-CH=CHS
/X
\/
OCHs
C H S-CH
CHS
I
I
HgCl OH
QCH3
/ s
\/
CHg-CH-CH,
OH HgCl
XVIII
XIX
Balbiano and Paolini
XX
prepared the mercury derivatives
of methyleugenol (XXI) by evaporating equimolecular quantities
of methyleugenol and saturated mercuric acetate on a steam
bath.
The product was changed into the chloride and the two
isomeric mercurichlorides (XXII and XXIII) separated by solu­
tion in alcohol.
OCHi
OCH
C H S-CH=CHS
OCH3
OCH
CHo-CH-CHft
I I
OH HgCl
och3
/ X
OCHi
CHo-CH
CH2
I
I
HgCl OH
XXI
XXII
XXIII
These authors found that methylisoeugenol (XXIV) reacted
to form isomeric glycols and free mercury.
These glycols were
as
obtained previously by Kolokoloff.
The melting points of
the isomers are 120-121° and 88-89°.
0CH3
OCH
CH=CH-CH3
XXIV
Manchot
found that eugenol (XXV) formed no definite
isolable product with mercuric
acetate.
He concluded from
his researches that it is the unsaturated side chain that d e ­
termines the course of the reaction with mercuric acetate,
but, irrespective of the position,
tially ethylenic in nature.
the double bond is essen­
In support of this idea he ad­
vanced as an argument the reduction of mercuric acetate by
trimethylethylene.
Balbiano and Paolini with Luzzi
of reactions for safrole (XXVI)
81
reported the same types
and isosafrole (XXVII)
by the allyl and propenyl ethers mentioned above.
0— CHS
0— CH
OH
X
/
0CHs
C H 2-CH=CHS
XXV
24.
C H S-CH=CHS
CH=CH-CHS
XXVI
XXVII
Manchot, Ann. 421, 519 (1919).
as given
13.
85
Tsukamoto
prepared the chloromercurial of safrole u s ­
ing mercuric acetate, water and sodium chloride.
the melting point of the mercurial as 135°.
He reported
Reaction of the
chloromercuri addition product with hydrochloric
acid, aqueous
sodium sulfide or zinc and potassium hydroxide resulted in re ­
generation of safrole.
Iodine in potassium iodide solution
gave the iodohydrin (XXVIII) which reacted with dimethyl aniline
to form the compound (XXIX).
Hydrolysis of the iodohydrin
gave the glycol (XXX) which melted at 76°.
0—
0 ---CH e
G H ft
0
\
N /
/
OH I
|
|
G H 3-C K -C H 3
\
X /
/
OH N - (C H « ) a
I
|
CHa -C H -C H s
xxvm
::xxix
\
/
OH OH
C H g-C H -C H g
xxx
o0 27
Balbiano and coworkers
9
reported that myristicin(XXXI)
and Isomyristicin (XXXII) react to form the expected mercurial
and glycol,respectively, and that asarone (XXXIII) reacts in
the usual manner to form isomeric glycols.
0
C H s0 “
/V
CH*
■ v
CHS-CH=CHS
XXXI
25.
26.
27.
0 — CKa
gh3
0
OCH
CH« 0 —
V
C H =C II-C H S
XXXII
XXXIII
Tsukamoto, J. Pharm. S o c . Japan 50, 7 (1930)5 Chem.
Abstracts 24, 1853 (1930).
Balbiano, Atti. R. Accad. Lincei 1 8 , V, i, 372 (1909);
J. Chem. Soc. 961, 401 (1909).
Balbiano, Paolini, Nardacci, Tonazzi, Luzzi, Bernardini,
Cirelli, Mammola and Vespignani, Atti. R. Accad. Lincei
5, V, i, 515 (1905); J. Chem. Soc. 90i, 186 (1906).
Apiol (XXXIV) was found to react normally yielding the
£ 1,a £
isomeric mercurials,
Isoapiol,(XXXV) on.the. other hand,
reacts with mercuric
acetate to form a mercurial, possibly
2- ( 2 ,5 dimethoxy-3,4-ethylenedioxyphenyl)-l acetoxymercuri-2propanol (XXXVI), in addition to the expected glycol.
GH,
0
CHS
1
2
/ \ -0
C H eO-
\/
-OCH.
0
I
C H e0
£1
3
££
-CHS
'0
— OCHi
-0CHs
I
CH=CE-CHS
CH-
CH-CH3
HgCgHsOs OH
XXXIV
XXXV
XXXVI
This anomolous reaction was explained on the insolubility
of the addition compound in the reaction medium.
This state­
ment implies that Balbiano and coworkers believe that the
mercury addition compound is the intermediate in glycol
formation from the propenyl ethers.
In general, therefore,
a propenyl compound will react
with mercuric acetate to form isomeric glycols, whereas an
allyl compound will form isomeric mercury derivatives.
£8 , £9
Balbiano and Paolini
propenyl and allyl compounds.
used this reaction to separate
In their researches they were
able to separate anethole from methyl chavicole,
safrole from
K
isosafrole, myristAin from isomyristin and apiol from isoapiol
28.
29.
Balbiano, Ber. 42, 1502 (1909).
Balbiano and Paolini, Atti. R. Accad. Lincei 18, V, i,
372 (1909); J. Chem. Soc. 961, 401 (1909).
In these cases only the acetoxymercuri compound of the allyl
compound was formed.
steam distillation,
The propenyl compound was removed by
and the allyl compound was regenerated by
reaction of the mercurial with zinc and aqueous sodium
h y d r o x i d e.
so
Lauer and Leekley
useo the reaction of mercuric acetate
to test the completeness of reaction of substituted phenyl
allyl ethers into propenyl phenols.
The reaction was run on
the methyl ether and the merciirous acetate formed was weighed
to give a quantitative determination of the amount of propenyl
compoimd formed.
2. Reactions of Aromatic Compounds with Mercuric Acetate
When benzene is reacted with mercuric acetate at higher
temperatures in an appropriate solvent phenylmercurie acetate
is formed.
31, S2,SS,34:}B6
Most of the higher homologs can be prepared by reacting
the appropriate mercuric salt with the Grignard reagent of
the desired compound or by reacting the diaryl mercury with a
37 ,36
mercuric salt.
Direct action of toluene with mercuric acetate results
in a mixture of ortho and para isomers which can be separat- :
33,34,66,36
ed.
30.
31.
32.
33.
34.
35.
36.
37.
38.
Lauer and Leekley, J. Amer. Chem. Soc. 61, 3042 (1939).
Otto, J. prakt. Chem. 29,
2 , 136 (18847.
Maynard, J. Amer. Chem. Soc. 46, 1511 (1924).
Dimroth, Ber. 31, 2154 (1898).
Dimroth, I b i d . 5 2 , 758 (1899).
Dimroth, I bid. 35, 2853 (1902).
Whitmore and Sobatzki, J. Amer. Chem. Soc. 5 5 , 1128 (1933).
Hilpert and Gruttner, Ber. 48, 906 (1915).
Kunz, Ber. 31, 1528 (1898).
16.
The structure of aromatic mercurials is t r i f l e d by
phenylmercuric
acetate
(XXXVII).
It is to be noted that these
are true substitution compounds and are not merely additions
of mercuric salts to the double bond as in the aliphatic com­
pounds .
XXXVII
3. Reaction of Heterocyclic Compounds with Mercuric Acetate
Sachs and Eberhartinger
mercuripyridine
prepared the 3,5-dichloro-
(XXXVIII) and the 3-iodomercuripyridine
(XXXJX)
by heating together pyridine and mercuric acetate at 175-180°
for 2*5 hours,
solution.
and pouring the mixture into sodium chloride
Addition of sodium iodide to the mother liquor
precipitates the iodo compound.
ClHg-
-HgCl
\
N
/
XXXVIII
-Hgl
\
N
/
(XXXIX)
A mercurial is formed when 2-anisylindole is reacted
with mercuric acetate in hot ethanol.
40
The mercurial Is
given as 3-chloromercuri-2- (p-anisylindole) (XL) after the
39.
40.
Sachs and Eberhartinger, Ber. 56B, 2223 (1923); see also
McCleland and Wilson, J. Chem. Soc. 1932, 1263.
Boehringer and Sohne, German Pat. 236,893 (1910); Chem.
Abstracts 6 , 1500 (1912).
17.
reaction mixture is poured into sodium chloride solution.
(Compare with anethol.)
-HgCl
^
QCHa
/
N
N
H
H
XL
XZ>H‘
XLI
Ciusa and Grillo
41
prepared tetraacetoxymercurifuran hy
shaking furan w ith aqueous mercuric acetate.
On shaking this
mercurial with iodine in potassium iodide solution,
tetraiodo-
furan is obtained.
Gilman and Wright
prepared a series of furan mercurials
by the direct action of a sodium acetate buffered mercuric
chloride solution on several furans.
The mercuration proceeds
stepwise giving a mixture of 2-chloromercurifuran (XLII), which
is soluble in hot ethanol,
and 2,5-dichloromercurifuran (XLIII),
which is insoluble in hot alcohol.
v
XLXI
-HgCl
C l H g - ^ ^j-HgCl
XLIII
Proof of structure of the mercurial was obtained by pre­
paring a series of compounds from the mercurifurans.
The
following reactions were run on the monomercurial:
41.
42.
Ciusa and Grillo, Gazz. chim. Ital. 5 7 , 323 (1927);
Chem. Abstracts 21, 2686 (1927).
Gilman and Wrigh¥7 J. Amer. Chem. Soc. 5£5, 3302 (1933).
18.
Reactant
Product
Yield
acetyl chloride
2-furyl methyl ketone
21$
furfuryl chloride
difurylmethane
iodine in potassium iodide
2-iodofuran
me thy 1 sulf at e
fur an
aqueous sodium thiosulfate
2- 2 »-difurylmercury
bromine in carbontetrachloride
9 .5$
32$
2-bromofuran
14.5$
In the mercuration of 2-methylfuran an intermediate pro­
duct analyzing for G sH 6OHQ (OH)Cl 'HgClg was isolated.
This
Intermediate formed 5—methyl-2-chloromercurifuran on boiling
in absolute alcdhol.
Summerbell and Umhoefer
prepared the dimercurichloride
of dioxadiene (XLIV) by reacting dioxadiene with a solution
of mercuric chloride buffered with sodium acetate.
mercurial showed no definite melting point,
The di­
and was insoluble
in alcohol, ether, dioxane, benzene and acetic acid.
compound analyzed for C^HgOgHggClg.
The
The structure of this
compound has not been proven, but it is probably the 2,5 or
the 2,6 dichloromercuridioxadlene (XLV or XLVI).
/°\CH
CH
CH
V
XLIV
43.
CH
ClHg-C
/ \ CH
HC
C-HgCl
\/
XLV
ClHg-C
/ \ C-HgCl
HC
CH
\/
XLVI
Summerbell and Umhoefer, J. Amer. Chem. S o c . 61, 3023
(1939); Umhoefer, Ph. D. Thesis, Northwestern Univer­
sity, 1938.
Heterocyclic compounds which, show aromatic properties
react with mercuric salts to form substituted mercurials in
much the same manner as simple aromatic compounds.
Appar­
ently the ether grouping in fur an and dioxadiene has no ef­
fect on the structure of the product obtained in this reac­
tion,
4.
Miscellaneous Oxidizing Reactions of Mercury Salts on
Organic Compounds„
As early as 1892 Tafel
used mercuric acetate and sil­
ver acetate at higher temper atures as a dehydrogen at ing agent.
Thus, piperidine was converted into pyridine, coniine
(XLVII) was converted into conyrine (XLVTII) and tetrahydroquinoline was converted into quinoline by prolonged action
of mercuric acetate in a sealed tube.
h2
H3
Ho
-CHa-CHs-CHs
\ HH/
XLVII
/ - C H o-C K o-C H .
11
XLVIII
45
Leys
*
found that mercuric acetate reacted with the
unsaturated acids, crotonlc, oleic, elaidic and linoleic,
44.
45.
46.
to
Tafel, Ber. 25, 1619 (1892).
Leys, Bull, s o c . chim. 4 , 1 , 262
(1907); Chem.Abstracts
1, 1689 (1907).
Leys, Bull. Soc. chim.
4 , I, 633 (1907); Chem. Abstracts
1 , 2683 (1907).
form mercurous acetate and mercury containing organic com­
pounds.
acids*
Their structures were not proved.
Saturated fatty
on the other hand* formed no mercurous acetate.
Leys
stated further that the main reaction was fixation of mer­
cury to the double bond and formation of the salts.
ulated, however,
He post­
an ethylene oxide type of binding to account
for reduction of the mercuric salt.
4.7
Goswarni and Ganguly
reacted glycerol with mercuric
chloride in a sealed tube for 3 hours at 180° and obtained
glyceraldehyde, formaldehyde and aorolein in addition to mer­
curous chloride.
4:3
Zappi
reacted a series of compounds* capable of enol-
izing* with mercurous nitrate in aqueous solution.
In all
the enolic compounds tested* free mercury was obtained.
This
author considered at first the possibility of salt formation
wit h substances like the enol of acetoacetic ester which
would then decompose to give the mercuric salt and free mer­
cury.
Apparently this is not the case* however* for all
mercurous salts would be anticipated to give free mercury
and this Is contrary to experiment.
The reagent is quite
sensitive* for it has been found to work with slightly enolized substances like butanone*
acetophenone and formamlde.
It is interesting that phloroglucinol and isoeugenol as well
as eugenol give this test.
47.
48.
The reactive structures which
Goswarni and Ganguly, Chem. Abstracts 24, 1048 (1930);
J. Indian Chem. Soc. j6, 711 (1929).
Zappi* Bull. soc. chim. 51, 54 (1933).
give the test are listed as:
OH
-C=C
OH
i
U i
o oII II
te! a
W
(a) enolic substances
(t>) amides
(o) isonitites
isocyanates
G=C=HH
(e) isothiocyanates
S=C=NH
(£) hydroc arbons
R-CHS-CH=CHS
(a)
R-CHa-CH=CHR
R-CH CHR
49
Zappi and Williams
showed by absorption measurements
that* in the cases tested, the enolic form is present in the
substances that give mercury from mercurous nitrate.
itional support to the hypothesis,
Add­
that the enolic form is
responsible for the reduction of mercurous nitrate, is based
on the non-re action of e thy If ormate, ethyl oxalate and ethyl
acetate.
Ethy If ormate and ethyl oxalate are known to be good
reducing agents.
These compounds do not give free mercury,
however, because they are not capable of existing in an enol—
ic form.
Dansi and Sempronj
found that methyl ethyl ketone,
methyl hexyl ketone and methyl nonyl ketone give the Zappi
reaction.
curials,
49.
50.
Yellow intermediate compounds, assumed to be m e r ­
are formed when p-tolyl methyl ketone and ace to-
Zappi and Williams, Bull. soc. c h i m . 51, 1258 (1932).
Dansi and Sempronj, Chem. Abstracts 28, 1331 (1 934;,
Grazz. chim. ital. 6 5 , 560 (1933).
phenone are made to react with, mercurous nitrate.
These
yellow solids decompose on heating to give nitrous fumes
and free mercury*
51
Zappi and Manini
explain the reduction on the basis
of an equilibrium between mercurous nitrate, mercuric nitrate
and free mercury,
according to the equation
HSa(NOe )a —
Hg
+
Hg(NOa )a
Mercuric nitrate is assumed to react with the e n d to form
relatively insoluble complexes,
to the right*
thus driving the equilibrium
Isolation of the products of the reaction
would determine the correctness of this hypothesis.
Connor and Van Campen
reported that mercuric chloride
or mercuric acetate in alcoholic solution forms white pre­
cipitates with enolic-type compounds.
Small amounts of so­
dium ethoxide are added to the reaction mixture, presumably
to increase the amount of enolic form.
The compounds tested
are similar to those of Zappi (loc. cit. ) but the reaction
is more limited in scope.
It works well only on neutral
compounds containing carbon, hydrogen and oxygen.
The test
is specific for structures,
0
II
H- c -C-R
XLIX
51.
52.
and
R0
iif
X-CH-C-OR
L
Zappi andManini, Chem. Abstracts
33, 2063(1939);,
Chem. Zent. (1939), I,3427; Anales.
assoc, quin,
argentina 26, 89 (1938).
Connor and Van Campen, J. Amer. Chem. Soc. 58, 1131
(1936).
23.
where Y is a labilizing group and R is hydrogen,
group,
an alkyl
or an aryl group.
These authors postulate the formation or mercury com­
pounds whose structures have not "been determined.
list, however,
They do
the following structure types as possibil­
ities .
COOE+
Hg=C
HO-Hg-CH- (COOE+)s
x COOE+
LI
LI I
(GlHg)s-G-(GOOE+)s
E+OOC.
^COOE+
CH-Hg-CH
E+OOC
^COOEH-
LIII
LIV
GOOE+
COOE+
(
I
— C
Hg — C
Hg
I
I
COOE+
COOE+
COOE+
I
C --I
COOE+
LV
5sa
Indovina and Manfroi
re anted ascorbic acid (LVI)
w it h mercuric chloride.
A compound, C 6H 60 6 , and mercurous
chloride were isolated as the products.
The reaction is of
third order and reaches completion in 36 hours at room temperature.
53b
Mercuric acetate can also be used for this reaction.
Ascorbic acid is an enediol type compound,
so that this re­
action may be related to the Zappi reaction.
The reaction is
reversible so that the compound C QH 606 can be converted ba.ck
53.
a. Indovina and Manfroi, Gazz. chim. ital. .69* 117 (1939).
b. Emmerie, Bioehem. J. 28, 268 (1934).
HO-0=0-015,
I \
HC-0-C=0
I
HO-C-H
I
GHgOH
LVI
to ascorbic acid by treatment with, hydrogen sulfide.
Rao and Seshadri
found that benzoin is oxidized to
benzil by the action of mercuric acetate in water or abso­
lute methanol.
5.
Reaction of Olefins with Silver Acetate and Copper
Acetate
55,
56
Lucas and coworkers
have shown that silver ions
form a nrapid and reversible” coordination complex with ole­
fins.
The coordination compound is assumed to be a reson­
ating structure intermediate between the following three
isomers:
C
C
/+
/
|\
Ag
(a)
x
C
C
/ \ +\
/
X
C = C
/
r "\
Ag
Ag
(b)
(c)
Several monoolefins, diolefins and the unsaturated ox­
ygen - containing compounds listed below - have been tested
and have been found to form coordination complexes.
54.
55.
56.
Rao and Seshadri, P r o c . Indian Acad. Scl. 11A, 25 (1940).
Eberz, Welge, Yost and Lucas, J. Amer. Chem. Soc.
59, 45 (1937).
WTnstein and Lucas, J. Amer. Chem. Soc. 60, S36 (1938).
allyl alcohol
crotonic acid
crotyl alcohol
phenol
croton aldehyde
W i t h biallyl and dicyclopentadiene solid silver complexes
were Isolated.
Silver analyses of the solid complexes In­
dicate a 1 to 1 molecular ratio: of organic radical to sil­
ver salt.
DISCUSSION
4
;3
Summerbell and Umhoefer
found that dioxadiene re­
acts with mercuric acetate to form a dimercurial similar
to that obtained from fur an.
These substances (dioxadiene
and fur an) are essentially aromatic in character so that
the reaction is one of substitution.
Evidences of the aro­
matic ity can be seen in their stability and the variation
of boiling point with increasing unsaturation.
A table
of the boiling points of these series with the ethyl ether
series follows:
Boiling Point (760mm. pressure) in C°
Dioxane
101°
Ethyl Ether
34.5° Tetrahydrofuran
Dioxene
94°
Ethyl Vinyl Ether 35.7° Dihydrofur an
67°
Dioxadiene
75°
Vinyl Ether
32°
28°
Furan
65°
The most aromatic compounds have the lowest boiling point
in all of the cases cited.
Dioxadiene, however,
shows at
least one usual property of aliphatic compounds in its ability to add two atoms of bromine or four atoms of chlo­
rine.
This property is not surprising, for benzene can
be made to add six molecules of bromine under the correct
conditions.
It is interesting that the introduction of
one double bond into the dioxane nucleus decreases the boil­
ing point, whereas in the series the boiling point is in-
creased.
This phenomenon would seem to indicate the pos­
sibility of weakly aromatic properties in dioxene.
In
view of these facts it seemed desirable to prepare a mer­
curial of dioxene and to use this mercurial in the prep­
aration of dioxane derivatives which had not been previ­
ously reported.
The potentialities of this approach are
evident from the work on fur an by Gilman and Wright.
£3
In the first experiments equimolar quantities of dioxene and mercuric acetate solution were mixed together.
Within a minute a white precipitate was formed,
and after
approximately 15 minutes the precipitate began to turn
greyish.
The reaction was accompanied by the liberation
of appreciable quantities of heat.
After 45 minutes the
precipitate, which was grey-black in color at this point,
was filtered from the solution and allowed to stand In
the filter paper overnight.
The next day a small globule
of mercury was noted in the filter paper, indicating that
dioxene had reduced the mercuric mercury to the free met­
al.
In another experiment, using two mols of aqueous mer­
curic acetate for each mol of dioxene, the same phenome­
non was observed, except that the end product was mercur­
ous acetate instead of free mercury.
Accompanying this
reduction was the oxidation of dioxene to glyoxal and
28.
ethylene glycol.
Because of the extreme solubility of
these two substances in water it was necessary to iso­
late them as the osazone and dibenzoate respectively.
Apparently,
the double bond in dioxene is quite suscep­
tible to oxidation by mercuric salts, for the reaction
occurs very rapidly at room temperatures.
These data initiated a search of the literature to
discover whether such phenomena had been observed previ2 3, 2 a
ously.
It was discovered that Balbiano and coworkers,
working with propenyl anisoles, had obtained reduction
of mercuric acetate.
In all the cases investigated,
at
least one methoxy group was ortho or para to the propenyl
group on the benzene ring.
The active structures may be
considered as:
OCH
OCH
CH-CH-CH,
CH=CH-CH
57
By applying the principle of vinylogy
a profound sim­
ilarity between the structure of these compounds and di­
oxene can be seen.
57.
This principle states that the in-
Fuson, Chem. Rev., 16, 1 (1955).
troduction of a -GH=CH- group between a system A-B, in
w hich A is the activating group, to form, A-C=C-B, the
activity of group B remains essentially unchanged.
Re­
moving the -C=C- bond in portions 1 and 2, we obtain the
basic structure of the group
OCHa
/
C
C
n
(a)
(b)
Similarly by removal of the two -C=C- groups
compound the same
structure (b) is obtained.
in the para
One can
see, therefore, that the compounds of Balbiano and co­
workers are intrinsically vinyl ethers, and that the ac­
tive structure is
-0-C=C-. Dioxene has a similar struc­
ture, except that
there are two oxygen atoms
the double bond.
to activate
The activating influence of these two
ether linkages readily explains the rapidity of reduction
of mercuric mercury when compared with the methoxy propenylbenzenes, which usually require from ten days to two
weeks to progress to the same point that dioxene attains
in 45 minutes.
The difference in solubility is probably
also of prime consideration.
30
To discover wh.eth.er the oxidation of dioxene was the
only reaction, mercuric acetate and dioxene in water were
reacted at room temperature to obtain maximum yields.
W i t h one mol c of the acetate for each mol u of dioxene,
the mercury was obtained in 97.3$ of theoretical yield,
glyoxal (as the osazone) in 95*5$ of theoretical yield and
ethylene glycol (as the dibenzoate) in 87.3$ of theoretical
yields.
Using two mols of the acetate per mol of dioxene,
the yield of mercurous acetate was 97.5$ of theoretical,
glyoxal osazone was 98.6$.
In both of these reactions the
mixtures were shaken for .5 hour.
On the basis of these
results it seems that the reaction of dioxene with mercuric
acetate is unidirectional.
Dioxene is apparently a better reducing agent than
glyoxal for the aldehyde was isolated as one of the pro­
ducts of the reaction even though an equimolar quantity of
mercurous acetate was present.
The reaction may be formu^
lated as follows:
0
H SC
|
H n
CH-OAe
CH
II
+
+
Hg(0Ao)a
H 8C
CH
Hg°
CH-0Ac
(1)
CH-OH
CHO
+
+
C H a0H
CHO
H eC
CH-OH
2H0Ac
The reaction mixture is acid by hydrolysis of the mercuric
acetate.
It is possible that the diacetate may have a fi­
nite existence in aqueous solution for it may be reerystalllzed from water.
In one experiment to determine the solu­
bility of the diacetate and its reaction with phenylhydrozine, it was found that the diacetate would just dissolve
in the amount of water used in the mercuric acetate experi­
ments and that there is no noticeable effect on the rate
of precipitation of the osazone.
It was found, also, that these reactions proceed in
methanol solution.
The rate is about as rapid as in aque­
ous solution.
In an attempt to discover the true nature of this oxi­
dation several experiments were performed in dry benzene.
It was found that no reaction occurred when equimolar quan­
tities of mercuric acetate and dioxene in benzene were
shaken for two days.
In another experiment equimolar quan­
tities of dioxene and mercuric acetate in benzene were re­
fluxed for two days, whereupon a black precipitate of mer­
cury was observed.
After removal of the mercury by filtra­
tion and distillation of the benzene, the residue was frac­
tionally distilled.
A few drops of a substance boiling at
158° under 25mm. pressure.
Hydrolysis of this fraction
gave a solution which was acid to litmus.
Treatment of the
solution with an aqueous solution of phenylhydrazine and
acetic acid gave a substance melting at 160°.
point of glyoxal osazone is given as 170°.
The melting
The quantity
obtained was too small for recrystallization, but it seems
that some glyoxal was obtained in hydrolysis of this frac­
tion.
Several other experiments patterned after the out­
line given above were performed and in all cases free mer­
cury was obtained but in no case were definite organic pro­
ducts isolated.
In anhydrous media the reaction should
follow the reaction shown below.
CHa
CH«
||
CH
+
CHS
CH-OAc
CHa
CH-OAc
Hg (0Ac )s
+
Hg°
(2)
In all the experiments where benzene was used as a solvent
the reactants were dried as well as possible.
Benzene was
dried over calcium chloride and the mercuric acetate In a
vacuum dessicator prior to use.
In an effort to Isolate the 2,3- diacetate of dioxane,
which should be one produet of the reaction under anhydrous
conditions, equimolar quantities of dioxene and mercuric
acetate were mixed without any solvent.
duction period of about ten minutes,
ous reaction,
There was an in­
after which a vigor­
accompanied by the evolution of considerable
heat, occurred.
At the end of one—half hour the solid In
the flask was grey— clack In color.
After shaking the mix­
ture overnight an additional amount of dioxene was added.
The mixture was shaken for one week and then allowed to
stand for one week.
After removal of the precipitate and
excess dioxene, the residue, which smelled strongly of ace
tic acid, was fractionated.
A small quantity of a thick
oil, boiling at 110°-130° under 7mm. pressure
(2,3-diaceto
dioxane boils at 150°-155° under I7mm. pressure),
lected.
was col
Water was added to this material and, after long
cooling in an Ice bath, long needle-like crystals of the
diacetate were obtained.
These crystals melted at 105.5-
106° and gave no melting point depression when a mixed
melting point with a known sample of the diacetate was de­
termined.
This latter evidence gives, therefore,
some basis for
writing 2,3-diacetate of dioxane as an intermediate in
equation (1).
It might be argued that the reactions in
anhydrous media follow, a different path than they do in
water solution, because the rate is so different.
This
difference can be attributed to the lesser solubility of
mercuric acetate in the anhydrous media.
From this series of experiments one must assume that
the reactions of dioxene with mercuric acetate are due to
the vinyl ether grouping in dioxene and not to any enolic
form which might result from hydrolysis as shown below.
58.
J:’
Boeseken, Tellegen and Henriquez, J. Amer. Chem. Soc.
54, 3777 (1932); ibid. 55, 1284 (1933).
Tli© double bond Is apparently activated by the ether link­
ages, to such a degree that it is easily attacked by mercuric
acetate,
49,81
Zappi and coworkers,
50
and Dansi and Sempronj
have
demonstrated that compounds, capable of existing in enolic
forms, reduce mercurous nitrate to free mercury.
They postu­
late the enolic structure as being the active grouping.
Di­
oxene may be considered as the cyclic ether of an enediol
with a grouping similar to that of the enolic forms of acetoacetic ester or malonic ester.
Thus we can write hypotheti­
cally:
(4)
C H 3-OH
|
C H a-OE
+
HO-CH
|
HO-CH
^
CHa-G-CH
|
||
CHa-O-CH
+
2Ha0
to demonstrate the similarity between dioxene and the enol
of acetoacetic acid (LVIX).
OH
0
I
II
C H a — G = G H - C — 0E+
LVII
Mercuric mercury is a better oxidizing agent than mercurous
mercury (assuming equivalent activities of the ions in solu­
tion) and, therefore, one would anticipate that all enolic
structures would reduce mercuric mercury,
experimentally.
This is not found
Connor and Van Campen6* showed that enols
in alcoholic solution react, m
the presence of small amounts
of sodium ©thoxide, to form mercury—containing compounds.
The sodium ethoxide is added to increase enolization.
The
results of these other workers seem to he in disagreement
with the work reported in this investigation.
planations are possible.
Several ex­
In the first place the conditions
of Connor and Van Campen’s reactions are quite different
from the conditions of the reactions reported in this disserts
tion.
C onnor’s reaction is carried out in an alkaline medium
whereas the reactions reported here are all in acid media.
Zappi’s reactions are carried out in 10# nitric acid solution,
so these conditions are also unlike the conditions in this
experiment.
It might he argued that dioxene is more active
due to the presence of two ether linkages activating the
double bond.
This; is probably true, but the reduction of
mercury by ortho and para propenylanisoles (which will be
discussed later) then becomes an anomaly.
Apparently the
differences In activity require more profound study before
any plausible explanation can be made.
A discussion of the
reactions of dioxene with silver acetate and cupric acetate
will throw some light on these apparent divergences in
reactions.
W h e n dioxene is shaken with a solution of silver acetate
in aqueous solution reduction of the silver to the free metal
occurs.
The reaction is, however, much slower than with mer­
curic salts.
After being shaken for four days the weight of
the precipitate was 5.624 g. whereas the theoretical weight
of silver for quantitative reaction was 4.76 g.
The osazone
of glyoxal was isolated in 14.9# of theoretical yield.
Di­
oxene reacts with silver acetate in dry benzene, but the mix­
ture must be held at the refluxing temperature of benzene.
In one experiment silver acetate and a benzene solution of
dioxene were shaken for three days.
A slight brown precipi­
tate was noted but the quantity was quite small.
W i t h cupric acetate in aqueous solution, using two mols
or one mol per mol of dioxene, no precipitate of copper was
obtained after shaking the mixture for thirteen days.
These results are in accord with the findings of Lucas
2.3, 53, 66
and coworkers
if an Intermediate coordination compound
is postulated as the mechanism.
They reported that in general
olefins coordinate more rapidly with mercuric salts than they
do with silver salts,
and that cupric ions do not coordinate
with an olefinic double bond.
These comparisons suggest that
some sort of coordination complex may be intermediate In the
oxidation of these vinyl ethers.
Lucas et al believe that
these complexes exist in equilibrium with the olefin, the
salt,
and (In the case of mercury) the true mercurial.
jLS
On the assumption that there is a common Intermediate for
oxidation and mercuration,
the anomalous reaction of isoapiol
to form a mercurial besides the expected reducing of mercury,
can be explained.
L u cas’ experiments dealt only with aqueous
solutions of the metal salts.
The work of Hugel and Hibon,1*
however, showed that complexes are formed in non-aqueous solu­
tions also.
Assuming a mechanism similar to that of Lucas
(loc. cit.) involves some rather peculiar transformations.
Thus we could write:
^ 0
H
?H s 9
CHa G
\
••
O
-0:C:"
.. ,
- 0 :C
*
^
H
(a)
„
HgOAc*
^
-0:C:Hg:0:
-Q:C+ &'C
" I
H
CH 0
(b)
H
-0 :C :Eg:0 :
0:c£:0Tc+
H
H
(c)
H __ ^
-0:c£g£*Sfc:
H
-0 :C:Hg:0®
^
-0 :C:6 :' C+
CHa
H
(d)
^
oh8
- 0 :C:6 :C-CH3
h
(e)
(f)
H
H
—OsG**" ;0s
**
**
-OsCsC:C-CH0
+
Hff°
••
•OAc
>
—OtCsO*CsCHs
**
-0:C:§!C:CHs
..
**
H
H
(s )
.0=
* I
I
o
I11)
^
38.
The transf ormations to compound (f) are well known.
5©
Prom
intermediate (f), which is essentially similar to Lucas*
resonance isomers, two paths can be taken.
Mercury can be
forced from the intermediate and an acetate radical can enter
to assume its position, or the acetate group can attach itself
to the mercury as shown below.
■'
5
0:C:Hg+
-0sC:0:C :CHS
««
H
H
0
-0:C:Hg:Q-fi-CHa
:m0:
-0:C:£:C-CH3
H
(£)
(1 )
This is the path taken by isoapiol when it forms a mercurial.
The step from (f) to (g) is the weakest point of this
formulation.
Mercury would then draw the electrons away from
the carbon, forming the free mercury and leaving the carbon
atom positive.
The negative acetate ion would be attracted
to this carbon and would share its electrons forming the di­
acetate,
With two mols of mercuric acetate, the excess mer­
curic acetate would react with the free mercury to form mer­
curous acetate.
A similar explanation can be used with silver
acetate.
Another explanation of the reaction is the assumption
that mercuration and oxidation occur by different mechanisms.
58.
Gilman, Organic Chemistry, pp. 1637
and Sons (1938).
, John Wiley
39.
Lucas states that the intermediate, the:
mercuric salts are in equilibrium.
mercurial and the
In addition to this
reaction there may be one of irreversible oxidation result­
ing in a continual decrease in mercuric salt as the reaction
proceeds.
Thus we can write an equilibrium
A
Hgc+
/°\
H(j~°AC
HC-OAc
^S(OAo)a
■
\0 /
! + h S (Oac)8c
\0 /
(3)
T'*80*
j+
c
V/
0
(k)
Lucas Intermediate
0H“
G-HgOAc
I
C-OH
V
(1 )
Balbiano and coworkers found that all ortho and para
propenylan!soles,
except isoapiol, react with mercuric
acetate to form only mercurous acetate or free mercury and
a glycol.
On the basis of the latter mechanism, it must be
assumed that apiol is unique, in as much as it alone forms a
mercurial sufficiently insoluble or stable to cause the
reaction to proceed to the right as well as to the left. Thus
with Isoapiol a mercurated product and a glycol are formed
simultaneously.
In all other cases the mercurial is suffi­
ciently soluble or unstable to establish, equilibrium, condi­
tions.
The equilibrium is therefore forced to the left by
the irreversibility of the oxidation— reduction reaction.
If this latter explanation is adopted, the oxidation
0Q
can be explained on the basis of a modified Criegee
mechanism.
*
For the oxidation of olefins to glycols using
hydrogen peroxide with osmium tetroxide as the catalyst, he
writes:
-C
0.
8 + J-0 3oa
-c cr
-C-0
| y>aoa _£•£.
-c-o
-C-OH
|
+ Haoao4
-e-os
Modifying this formulation to mercuric or silver acetate, we
can w£ite
o
o
/ \ H
C
P
/H
\
0
i °
/ \H _
G:
O s s Cn .
0V
P
/H
v
:6:+ C
'
|
CH0
0
o
\
O
(m)
0
CHa
/ \H
I
.
C: Os:CsO:Hg+
I
' 0 "
— ►
C-O-C
V »
oh.
(o)
59.
60.
CH0
0
y \ H .. I ... ?+
\
CsOsCjQRHg
1
V
— »■
C-O-G^I
^ e“
s
(p)
x.
1
(P
O;0:+C^"
H
|
CHS
(n)
,0
V
<rH°
/ \ H 9 : sCn
C
0
CHS
H .. I
C-0-C=0
1 ■ -0
+ H
G-O-C^i-CHa
v
(q)
Criegee, Ann. 481, 263 (1930).
Organic Chemistry, Karrer (Translation by Mee), p. 51,
Hordemann Publishing Company, Inc. (1938).
41.
W i t h two mols of mercury a similar procedure could be used
to show formation of mercurous mercury in the reaction.
The
reaction above shows only one molecule of mercury taking
part in the reaction.
It is quite possible that two mole­
cules may take part in the reduction of one molecule of di­
oxene resulting in a three body collision.
Indovina and
sea
Manfroi
found that the mercuric chloride oxidation of
ascorbic acid;
collision.
an enediol,
actually involves a three body
The differences In activity between mercury and
silver and the non-reaction of cupric acetate can be explained
on the relative ability of the metals to polarize the carbonyl
group (as in m ) .
The two types of mechanisms are different
in that one postulates a carbon to mercury bond while in the
other only carbon to oxygen bonds are postulated as Inter­
mediates .
From dioxene the investigation was turned to a study of
the more simple vinyl-type ethers.
were run on vinyl ether.
The first experiments
If this ether acts like dioxene
towards mercuric acetate, glycollic aldehyde and acetaldehyde
or two molecules of glycollic aldehyde would result (see
equation (4) ).
Experimentally no aldehydes were obtained.
When the reaction was carried out at ice temperature very
little reaction, besides polymerization, was noted.
At room
temperature a small quantity of a white crystalline substance,
42.
^CH^CHa
0
+ H g (O A c )e + H 20
y GE-CEs
0
GH=GHa
Hg
HO Ac
x CH-CHa
i
I a
OH OH
\
Hg (OAc
U)
H sO + H+
X
OH OH
I
CHa-OE
2
|
CHO
ch=ch2
I
s
OH
I
.CH-CHa
0
\
I
OH
'If
HC-CHa
II
0
CH-CHg
i
CHa-CHO
I
OH OH
which turned black at 250° but did not melt below 285°, was
obtained in addition to considerable quantities of polymerized
products.
Polymerization might be expected since it is well
known that acids and certain metal salts do promote the
68
formation of polymers.
Prom these experiments there were
some indications that the double bond might reduce mercuric
mercury if polymerization could be prevented.
Because the experiments with vinyl ether showed little
possibility of obtaining additional data on the mercuric
acetate oxidation,
and because only one aldehyde could be
formed by partial reaction,
a monovinyl ether.
it was decided to investigate
The monovinyl ether, it was hoped, would
show less tendency to polymerize.
The reaction in this case
should be:
(5)
/
R
0
Hg (OAc )g
ROH + HC-CH-Ri
II I
0 OH
H*0
'C = C -R t
H H
Hg'
62.
Carothers, Chem. Rev., _8, 394 (1931).
2H0AC
A higher boiling ether vinyl ether seemed to be desirable
so
-ethylvinyl n-butyl ether was selected for the experi­
ments.
Several sets of conditions were used, including (a)
shaking the ether with a saturated solution of mercuric
acetate,
(b) shaking a benzene solution of the ether with
aqueous mercuric acetate and (c) dropping a benzene solution
on w a r m aqueous mercuric acetate.
All of these experiments
resulted in a yellow, rubber-like polymer.
Although slight
indications of reduction of mercurous acetate were observed
in the latter experiment, no oxidation products were obtained.
In all of the above experiments with @ -ethylvinyl
n-butyl ether the solution was acid due to hydrolysis of
mercuric acetate.
It seemed possible that polymerization
was caused by the catalytic effect of the acid.
To test this
hypothesis an experiment was performed in which the aqueous
solution was buffered by the addition of sodium acetate.
In
spite of the buffer action, however, the usual yellow, gummy
polymer was obtained.
It is apparent that the polymeriza­
tion is catalyzed by the salt, and may or may not be cata­
lyzed by the acidity of the solution.
Since polymerization was observed in all these reactions
with mercuric acetate,
advisable.
a change of salt and of conditions seemed
The ether was refluxed with silver acetate In
benzene solution.
After ten minutes a black precipitate was
44.
obtained showing reduction of th© silver.
products could not b© ascertained* however.
The organic
By analogy
w it h the reaction dioxen© in non—polar media* the equation
representing the change is probably:
CHs -C H a -C H 3-C H s
o '
+
n c e = c e - c h 3- c h b
G H g-C H a-G H g-C H g
2AgOAc —
0
\jh
-C H -C H s-C H s
I I
OAc OAc
The preparation of 0 -ethylvinyl n-butyl ether, used
in this work* has not been recorded.
formation of the
The method involves
-chioro ether by passing dry hydrogen
chloride into a mixture of butyraldehyde and n-butyl alcohol,
drying over calcium chloride,
and direct bromination of the
chloro ether without isolating it.
These reactions were
carried on according to the method of Boord and coworkers.
63 ,64
The dibromo ether was then dehalogenated with magnesiummagnesium iodide mixture, using the method of Summerbell and
48
Um h oefer.
To investigate the reaction of vinyl ethers with mer­
curic acetate further, the work of Balbiano and coworkers
was continued.
As was previously stated in all the anisole
compounds that reduced mercury the methoxy group was either
ortho or (in most cases) para to the propenyl group.
There
remained the possibility that the double bond was activated
63.
64.
Swallen and Boord, J. Amer. Ghem. S o c ., 52, 651 (1930).
Dykstra, Lewis, and Boord, J. Amer. Chem. Soc. 52, 3396
(1930).
by the benzene ring.
however.
Manchot
Evidence to the contrary was recorded,
had reported that styrene forms a mer­
curial of composition, 308H 8 -3Hg(0H)Cl*HgCl ,
and Hesmeyanov
15
and Freidlind
styrene.
reported two mercurials,
(XI) and (XII), from
If the reducing power of these compounds is due to
the vinyl-type grouping, m-propenylanisole should mercurate.
57
By the principle of vinylogy
m-propenylanisole is not a
vinyl ether but an allyl ether.
Balbiano and coworkers
g ^ gg S3
found that allyl ethers mercurate to form two isomers.
9 9
The
allyl nature ofm-propenylanisole can be seen by the dia­
grams below:
0CHo
/
OCH0
S
/
V
I-CH=GH-CH\
/
Eliminating the -CH=CH- group in the benzene ring there is
a single bond between carbons 3 and 4 in the first reson­
ance Isomer,
and a single bond remaining between carbon 1
and 4 In the second isomer.
To ascertain the correctness
of this hypothesis, m-propenylanisole was shaken with an
equimolar quantity of mercuric acetate in aqueous solution
for twelve days.
During this time a solid white precipi­
tate was formed.
An equimolar quantity of aqueous sodium chloride was
added and the mixture was shaken overnight.
A white solid
was filtered from the solution, washed with water,
dried.
A small portion was soluble In alcohol.
and then
On remov­
al of the alcohol a white solid, which did not melt below
250°C, remained*
The alcohol insoluble portion did not melt
below 235°C but sublimed at 200°G.
On a spatula it burned
w ith a smoky flame, leaving a black charred residue.
On a»
nalysis this material was found to contain 63.77 percent
mercury.
Recrystallization from alcohol yielded a substance
whi c h analyzed as follows: carbon, 6.56 percent; mercury,
74.26 percent;
and hydrogen, 1.34 percent.
This analysis
does not correspond to any logical formulation of a simple
mercurial.
The difference in mercury content indicates that
a compound with less mercury, than the recrystallized mater­
ial, remained in the alcohol solution.
Although evidence
for the formation of a mercurial is lacking, nevertheless,
m-propenylanisole did not give free mercury when it was al­
lowed to react with mercuric acetate, whereas the ortho and
p a r a anisoles did yield free mercury under identical condi­
tions.
The m-allyl compound was reacted In the same manner.
Two isomers were obtained,
an oil soluble in alcohol and a
solid (decomposes 195°C), insoluble in ethanol.
As controls
o and p-propenylanisoles and methyleugenol and methyliso-
eugenol were reacted, with, mercuric acetate under the same
conditions.
With the two control propenylanisoles and
methylisoeugenol free mercury was obtained and the glycols
isolated.
The otho-glycol boiled at 168-172°C under 7mm.
pressure.
No attempt was made to separate the isomers,
which should exist by analogy with the para glycol.
Car­
bon and Hydrogen analysis showed the compound to be C loH 14!03 ,
the correct formula for this glycol.
With methyleugenol
the two Isomeric mercurials were obtained, substantiating
the work of Balbiano.
In addition to Indicating that the vinyl ether group­
ing Is necessary for reduction of mercuric acetate, the re­
sults prove that hydrolysis to a vinyl alcohol structure is
not necessary for reduction.
In view of the results of this investigation some doubt
was cast on the w -ethoxystyrene studies of Manchot.
decided,
tions.
therefore,
It was
to repeat the work varying his condi­
To obtain results comparable to those on the ani­
soles, ^ -ethoxystyrene was shaken with one mol of mercur­
ic acetate and with two mols of mercuric acetate in two sep­
arate reactions,
and, indeed a mercurial was formed.
one mol of mercuric acetate,
With
and subsequent transformation
to the chloride a mercurial was formed which analyzed for
CisHiLaOaClaHga.
£>u© to the extreme insolubility of this
material a molecular weight determination could not be run.
This compound may have the structure:
HgCl
HgCl
Xts formation can be postulated as follows:
H H
C=C-0E+2Hg(0Ac)
2
\
/ V
H
H
/ ^ - H - C-OE+
I
I
HgOAOH
/
H
H
-C=C-0-Hg-Q-C=C
/\
/
\
H
-C=C-OH
HgOAc
\
/
Hg (O A o )g
HgCl
\
/
If tills reaction were in accord with, the other results ob­
tained in this investigation free mercury would be the an­
ticipated product.
However, this is probably another case
similar to that of isoapiol.
The melting
pound is 164-166°C although decomposition
point ofthe com­
occurs atthis
temperature with the formation of a grey-brown infusible
residue.
With two mols of mercuric acetate, a compound similar
to Manchot* s was obtained.
It did not melt below 250°C,
but decomposition occurs when the temperature reaches 115°C.
Manchot* s analysis led him to propose the
C eH lo0 3H g sC l s
and the structure:
/ V
/
H
H
^-C=C-0H*2Hg(0H)Cl
formula
It is quite possible that this represents one of the stable
13
mercurial intermediates as mentioned by Lucas and coworkers.
The structure of this compound would be, therefore:
HgCl(OH)
OH
\
HgCl 0H
This might be intermediate to the mercurial:
OH
f
O
‘C I
HgCl
HgCl
I
C-OH
I
OH
The structure proposed is in accord with the reactions, as
determined by Manchot.
One application of the reaction with mercuric acetate
is that of structure proof.
To ascertain the position of
6e
the double bond in phenyldioxene,
and to offer more evidence
on the structure of this compound, phenyldioxene was reacted
w i t h mercuric acetate in aqueous solution.
If the structure
is such that the phenyl group is attached to one of the dou­
ble bonded carbon atoms, the following reaction would be an­
ticipated:
y0
/
0
\
CHS
I
GHg
a
X
>
II--GH
\ /
0
Actually,
63.
H s°
C H s-OH
+ Hg (OAc )2 — >■ Hg * I
+
C H sOH
/ Y 0-0110
I
\/
the material reduces mercuric acetate, but no os-
W i l liam Smedley, Master of Science Thesis, Northwest­
ern University (1940).
azone was obtained when phenylhydrazine was reacted with
the organic products of the reaction.
This experiment will
be repeated to ascertain the organic products.
A dioxadiene mercurial was reported by Umhoefer and
Summerbell.
This work was repeated and substantiated.
Reaction of the dimercurial with iodine in potassium iodide
solution resulted in an iodine-containing oil, soluble in
ether.
The material decomposed to give free iodine and a
tarry residue when isolation was attempted.
EXPERIMENTAL
A.
Reactions of Dioxene
1.
Preparation of Dioxene:
Dioxene was prepared according to the method of Sum45
merbell and TJmhoefer
, from 2,3-dichlorodioxene using
magnesium-magnesium iodide mixture in dry ether.
The
yields varied between 40 and 47 percent.
2.
Reaction of Dioxene and Mercuric Acetate (mol for
mol) in Water.
To the dioxene (1.7329 g, .0200 mols) and 10 c.c. of
water was added an aqueous solution of mercuric acetate
(7*0212 g,
.0200 mols In 40 c.c. of Water).
precipitate began forming immediately.
shaken for one-half hour.
A grey-black
The mixture was
The solid formed In the reac­
tion was removed by filtration through a previously weighed
G-ooch crucible.
w i t h water,
After washing the precipitated mercury
alcohol,
and finally ether, the Gooch crucible
was placed in a vacuum dessicator over calcium chloride
overnight,
and then weighed.
The mercury weighed 3.361 g.
corresponding to 95.98 percent of theoretical.
The aqueous filtrate from above was made up to 100 ml.
In a standard flask and aliquot portions were used for analysis.
To 25 ml. of the solxition was added 1.5 c.c. of phenyl-
hydrazine in 15 c.c* of water and sufficient acetic acid
to dissolve the hydrazine.
ly,
Hie mixture was warmed slight­
allowed to stand for thirty minutes,
ed in an ice hath.
and then was cool­
The glyoxal osazone was filtered on a
G-ooch crucihle, taken up in ethanol and then crystallized
from an alcohol—water solution.
Weight of recrystallized
material was 1.148 g. (96.40 percent of theoretical, m.p.
161-164®).
After several recrystallizations from alcohol-
water and finally carbon tetrachloride, yellow crystalline
plates, melting at 167-168°C (uncorr.) with slight decom­
position, were obtained.
ss
(d.).
The literature records 169-17G°C
The semicarbazone of glyoxal was prepared from another
aliquot portion according to the directions given by Schries
ner and Fuson . After two recrystallizations from alcoholwater, the semicarbazone melted at 269-270°C ( c o m ) .
66
literature records 270°C (corr.).
The
The dibenzoate of ethylene glycol was prepared by shak­
ing 1 c.c. of benzoyl chloride with a 25 ml. aliquot of the
filtrate,
adding 5 c.c. of 20 percent sodium hydroxide so­
lution in portions so that the solution was kept slightly
alkaline at all times.
65.
66.
The precipitate was filtered, wash-
Fischer, Ber., 17, 575 (1884).
R. L. Schriner and R. G. Fuson, The Systematic Identi­
fication of Organic Compounds, John Wiley and Sons Inc.
(1935), page 145, procedure A.
e& with, dilute alkali and then with water.
The precipitate
weighed 1.179 g., corresponding to 87.26$ yield.
After re­
crystallization from alcohol-water solution the dibenzoate
melted at 72.3— 73*0°0
(uncorr•)«
Gabriel and Heymann re­
corded 73-74° (corr.).
In another experiment in water 96.4 percent of theo­
retical mercury was obtained.
3.
Reaction of Dioxene and Mercuric Acetate (One Mol
of Dioxene to Two Mols of Salt) in Water.
To dioxene (1.5098 g.,
.0176 mols) was added 11.184 g.
(.0352 mols) of mercuric acetate In 50 c.c. of water.
A
white mother-of-pearl-like precipitate began to form im­
mediately with evolution of heat.
The reaction mixture was
shaken for one-half hour and filtered through a Gooch cru­
cible.
The precipitate was washed with 5 c.c. of water,
followed by alcohol and then ether,
vacuum dessicator.
and then dried in a
The mercurous acetate, precipitated,
weighed 8.889 g. corresponding to a 98.29 percent yield.
The solubility of mercurous acetate in water is appreci­
able,
accounting for the divergence from theoretical.
It was found that mercuric or mercurous ions In the
aqueous solution interfered In the preparation of glyoxal
osazone.
67.
The filtrate was, therefore, reacted with hydro-
Gabriel and Heymann, Ber., 25, 2498 (1890).
gen sulfide,
and the precipitated mercury sulfides removed
from solution.
The solution,
after removal of mercury salts, was made
up to 100 ml*, and 18.75 ml. were taken for preparation of
the glyoxal osazone.
The same procedure as in part 2 gave
.8000 g. of glyoxal osazone (98.78 percent of theoretical)
which,
after recrystallization from ethanol-water mixture
and then carbon tetrachloride, melted at 168°G.
The ethylene glycol dibenzoate melted at 71-72°C.
after
two recrystallizations from ethanol-water mixtures.
To test the possibility of the 2,3-di acetate of dioxane as the possible intermediate,
the 2,3-diacetyldioxanb
(1 g.) was added to 35 c.c. of water.
goes into solution Immediately,
Most of the acetate
and the rest slowly.
Af­
ter shaking for ten minutes, phenyl hydrazine (1.5 g.), in
7 c.c. of water and enough acetic acid to obtain a clear
solution, was added.
The yellow precipitate of the osa­
zone formed immediately.
4.
Reactions of Dioxene and Mercuric Acetate in Meth­
anol.
To dioxene (3.3 g.,
.038 mols) In 100 c.c. of abso­
lute methanol was added mercuric acetate (25.0 g., .078
mols).
A white precipitate of mercurous acetate began
forming immediately.
The mixture was shaken for one-half
hour.
At the end of this time the precipitate was filter­
ed, washed with dry methanol,
cator.
and dried In a vacuum dessi-
The weight of precipitate was 19.6 g. or 96.2 per­
cent of theoretical.
In a second reaction in methanol, dioxene (4.8 g.,
.056 mols) wage added to 10 c.c. of methanol, dried over
anhydrous MgSO^.
Then mercuric acetate (17.8 g.,
.056 mols),
suspended in 50 c.c. of anhydrous methanol, was added in
small portions.
mediately.
A grey-black precipitate began forming im­
After standing for thirty minutes,
tate was filtered.
overnight,
the precipi­
The precipitate was allowed to stand
and the globule of mercury that coagulated in
the bottom was removed, washed; and dried with absorbent pa ­
per.
The mercury weighed 10.4 g. (92.8 percent of theoret­
ical).
Some of the precipitate, which remained in the fil­
ter paper, was probably finely divided mercury.
An unsuc­
cessful attempt was then made to determine the organic con­
stituents in the methanol solution, by vacuum distillation
of the residue after removal of the methanol.
Separation
of the products by addition of water seemed inadvisable, be­
cause of the possibility of hydrolysing the product.
5.
Reactions of Dioxene and Mercuric Acetate In Benzene.
In a test run equimolar quantities (approximately .05 mol)
of dioxene and mercuric acetate were placed In a round bot-
tom flask with 25 c.c, of dry benzene (dried over calcium
chloride).
The reaction mixture was shaken for two days at
room temperature.
At the end of this time no evidence of
reaction was apparent,
for six hours.
so the mixture was heated under reflux
At the end of this time a black precipitate
of mercury was obtained.
Two runs were made by refluxing a benzene solution of
dioxene with an equimolar quantity of mercuric acetate.
Since they were quite similar only one will be described.
Dioxene
(9.920 g.,
acetate (36.97 g.,
.116 mols) was reacted with mercuric
.116 mols) in dry benzene (75 c.c.).
The
mercuric acetate used in the reaction was previously dried
In a vacuum dessicator.
The reaction was carried out In a
200 c.c. round bottom flask fitted with a reflux condenser.
The condenser was fitted with a soda-lime drying tube to
exclude any moisture.
gently for two days.
The reaction mixture was refluxed
At the end of this time the precipitate
which was grey-black in color, was removed by filtration,
the benzene was removed by distillation.
and
Approximately
10 c.c. of a liquid, which smelled strongly of acetic acid,
remained in the flask.
Vacuum fractionation of the liquid
gave a small portion distilling at 158°C under 25mm. pressure
Attempts to cause the material to crystallize were fruitless.
The fraction was almost Insoluble in water, but when boiled
with water it hydrolysed readily.
The hydrolysate was acid
57.
to litmus.
Addition of phenylhydrazine in dilute acetic
acid gave a slight crystalline precipitate* too small to
recrystallize.
The derivative melted about 160°G
Melting point of glyoxal osazone 169-170°C (d).
(d).
The pre­
cipitate filtered from the reaction mixture contained con­
siderable quantities of white material* presumably mercurous
acetate*
along with the dark grey precipitate, obtained when
mercury is precipitated in these reactions.
6.
Reaction of Dioxene and Mercuric Acetate without
Solvent,.
To dioxene (8.421 g.,
.0976 mols) was added 31.18 g.
(.0976 mols)
of mercuric acetate.
ten minutes*
after which a reaction*
able heat* was noted.
darken.
There was a lag of about
accompanied by consider­
The white mercuric acetate began to
After shaking the reaction mixture overnight an
additional 10 c.c. of dioxene was added.
The mixture was
then shaken for one week and then allowed to stand for one
week.
The precipitate* grey-black in color, was filtered
from the solution and washed with ether.
It weighed 20.78 g.
(theoretical weight 19.59 g . ) after drying.
Apparently some
mercurous acetate was not reduced to free mercury.
The
ether and dioxene was removed by distillation at atmospheric
pressure*
and the residue* which had a strong acetic acid
odor* was distilled under reduced pressure.
A
2.13 g.
fraction boiling at 110-130°C under 9 mm. pressure was collected.
This material was dissolved in about 10 c.c. of water and
allowed to stand in an ice ba.th overnight•
needles crystallized from the solution*
Long white
The crystals were
washed with ice water, dried in a vacuum dessicator,
weighed (.10 g. obtained).
to be 105.5°C (softening,
and
The melting point was determined
appeared at 105°C).
A mixed melt­
ing point with the diacetate of dioxane, prepared from 2,36©
dichlorodioxane and sodium acetate in glacial acetic acid,
showed no depression.
Yield of di acetate .50 percent.
The
major portion of the residue after removal of ether and
dioxene was left as tar.
Only a small portion could be dis­
tilled.
7.
Reactions of Silver Acetate and Dioxene
Dioxene
(1,923 g*,
.0223 mols) was added to 7.48 g.
(.0446 mols) of silver acetate and 21 c.c. of water.
The
mixture was shaken for four days, after which the precipi­
tated material was filtered and weighed.
tate 5.624 g.
Weight of precipi­
(Theoretical 4.76 g.).
The filtrate was made up to 200 c.c.^and 100 c.c. were
taken for analysis.
The excess silver was removed by
precipitation as the sulfide and the glyoxal formed was
determined as the osazone.
14.9 percent of theoretical.
Weight of osazone .385 g. or
The melting point of the crude
material was 161-163°C.
Several other experiments with aqueous silver acetate
substantiated the findings in this experiment, i.e., that
68.
Boeseken, Tellegen and Henriquez,
55, 1284 (1933).
J. Amer. Chem. Soc.
the reaction proceeds, but at a much slower rate than with
mercuric ac e t a t e .
To dioxene (approximately *05 mols) in 50 ml. dry benzene
was added anhydrous silver acetate (approximately .1 mol).
The mixture was shaken Tor two days without any evidence of
reaction.
hours.
The reaction mixture was then reTluxed Tor six
A silver mirror and a precipitate oT silver was Tormed
but the organic products were not ascertained.
Tollen*s reagent was prepared according to the method
66
oT Shriner and Fuson,
page 35, and a small quantity oT di­
oxene added to the reagent.
8.
The test was negative.
Reactions oT Cupric Acetate and Dioxene.
Two experiments, using two mols oT cupric acetate and
one mol oT cupric acetate per mol oT dioxene, respectively,
were run in aqueous solution.
The mixture was shaken Tor
two weeks but no indications oT reaction were observed.
B.
Reactions with Vinyl Ether.
The vinyl ether used boiled at 27-28°C.
ether (4.1 g . , .059 mols)
32.0 g.
and 15 c.c. oT water was added
(.118 mols) oT mercuric acetate in 120 c.c. oT water
in small portions.
bath.
To the vinyl
The reaction mixture was kept in an ice
A slight grey-black precipitate was noted aTter thirty
minutes standing, but the main prodiict was a white polymer.
In another attempt vinyl ether (6.384 g.,
.0913 mols)
was added dropwise to 58.17 g. (.1825 mols) oT mercuric
60.
acetate in 250 ml. of water.
ately
Ho precipitate formed immedi­
in tiie case of dioxene, tut after standing over**
night a small amount of a white flaky material was formed
in addition to a polymer.
mercurous acetate.
The white material looked like
It did not melt below 285°C, although it
darkened at about 250°C.
C.
Reactions with ^ -Ethylvinyl n-Butyl Ether.
1.
Preparation of the Ether.
The preparation of this ether involved preparation of
<*. -chlorobutyl ether, bromination of the chloroether to
0 -dibromobutyl ether,
vinyl n-butyl ether.
,
and finally debromination to £ -ethylThe first two steps were carried on
60,64
according to the method of Boord and coworkers,
and the
last step according to the method that Summerbell and
40
Umhoefer
reported for the preparation of dioxene from 2,3dichlorodioxane.
The butyr aldehyde (72.0 c.c.,
added to the alcohol (75 c.c.,
by an ice bath.
.75 mols) was
.75 mols) in a flask cooled
The mixture was transferred to a 500 c.c.
separatory funnel, partially submerged In an Ice bath, and
dry hydrogen chloride was passed into the mixture for six
hours.
Towards the end of the reaction the absorption of the
gas was very slow.
The mixture was allowed to stand In the
ice bath for one-half hour and then the lower (water) layer
was removed.
The upper layer was transferred to a 500 c.c.
Erlenmeyer flask,
anhydrous calcium chloride was added,
and
the hydrogen chloride was removed under reduced pressure.
The ** -chloroether was dried overnight by contact with cal­
cium chloride.
The ether was kept in a refrigerator, be­
cause considerable decomposition occurs at room temperature.
The intermediate “^-chloroether was not isolated.
To
the crude product was added the theoretical amount of bromine
(120 g.,
*75 mols) in small portions.
The reaction was
carried out at ice temperature in a three neck flask, fitted
with a mercury seal.
complete,
After the addition of bromine was
the mixture was stirred for one-half hour at ice
temperature and then for one-half hour at room temperature.
The hydrogen chloride dissolved in the mixture was removed
under reduced pressure,
ated.
and the residue was vacuum fraction­
The main portion of the mixture (142.1 g.) distilled
between 117 and 119°C under 19 mm.
Yield of ** , f -dibromo­
butyl ether 61.5 percent of theoretical.
The next step Involved debromination of the ether.
To
14.6 g. (.60 mols) of magnesium and 100 c.c. of Grignard
ether was added 15 g. (.12 mols) of Iodine in 100 c.c. of
Grignard ether.
The addition was made slowly so that the
color of the solution was never darker than lemon yellow.
After all the iodine was added the mixture was stirred until
It became white.
Then 61.4 g. (.2 mols) of the dibromo-
ether, dissolved in 50 c.c. of dry ether, was added dropwise.
The reaction is exothermic so the addition was made at such
a rate that the ether refluxed gently.
was complete,
After the addition
the mixture was refluxed for one-half hour,
and then poured into 400 c.c. of ice water.
The ether layer
was separated and dried overnight by contact with anhydrous
calcium chloride.
The ether was removed by distillation on
a steam cone and the residue was vacuum fractionated.
The
0 -ethylvinyl n-butyl (b.p. 70-85°/83mm.) ether was collected
as a clear liquid.
The product decolorized a bromine carbon -
tetrachloride solution rapidly without evolution of any
hydrogen bromide.
2.
Reaction with Mercuric Acetate in Water and Methanol.
The ether (3.02 g.,
(.024 mols) of mercuric
.024 mols) was added to 7.52 g.
acetate in 35 c.c. of water.
mixture was shaken for one hour.
At the end of this time
a yellov/, gummy precipitate was observed.
then refluxed for eight hours.
The
The mixture was
In the reaction mixture a
few mother-of-pearl-like crystals, resembling mercurous
acetate, were observed.
Continued refluxing did not cause
any mercury precipitation.
No precipitation of a hydrazone
was observed when the solution, freed of mercury by hydrogen
sulfide precipitation, was tested with phenylhydrazine.
A polymer was obtained when dry methanol was substituted
for water as the solvent.
A similar gummy, yellow, polymerized product was obtained
63.
w hen 1*6 g.
(.012 mols) of the ether was added to 3.8 g.
(.012 mols) of mercuric acetate in 20 c.c. of water buffered
with 5.0 g.
(*06 mols)
of sodium acetate.
In a test run @ — ethylvinyl ether was dropped onto a
hot solution of aqueous mercuric acetate In a three—neck
flask fitted with a dropping funnel, mercury seal stirrer
and a reflux condenser.
during the addition.
The mixture was stirred rapidly
The resulting mixture was refluxed
for ten hours and then was allowed to stand for two weeks.
The same yellow polymer was obtained.
The solution,
removal of the mercury salts, was tested with
after
p -nitro-
phenylhydrazine, but no hydrazone was obtained.
3.
Reaction with Silver Acetate in Benzene
To 4.0 g.
(.031 mols) of the ethylvinyl butyl ether
was added 10.3 g. (.062 mols) of silver acetate and 25 c.c.
of benzene.
The mixture was refluxed for 10 hours.
Removal
of precipitate, black in color due to reduction of silver
acetate to silver,
and the benzene left an oily material.
No definite products were obtained on distillation.
D.
Reaction with o-Propenylanisole.
1.
Preparation of o-Propenylanisole.
This compound was prepared from o-methoxybenzaldehyde
(b.p. 123-125° at 17-21 mm. pressure)
material.
as the starting
The aldehyde was converted to 1-(o-anisyl)-1-pro­
panol, 70 and the alcohol was dehydrated to the propenylanisole.
70.
Hill and Hofmann, Ber. 37, 4188 (1904); ibid. 38, 1677 (1905).
To 6.1 g. (.25 mols) or magnesium and 10 c.c. of Grig­
n a r d ether in a 200 c.c. three neck flask, fitted with a re­
flux condenser,
a mercury seal stirrer and a dropping funnel,
was added 27.25 g.
of ether*
(.025 mols) of ethyl "bromide in 50 c.c.
The rate of addition was such that the ether re­
fluxed gently*
After the addition was complete, the mixture
was refluxed gently for fifteen minutes.
The mixture was
cooled and 26.7 g. (.197 mols) of o-methoxybenzaldehyde in
50 c.c. of ether was added dropwise with rapid stirring.
The mixture was allowed to stand overnight, and then was de­
composed in ice water and ammonium chloride.
The ether
layer was separated and dried over anhydrous magnesium sul­
fate*
The ether was removed, leaving the crude l-(o-anisyl)
-1-propanol.
The crude alcohol was dehydrated by vacuum distillation
in the presence of a few crystals of iodine.
Three fractions
were collected.
21
Fraction
Temperature
Pressure (mm.)
1
64-65°
1.5
1*5581
2
65-84°
5.3
1.5582
3
84-85.5°
4.5
1.5585
Redistillation of these fractions gave 8.5 g. of
o—propenylanisole boiling at 113—116°C under 19 mm. pressure
(hD
ps
*LSi
1.5612, U D
1.5590).
The literature records the fol­
lowing constants for this compound; b.p. 222— 223°C (atmos—
65
,
_
70
SO
pheric pressure); Mp
2.
71
1.5604,
Reaction of o-Propenylanisole with. Mercuric Acetate
and Silver Acetate.
To 16.77 g.
7.80 g.
(.0526 mols) of mercuric acetate were added
(.0526 mols) of o-propenylanisole.
shaken for two weeks.
after two days.
The mixture was
The formation of mercury was noted
At the end of the shaking the precipitate
was filtered, washed with ether and dried.
Weight of pre­
cipitated mercury 11.74 g. (Theoretical weight 10.55 g.).
The water solution was extracted with ether, and this
ether solution was combined with the ether, used for washing
the mercury precipitate.
The ether solution was dried over
anhydrous magnesium sulfate.
The ether vsras removed by dis­
tillation and the residue vacuum fractionated, giving 3,41 g.
of l-(o-anisyl) -1,2-propanediol.
The material was analyzed
for carbon and hydrogen, giving the following:
3.086 mgm. sample gave 2.158 mgms. of water
7.434 mgms. of carbon dioxide
Found
Hydrogen
Carbon
7.82%
7.74%
65.70%
65.92%
Silver acetate (1.55 g.,
(.69 g.,
.0046 mols)
gether for two weeks.
Calculated
.0092 mols), o-propenylanisole
and 10 c.c. of water were shaken to­
A black precipitate of silver was
observed.
71.
Gladstone,
J. Chem. Soc. 59, 293 (1891).
E.
Reactions with m- Propenylanisole.
1*
Preparation of m-Propenylanisole•
The starting material Tor this compound was nitro­
benzene,
Nitrobenzene was brominated according to the
72
method described in Organic Syntheses*
The m —bromnitro—
benzene was reduced with tin and hydrochloric acid to
m-bromanlline, and the aniline diazotized according to the
7&
method of Koelsch.
The phenol was methylated in the following manner* To
49.0 g.
(.282 mols) of m-bromophenol dissolved in 22*5 g*
(.57 mols) of NaOH in 200 c.c. of water cooled to 5-10°C,
was added 71.6 g.
(.57 mols) of methyl sulfate.
During
this addition the reaction mixture was stirred rapidly.
The mixture was stirred and maintained at 5-10°C for one
and one half hours.
At the end of this time 12.0 g. (.50
mols) of sodium hydroxide in 50 c.c. of water and 35.8 g.
(.268 mols) of methyl sulfate were added.
The mixture was
then refluxed for three-fourths of an hour, cooled, ex­
tracted with ether and dried over anhydrous magnesium sul­
fate.
The ether was removed and the anisole distilled under
vacuum.
residue.
There was no forerun and only a small amount of
Exactly 44.7 g. of m-bromoanisole (B.P. 77.5-78.0°/
9 mm.) corresponding to an 84.8 percent yield.
72.
73.
This method
Johnson and Gauerke, Organic Syntheses, VIII, 46 (1928).
Koelsch, J. Amer. Chem. Soc., 61, 969 (1939).
is a modification of the method of Diels and Bunzl, who
reported a 73 percent yieldl*
In the next step m-bromsnisole was converted to
1— (m— anisyl)—1-propanol using the Grignard reaction*
5.84 g.
ether,
To
(.240 mols) of magnesium covered with 30 c.c. of dry
as rapidly as refluxing would permit.
This Grignard
reaction was rather sluggish in starting so that innoculation with a small amount of ethylmagnesium iodide was nec­
essary.
After addition of the bromanisole the reaction
mixture was refluxed for one-half hour.
cooled and 14.5 g.
The mixture was
(.250 mols) of prop ion aldehyde in 30 c.c.
of ether were added dropwise at such a rate that the ether
refluxed gently.
After the addition was complete the re­
action mixture was refluxed gently for one-half hour,
and
then was poured into a mixture of 200 g. of ice and 40 g.
of ammonium chloride.
The ether layer was removed, and
the aqueous solution was extracted twice with ether.
The
ether layers were combined and dried over anhydrous mag­
n esi u m sulfate.
fractionated.
The ether was distilled and the residue
The 1 - (m-anisyl)-1-propanol (27.1 g.) dis­
tilled at 104-105.5°G at 4 mm. pressure.
Yield 68.4 per­
cent of theoretical, based on the weight of m-bromanisole.
%
This compound has not been reported so the physical con­
stants were determined.
74.
Diels and Bunzl, Ber., 38, 1496 (1905).
D e n s i t y : Weight of pyncnometer +water (2Q°C)
2.2896
g.
Weight of pyncnometer alone
1.0749
g.
Weight of water (20°G)
1.2147
g.
Weight of pyncnometer * sample (20°G)
2.3747
g.
Weight of pyncnometer
1.0749
g.
Weight of sample
so
D So 1.070
so
Refractive Index: &£>
1.5728
1.2998
g.
M.R.
a
Calculated from M.R=21&li. M
ns+2 D
(observed)
47.68
M.R.
(calculated)^ 47.95
Molar Hefractivity:
Molecular W e i g h t : Weight of benzene
25.726 g.
Weight of sample
.6201 g.
Freezing point of pure benzene4.180°C
F.P. of benzene + sample
5.445°
.737°
Molecular Weight: 167.4
166.2
(found)
(calculated)
Analysis:
2.653 mgms. of sample gave 6.973 mgms. of carbon dioxide
1.860 mgms. of water
Found:
71.84$ Carbon
7.84$ Hydrogen
*
Calculated:
72.26$ Carbon
8.50$ Hydrogen
Values from Oilman Organic Chemistry, p. 1739
69 •
Several attempts at dehydrating this alcohol catalyt­
ic ally in the presence of iodine or potassium acid sulfate
were "unsuccessful.
Finally,
the method of Suter and co-
7 5
workers
was found to give m-propenylanisole from the
1 - (m-anisyl)-1-propanol.
The propanol
(10 g.,
.06 mols)
was dropped onto 10 c.c. of syrupy phosphoric acid in a small
Claisen flask immersed in an oil hath.
The oil hath was
maintained at 200°C during the addition.
at reduced pressure (24 mm.).
The system was kept
After the addition was complete
the oil hath was heated slowly to 235°C.
Ether was added to
the distillate and then separated from the water.
drying the solution over magnesium sulfate,
removed and the residue fractionated.
After
the ether was
A fraction (2*13 g.),
hoiling at 118-120°C at 19 mm. pressure, was collected as
m-propenylanisole.
pressure.
B.P.
(micro method) 224° at 750 mm.
7e
Yields 23.8 percent of theoretical.
Moureu
reported the hoiling point as 226-229°C.,
as 1.0013 at 0°G.
he 1.5530.
and the density
The refractive index was determined to
Using Moureu1s value for the density the molar
refractivity was found to he 47.4 (calculated value 45.95).
75.
76.
I
Suter, Lawson and Smith, J. Amer. Chem. S o c . 61, 164
(1939).
Moureu, J. Chem. Soc. 7 0 i , 646 (1896).
2.
Reaction of m-Propenylanisole with Aqueous Mercuric
Acetate.
Mercuric acetate
(4.33 g.,
.014 mols) in 21 c.c. of
water was shaken with m-propenylanisole (2.00 g.,
for two weeks.
.014 mols)
After eight hours a white precipitate was
noted in the reaction mixture.
sodium chloride (2.0 g.,
At the end of two weeks
.034 mols) in 10 c.c. of water was
added and the reaction mixture was shaken overnight.
After
standing two days, the white granular precipitate was fil­
tered from the solution, washed with water and alcohol.
After removal of the alcohol a white solid (weight 0.13 g.)
remained.
This solid did not melt below 250°C.
Similarly,
alcohol insoluble material did not melt below 235°C., but
sublimed at 2 0 0 ° C .
mercury.
This crude material was analyzed for
The sample was digested with fuming nitric acid
77
(Carius method),
and the mercuric ion was precipitated as
7S
mercuric sulfide.
The sulfide was weighed as such.
The
following data was obtained.
77.
78.
Weight of
test tube +
Weight of
test tube
Weight of
sample
sample
4.5121 g.
4.3290 g.
.1831 g.
G-attermann and Wieland, Laboratory Methods of Organic
Chemistry, p. 65.
Translation by McCartney, Macmillan
and Co., London (1932).
Tredwell and Hall, Analytical Chemistry, p. 172, John
W iley and Sons, Hew York (1930).
Weight of crucible + mercuric sulfide
18.3962 g
Weight of crucible
18.2605 g
Weight of mercuric sulfide
Mercury
.1359 g
63.77 percent.
An attempt was made to recrystallize this material.
Less than .l::g. could be recrystallized from 230 c.c. of
alcohol.
Analysis of this material gave:
4.324 mgm. sample gave 3.211 mgm. mercury (74.26$)
3.322 mgm. gave:
.399 mgm. of water
.799 mgm. of carbon dioxide
Pound
1.34 percent hydrogen
6.56 percent carbon
P.
Reactions w ith Anethol,
1
The anethol used was redistilled (B.P. 119-120°C under
S3
17 mm.
2.
, 1.5618).
Reaction of Anethol with Aqueous Mercuric Acetate.
The anethol
(12.91
14.6
pressure; nj) , 1.5591; n^
g.,
(6.00 g . , .0404mols), mercuric acetate
.0405 mols),
and 65 c.c. of water were treated
in the same manner as m-propenylanisole.
After the mixture
was shaken for two weeks, the precipitate was filtered from
the solution,
and washed with ether.
The precipitate
weighed 9.42 g. (theoretical weight 8.14 g.).
The filtrate
J
j
was extracted with ether and combined with the ether used
for washing the precipitated mercury and mercurous acetate*
After steam distillation to remove the unused anethol, the
glycols were taken up in ether and dried over anhydrous
magnesium sulfate*
After removal of the ether 4.84 g, of
the glycols remained (65.8$ of theoretical yield).
This
glycol reacted with acetyl chloride to form an oil.
3.
Reaction with Aqueous Silver Acetate.
A mixture of anethol (1.84 g.,
acetate (4.14 g.,
.0248 mols)
shaken for two weeks.
material darkened.
.0124 mols),
silver
and 20 c.c. of water were
During this time the precipitated
Weight of precipitated material 3.51 g.
(Theoretical weight based on pure silver 2.67 g.).
I
G.
Reaction with Eugenol Methyl Ether.
The ether, obtained from Eastman, was vacuum distilled.
The fraction boiling between 137 and 138°C. under 19 mm.
30
was used for these experiments, n^ , 1.5328.
I
Eugenol methyl ether (6.04 g.,
acetate (10.82 g.*
.034 mols)
treated in the same way
i
.034 mols), mercuric
and 44 c.c. of water were
/as the m-propenylanisole.
After
the addition of sodium chloride, the mixture was shaken
j
!
overnight and the precipitate was filtered and dried.
|
j
Weight of total mercurial: 16.2 g. (92.4 percent of theoret­
ical based on C 14H 16O0H g Cl).
The isomeric mercurial was
73.
separated "by differential solubility in alcohol.
soluble isomer melted at 115-116°C.
(softening at 112°C.)
and contained 46.84 percent mercury.
Clo^iaOsHgCl 47.28 percent.)
(Theoretical for
After removal of the alcohol
solution
of the one isomeric mercurial, the other
remained
as a gummy viscous oil.
H.
The alcohol
isomer
Reaction with Isoeugenol Methyl Ether.
Isoeugenol methyl ether (5.99 g.,
acetate
(10.72 g.,
.0346 mols)
.0347 mols), mercuric
and water (10 c.c.) when
treated as before gave 6.08 g. of mercury and mercurous
acetate.
(Theoretical weight 8.75 g. of mercury).
steam distillation 5.34 g. of the
After
mixed isomeric glycols
remained.
J.
Reactions with <*/ -Ethoxy Styrene.
1.
Preparation of
i>u-ethoxy styrene.
The starting point was cinnamic acid.
The acid was
7s
brominated according to the method of Ref
yield..
cinnamic
in 82.9 percent
Using the method of this same author, the dibromoadid was converted to ^ -bromostyrene in 55.6 per-
j
cent yield by reflrixing with 10 percent sodium carbonate.
!
Heating the
oj
-bromostyrene (65 g.,
.355 mols) with alco­
holic potassium hydroxide gave 6*19 g.
phenylacetylene
79.
( B.P. 4 5 - 5 2 % . /30 mm.)
Nef, Ann., 3 0 8 , 267 (1899).
(.0606 mols) of
and 10.13 g.
(.0684 mols) of ^ -ethoxystyrene (B.P. 102~104°C./l6mm.).
Yield of phenylacetylene 17.1 percent; yield of ^ -ethoxystyrene 19.5 percent, based on “'-bromostyrene.
The phenyl acetylene was converted into ^ -ethoxy styrene
(B.P, 105-106.5°C.
at 18 mm. pressure) by refluxing with
alcoholic potassium hydroxide for ten hours.
The yield was
36.6 percent.
2.
Mercuration of
uj
-Ethoxystyrene with Equimolar Quan­
tity of Mercuric Acetate in Water.
To mercuric
acetate (7.06 g.,
.0222 mols) dissolved in
35 c.c. of water was added. (*/-ethoxy styrene (3.28 g.,
mols).
The mixture was treated in the same manner as the
other mercurations.
Filtration of the reaction mixture gave
3.44 g. of a white solid., insoluble in water,
ether.
.0221
alcohol and
The melting point of the solid is 164-165°C.
(d).
When heated above this temperature the material decomposes
into a grey-brown solid which does not melt below 250°C.
Analysis of the white solid gave the following data:
4.757 mgm. sample gave 3.038 mgm. of mercury
4.598 mgm.
sample gave:
.634 mgms. of water
3.4-86 mgms. of carbon dioxide
Calculated for C lQH lsOsH g sCla
Pound
Mercury
66.21
63.86
C arbon
21.14
20.68
1.33
1.54
Hydrogen
The mercurial has a strong odor of phenylacetaldehyde •
However, extraction with ether,
gave the oil mentioned above.
and evaporation of the ether
This oil was tested with
phenylhydrazine, but no precipitate was obtained.
3.
Mercuration of v* -Ethoxystyrene with Two Mols of
Mercuric Acetate for Each Mol of the Styrene.
The mercuration was carried on as in the previous ex­
periments.
For this experiment 6.81 g. ( - ■ * mols) of
w - ethoxy s t yr en e , 29,30 g.
(
and 150 c.c. of water are used,
were obtained.
115°C.
mols) of mercuric
acetate
and 20.76 g. of product
The material softened and decomposed at
This is the same material that Manchot obtained (loc.
c i t . ).
K.
Reaction of
To 1.97 g.
-Phenyl-2-Dioxene with Mercuric Acetate.
(.0061 mols) of mercuric acetate in 10 c.c.
of water and 1 c.c. of benzene was added 1.00 g. (.0061 mols)
of phenyldioxene
(Prepared by Mr. William Smedley).
mixture was shaken for two days.
The
At the end of this time,
a dark precipitate of mercury was noted.
The precipitate
was filtered from the solution and Yirashed with ether.
solution was extracted with ether.
The
The combined ether
solutions were dried over anhydrous magnesium sulfate.
After removal of the ether by distillation a brown oily
aresi due was obtained.
The residue was dissolved in alcohol
and placed in a beaker in a dry ice-acetone cooling mixture.
On standing overnight .05 g. of white crystals, M.P. 68-69°C.,
was obtained.
drazme
This substance did not react with phenylhy-
and was not,
therefore, the expected phenylglyoxal•
Water was added to the mother liquor until cloudiness was
observed.
of ethanol.
The solution became clear on addition of one drop
No precipitate appeared when phenylhydrazine
was added.
The aqueous solution was treated with hydrogen sulfide
and the precipitated sulfides were removed.
After boiling
to remove the dissolved hydrogen sulfide, the solution was
treated with phenylhydrazine, but again no precipitate was
obtained.
L.
Reaction of.Dioxadiene with Mercuric Acetate.
To 1.747 g.
(.0208 mols) of dioxadiene in 10 c.c. of
ethanol were added 11.29 g. (.0416 mols) of mercuric chloride
and 10.5 g. (.125 mols) of sodium acetate in 100 c.c. of
water.
At the end of four hours a heavy white precipitate
h a d formed.
After standing overnight, the mercurial was
removed by filtr action.
The mercurial, which weighed 6.15 g.
(92.6 percent of theoretical,
assuming G^HgOgHggClg as the
product) did not melt below 235°C.
The mercurial was reacted with 9 g. (.035 mols) of
iodine in 60 c.c. of 14.5 percent aqueous potassium iodide
soluition.
The excess iodine was removed by adding a small
amount of sodium thiosulfate solution.
The solution was
77.
extracted four times with, ether.
The combined ether portions
were dried over anhydrous sodium sulfate.
removed by distillation.
The ether was
A tarry residue, which gave no
^•®fin,ite products remained.
Evidence of the formation of an
ether-soluble compound, containing iodine, was obtained,
however.
During removal of the ether iodine was liberated,
for a blue coloration was obtained when moist starch paper
was touched to the solution.
Note: Microanalyses by Dr. T. S. Maj Jones Chemical Laboratory,
University of Chicago, Chicago, Illinois.
78.
SUMMARY
1*
mercuric
2.
Xn contradistinction to dioxadiene, dioxen© reduces
acetate*
The reaction lias been studied in aqueous solution,
metlianol solution, benzene solution and in an excess of
dioxene without other solvents.
In most of the reactions
studied the organic products have been ascertained.
3.
The ability of dioxene to reduce mercuric acetate
in non—polar solvents indicates that the reducing action is
a function of the special type of double bond and not of an
intermediate hydrolysis product.
4.
Two possible reaction mechanisms have been proposed
for the reaction.
5.
Silver acetate oxidizes dioxene and several, of the
similar compounds studied,
although the reaction is consider­
ably slower than with mercuric acetate.
6.
Gupric acetate does not oxidize dioxene.
7.
m-Propenylanisole does not reduce mercuric ions to
free mercury, whereas the corresponding ortho and para
isomers, when treated under the same conditions, do cause
reduction of mercuric mercury to the free metal.
The differ­
ence In behavior is attributed to the fact that compounds
which reduce mercuric acetate are vinylogues of vinyl ether,
whereas the meta compound Is a vinylogue of allyl ether.
8.
A new mercury derivative of u/ -ethoxystyrene has
Ww4v«rstt
ygLlterary
been reported and a structure proposed.
A structure for
another u> -ethoxystyrene mercurial, prepared first by
Manchot (loc. cit.) has been suggested.
9.
The reducing powers of vinylogous vinyl ether are
greatest when the double bond is activated by two vicinal
ether linkages or when it is activated hy a benzene ring in
addition to an ether linkage.
10*
ethers.
This reaction is not applicable to all vinyl— type
Ethers that (1) are polymerized by the reagent,
(2) form unusually stable or insoluble mercurials,
or (5)
do not retain the aliphatic nature of the double bond,
not oxidized by mercuric acetate.
are
80.
VITA
Georg© Herbert Kalb
Bom:
August 1, 1915, Woodhaven, Long Island, N. Y.
Education:
Altoona, Pennsylvania High School, 1929-1952*
Lehigh. University, 1932-1938.
Northwestern University, 1938-1940.
Degrees:
B.S. in Chemical Engr., 1936, Lehigh University.
M.S. in Chemistry, 1938, Lehigh University.
Positions Held: H u n t Rankin Research Fellow in Chemistry, L . U . ,
1936-1938.
University Scholar, N.U., 1939-1940.
Publications:
Theory of Two Bath Chromium Tanning, with
E. R. Theis.
J. A. L. C. A . , 33, 120-144 (1938).
Societies:
Phi Eta Sigma
Pi Mu Epsilon
Phi Lambda Upsilon
Sigma XI
American Chemical Society
i
ERRATA
Page ii.
Page
Page
Page
Page
Page
Page
Page
Page
Page
Page
Page
Page
Page
Page
Si
Page
Page
Page
Page
Lines 14 and 16 read Mercuration. instead of
Mercuriation.
2. Formula VXIX insert H on triv alent carbon*
9* Line 22, read Pinene for Pineni#
10• Formula XIV, Add bond to isopropyl group.
Ref. 23, read Zent. for Cent.
11. Lines 10 and 11, read eugenol methyl ether
for methyleugenol.
12. Line 1, read Isoeugenol methyl ether for
me thyII soeugenol •
13. Line 8, insert at end of sentence, after
Hofmann degradation.
14. Line 4, read methylenedioxy for ethylenedioxy-.
21. Line 3, add (iso structure).
Line 4, read isonitriles for Isonitites.
24. Line 12, replace - b y ,.
26. Line 10, after point insert of the series.
Line 15, read atoms for molecules.
Line 17, read in the other seriea for in the series.
38. Line 17, read the reaction is based on.
43. Line 6, omit a benzene solution on.
46. Line 24, read eugenol methyl ether for methyleugenol,
read isoeugenol methyl ether for methyl!soeugenol.
47. Line 3, read isoeugenol methyl ether for
me thyli s oeugenol •
54. LI ne 14, read went for goes.
61. Insert oc before
-chloroether.
70. Line 18, read were for was.
79. Line 4, vinylogous vinyl ethers instead
of
vinylogous vinyl ether.
Документ
Категория
Без категории
Просмотров
0
Размер файла
3 819 Кб
Теги
sdewsdweddes
1/--страниц
Пожаловаться на содержимое документа