close

Вход

Забыли?

вход по аккаунту

?

Studies on the sulfonation of olefins

код для вставкиСкачать
Northwestern
University
Manuscript
Library
Theses
U n p u b l i s h e d t h e s e s s u b m i t t e d for the M a s t e r ’s a nd
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 , but a re to be u s e d o n l y w i t h
d ue r e g a r d to the r i g h t s of the 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 , but 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
the p e r m i s s i o n of t he 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 or p u b l i s h e d w or k.
Extensive
c o p y i n g or p u b l i c a t i o n of the t h e s i s in w h o l e or in p a r t
r e q u i r e s a l s o t h e 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 .
T h i s t h e s i s by..^h a s b e e n u s e d by the f o l ^ o ^ i n g
a t t e s t t h e i r a c c e p t a n c e or the
i ts
persons, whose signatures
above restrictions.
A L i b r a r y 'which b o r r o w s
p a t r o n s 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 ach user .
DATE
NORTHWESTERN UNIVERSITY
STUDIES ON THE SULFONATION OF OLEFINS
A DISSERTATION
SUBMITTED TO THE GRADUATE SCHOOL
IN PARTIAL FULFILLMENT OF THE REQUIREMENTS
for the degree
DOCTOR OF PHILOSOPHY
DEPARTMENT OF CHEMISTRY
BY
JAMES MARION HOLBERT
EVANSTON, ILLINOIS
AUGUST, 1940
ProQuest Number: 10101537
All rights reserved
INFORMATION TO ALL USERS
The qua lity o f this re p ro d u ctio n is d e p e n d e n t upon th e quality o f th e c o p y subm itted.
In th e unlikely e v e n t th a t th e author did n o t send a c o m p le te m anuscript
a n d th e re are missing pages, these will be no te d . Also, if m aterial had to be rem oved,
a n o te will in d ica te th e deletion .
uest.
ProQuest 10101537
Published by ProQuest LLC (2016). C opyright o f th e Dissertation is held by th e Author.
All rights reserved.
This work is p ro te c te d against unauthorized co p yin g under Title 17, United States C o d e
M icroform Edition © ProQuest LLC.
ProQuest LLC.
789 East Eisenhower Parkway
P.O. Box 1346
Ann Arbor, Ml 48106 - 1346
ACKNOWLEDGMENT
The author wishes to express
his sincere appreciation for the
invaluable aid and encouragement
of Dr. C. M. Suter, under whose
supervision this work was carried
out*
TABLE OP CONTENTS
page
INTRODUCTION.........................................
1
HISTORICAL
I* The Dioxane Sulf otrioxide Reagent • • • « • • •
II • The Sulfonation of E t h y l e n e .............. • • •
III* The Sulfonation of Propylene
•
IV* The Sulfonation of wAmylenesM •
V* The Sulfonation of
Cyclohexene.
........
VI* The
Sulfonation of Styrene •
VII* The Sulfonation of Higher Olefins • • • • • • •
2
4
7
8
8
8
10
DISCUSSION
I* The Reaction of Dioxane Sulfotrioxide with
Ethylene* • • . • • • • • » • * ............ •
12
II* The Reaction of Dioxane Sulf otrioxide with
Propylene...................................
16
III* The Reaction of Dixoane Sulf otrioxide with
l-Pentene . . . . ..........................
21
A* Possible Products from 2-Pentene * . • • • 24
IV* The Reaction of Dioxane Sulf otrioxide with
Cyclohexene • •
• • • • • • « • • •
25
V* The Reaction of Dioxane Sulf otrioxide with
Styrene • • * • • • ' • • • • • • • • • • . • •
27
VI* The Reaction of Dioxane Sulfotrioxide with
1-Pentadecene . . . ..........................
30
VII* A Proposed Mechanism 3ov the Sulfonation of
Olefins
32
EXPERIMENTAL
I* Preparation of Dioxane Sulfotrioxide Reagent. »
II* The Sulfonation of Ethylene • • • • • • , • • «
III* The Sulfonation of Propylene. • • • • « • • • •
IV. The Sulfonation of l-Pentene. . .............
A. The Sulfonation of 2-Pentene • • • • • • •
V. The Sulfonation of
Cyclohexene.......
..........
VI. The Sulfonation of Styrene.
VII. The Sulfonation of 1-Pentadecene. . . . . . . .
A. The Preparation of 7 -Pentadecene . . . . .
34
34
39
49
52
53
55
60
65
SUMMARY...............................
67
B I B L I O G R A P H Y .....................................
69
VITA...............................................
70
INTRODUCTION
This investigation is a study of the reaction of dioxane
sulfotrioxide with straight chain olefins with terminal
unsaturation.
The dioxane sulfotrioxide reagent was
1
developed in this laboratory by Evans,
who found it to be
an excellent sulfonating agent, reacting readily with olefins
at room temperature to produce water soluble compounds,
S,3
Kiefer,
in a more detailed investigation,
studied the
action of this reagent on propylene and 1-nonene.
Malkemus,
in an investigation of the sulfonation of isobutylene,
demonstrated that the reagent reacted b y substitution rather
than addition,
the products being unsaturated sulfonic acids.
This thesis is concerned with the reaction of dioxane
sulfotrioxide on ethylene, propylene,
cyclohexene and
1
1
-pentene, styrene,
-pentadecene, and the identification of the
products formed.
(1)
(2)
(3)
(4)
Evans, Ph.D. Thesis, Northwestern University, 1935*
Kiefer, M.S.Thesis, Northwestern University, 1937.
Suter, Evans and Kiefer, J.Am.Chem.Soc., 60, 538 (1938).
Malkemus, Ph.D. Thesis, Northwestern University, 1939.
2.
HISTORICAL
I* The Dioxane Sulfotrioxide Reagent:
It was found that when sulfur trioxide is added to a
chilled solution of dioxane in some diluent such as ethylene
dichloride or carbon tetrachloride a white, flakey addition
product settles out which may have either of two structures
3
as indicated b y the following equations.
1.
0 ( 0 ^ 0 1 ^ ) 3 0 + S0a
2.
0(CH2CHs)3 0 + 2 S0 3
---► 0 (OHgCHg )a 0S0 3
»
0aS 0 (CHaCHa )a OS 03
Both dioxane sulfotrioxide and dioxan«lisulfotrioxide are
stable under anhydrous conditions at room temperature,
hydrolyze instantly to dioxane and sulfuric acid, and exhibit
similar sulfating and sulfonating action.
The reaction of dioxane sulfotrioxide with alcohols is
practically quantitative, resulting in alkyl hydrogen
6
sulfates.
Reaction also occurs with a variety of aromatic
compounds yielding sulfonic acids#
By far the most important characteristic of dioxane
sulfotrioxide is its reaction with simple olefins.
The
product of this reaction may be readily converted into
hydroxysulfonates by hydrolysis as Indicated in the following
equation.
CHa -CH=GHa + 2 OfCHsCHgJOSOg
-- > C H s - C H - C H s
1
I
?
I
0aS-0-S0s
(5) Suter, U.S.Patent 2,098,114.
—
3.
CH 3 -CHOH-CHsSGaH + E 3 SO 4
This reagent and reaction opened a new field of chemistry for
investigation,
as a convenient method of preparing pure
hydroxysulfonates from olefins has not been available before.
This reaction when extended to higher olefins, C 9
to C18,
produces compounds of marked activity as detergents and
6
wetting agents#
In addition to the hydroxysulfonates,
unsaturated nature have also been obtained,
compounds of an
showing that
reaction of the dioxane sulfotrioxide with an olefin may
occur either by addition or substitution, depending upon
the nature of the olefin and the conditions of the experiment#
Malkemus
found that the sulfonation of isobutylene at 0°,
is not appreciably affected by the concentration of the
reagents nor the manner in which they are added.
Hydrolysis
of the sulfonation mixture with barium hydroxide led to a
mixture of three products,
CH 3
CHS -C-CH 3 SO 3
Ba,
OH
CHS
CHs=C-CHs -S0a
Ba, and
CH 3
CH»-C=CH-S0:
Ba.
These salts
2
could not be separated by fractional crystallization*
It was also shown that when the sulfonation mixture,
obtained by the interaction of dioxane sulfotrioxide and
Isobutylene at 0°C, was heated to 70° a voluminous precipitate
formed.
This precipitate proved to be 2-methylpropene-l,3-
(6) Suter, IT.S.Pat.
2135358
4
disulfonic acid coordinated with one mole of dioxane,
ch 3
H 0 3 SCHs -C=GHS0 3 H #G 4 :H q0s . Hydrolysis of this intermediate
with barium hydroxide led to the expected barium
propene-1,3-disulfonate.
2
-methyl-
It is interesting to note that the
intermediate dioxane salt when refluxed with thionyl chloride
is converted into its corresponding anhydride,
CHg-C=CH ,
I
I
S0s -0-S0 3
the first example of a cyclic aliphatic sulfonic anhydride.
II.
The Sulfonation of Ethylene:
7
Regnault,
in 1837, was the first to study the action
of sulfur trioxide on ethylene.
Ke found that when the two
anhydrous gases were mixed carbyl sulfate,
1 1
OgS-CHg-CEg-OSOg,
0
crystallized on the walls of the container.
This compound
when treated with water was converted to a mixture of
ethionic acid,
H0sS-CEg-CEg0S0 3 H, and isethionic acid,
I E0GHsGHsS0 3 H.
Huber ,
8
in an investigation of isethionic acid, found
! that when sulfur trioxide reacted with anhydrous ethyl ether,
i
several products were formed.
In the two phase system
] resulting from the aqueous hydrolysis of the reaction
mixture, Huber found that the major product,
remained in the ether layer.
ethyl, sulfate,
This was identified by con­
version to a barium salt.
(7) Regnault, A h n ., 25, 32 (1837).
(8 ) Huber, A n n . , 2 2 3 , 1S8 (1884).
Prom the water layer, he isolated additional ethyl
sulfate, methionic acid, and a mixture containing 15%
ethionic acid and 85% isethionic acid*
This latter mixture,
he converted completely to barium isethionate by treatment
with barium hydroxide.
Prom his results, Huber concluded
that the initial product of the reaction was ethyl sulfate,
and that the additional products arose from the further
reaction of sulfur trioxide with this substance*
To support
his theory, he prepared a quantity of ethyl sulfate and found
that on treatment with sulfur trioxide it was converted to
a mixture of methionic acid and isethionic acid*
This led
him to propose the following steps for the reaction
1 * CgHgOCgHg + SQg
——+
SOg (OCgHg)g
2. SOg (OCsH s )s + 3 S0 3
»
CHoSOgH
l,H os
ls
CHS 0S03H
3. qjj gQ H
-- *
+ 2 S°s
3x
+
OgS-CEg-CEg-
I
0-----
CHS CSOsH)3 + 2 S 0 s + C 0 S + Hs 0
9
Plant and Sidgwick
showed that carbyl sulfate and
ethyl hydrogen sulfate were formed when ethylene is absorbed
in fuming sulfuric acid*
As a result of his work on the action of nitric acid
io
on olefins Wieland
concluded that fuming sulfuric acid
added to ethylene as HO- and SOGH, thereby forming isethionic
acid directly.
This theory is not only in contradiction to
(9) Plant and Sidgwick, J.Soc.Chem.Ind., 40, 14 (1921).
10) Wieland and Sakellarios, B e r . , 5 5 , 205 (1920)*
6
the work of Plant and Sidgwick,
but also has been shown
1 1
to be incorrect by Michael and Weiner.
These investi­
gators pointed out that carby^sulfate is due to the action
of sulfur trioxide, acting in the bitnolecular form,
on
ethylene while ethionic acid results from the reaction of
pyrosulfuric acid with the olefin.
It was also found that
isethionic acid was converted into carbyl sulfate by the
action of two moles of S0 3
[Ss OsJ
, while with only one
mole of sulfuric acid or S03 , ethionic acid was formed*
is
Kohler
prepared 1, 2 -ethane^disulfonic acid by the
reaction of sodium sulfite with 1,2-dibromoethane.
Hydrolysis
of sodium- 2 -bromoethane- 1 -sulfonate produced sodium isethionate
in a 9h% yield.
sulfonic acid,
13
In a later investigation of unsaturated
Kohler prepared ethylenesulfonic acid by
three methods; namely,
1
. hydrolysis of ethanedlsulfonyl chloride
2
. distillation of l-broxno -2 -ethane sulf onyl chloride
3. from isethionic acid
The last method is of interest in that all attempts to
dehydrate isethionic acid led to the formation of di-isethionic
acid, H 0 3 SCHsCHs -0-CEs -CH 2 SG 3 H;
however,
is first converted to the acetate,
it loses acetic acid
readily to give the unsaturated acid.
(11)
(12)
(13)
if the isethionate
Ethylenesulfonic
Michael and Weiner, J.Am.Chem.Soc.,
Kohler, Am.Chem.J., 19., 728 (1897).
Kohler, ibidem, 20, 680 (1898).
58, 294
(1936).
acid reacts readily with bromine water and neutral permanganate,
and may be hydrated to isethionic acid by heating with water
in a sealed tube at 150°.
14
Koiker and Lapworth,
various double bonds,
in a study of the activity of
reported that an acid sulfite reacts
readily with ethylene to produce ethaneSsulfonic acid as
the major product.
A more recent investigation by Kharasch,
15
May and Mayo
confirmed this result and in addition showed
that the presence of some oxidizing agent is essential for
the success of the reaction.
III.
The Sulfonation of Propylene:
The reaction of propylene with the dioxane sulfotrioxide
s,s
reagent was investigated In 1937 by Suter and Kiefer
who
found that at room temperature the reaction occurred readily
according to the following equation:
2 C 4 H s0-3«S0s + CH 3 -CH=CHs
-- >
CHa -CH-CHs
+ C 44 H
8 0
j
X18^J8
homologue was not isolated but the solution
hydrolyzed with barium hydroxide to produce,
product, barium-2-hydroxypropane-1-sulfonate.
as the final
The structure
of this compound was proven by its oxidation to barium
acetonesulfonate and subsequent hydrolysis to acetic acid.
(14) Kolker and Lapworth, J.Chem.Soc., 127. 313 (1925).
(15) Kharasch, May and Mayo, J.Org.Chem., 3, 175 (1938).
8.
15
Kharasch
found that propylene reacts with ammonium
bisulfite only in the presence of oxidizing agents to
produce propane-l-sulfonic acid*
The best yield was
obtained in the presence of nitrates*
IV*
The Sulfonation of Amylenes;
1
Evans
demonstrated that wamylenen reacts readily with
dioxane sulfotrioxide forming a reddish oil readily
/
soluble in water to produce an acidic solution.
That crude
amylene reacts readily with ammonium hydrogen sulfite was
14
shown b y Koiker and Lapworth,
who found that this olefin,
unlike many others, was converted completely to saturated
sulfonic acids.
Since the olefin was a mixture of isomers,
the structure of the product was not further investigated.
V.
The Sulfonation of Cyclohexene:
Cyclohexene is sulfonated readily, although not rapidly,
by the action of M/4 ammonium bisulfite solution In the
presence of kieselguhr as an emulsifying agent.
The
product Is composed of approximately 90% of ammonium cyclo­
id
hexanesulfonate
and 10% of an organic compound which yields
sulfurous acid or sulfites on hydrolysis.
j
The major product
|was Identified by its conversion to the corresponding sulfonanilide.
i
VI.
The Sulfonation of Styrene:
1 6
j
Quilico and Pleischner
first prepared 1 -phenyli
iethylene-2 -sulfonic acid by the action of sulfamic acid,
I}
(16) Quilico and F l e i s d m e r , Atti.accad.Lincei, 6 , 7 1 0 5 0
(1929); G.A., 23, 1628
9«
KHe SOaH,
on styrene*
Their assignment of structure was made
on the basis of the fact that the compound was oxidized to
benzoic acid by permanganate and that fusion with sodium
formate resulted in cinnamic acid*
Derivatives prepared were
the sulfonyl chloride melting at 85° and the sulfonamide
melting at 140°*
17
In 1929 it was reported by Ashworth and Burkhardt
that
the sulfonation of styrene with ammonium hydrogen sulfite
resulted in 1-phenylethane-l-sulfonate.
assigned since the reaction of
This structure was
^-bromoethylbenzene with
ammonium sulfite resulted in an identical product, both
being converted to the same sulfonamide*
The reaction
product from ^ - b r o moethy l b e n z e n e and ammonium sulfite
produced a sulfonamide differing from the above*
These results are not in accord with those reported by
15
Kharasch and co-workers,
who found that the action of
bisulfite on styrene produced a compound identical with
|Quilicofs l-phenylethylene-2-sulfonic acid*
|discrepancy was explained by the fact that
This seeming
«x-bromoethyl-
benzene, under the conditions imposed b y Ashworth and
Burkhardt,
is dissociated into styrene and hydrogen bromide.
The halogen acid is then absorbed in the aqueous layer with
the evolution of sulfur dioxide*
Thus, under such conditions,
the reactive agents were styrene and bisulfite, the same
reagents that were used in the production of the compound
(17) Ashworth and Burkhardt,
J.Chem.Soc., 1791
(1928)
10.
in question.
J
The reaction of c*-bromoe thy lb enzene with bi-
sulfite was later carried out in a strongly ammoniacal
solution to prevent the formation of styrene.
The resulting
compound could not be converted to the sulfonyl chloride, all
attempts leading to the formation of secondary phenylethyl
chloride.
A mechanism for the sulfonation of styrene has
| been proposed by Kharasch, but this will be presented in a
J
later section of this thesis.
| VII.
|
|
The Sulfonation of Higher Olefins:
The reaction of the dioxane sulfotrioxide reagent
with higher molecular weight olefins, 9 to 18 carbon atoms,
j occurs readily at 20-25° without more than slight darkening,
jI The
10
sodium hydroxysulfonates, prepared by the hydrolysis of
j
| the sulfonating mixture with sodium hydroxide or sodium
1
i
carbonate,
show, in many cases, decided soaplike properties.
| The straight chain products seem to exhibit this property to
j
\ a greater degree than do the branched chain olefins, or
I
| olefins of the type R-CH=CH-R.
The fact that these hydroxy!i
j sulfonates possess detergent properties will make this method
j
I of sulfonation extremely interesting commercially should a
!
! convenient source of these higher olefins be found.
|
!
A brief resume of compounds investigated Is given below:
Sulfonation of 1-Nonene.
- 1-Uonene, prepared by the
!j action of n-hexylmagnesium bromide on allyl bromide, was
(18) Suter, Unpublished Review, northwestern University, 1937.
11
sulfonated at room temperature by adding the olefin to the
dioxane sulfotrioxide reagent in ethylene dichloride•
Refluxing the mixture with aqueous barium hydroxide resulted
in the formation of the insoluble barium- 2 -hydroxynonane sulfonate*
1
-
This salt was converted to the corresponding
sodium salt in a practically quantitative yield by treatment
with sodium sulfate#
The sodium sulfate-sulfonate was pr e ­
pared by exactly neutralizing the sulfonation mixture with
sodium hydroxide and removing the solvents at room temp­
erature under reduced pressure.
Sulfonation of Tridecene.
-
1-Tridecene, prepared from
n-decylmagnesium bromide and allyl bromide, was sulfonated
as described and the product converted to a sodium salt by
hydrolysis with sodium hydroxide.
A sample of this salt re-
crystallized from water analyzed correctly for sodium- 2 hydroxytridecane-1 -sulfonate.
Sulfonation of Cetene.
- Getene
(du Pont product) was
sulfonated by the same method as described above and c on­
verted to a sodium salt by hydrolysis with sodium hydroxide.
A water solution of this salt is soap-like in behavior,
foaming when heated to boiling.
Sulfonation of 1-Pentadecene and 1-Heptadecene.
-
These
olefins, prepared by the Grignard reaction, were sulfonated
in the usual manner at room temperature.
were prepared by alkaline hydrolysis,
amorphous rather than crystalline.
cussion of
1
The sodium salts
the product being
A more detailed di s ­
-pentadecene is given later in this thesis.
12.
DISCUSSION
Reaction of Dioxane Sulfotrioxide with E t h y l e n e :
It was found that no reaction occurred when ethylene
was passed into the dioxane sulfotrioxide reagent at room
temperature,
2
2
° , although all other olefins investigated
reacted readily even at lower temperatures.
This, however,
is not surprising when one recalls that the absorption of
ethylene by sulfuric acid is much slower than that of higher
olefins.
For example,
in the separation of gaseous olefins,
63-64 % sulfuric acid is used for the absorption of Iso­
83-84 % sulfuric acid for the absorption of
butylene,
ie
propylene,
and
1 0 0
-1
0 2
% acid for the absorption of ethylene.
2 0
Mutuszak
reports that the 63-64% acid absorbs Isobutylene
500 times as fast as propylene,
and propylene,
in turn,
absorbed 500 times as fast as ethylene In 83-84% acid.
Is
With
this In mind, the temperature of the sulfonating solution
was raised to 50° and ethylene again passed In.
Reaction
occurred readily producing a light straw colored solution.
It was later demonstrated that the reaction occurred slowly
at 35-40°.
Since the reaction of ethylene with sulfur trioxide is
7 11
known to produce carbyl sulfate,
,
the reaction mixture
was examined closely for any indication of its formation;
however,
the formation of a new solid was not observed, nor
(19) Dobryanskii, Neftyanoe Khozyalstvo, 9, 565 (1925);
C.A., 20, 1576 (1926).
(20) Mutuszak, Ind.Eng.Chem.,Anal.Ed., 10, 354 (1938).
could carbyl sulfate,
products.
as such, be Isolated from the reaction
The products isolated were methionic acid, as Its
slightly soluble barium salt, and an unsaturated salt of
uncertain structure*
The formation of methionic acid from the sulfonation
of ethylene was surprising but not without parallel, for
8
Huber
has shown that one of the products obtained by the
action of sulfur trioxide on ethyl ether is methionic acid,
GII3 (S03 E)s *
Huber concluded that methionic acid was formed
by the action of sulfur trioxide on ethionic acid and suggested
the following equation to represent the reaction.
CE s 0S03H
I
CHa SOsH
That this,
+ 2 S0a
> CES (S03 H)s + 2 S0 2 + C0S + Hs 0
or some very similar method of formation,
is
quite plausible Is indicated by the fact that the sulfonation
carried out at 50° produced appreciable quantities of
methionic acid while at 35-40° little or no methionic acid
was detected.
This also eliminates the suggested possibility
that the methionic acid might have arisen by the reaction
of sulfuric acid and acetylene,
ethylene,
a possible Impurity in the
since similar results should have been obtained at
both temperatures•
Strength is also given to this argument
by the fact that sulfur trioxide often leads to the oxidation
ai
of hydrocarbons, itself being reduced to sulfur dioxide.
The methionic acid was isolated as Its sparingly
(21) Brooks, The Hon-Benzenoid Hydrocarbons,
1922, p. 143.
14.
soluble barium, salt which crystallizes from aqueous solution
with two moles of water.
An anhydrous sample of this salt
analyzed correctly for barium.
These results,
other checking physical properties,
combined with
leave little doubt as to
its correct identification.
The major product obtained from the sulfonation of
ethylene with dioxane sulfotrioxide has so far not been
properly identified.
Analysis of the dry salt showed it
contained approximately 32$ barium.
expected ethane derivatives,
barium content,
A list of the normally
together with their corresponding
is given below.
% barium
C omp ound
1
.
(CH3 OECHeS03 )sB a ........... .
2
.
fOaSCH*CHa OSOg ) B a ......... .
3.
(CHS =CHS03 )sB a ............. .
4.
OfGH 3 CH 2 SOs )sB a ........... .
That it is plausible to expect these compounds is shown by
the fact that the sulfonation of propylene by this process
resulted in homologues of 1 and 2.
It will presently be
shown in this thesis that compounds of type 3 are also
is
produced by this same process*
Kohler
reports that diisethionates, 4, are produced when isethionates,
1, are
dehydrated, by heat.
The formation of large amounts of barium sulfate, when
the sulfonation mixture was hydrolyzed with barium hydroxide,
is evidence that some type of sulfate ester linkage must have
been formed in the sulfonation process.
Reasoning would
then lead one to suspect that carbyl sulfate was first formed
by the action of sulfur trioxide on ethylene, and that it,
in turn, was hydrolyzed to barium isethionate and barium
sulfate.
Barium analysis, however,
not the case.
indicated that this was
It is possible that the barium sulfate might
have arisen by the hydrolysis of excess dioxane sulfotrioxide,
but the copious quantity of barium sulfate obtained, coupled
with the fact that all solid dioxane sulfotrioxide had
disappeared when only two-thirds of the theoretical amount
of ethylene had b e e n passed In, makes this possibility
extremely doubtful.
The fact that the product reacted rapidly with neutral
permanganate and bromine water points strongly to ethylene1S
sulfonic acid,
3, as the probable answer, but here also
the barium analysis was far too low.
Since the barium salt
was very difficult to work with, being extremely hygroscopic,
it was converted to the sodium salt, but this was of little
value since the sodium salt was also hygroscopic.
A portion
of the sodium salt was recrystallized from alcohol and gave
on analysis a value corresponding closely to that of sodium
ethylenesulfonate; however,
since no other proof could be
brought to bear, the Identification is considered incomplete.
Since the barium analysis was consistently low, the
possibility of a polymerized sulfonated product immediately
presents itself.
Isobutylene when sulfonated by the dioxane
sulfotrioxide reagent has been shown to produce not only
sulfonated dimers but also some sulfonated dodecene
16.
££
derivatives#
However it must be remembered that while
isobutylene is easily polymerized,
ethylene is polymerized
only with great difficulty b y the action of acids#
Fr o m the results,
it seems that the principle product
obtained by the sulfonation of ethylene with dioxane sulfotrioxide is either a complex mixtuhe of some or all of the
suggested compounds together with a rather high molecular
weight polymer,
or that another compound, unexpected and
heretofore unobtained,
is formed by the reaction.
The Reaction of Dioxane Sulfotrioxide with Propylene#
One of the chief disadvantages in the type of work
described in this thesis is the lack of rapid identification
of the compounds by melting point,
been proven by analysis#
once their structure has
For example, any attempted reaction
involving the salts must be followed by a time consuming
analysis before it is known whether or not reaction has
actually occurred#
Consequently,
an attempt was made to
find a simple solid derivative by which the compounds
involved could be rapidly identified#
For this investigation
barium- 2 -hydroxypropane-l-sulfonate, obtained b y the action
of dioxane sulfotrioxide on propylene, was chosen, as its
structure had been proven by the work of Kiefer.
Contrary to the report of Kiefer,
it was found that
(22) Malkemus, This Laboratory, Private Communication.
(23) Whitmore,
Organic Chemistry, 1S37, p. 35#
17.
the reaction of propylene with dioxane sulfotrioxide occurred
"below room temperature,
12-15°, to produce a solid similar
in color and texture to the original dioxane sulfotrioxide*
The compound proved too unstable to identify directly, as
it liquefied rapidly forming a brown oil even when kept in
a vacuum desiccator over phosphorus pentoxide*
The structure
seeming most likely for this solid is that of the next
higher homologue of carbyl sulfate, CHSC H — CHs -SOs *
OSO-s
agreement with this structure,
In
0
It was found that the oil
reacted vigorously with barium hydroxide to produce barium
sulfate and barium- 2 -hydroxypropane- 1 -sulfonate in approxithe
mately the correct ratio required by/following equation
2 CHSC H —
lsoB
CEg-SOg
+ 3 Ba(OH)g
►
(CH3 CH0KCHs S0 3 )sBa + 2 BaS0 4
CH
Hydrolysis of an unweighed sample of the oil with barium
hydroxide resulted in the formation of 16*42 g. of barium
sulfate*
After removal of excess barium hydroxide, evap­
oration to dryness led to 15*08 g. of barium-2-hydroxypropane-1-sulfonate.
According to the above equation 15*08 g*
of the hydroxysulfonate should be accompanied by 16.95 g. of
barium sulfate if the original product is the pure homologue
of carbyl sulfate*
However,
since the final product obtained
!
J
1
gives the -usual tests for slight unsaturation,
it must be
assumed that the hydroxysulf onate Is contaminated with some
sodium propylenesulfonate.
If this arose by the dehydration
of the hydroxy compound, the barium sulfate would run high
when calculated on the basis of the sodlum- 2 -hydroxypropane-lsulfonate obtained.
If, on the other hand, the unsaturated
product arose from a substitution rather than an addition
product of the reaction of propylene and dioxane sulfotrioxide,
the amount of barium sulfate would be less than
calculated.
This latter suggestion is in accord with other
results.
The persistent odor of ethylene chloride, which remains
with the oil even after several months, suggests that the
solid may be carbyl sulfate or some similar structure co­
ordinated with one or more moles of ethylene chloride.
On
this basis, the gradual loss of ethylene chloride would
account for the decomposition of the solid.
Normally propylene was sulfonated at room temperature,
the temperature rising to about 30° as the reaction progressed.
This produced a compound which consistently analyzed high for
barium content.
The fact that an aqueous solution of the
salt rapidly reduced cold, neutral permanganate and decolorized
bromine water indicated that some barium propylenesulfonate
had been formed either by dehydration of barium- 2 -hydroxy-
j
propane- 1 -sulfonate or that the dioxane sulfotrioxide had
jj reacted by substitution rather than addition.
Although in
|| the normal reaction of dioxane sulf otrioxide with olefins
j| it has been assumed that reaction occurs by addition across
i!
j the double bond, it has been demonstrated by Malkemus and
j will be shown later
(see styrene) that reaction may proceed
i
j almost entirely to yield unsaturated products.
Analysis of
19
the acetyl derivative also indicated the presence of the
unsaturated derivative in the same amounts as calculated
from the original analysis.
Since it has been shovjn the sodium -2-hydroxy-propane-l2
sulfonate is readily oxidized to barium acetonesulfonate,
the question was raised as to whether or not the reaction
with cold, neutral permanganate actually indicates unsat­
uration.
This objection was answered by the preparation of
a pure sample of sodium- 2 -hydroxypropane- 1 -sulfonate, which
was shown to give no reaction with either permanganate or
bromine water.
The pure sample was also converted to
sodium- 2 -acetoxypropane-l-sulfonate and found to analyze
correctly for sodium content.
Attempts to prepare the
benzoyl derivative resulted in failure, apparently due to
the insolubility of the salt in benzoyl chloride.
As the conversion of sodium 3 -hydroxypropane- 1 -sulfonate'
to the sharply melting 3-chloropropane-l-sulfonamide has
15
been successfully carried out,
an attempt was made to
prepare similar derivatives for the compound in question,
j Following the directions given by Kharasch, the product
j obtained from the sulfonation of propylene was first
converted to the corresponding chlorosulfonyl chloride.
Subsequent reaction with ammonia produced an oil from
which crystals could not be obtained.
Similar results
were obtained by reacting the chlorosulfonyl chloride with
! xenylamine and p-toluidine.
I
!
A possible explanation of the failure to obtain solid
I
derivatives by the above procedure lies in the fact that the
20
starting material is a mixture of sodium propylenesulfonate
and sodiuni'-2-hydroxypropane-l-sulf onate.
Since these could
not he separated hy fractional crystallization,
the obvious
procedure was to separate their sulfonyl chlorides by
distillation.
This procedure resulted in two fractions
boiling about 9 degrees apart.
Analysis indicated the low
fraction to be a propylenesulfonyl chloride and the higher
fraction to be 2 -chioropropane-1-sulfonyl chloride.
So far
no attempt has been made to react these compounds with amines.
Considerable doubt as to the value of the above sep­
aration arose when it was found that
2
-chloropropane-l-
sulfonyl chloride, prepared from the pure sample of s o d i u m
2
-
hydroxypropane- 1 -sulfonate, also produced two fractions
when distilled.
These fractions were identical with those
obtained in the above distillation.
The suggestion that occurrence of sodium propylenesulfonate, from the sulfonation of propylene,
explained by the dehydration of sodium
2
could be
-hydroxypropane- 1 -
sulfonate is not without basis when one recalls the instability
of a^?-hydroxy carboxylic acid.
A similar situation exists
j in the above case, since the hydroxy group is
to the
|negative sulfonic acid group and should, as a result of its
position, be extremely active.
While this does not seem
to be the case in the sodium salts, as indicated by the
i| apparent stability of the pure sample, it is not unlikely
!
|that the conditions imposed by the preparation and subsequent
distillation of the sulfonyl chloride were severe enough to
cause a splitting out of hydrogen chloride thus producing
propylenesulfonyl chloride.
separation,
As a more probable method of
it is suggested that the acetyl derivative
first be prepared and the mixture then converted to the
sulfonyl chloride.
Such a procedure v;ould eliminate the
formation of propylenesulfonyl chloride by the splitting
out of hydrogen chloride from the chiorosulfonyl chloride.
Of general interest is the pyrolysis of a pure sample
of sodium~2-acetoxypropane-l-sulfonate.
This compound on
heating was found to completely liquify at 235° and exude
an acidic gas.
The product recovered after this treatment
reduced cold, neutral permanganate rapidly and absorbed
copious quantities of bromine water,
indicating the
presence of sodium propylenesulfonate.
action is reported for sodium
2
An analogous r e ­
-acetoxyethane-l-sulfonate,
in which acetic acid was lost by heating at
2 0 0
° to produce
1 2
sodium ethylenesulfonate,
III. The Reaction of Dioxane Sulfotrioxide with 1-Pentene.
The olefin, 1-pentene, was found to be readily sulfonated
by dioxane sulfotrioxide at room temperature, but at ice
temperature no reaction was observed*
recent investigations,
In the light of more
it might well be that the last
observation is erroneous as It has been shown that new
solids, similar In color and texture to dioxane sulfotrioxide,
are produced by low temperature sulfonation.
The product of this reaction,
isolated as its barium
salt, was found to reduce neutral permanganate in the cold
22.
and to react rapidly with bromine water.
A high barium
analysis of 31.50 % as compared to a theoretical value of
29.08?& also pointed to the presence of unsaturated material
in the expected barium-2 -hydroxypentane-1-sulf onate.
This
unsaturated material probably originated from a substitution
reaction of dioxane sulfotrioxide with
bility already discussed.
1
-pentene, a possi­
It is logical to suppose that
substitution occurred on the carbon atom ,,allyl,f to the
double bond,
as this should be the position of greatest
reactivity.
On this basis, the structure proposed for the
unsaturated material is
fCH3 CHs -CHS0 3 CH=CHs )sBa.
Since the barium salts of these isomers are not as
extremely soluble in water as the lower homologues, a
fractional crystallization was undertaken in order to
effect a separation.
The following diagram represents the
course of the crystallizations.
filtrate
residue
a
10
11
12
13
14
Analysis of samples
8
and 14 gave 30.18 and 29.30/£ barium,
respectively, indicating that qualitative separation had
occurred as expected; i.e., the unsaturated product should
the
be/less soluble of the two, while the hydroxysulfonate would
b© concentrated in the filtrates.
While the value of 14
checks within experimental limits the calculated barium
content of barium- 2 ~hydroxypentane- 1 -sulfonate, the fact
that it still reacts with dilute permanganate points to
its contamination with barium pentenesulfonate.
Fraction 4, which was very small, gave the surprisingly
high analysis of 39.42% barium and in addition reacted with
neither permanganate nor bromine water.
At first these
results were regarded as meaningless, but in view of the
i
results obtained from the sulfonation of ethylene,
it is
now believed that this compound was, in all probability,
barium methionate.
It will be recalled that barium methionate
crystallizes from water as a dihydrate which contains
| 39.40%' barium.
If one accepts the work of Huber, the formation
| of methionic acid from the sulfonation of
1
-pentene could
| be explained by a similar process; that is, the action of
j|
sulfur trioxide upon the intermediate anhydride.
Since the
i
!
(! carbon atom which is attached directly to the sulfur is
I
!j the one broken off in the formation of methionic acid, it
| would not be surprising if methionic acid were formed as a
| by-product when any simple olefin with terminal unsaturation
l
i
!
| is sulfonated at elevated temperatures.
;
l
It has been shown that sodium 2 -hydroxypropane-1 i
;
j! sulfonate is oxidized by chromic acid to sodium acetoneSj
I
sulfonate, which in turn is hydrolyzed by concentrated
2
i| alkali to acetic acid and methanesulf onic acid.
An
!
I attempt to apply the same procedure to barium 2 -hydroxy-
24.
pentane- 1 -sulfonate resulted In the formation of a mixture
of propionic and acetic acid as indicated "by Duclaux
constants*
This result does not mean that the proposed
structure of the original compound is incorrect; for it
was doubted at the outset if the oxidation would stop at
the expected butyric acid*
2-Pentene was also sulfonated by means of the dioxane
sulf otrioxide reagent, but a preliminary survey of the
resulting material indicated such a complex mixture that
further work was discontinued.
It is of interest, however,
to note the number of possible compounds theoretically
obtainable from such a reaction.
Primarily, the 2-pentene, as prepared by the dehydration
of diethylcarbinol, consists of a mixture of cis and trans
isomers.
The refractive index of the constant boiling
fraction used in the sulfonation,
indicated the olefin to be
composed largely of the trans compound.
Sulfonation to
give 3-hydroxypentane-2-sulfonic acid would lead to the
formation of two asymmetric centers and result in the
production of two racemates or four optically active diasterioisomers.
Similarly,
if the sulfonation resulted
in the formation of 2-hydroxypentane-3-sulfonic acid four
additional isomers would be formed,
of eight isomers
giving a possible total
(four racemates) if the reaction occurred
by addition across the double bond.
If, however, reaction
occurred by substitution, as is entirely plausible,
would be expected that the
2
it
-pentene would react either at
positions 1 or 4.
Substitution at the 4 position would lead
to the production of a new asymmetric center and therefore
result in a d- and 1- modification.
1
Substitution at the
position would result in the formation of only one
compound, 2-pentene-l-sulfonic acid*
Therefore the trans
compound would result in three isomers as would the cis,
1 producing a possible total of six isomers.
Thus
the maxi-
I mum number of products obtainable from such a reaction is
fourteen*
type of
2
Prom this it is apparent that olefins of the
-pentene would lead to exceedingly complex mixtures
| which would require special methods for separation.
IV.
I
J
The Reaction of Dioxane Sulfotrioxide with Cyclohexene.
The chief interest associated with the sulfonation of
cyclohexene is that it was the first compound investigated
| in which a solid formed during the actual sulfonating process.
I The fact that this solid formed when the sulfonation was
i
| carried out at low temperatures
(below
1 0
°) while its
| appearance was not noted at room temperature and above, led
j
| to the discovery of the formation of a similar solid from
!
j the sulfonation of propylene.
i
j
This fluffy white solid was immediately suspected of
! being the sulfuric-sulfonic anhydride, postulated as an
'5
jj
|! intermediate In this sulfonation process but never Isolated.
jj
ij In order to avoid its immediate decomposition,
i!
j
the solid
was removed by filtration at ice temperature under anhydrous
5 conditions.
This was of little value for the solid dei
j
]j composed rapidly even in a vacupm desiccator over Ps 0 5 to
26.
form a deep purple oil.
Due to the fact that the odor of
I ethylene chloride remained with the solid and resulting
oil even after prolonged washing with dry air, and that
under reduced pressure the oil bubbled vigorously indicating
the presence of some extremely volatile component, the
solid was suspected of being in some way coordinated with
one or more moles of ethylene chloride.
To test this theory,
cyclohexene was sulfonated at the same temperature in a
solvent of dry carbon tetrachloride.
In this case no solid
formed but an oil very similar in appearance to that ob­
tained by the decomposition of the solid separated from
solution.
Both oils on hydrolysis with barium hydroxide
i
| produced barium sulfate and barium
2
-hydroxycyclohexane-l-
! sulfonate along with a trace of unsaturated material.
The
| significance of the production of these products was dis!
) cussed under the sulfonation of propylene*
|
Hydrolysis of the filtrate from the sulfonation of
| cyclohexene produced as the major product barium
2
-hydroxy-
| cyclohexane-1-sulfonate.
That this material was contaminated
i
; with some unsaturated product was indicated by its slightly
j high barium content, 28.40/c as compared to a calculated
! value of 27.82^, and the fact that the product reacted
I readily with neutral permanganate and decolorized small
i
quantities of bromine water.
It was found that the product
'
i
tj
| could be purified slightly by recrystallization from alcohol.
27
V*
The Reaction of Dioxane Sulfotrioxide with Styrene.
The reaction of styrene with dioxane sulfotrioxide
produced one of the most interesting and unexpected results
studied in this investigation.
Styrene was slowly added to
the dioxane sulfotrioxide reagent in ethylene chloride at
5° with the idea of obtaining a solid similar to that
obtained in the sulfonation of propylene and cyclohexene.
At first the solution seemed to be clearing of solid, but
toward the end of the styrene addition a white solid began
to separate.
On standing in the ice box for several days,
the amount of this solid increased.
It should be noted at
this point that the formation of a solid during the sulfonation
process seems to depend upon several factors,
the principle
ones being the rate of addition of styrene and the temp­
erature of the sulfonation mixture.
In some cases, where
these precautions were not observed, no solid was formed
during the addition of the styrene; however, when any of
the final solutions were allowed to stand for five to six
days at ice temperature,
the formation of some solid material
was always observed.
This solid, naturally being assumed to be similar to
that obtained from propylene and cyclohexene, was removed
under anhydrous conditions.
On standing it showed very
little tendency to liquify as did the previous examples.
It
was found that most of this material was insoluble in water
and when put into solution by prolonged boiling, produced
no barium sulfate when hydrolyzed with barium hydroxide.
28
This indicated that here was a new type of intermediate,
differing radically from those previously obtained.
The
solid reacted readily with permanganate but showed very
little tendency to decolorize bromine water.
Hydrolysis
of the compound with barium hydroxide led to the formation
of barium 2-phenylethylene-l-sulfonate.
A portion of the
solid, recrystallized from a mixture of acetone and high
boiling petroleum ether, melted with decomposition at 134136 °.
This indicated that the compound was not 2 -phenyl^ 16
ethylene- 1 -sulf onic acid which is known to melt around 70°.
A sulfur analysis of 17*49$, together with a molecular
weight determination of 176-177,
limited the composition of
the compound to one mole of styrene combined with one mole
of sulfur trioxide.
That the compound was not some type of
benzothiophene derivative was shown by its oxidation to
benzoic acid and the sulfate ion.
As the above mentioned
method of recrystallization led to the recovery of only
small amounts of purified product, an attempt was made to
recrystallize the product from methyl alcohol.
enough,
the recovered compound melted at 66-67°.
Surprisingly
Prom
ethyl alcohol a compound melting at 46-48° was obtained.
This immediately suggested that reaction of the
compound with alcohols led to the formation of esters.
Since the compound has been shorn not to be 2-phenylethylene- 1 -sulfonic acid, a possible though heretofore
unreported structure was suggested,
that of the
suit one
of 2 -hydroxy-2-phenylethane-1-sulfonic acid, G 6 H 5 GH-CE 3 -S0s •
i— —
0—
I
29.
Reinvestigation showed that the sulfnr analysis and
molecular weight checked this compound within experimental
error*
Reaction of the compound with methyl alcohol was
shown, by sulfur analysis,
to result in methyl
ethylene-l-sulfonate, C 6 H 5 CH=CES0 3 CHa .
to the formation of barium
2
2
-phenyl-
This is analogous
-phenylethylene-l-sulfonate by
the action of barium hydroxide on the suit one.
The insta­
bility o f hydroxy acids has been discussed, and it has
been shown that in general the salts of
acids exhibit no tendency to dehydrate.
-hydroxy sulfonic
It will be noted
j that the hydrolysis of the sultone should result in
2
2
-hydroxy-
-phenylethylene- 1 -sulfonic acid, but here the hydroxy
group In addition to b e i n g t o
a sulfonic acid group Is
on a carbon atom attached to the benzene ring.
Such a
position should result in the enhanced activity of the
| hydroxy group.
This seems to be the case, for in no
instance did any reaction of the sultone, however mild,
result in the formation of a $ hydroxy derivative.
The filtrate from the
sultone was hydrolyzed with
barium hydroxide to produce barium sulfate and barium
2
-phenylethylene-l-sulfonate.
This indicates that the
I expected intermediate, phenyl carbyl sulfate, was also
i
formed b y the reaction.
!
of barium sulfate and barium
|
sulfonate,
|
compound.
jt
Its hydrolysis led to the production
2
-hydroxy- 2 -phenylethane
which Immediately dehydrated to the isolated
Oxidation of barium 2-phenylethylene-l-sulf onate with
30.
neutral permanganate resulted In, first, the formation of
benzaldehyde,
Identified by its phenylhydrazone,
final production of benzoic acid.
and the
Reaction of the barium,
salt with phosphorus pentachloride produced
2
-phenyl-
ethylene- 1 -sulfonyl chloride; this on reaction with ammonia
resulted in the isolation of
2
phenylethylene- 1 -sulfonamide.
The melting point of both these derivatives check the
15,16
accepted values given in the literature,
and serve to
Identify the compound.
VI.
The Reaction of Dioxane Sulfotrioxide with 1-Pentadecene.
As it has been shown that the sodium. 2 -hydroxyalky1-1-
sulfonates,
obtained by the sulfonation of high molecular
weight olefins, possess detergent properties,
this investi­
gation was undertaken to prepare a representative higher
hydroxysulfonate for purposes of investigating Its chemical
and physical properties in more detail.
The sulfonation of 1-pentadecene occurred smoothly at
5° to produce as the final product sodium 2-hydroxypentadecane-l-sulfonate.
Its solubility in water was such that
it could be removed from the sodium sulfate, also formed by
the hydrolysis, by several crystallizations.
The fact that
it reacted with neither permanganate nor bromine water plus
a satisfactory sodium analysis indicated the compound to be
pure sodium 2-hydroxypentadecane-l-sulfonate.
version of this compound to sodium
2
The con­
-acetoxypentadecane-I-
sulfonate was accomplished by the action of acetic anhydride.
Il
( Reaction of the hydroxysulfonate with benzoyl chloride did
j
not produce the benzoyl derivative*
!
]
j
Several attempts were made to oxidize the hydroxysulfonate to sodium
2
-pentadecanone-l-sulfonate, but attempts
to isolate this compound as its 2,4-dinitrophenylhydrazone
led to inconclusive results.
Attempts to hydrolyze the
oxidation mixture as indicated on page 23 resulted In
failure for no myristic was isolated.
The problem of preparing derivatives of the hydroxy­
sulf onates that could be Identified by their melting points,
j
originated at this stage of the investigation.
j
in this direction,
a solution of sodium
2
As a step
-hydroxypenta-
decane-l-sulfonate was mixed with p-toluidine hydrochloride,
i Salt formation should occur according to the following equation
i
(
j
Cl a HS7CH0HCHsS03 Na + p -C H 3 CQH4 MH3 C l
I
!
j
----->
CHaCQH 4 NHaS0 3 CHsCHQHClaH S
7
+ NaCl.
Unfortunately the salt obtained from the reaction did not
I melt sharply.
!
j
2
-Chloropentadecane- 1 -sulfonyl chloride
was prepared
! by the action of phosphorus pentachloride on sodium
2
-hydroxy-
' pentadecane-l-sulfonate. The sulfonyl chloride was treated
l
! with ammonia, aniline, p-toluidine, and 0 * -naphthylamine
j
respectively but all products were oils which showed no
jj tendency whatever to crystallize.
;
|
ij
j|
'!
34
It had been found earlier
that sodium
2 -hydroxy-
(24) McAllister, Private Communication, The Procter and
Gamble Company, Ivorydale, Ohio.
pentadecane- 1 -sulfonate possessed marked detergent properties
comparing favorably with the commercial products containing
sodium lauryl sulfate.
VII.
A Proposed Mechanism to Explain the Products Formed
"by the Action of Dioxane Sulf otrioxide on Olefins.
35,
According to the suggestion of several investigators,
any addition to the olefin linkage must be preceded by a
polarization of the double bond.
The adding positive ion
then attaches itself to the carbon atom possessing a
negative charge.
Assuming that the addition of sulfur
3
trioxide occurs by a similar mechanism, Suter has suggested
the following mechanism to explain the formation of the
hydr oxy sulf ona t e s .
H
H
H
R : 0 :: 0 : H
t
;
R
H
: 0 : C : H
0(CHsCHs )3 0*S0 3
II
I
H
H
R : C : C : H
««
:0 :
:0 :
..
:0: S :0: S :0:
III
IV
jj This final compound on hydrolysis produces the normal hydroxy
i
j
!' sulfonate.
A logical explanation of the formation of unsaturated
products such as phenylethylenesulfonic acid would be as
ij
!i
(25) Lowry, J.Chem.Soc., 822 (1923)
(26) Kharasch and Reinmuth, J.Chem.Ed.,8 , 17 03
(1931)
53
follows:
Compound III is first formed as indicated above,
but instead of adding another mole of sulfur trIoxide to
satisfy its unbalanced structure,
a proton is lost followed
by the regeneration of the double bond.
H
H
H
R : C : C : H
:---- *
R
: C : C : H
:p0•:S :#
0 :
«
:0 :S:0 :
:0 :
:0 :
III
V
H
V
----*
H :0 :
R:C : :C :S :0:
:S:"*
The formation of the y S sultone of 2-hydroxy-2-phenylethane-l-sulfonic acid by the sulfonation of styrene is
explained by a slight variation of the above mechanism.
It
must again be assumed that an intermediate of type III is
first formed.
This time the unbalanced electron structure
Is not satisfied by either the addition of another mole of
sulfur trioxide or by the loss of a proton, but rather by
the sharing of a pair of electrons of one of the already
present oxygen atoms with the carbon atom possessing the
,Jopen sextet*1.
H
R
This may be represented as follows:
H
: C : C : H
:b :S :0 :
:0 :
(R = C6H 5 )
--- >
H
H
R : C : C : H
:0
: S :
:0 :
0
:
EXPERIMENTAL
I.
Preparation of Dioxane Sulfotrioxide Reagent,
The dioxane sulfotrioxide reagent
(hereafter referred
to as the D, S. reagent) used in all sulfonating reactions
described in this thesis was prepared according to the
s
method given by Kiefer,
Briefly this consists of distilling
liquid sulfur trioxide, from
6
0
% oleum, into a chilled
solution of dioxane dissolved in several times its own
volume of ethylene chloride.
It is desirable to keep the
j temperature as low as possible during the addition of the
j
sulfur trIoxide as considerable heat is evolved by the
!
| reaction and charring may occur if the temperature rises
j much above 20°.
As the liquid sulfur trioxide drops into
j the cold solution., the formation of the B.S. reagent is
I evinced by the immediate appearance of a white solid.
The
| first few grams of this material dissolves in the ethylene
| chloride solution.
The amount of sulfur trioxide added
j
| was determined by weighing the reaction flask before and
I
I after the addition of the sulfur trioxide,
j II.
The Sulfonation of Ethylene.
Commercial ethylene was bubbled into a solution of the
i
; D.S. reagent in amounts necessary to conform to the equation
I
o
L
I The amount of ethylene required was measured volumetrically
55.
by passage through a wet flow meter.
The emerging gas was
dried by conducting it through two drying towers and then led
into the sulfonating reagent.
Experiment A.
To a solution of 520 cc. of ethylene chloride and
100 cc.
(1.19 moles)
of dioxane was added 50 g.
(.625 moles)
of liquid sulfur trioxide under the condition described
above.
At a temperature of 22° and a pressure of 761.7 mm.,
.2885 cu. ft.
(.54 moles)
of ethylene was bubbled slowly
into the solution of the D.S. reagent which was kept at 15°.
There was no apparent change in composition or amount of the
D.S. reagent.
With no ethylene entering, the temperature of
the sulfonating solution was raised to 50° by heating on a
water bath.
The solid present did not dissolve confirming
the original assumption that no reaction had occurred at 15°.
It should be noted here that in cases where a solid was
obtained by low temperature sulfonation
propylene)
to 40°.
(see cyclohexene or
it dissolved readily when the solution was heated
The D.S. reagent seems to be perfectly stable up
to about 80°.
Ethylene was again passed in until an additional
.2318 cu. ft.
(.32 moles) had been added.
Sulfonation had
occurred to give a light yellow, clear solution.
This solution on standing produced a small amount of an
oil which settled to the bottom of the reaction flask.
A
portion of this oil was removed but showed no tendency to
crystallize either on cooling or from solution.
This sarnie
oil was precipitated when the clear ethylene chloride solvent
jwas diluted with carbon tetrachloride.
|
All samples were combined and the mixture hydrolyzed
J by refluxing it with 1.5 1 . of distilled water. The aqueous
i
I layer was separated and after another extraction of the
I ethylene chloride layer, the combined aqueous layers were
made basic by the addition of a slight excess of barium
hydroxide.
This neutralization process evolved considerable
heat, making it necessary to cool the solution in a water
bath during the addition of the solid barium hydroxide.
The
solution was boiled for an hour and then digested.on a
steam bath for two hours in order to avoid the coprecipij tation of the desired product along with the barium sulfate.
S
The barium sulfate was filtered and excess barium hydroxide
|removed from the filtrate by treatment with carbon dioxide
until neutrality was obtained.
The clear solution, after
removal of the barium carbonate, was evaporated to approxiImately 600 cc.
On cooling, the solution produced 6.95 g.
! of shiny v/hite crystals.
I
j
These crystals were very slightly,
if at all, soluble
| in cold water but dissolved rather readily in hot water.
i
ITheir water solution failed to react with either bromine
|water or neutral permanganate.
i!
8
''Huber,
By analogy to the work of
these crystals were suspected of being barium
jmethionate, which crystallizes from water as the dihydrate.
'
i
Analysis:
Calcd. for CHsSs 06 B a » 2 H ^ 0 : Ba, 39.40;
IFound: Ba, 39.28, 39.17;
0,10.3
H s 0, 10.27.
,1A sample of the crystals were recrystallized from water and
j dried to a constant weight at 1 11 0 and 15 mm. pressure.
I
Analysis:
Galcd. for CHsSs OsBa: Ba, 44.05.
Found:
IBa, 44.07, 43.83.
J
The filtrate from the barium methionate .was evaporated
to dryness, the last 50 cc. of water being removed at
reduced pressure by heating on a steam bath.
93 g. of a white,
crystalline,
product was obtained.
A yield of
extremely hygroscopic
This product was soluble in water
and reacted readily with neutral permanganate and bromine
water;
thereby indicating unsaturation.
As no satisfactory
method of crystallization was fou„nd for this salt, an
i
ij
jjanalysis was run on a sample of the product obtained by
j evaporation to dryness.
This product contained 30.34 and
i
|-30.32$ barium and analyzed for 4.68$ water; thereby making
i
j the barium analysis on the dry basis run about 31.80$.
j Experiment
B.
I
To 70 cc.
(.84 moles)
of dioxane in 250 cc. of
ethylene chloride was added 64 g.f.SO moles)
of liquid
sulfur trioxide.
The sulfonating reagent was heated to
l
i|35° on a water bath, and .3050 cu. ft. (.35 moles) of
I
j|ethylene at 24° and 748 mm. was bubbled slowly into the
D.S. reagent.
Reaction occurred very slowly at this temp-
ierature and for the reaction of the last one-third of the
il
jolefin, the temperature was raised to 40°.
On standing, an
i
il
;
!oil similar to that formed in experiment A settled from
'!so lution.
ij
■j
The entire mixture was hydrolyzed with water and the
38
final product obtained exactly as described for the previous
experiment.
It is interesting to note that the formation
of barium methionate was not observed in this experiment.
The product obtained, after being thoroughly dried, gave a
barium analysis of 32.12 and 31.80/o.
Conversion of the Barium Salt to the Sodium S a l t .
Fifteen grams of the barium salt obtained above was
dissolved in 500 cc. of distilled water and heated to boiling.
A sortition of 5.63 g. of sodium sulfate was added dropwise
to the boiling solution with vigorous stirring.
precipitate of barium sulfate formed.
was removed,
An immediate
After digestion, this
and the filtrate evaporated to dryness, pro­
ducing a waxy solid of hygroscopic nature.
A portion of the sodium salt was boiled with 9b% alcohol
but complete solution could not be effected.
was removed,
and on cooling, a small amount of white solid
separated from solution.
pressure,
Excess solid
This was dried at 100° and 15 mm*
and on analysis found to contain 18.07^ sodium.
The fact that the product reacted with neutral permanganate
suggested the product to be sodium ethylenesulfonate, but
the analysis is not within experimnntal error.
Attempt to Acetylate the Barium S a i t .
;!
Five grams of the barium salt was moistened with acetic
j,
ianhydride and heated on a steam bath for two hours.
Some
decomposition occurred.
The solid was washed free of acetic
i
j
anhydride with boiling ether and dried.
Analysis indicated
'
I
ii:ino acetylation had occurred.
39.
I
i
i
i
f
| III.
The Sulfonation of Propylene.
| Experiment A.
i
To
8 8
g.
(1 mole)
of dioxane dissolved in several times
I its own volume of ethylene chloride was added 6 8 g. (.85
I
j moles) of sulfur trioxide.
The temperature of the solution
i
j was allowed to rise to that of the room and commercial
j
propylene passed In until the D.S. reagent h a d disappeared
and a clear yellow solution resulted.
The temperature rose
to about 30° during the sulfonation process.
The solution
was hydrolysed with an excess of barium hydroxide and
j ethylene chloride and dioxane distilled from the emulsified
i
jmixture.
The excessive foaming, often encountered in
j removing the volatile components of a sulfonation mixture,
i
!
; may be avoided by directing a small stream of air upon the
! surface of the boiling liquid.
|
The barfum sulfate formed by the hydrolysis was removed,
J and the filtrate brought to neutrality Ytfith carbon dioxide.
i After removal of the barium carbonate, the s olution was
ji
| evaporated to dryness yielding 39 g. of dry material.
This
| corresponds to a 22 %g yield of barium
jjsulfonate.
2
-hydroxypropane- 1 -
In the light of present knowledge, this low
i yield is explained by coprecipitation of the hydroxy sulf onate
ji
iwith the barium sulfate, and also by the fact that disap!
)
!pearance of the D.S. reagent does not mean the reaction is
■
i
;
i
complete.
The D.S. reagent is appreciably soluble in
ij
\\
!jethylene chloride.
i
!
I
!
40.
Preparation of
2
-Chi or opr opane -
1
- s ulf onyl Chloride.
A mixture of 10 g. of barium 2 -hy dr oxypr op an e -1 sulfonate and
g. of phosphorus pentachloride in
2 0
1 0 0
cc.
of dry carbon tetrachloride was refluxed for eight hours.
The remaining solid was filtered,
at 40° b y vacuum distillation.
and the solvent removed
A yellowish oil remained
which was dissolved in ether, filtered,
calcium chloride.
and dried over
The oil has a pungent,
irritating odor
and is a lachrymator.
Reactions of 2 -Chior opr opane-1-sulf onyl Chloride.
1. With p-toluidine.
A sample of .40 g. of p-toluidine was dissolved in
ether and to this was added an ether solution containing
.35 g. of the sulfonyl chloride.
Reaction was instantaneous
resulting in the formation of a precipitate of p-toluidine
hydrochloride.
After removal of this solid, evaporation of
the ether resulted in a light yellow oil soluble in b%
sodium hydroxide.
This oil could not be made to crystallize
from any of the common solvents.
2. With ammonia.
To a benzene solution containing one gram of the
; sulfonyl chloride was added gaseous ammonia, until the
!|
'
jinitial violent reaction had subsided.
After removal of
the ammonium chloride, the benzene was distilled at low
j
!pressure.
The resulting oil refused to crystallize.
il3. With xenylamine*
Five-tenths gram of the oily sulfonyl chloride in
ether was added to an ether solution of 0*95 g. of xenylj
I amine.
j
A precipitate of xenylamine hydrochloride formed
slowly and was later removed.
A small amount of solid
j
remaining after the removal of the ether could not be r e ­
crystallized.
Experiment B •
Liquid sulfur trioxide was added to a solution of
dioxane and ethylene chloride until the gain in weight was
60 g.
f.75 moles).
To this was added 23 g.
( # 5 5
moles)
of
propylene, the temperature of the reaction being kept
j around 12°.
A heavy white solid, similar in appearance to
dioxane sulfotrioxide, formed during the addition of the
olefin.
I
After standing in the ice box for two days, the solid
i
|was filtered at ice temperature under anhydrous conditions.
||This was accomplished by means of a sintered glass funnel
[fitted with a tight metal top into which had been soldered
)
I two tubes, a large one for introducing the solution and a
I
i|
smaller one for dry air.
The stem of the funnel was placed
in a large rubber stopper which fitted tightly into a hole
;cut in the bottom of a granite pot.
The pot could then be
Ifilled with ice-salt mixture and the filtration carried out
j!
|iwith suction if desired.
The solid remaining after filtration was washed several
f
Utimes with cold ethylene chloride.
Dry air was sucked
1
through the solid to remove any ethylene chloride adsorbed
42.
|
i
i
]
on the surface*
The solid was rapidly transferred to a
vacuum desiccator containing PS 0 5J|
The pressure was
reduced to 18 mm* and dry air then allowed to flow slowly
into the desiccator*
This process was repeated several
j times in an attempt to remove any remaining solvent*
In
spite of all precautions the solid completely liquefied
within four hours to for m a rather thick brown oil*
An unweighed portion of this oil was hydrolyzed with
j excess barium hydroxide*
The barium sulfate formed was
| washed with dilute hydrochloric acid to remove any barium
| carbonate, dried,
and found to weigh- 16*42 g.
The filtrate,
after removal of excess barium hydroxide, was evaporated
! to dryness to yield 15*08 g. of barium
2
-hydroxypropane-l-
J
sulfonate mixed with some unsaturated material*
i
I
|Experiment C.
i
!
Sulfur trioxide,
to the extent of 70 g*
(.87 moles),
I was distilled into a flask containing 105 g.
(1*19 moles)
j dioxane and 300 cc. of ethylene chloride*
I of 21° and 746 mm. pressure,
.39 cu. ft.
of
At a temperature
(.44 moles)
of
|jpropylene was bubbled into the sulfonating mixture kept at
ji
j!
5°.
The formation of a thick white solid occurred.
The
>i
'solid was filtered under cold, anhydrous conditions, washed
i j with cold ethylene chloride and sucked dry.
:
!
The solid was placed in a vacuum desiccator containing
Iphosphorus pentoxide and a block of paraffin.
The pressure
'i
'was reduced to 15 mm. and then dry air was admitted to
j
“raise the pressure to normal.
The desiccator was placed in
43
| an ice box ■where it stood for two days, forming a semiI solid.
On standing at room temperature, liquefaction
occurred within a few hours.
Experiment I).
To 80 cc.
(#95 moles)
chloride was added 56 g.
of dioxane in 350 cc. of ethylene
(.70 moles)
of sulfur trioxide.
The sulfonating mixture was heated to 50° on a water bath
and 14.7 g.
(.35 moles)
the solution.
of propylene bubbled slowly into
Reaction occurred readily to produce a clear
yellow solution.
This solution was hydrolyzed with distilled
jwater and the final product, barium
2
-hydroxypropane-l-
sulf onate, obtained in a 45%’ yield.
Analysis:
Calcd. for C 6 H 1
4
Ss 0 aBa:
Ba, 33.01.
Found:
|Ba, 32.81.
J Experiment
I
E.
A solution containing 500 cc. ethylene chloride and
I 125 cc.
(1.49 moles) was chilled to
0
° in an ice-salt bath.
J To this solution was added 130 g. (1.62 moles) of liquid
sulfur trioxide.
The solution was kept at 20° and .72 cu.
j ft.
(.81 moles) of propylene was added at 23° and 736 mm.
I
jAt the end of the addition a clear yellow solution was formed.
i
*This was refluxed with an equal volume of distilled water
I
|for an hour and the aqueous layer removed.
The ethylene
!|chloride layer was again extracted with an equal volume of
Jwater and the aqueous layers combined.
To the aqueous
5
f
\,
]jsorution was added 176 g. of barium hydroxide (a slight excess)
to give a dense precipitate of barium sulfate*
The solution
was boiled for an hour and then digested on a steam bath for
two hours*
The barium sulfate was filtered and excess
barium hydroxide removed by treatment with carbon dioxide.
Evaporation of the clear solution to dryness resulted in
108 g. of material.
Analysis:
Ba, 36.15.
This is a 6dfo yield.
Calcd. for G 6 H 1
Found:
4
Ss O eBa: Ba, 33.01;
C6 H 1
0
S 2 OsBa:
Ba, 33.60.
The analysis, plus the fact that the compound reacts readily
with permanganate and decolorizes small amounts of bromine
water,
indicates the presence of some barium propylene- 1 -
sulfonate in the barium
2
-hydroxypropane- 1 -sulfonate.
Preparation of Sodium-2-Eydroxypropane-1-sulfonate.
To a solution of 100 g. of the barium salt dissolved
in 1500 cc. of boiling water was added 34.8 g. of sodium
sulfate dissolved in approximately ICO cc. of water.
The
mixture was boiled for one hour, digested for three hours,
and the barium sulfate filtered.
The barium sulfate was
extracted with boiling water and the combined aqueous solutions
evaporated to dryness, producing 77 g. of the sodium salt
or practically a quantitative yield.
A portion of this
salt was recrystallized from 95^ ethyl alcohol.
i
!
Analysis:
Calcd. for CsIi7 S 0 4 ha; Ba, 14.20.
Found: ha,
|j14.62.
ji
The high analysis is explained by the presence of seme
!unsaturated material also present in the barium salt.
Preparation and Distillation of 2-Chloropropane-l-sulfonyl
Chloride.
In a solution of carbon tetrachloride, 50 g. (.31
moles) of the dry sodium salt was mixed with 125 g. (.60
Imoles) of ground phosphorus pentachloride.
Reaction
occurred vigorously for an hour even at ice temperature.
After the initial reaction had subsided, the mixture was
|refluxed for three hours on a steam bath and allowed to
ji
| stand over night.
The remaining solid was removed and
j
extracted with carbon tetrachloride.
The solvent was
J
removed from the combined solutions by vacuum distillation
i
|leaving a light yellow oil in the flask.
This was taken up
Iin ether, washed with ice cold water to remove any
|remaining phosphorus oxychloride, and dried over CaCls .
The ether was removed at reduced pressure and the oil
1
i
j
distilled through a short Vigreaux at 8 mm. pressure with
!
I:the following results.
i
i
|
1
j
1
fraction
1
2
3
4
5
b.p.
48-71
71-73
73-75
75-76
80-95
weight
•61
3.59
3.68
6.07
6.44
refractive
........
1.4802
1.4808
1.4818
1.4655
Fraction 5 was collected while vigorous pyrolysis of the
!residue was occurring and was later discarded.
The total
I
;
ii
weight of all fractions is 20.39 g. or a 37% yield.
■i
Redistillation of the first four fractions through a
i;
more efficient column at 5 mm. resulted in the following
!separation.
46
fraction
6
7
8
9
10
b*p.
48-49°
49-51°
51-53°
53-55°
55-56.5°
weight
refractive
1.4782
1.4797
1.4808
1.4819
1.4828
1.00
2.35
5*62
1.65
1.45
Experiment P.
A sample of sodium 2-hydroxypropane-l-sulf onate was
,,
is
prepared by a similar method used by Khar as eh
for the
preparation of sodium -l-hydroxypropane-3-sulfonate.
To a
solution of 126 g. (1 mole) of sodium sulfite in distilled
water was added 175 g. of a 54*6$ propylene chlorohydrin
(1 mole)*
The mixture was refluxed for two hours*
As the
solution was evaporated to dryness, the sodium chloride
which separated was removed from time to time*
On evap-
j oration to dryness 118 g* of the product contaminated with
j
a little sodium chloride was obtained*
| a 73$ yield*
j
This corresponds to
A portion of the solid recrystallized from
alcohol failed to react with either permanganate or bromine
water*
Analysis:
Calcd* for C3H7S04Ua; Na, 14*20.
Pound;
Ha, 16*56, 16*65.
A determination of the sodium chloride content revealed
| that the sodium 2-hydroxypropane-1-sulfonate was contaminated
jwith the equivalent of 2.60^ sodium.
Thus a corrected
1 analysis revealed 13*96 and 14*05^ sodium.
I
!Preparation of sodium 2-acetoxypropane-l-sulf onatS.
|
Seven grams of the sodium salt was treated with acetic
47 .
anhydride and refluxed for two hours*
The mixture was
cooled and the excess anhydride and acetic acid extracted
with boiling ether.
from alcohol.
The resulting solid was recrystallized
A solution of the salt gave a faint cloudiness
with silver nitrate.
Analysis:
Calcd. for C6HoS05Ha; Na, 11.28.
Pound;
Ha, 11.50.
Pyrolysis of Sodium 2"Acetoxypropane-1-sulfonate.
A portion of the acetate, which gave no reaction with
permanganate or bromine water, was placed in a test tube and
heated on an oil bath.
At 220° the compound began to soften
and at 235° it completely liquefied giving off an acid gas.
On cooling, a portion of the remaining substance iBhen
dissolved in water reacted readily with permanganate and
decolorized copious quantities of bromine water.
Preparation and Distillation of 2 -Chi or opr opane "1 -sulf onyl
Chloride.
Sodium 2-hydroxypropane-l-sulf onate (50 g., .31 moles)
was mixed with 125 g. (.70 moles) of phosphorus pentachloride in carbon tetrachloride.
The sulfonyl chloride
was isolated as a yellowish oil by exactly the same procedure
as described under Experiment E.
The crude oil was fractionated at 9 mm. pressure with
the following results.
.ction
b.p.
75-79
79-82
84-85
changing
l1
2f
3f
4f
weight
1.67
5.93
5.94
3.04
refractive index
1.4795
1.4808
1.4830
1.4828
j Fractions l 1 and 2 1 -were combined and distilled at 6 mm.
!
1 pressure*
fraction
b*p*
weight
refractive index
5*
61
7*
81
50-51°
51-55°
53-56°
58-59°
*61
3.37
.48
1.06
1.4785
1.4789
1.4810
1.4826
Samples 3 1, 4 f and 8 1 were combined and fractionated at
i
8 mm. pressure.
fraction
b.p.
91
101
ll1
12*
72-75°
75-76.5°
76.5-78°
78°
weight
refractive index
.89
1.44
4.48
1.40
1.4800
1.4813
1.4828
1.4829
Fraction 6 1 (A) was taken as representative of the low boiling
component and fractions 111 and 12* (B) combined to represent
! the high boiling component.
Analysis:
(A)Cl, 27.34.
Calcd. for CsHgSOgCl;
Cl* 25.27;
Calcd. for CsHeSOaClg; Cl, 40.11.
Found,
Found;
(B)
Cl, 58.52#.
)
27,28
j The analysis for chlorine as usually carried out
failed
■
:
i to give satisfactory results due apparently to the formation
•■i
Iof some sulfide.
results.
The following modification gave good
Approximately 1 g. of sodium was dissolved in
(27) Drogin and Rosanoff, J.Am.Chem.Soc., 38, 711 (1916).
! (28) Cook and Cook, Ind.Eng. Chem. (Anal.Ed.775* 1S6 (1933).
15 cc# of alcohol and to this was added the sample of
j "unknown#
After refluxing the mixture for 15 minutes, the
! usual procedure of analysis was continued#
For example,
j 1*08 g# of sodium was dissolved in 16 cc# of absolute
| alcohol#
To this was added #1324 g. of sample B#
After
j
refluxing for 15 minutes, alcohol was added to bring the
total to 21 cc#, and an additional 1#77 g# of sodium added
gradually over a period of one hour.
The final steps in
the analysis were by the usual method#
In the absence of commercial propylene, an attempt to
prepare propylene from both n-propyl alcohol and isopropyl
alcohol by dehydration with varying concentrations of
sulfuric acid led to unsatisfactory re stilts#
The dehydration
of n^propyl alcohol with sulfuric acid and aluminum sulfate
is reported to proceed readily, resulting in an 80$ yield
39
of crude product#
IV.
The Sulf onation of 1-Pentene.
The Preparation of 1-Pentene.
The preparation of 1-pentene was carried out according
30
to the directions given by Hurd.
Ethyl bromide (275 g.,
2.52 moles) in 800 cc. of dry butyl ether was added to 65 g.
ij (2.70 moles) of magnesium turnings.
The formation of the
!
Grignard reagent occurred readily.
The Grignard solution
ili
■
I
(29) Klstiakowsky, Ruhoff, Smith and Vaughan, J.Am.Chem.Soc.,
;
■
57 , 877 (1935).
? (30) Hurd, Goodyear and Golasby, J.Am.Chem.Soc., 58, 235
(1936).
was filtered through glass wool, by means of a filter stick,
Into a large separatory funnel and added slowly to a cold
i
solution of 215 g# (1.76 moles) of allyl bromide in 300 cc#
of butyl ether.
When the reaction was complete, the solution
was decanted into a 3 1. r.b. flask#
The remaining solid,
magnesium bromide, was washed thoroughly with dry butyl
ether.
The flask containing the ether solution of 1-pentene
was connected to a long, efficient condenser cooled by a
brine solution.
The ether solution was heated on an oil
bath at 140-160° until all 1-pentene had distilled.
Re-
distillation of the product gave 76.5 g. (62$ yield) of
26
j 1-pentene, b.p. 29-30°,
n^
31
1.3705.
(Hurd reported Up
| 1.3717).
Experiment A#
j
Dioxane (175 cc., 2#.l moles) was dissolved in 500 cc#
| of ethylene chloride and 154 g# (1.93 moles) of sulfur
trioxide distilled into the ice cold solution.
On the basis
i
j
| of sulfur trioxide added, 57#6 g. (.83 moles) of 1-pentene
!
was added dropwise to the sulfonating mixture#
At first
there was no apparent reaction so the solution was allowed
to come to room temperature#
Reaction occurred readily at
; this temperature to produce a clear, yellow solution.
!
The sulfonated 1-pentene was treated with an aqueous
i
ifI; solution
! basic.
of barium hydroxide until the upper layer remained
After removal of the ethylene chloride and dioxane
|iby distillation, the heavy precipitate of barium sulfate
i;
ijwas filtered.
Carbon dioxide was passed In to remove excess
51.
J
I
! "barium hydroxide as barium carbonate.
t
The solution was
| evaporated to 150 cc. and allowed to stand in the ice box
!
over night.
A heavy precipitate of white crystals formed,
which when filtered out and dried, weighed 54 g.
An
additional 78 g* of a white solid was obtained by evaporating
the filtrate to dryness.
or
a 65$ yield.
from
|j
Total material obtained was 132 g.
A portion of the solid was recrystallized
water, but still gave a positive test with permanganate.
Analysis:
Calcd. for CloHasS808Ba;
Ba, 29.08.
Founds
ji
j 31.72, 31.34.
|
A 25 g. sample of the salt was fractionally recrystal-
1
Iliged from water.
The course of the crystallization is
jj
j given on page 22.
Fraction 14 analyzed for 29.30$ barium,
j indicating a partial separation of barium-2-hydroxypentane-lj sulfonate from the unsaturated material.
i
j
i
SOxidation of barium 2-hydroxypentane-1*sulfonate♦
|
Ten grams f.022 moles) of the crude salt was dissolved
i
jin water to which was added 1.4 g. (.010 moles) of sulfuric
i
jacid.
The barium sulfate was coagulated by boiling and
I
''filtered.
To the filtrate was added 2.84 g. f.028 moles)
j
]
of chromium trioxide and 3 cc. of sulfuric acid.
The solution
|
l
!jwas heated on a steam bath for several days producing a
green colored solution.
The solution was hydrolyzed with
40$ sodium hydroxide and after prolonged heating was decanted
'from the chromium hydroxide.
After acidification with
sulfuric acid, the organic acid was removed by distillation.
;The distillate was redistilled to obtain a 110 cc. sample of
j the acid, a 10 cc# sample of which was found to contain the
equivalent of #025 g# of butyric acid.
A solution of 110 cc. containing#275 g. butyric acid
gave the following Duclaux constants:
20.5, 16.9, 14.7
(Shriner and Fuson give 17.9, 15.9, 14.6).
The Duclaux
I constants of the oxidation product were found to be 8.94,
8.27 , 8.03.
This indicates a mixture of propionic and
jacetic acid.
j
!
j The Sulf onation of 2-Pentene.
si
! Preparation of 2-Pentene.
I
|
To a cooled mixture of 200 cc. of water and 200 cc. of
I
J
j
|concentrated sulfuric acid was added 214 cc.
j
l
i
f technical 3-pentanol.
(2 moles) of
The flask containing these was
!i
jl
j attached to a long condenser cooled by brine. The flask
j
;
|was surrounded by a boiling water bath. Distillation
j
l
I started at 34° but rose rapidly to 51° as the reaction
!
j|became more vigorous.
On completion of the distillation,
1
j the hydrocarbon was washed with 25 cc. of 5$ sodium hydroxide
|
Ij and dried over calcium chloride.
A total of 110 g. (79$
|i
j!yield) of crude product was obtained.
I
The crude 2-pentene was fractionated through a long,
!i
iefficient column at a pressure of 753 mm. with the following
results.
i
(31) “Organic Synthesis”, John Wiley and Sons, Inc., New
York, N.Y., Coll. Vol. 1, 1932, p.421*
53
fraction
X
2
3
approx* vol*
20
b.p.
5 cc.
20 cc.
100 cc.
n^
32-35.4°
35.4-35.9°
35.9-36.3°
1.3783
1.3793
1.3805
About 10 cc. of a high boiling material remained ‘which was
probably polymerized pentene.
The reflux ratio of the
distillation varied from 50 -1 to 30 - 1.
Cis-2-pentene bolls at 36.5° at 755 mm.
so
(np 1.3825):
SO
trans-2-pentene boils at 36.0° at 755 (n-Q
33
Lucas and Prater
S
report
3S
1.3798).
O
1.3817 for cis-2-pentene.
Prom the results, it seems that fraction 3 contains a
predominance of trans material.
Experiment A.
|
Following exactly the same procedure used in the
i
|sulfonation of 1-pentene, 53.38 g. (.76 moles) of 2-pentene
Ifrom fraction 3 was sulfonated and converted to the barium
;
salt.
A sample of the salt, twice crystallized from water,
reacted rapidly with cold permanganate and bromine water.
Analysis:
Calcd. for CioHsaSsOeBa; Ba, 29.08.
Found;
Ba, 33.94, 33.88.
V.
The Sulf onat ion of Cyclohexene.
Preparation of Cyclohexene.
A mixture of 250 g. (2.5 moles) of cyclohexene and
8 cc. (.15 moles) of concentrated sulfuric acid was placed
(32) Kharasch, Walling, and Mayo, J.Am.Chem.Soc., 61. 1559 (1939).
(33) Lucas and Prater, J.Am.Chem.Soc., 59, 1683 (1937).
54.
i!
jin a Claisen flask attached, through a condenser, to a
|
i
|receiving flask packed in ice.
|
;oil hath to 150-160°•
|
!The
The flask was heated on an
The distillation required four hours,
distillate was saturated with sodium chloride, the
|cyclohexene separated and dried over calcium chloride,
|Fractionation through an efficient column gave 125 cc,
boiling at 82-82,2°,
>
Experiment A.
Thirty nine grams (,49 moles) of liquid sulfur trioxide
jwas added to dioxane dissolved in ethylene chloride.
j| the D,S, reagent was added dropwise 20 g,
jicyclohexene.
j10°,
;
!
To
(,244 moles) of
The temperature of the reaction was kept at
As the cyclohexene was added, the amount of solid in
J
jj
[the flask increased until at the end of the addition more
j
!
[ethylene chloride was necessary to permit stirring.
An
attempt to filter the solid under anhydrous conditions
jresulted in failure as the solid liquified before the
\
|filtration was complete. The entire solution was hydrolyzed
|!wlth barium hydroxide.
After removal of the barium sulfate
I
.
ft
jiand barium carbonate, the filtrate was evaporated to 150 cc,
jj
jOn standing, the solution solidified,
A portion of the
solid was crystallized from alcohol-water mixture and found
to react readily with permanganate and bromine water,
indicating the presence of some unsaturated material.
Analysis:
Calcd. for CeHnSO^Ba;
Ba, 23.50, 23.40.
Ba, 27.32.
^
Found;
jExperiment B.
Sulfur trioxide (55 g., *69 moles) was reacted with
j29 g. (.35 moles) of cyclohexene by means of the D.S.
ij
i
j
jreagent.
The temperature was kept at 5°, and again the
i
jjformation of a heavy white solid was noted.
The solid
was filtered at ice temperature under anhydrous conditions
and placed In a desiccator containing a block of paraffin,
jThe desiccator was exhausted from time to time and kept in
ian ice box.
In spite of all precautions, the material
1liquified to give a purple oil.
Experiment C.
j
Dioxane (75 cc., .90 moles) was dissolved in 300 cc.
jof carbon tetrachloride and to this was added 40 g. (.50
Imoles) of sulfur trioxide.
At a temperature of 5°, 21 g.
|
i
!j (.25 moles) of cyclohexene was added dropwise.
Instead
ji
i of the expected solid, a thick yellowish oil separated
from the solution.
This was separated, but crystallization
|could not be induced.
j
On hydrolysis, barium 2-hydroxy-
cyclohexane-1-sulfonate was produced along with unsaturated
|material,
j
IjVI.
i!
The Sulf onat ion of Styrene.
jExperiment A.
Dioxane (80 cc** #95 moles) was dissolved in 300 cc.
i
^ of ethylene chloride and treated with 64 g. (.30 moles) of
liquid sulfur trioxide.
Styrene (42 g., *40 moles) was
,added dropwise to the D.S. reagent at 5°.
In the initial
stages of the reaction the mixture seemed to be clearing
of solid, but when one-half to two-thirds of the olefin
had been added, a solid began to separate from solution.
Following the complete addition of the olefin, the mixture
was placed in the ice box for several days, during which
time the amount of solid seemed to increase.
j
The solid was
filtered under anhydrous conditions at ice temperature and
jplaced in a desiccator over phosphorus pentoxide.
i
Since
the solid showed very little tendency to liquify, it was
treated with cold water.
The portion failing to dissolve
j
i
■ was filtered, yielding 5.5 g. of a white, pellet-like
material which melted at 90-91?
A sample of the solid when
j
| suspended in water reacted readily with permanganate, but
f!
i
) Its benzene solution failed to give a positive test with
i!
I
!bromine*
i
Five-tenths gram of the substance was boiled with
water and found to dissolve slowly, producing an acidic
1 solution, which reacted readily with permanganate and
ibromine water.
i
i
The filtrate of ethylene chloride was extracted twice
iwith its own volume of water.
The aqueous extracts were
i
| combined and made basic with barium hydroxide.
After the
| solution had been boiled, the barium sulfate was removed by
r
filtration.
Following removal of excess barium hydroxide
!as barium carbonate, the solution was evaporated to a small
volume.
On standing in the ice box, a solid, proving to be
barium 2-phenylethylene-l-sulfonate, separated in white
crystals.
A sample of the solid was brought to constant
weight at 100° and 15 mm* pressure*
jl
!
Analysis:
Calcd* for C16H 18Ss0eBa; Ba, 27*28*
]
|
Pound; Ba, 27,58, 27.69.
)
IOxidation of Barium 2-Phenylethylene-1-sulf onate *
!
J
Five-tenths of a gram of the barium salt was dissolved
Iin water and neutral permanganate added slowly from a
i burette*
time*
The manganese dioxide was removed from time to
At one stage of the oxidation, the odor of benzaldehyde
ijwas noted; therefore, a small sample of solution was
j removed, made acidic with acetic acid, and treated
j phenylhydrazine. The precipitate which formed was
j crystallized
with
re-
from a water-alcohol solution, m*p* 157-8°*
ji
j!Melting point of phenylhydrazone of benzaldehyde Is given
!
as 158° (Shriner and Fuson; *
|
The addition of permanganate was continued until a
faint pink color remained*
|refluxed for two hours*
The solution was made basic and
After the manganese dioxide was
J removed, a portion of the solution was found to give a
precipitate with barium chloride, thereby indicating the
Ipresence of the sulfate ion*
ij
The solution was made acidic and excess permanganate
Iremoved with bisulfite*
The aqueous solution was extracted
'twice with ether and the ether in turn extracted with a
i:dilute solution of sodium bicarbonate*
The basic solution
■was acidified and on cooling gave a precipitate of benzoic
acid; m*p* 122°*
58
Preparation of 2-Phenylethy1ene -1 -sulfonyl Chloride*
Dry barium 2-phenylethylene-l-sulf onate (12 g., *015
j moles) was ground with 8 g# (*038 moles) of phosphorus
|pentachloride#
The mixture was heated on a steam bath for
h
| 8 hours, and after cooling, poured into ice water#
The
I solid was filtered, taken up in ether, and dried over
I calcium chloride#
1
The ether was removed leaving a 60^ yield
„
^
I of 2-phenylethylene-l-sulf onylchl or ide; m#p# 82-85#
15,16
| 2 -Pheny 1ethylene-1 -sulfonamlde was prepared by adding a few
j
| drops of liquid ammonia to a portion of the sulf onyl
chloride dissolved in ether#
iI the
solid was twice recrystallized from water; m#p# 142-3°#
jExperiment
i
After removal of the ether,
15
B *
Liquid sulfurtrioxide (75 g#, #94 moles) was added to
j a solution of 80 cc#
!
|
(#95 moles) of dioxane in 300 cc# of
i
! ethylene chloride.
Styrene (49 g#, #47 moles) was added
■ dropwise to the D#S# reagent at 5°.
The solution, containing
| considerable solid, was placed in an ice box for six days#
i
iThe solid was filtered at 0° under anhydrous conditions,
washed with cold ethylene chloride, and sucked dry#
The
■j
l
|material weighed 35 g#
The solid was treated with cold
|water to remove any water soluble portion, filtered, and
i
!dried#
A small sample, crystallized from acetone-petroleum
ether mixture, melted at 134-136°.
ij
A portion of the crude material was analyzed for
i
isulfur by the Parr bomb method#
J
Analysis:
i
17.28, 17.29.
Calcd# for C 8H QS03;
S, 17#44#
Pound; S,
59.
S
jAcid,
of y?-Suit one of 2-Hydroxy-2-phenylethane-l-sulf ofilc
/
A portion of the above crude material was dissolved in
boiling water.
The solution was cooled to room temperature
and permanganate added until a faint pink color remained.
The solution was made alkaline and refluxed for an hour.
i
j The manganese dioxide was removed; the filtrate made acidic
and extracted with ether.
On evaporation, the ether solution
deposited benzoic acid; m.p. 122-3°.
Titration of Suit one with Sodium Hydroxide.
i
j
Weighed samples of the crude ^x^sultone of 2-hydroxy-2-
!phenylethane-l-sulfonic acid were dissolved in boiling water
I
j
| and cooled to room temperature. Titration with standard
j
sodium hydroxide gave the following neutral equivalents.
|
Calcd. for C QH QSOs; m.w., 184.
Pound; m.w., 176,177.
l
|
!Hydrolysis of^-Sul tone to Bar lum-2 -Phenyl ethylene -1 -sulf onate ♦
j
A portion of the crude sultone was dissolved in boiling
j
t
|water and cooled to room temperature. The solution was
i1
treated with excess barium hydroxide.
*
(it is important to
note that no barium sulfate was formed by this reaction.)
jj
The excess barium hydroxide was removed as the carbonate,
jj
i
;and crystals formed from the concentrated aqueous solution.
j
j
!These were recrystallized from water and found to react
^readily with permanganate and bromine water.
Analysis:
Ba, 27.34.
H"
Calcd. for C16H laSsOQBa;
Ba, 27.28.
Pound;
60.
j
j
I
Ji
j
I
of Methyl 2 -Phenylethylene-1-sulfonate.
One gram of the sultone was dissolved in 15 cc. of
ji
jboiling methyl alcohol.
j hot.
The solution was filtered while
Distilled water was added to the boiling solution
until a faint cloudiness was observed.
j
The solution was
|jallowed to cool and produced .4 g. of a white crystalline
precipitate; m.p. 66-67°.
jj
The product reacted readily
i!
Iwith neutral permanganate and bromine water.
S
i
j!
Analysis: Calcd. for C0HloSO3 ; S, 16.11.
j
i
Pound;
Is, 16.15.
!
|
S'
!Ethyl 2-phenylethylene-l-sulf onate (m.p. 46-48°) may be
i
j prepared by an analogous reaction.
i
'i
i
:VII.
The Sulfonation of 1-Pentadecene*
3
|Preparation of 1-Pentadecene.
ij
j!
The 1-pentadecene was prepared by the action of lauryl-
j! magnesium bromide on allyl bromide according to the method
j
•
jgiven by Wilkinson.
!
3*
Lauryl bromide (250 g., 1 mole) in 500 cc. of dry ether
was added to 24 g. (1 mole) of magnesium turnings.
j
Gentle
j heating and a small crystal of iodine were necessary to
|start the reaction.
After the preparation of the Grignard
reagent was complete, 130 g. (1.07 moles) of allyl bromide
i
j
in an equal volume of dry ether was added at such a rate as
^to produce vigorous refluxing.
After the addition of allyl
!
,(34) Wilkinson, J.Chem.Soc., 3057 (1931).
*
bromide was complete, the mixture was refluxed for approxi­
mately 30 minutes, and then hydrolyzed by pouring into a
mixture of ice and water.
The ether layer was separated
|and dried over calcium chloride#
The ether was removed by distillation on a water bath
and the olefin distilled at reduced pressure#
j
fraction
j
1
2
3
pressure
12-13 am.
12 mm.
14-15 mm#
b#p#
120-127°
127-132
132-137
weight
14 g.
140 g.
18 g#
IThis gives a total yield of 172 g# (82$) of crude product#
jThe boiling point of 1-pentadecene is given as 127 •595
!
!128*5 at 10 mm#
j
A solid residue remained after removal of the olefin#
IThis was recrystallized from alcohol and identified as
I
|tetracosane (m.p* 51)*
l
i
I
Preparation of Sodium 2-Hvdroxypentadeoane-1-sulfonate#
|
Sulfur trioxide (76 g#, #95 moles) was added to 50 cc#
j (.59 moles) of dioxane dissolved in 300 cc* of ethylene
|
|chloride#
To this sulf onating solution was added 100 g#
! (.48 moles) of 1-pentadecene (fraction 2), the temperature
(being maintained at less than 10°. After the addition of
I
|the olefin, the solution was hydrolyzed by pouring it into
jan aqueous solution of 57 g* (1*42 moles) of sodium
i;
^hydroxide#
An emulsion formed which showed no tendency to
j:
j; f35) Kozacik and Reid, J.Am.Chem.Soc., 60, 2436 (1938).
62.
separate even after standing several days; therefore, the
ethylene chloride and dioxane were removed by distillation,
j a stream of' air being blown on the surface of the liquid to
li
prevent excessive foaming*
j|
The aqueous residue was con-
j! centrated and upon standing produced a eopious precipitate
i|
jiof sodium 2-hydroxypentadecane-l-sulfonate contaminated with
j sodium sulfate*
A portion of the solid was crystallized
j twice from water*
j
Analysis:
It gave no reaction with permanganate*
Calcd* for CleE31S04Na;
Na, 6*96*
Found;
| Ha, 7*01, 6*94*
Preparation of Sodium 2-Ac et oxypentade cane-1-sulfonate*
j
I
Five-tenths gram of the above pure sodium salt was
i|
jrefluxed with 5 cc* of acetic anhydride*
ji
jhours, solution was practically complete*
After about 4
The solution was
jfiltered while hot and upon cooling deposited a dense prej
j cipltate of a white solid* This was filtered and washed
1
j free of anhydride with ether*
Yield obtained *61 g*
ji
j
Analysis:
Calcd* for ClgH S3S06Ha; Ha, 6*18*
Found;
j Na, 6*54, 6*14*
j
Oxidation of Sodium 2-Eydroxypentadeoane -1 -sulf onate *
jj
An attempt was made to oxidize the above salt to s odium-2-
■pentadecanone-1-sulfonate according to the following equation*
3 C j.3H s 7CHOECHg S03 Na + 2 KMn04 + NaOH
i
-- ►
3 C13HS7C00KCNa) + 3 CH3S03K(Na) + 2 MnOs + 3 Es 0.
On this basis, 5 g* (*015 moles) of the hydroxy sulfonate
was dissolved In a b% solution of sodium hydroxide and heated
j to boiling*
Potassium permanganate Cl#6 g., .101 moles) was
dissolved In w%ter and added gradually to the hot solution*
! Reaction was evinced by the immediate formation of manganese
jj
j
!dioxide*
After addition of the permanganate, the solution
.
was refluxed for an hour and then filtered free of manganese
J dioxide*
Enough sodium hydroxide to make a 20$ solution was
j
added to the filtrate, which was then boiled in an attempt
i
j to split the bond between Gx and Cs *
The solution was
j filtered, made acidic, and extracted twice with its own
j
| volume of ether*
The ether layers were combined and the
j solvent removed on a steam bath, leaving a small amount of
!| a low melting solid resembling lard*
f
|
An attempt to prepare
■j the p-bromophenacyl bromide produced a solid, which, on
jj
crystallization from alcohol, melted at 110-112°* (The
j
imelting point of p-bromophenacyl Tester
derivative of
i|
myristic acid is given as 81°)
j
i
ji
jj Preparation of 2-Chloropentadeoane-l-sulfonyl Chloride*
i
j
Sodium 2-hydroxypentadecane-l-sulfonate (3*3 g*, *01
| mole) was finely ground and mixed with 2*4 g* (*011 moles)
jl
i!
of phosphorus pentachloride*
That reaction occurred was
]
j
1evinced by the evolution of hydrogen chloride*
The mixture
was heated on a steam bath, but as considerable decomposition
v occurred, the product was discarded, and the preparation
15
carried out by a method given by Khar as ch.
Twelve grams (*036 moles) of sodium 2-hydroxypentaji decane-l-sulfonate was added to 16 g* (#077 moles) of
64*
i
y
phosphorus pentachlorlde suspended in 50 cc# of carbon
i
| tetrachloride#
The mixture was warmed on a steam bath,
| initiating a vigorous reaction that lasted for 30 minutes#
j!
| After the initial reaction had subsided, the mixture was
refluxed gently for eight hours and allowed to stand over
|night#
j
After filtration,the solvent was removed at reduced
pressure, leaving a light yellow oil#
This oil was dis­
solved in ether, washed twice with ice water, and dried
over calcium chloride#
i
The oil could not be indhced to form
| crystals#
j
|Reactions of 2 -Chioropentadecane-1-sulf onyl Chloride#
i
!
An ether solution of the sulf onyl chloride was added
|dropwise to an ether solution of 6 g#
(#056 moles) of
jp-toluidine until no further reaction was observed.
The p-
j
'toluidine hydrochloride was filtered and the filtrate washed
several times with a dilute solution of hydrochloric acid#
After the ether solution had been dried over calcium chloride,
|the solvent was removed at reduced pressure leaving a reddish
|j brown oil which could not be crystallised
j| or from its solution of various solvents#
either on cooling
1With PC naphthylamine .
Sodium 2 -hydroxypentadecane-1-sulfonate (6 g#, #018 moles)
was converted to 2-chloropentadecane-l-sulfonyl chloride as
has been described#
To an ether solution of the sulf onyl
chloride was added 5 g# (#035 moles) of oC naphthylamine
also dissolved in ether#
rr
Formation of
oc naphthylamine
i
jhydrochloride occurred rapidly.
|
!with charcoal.
The filtrate was decolorized
After removal of the solvent, there remained
j!
||a yellowish oil.
j with
failure.
All attempts to crystallize this oil met
Both this oil and the one obtained from the
reaction of the sulf onyl chloride with p-toluidine were
kept for several months, but no evidence of crystal formation
was observed.
Preparation of 7 -Pentadecene.
J
Heptyl bromide (180 g., 1 mole) in approximately 500 cc.
| of dry ether was added to 24 g. (1 mole) of magnesium
I
Iturnings.
To the Grignard reagent was added 35 g. (.47
moles) of ethyl formate (b.p. 53-54°) at such a rate as to
i
|j produce refluxing.
The reaction product was filtered and
|hydrolyzed by pouring it into a mixture of ice and water
!
i
containing a little sulfuric acid.
The ether layer was
it
Iseparated, washed with a dilute solution of sodium bicarbonate,
I
I'and dried over anhydrous potassium carbonate.
jj
j
After removal
of the ether, the residue was distilled at 12 mm. pressure
j
lto give 75 g. (Q6% yield) of di-n-heptylcarbinol boiling at
149-151°.
A portion of the alcohol was crystallized from
I
36
jjpetroleum ether and found to melt at 46-48°.
Kipping
|49.5-50° for the melting point.
The stearate of di-n-heptylcarbinol was prepared by
the following series of reactions.
(36) Kipping, J.Chem.Soc., 455 (1893)
gives
j
(A) CE3 (CHsi)l6COOE + SOCls
J
(B) (C7H 15)aOHOE + CH3 (CHS )10COC1
ji
I
-- > CE3 (CHg )10COC1 + SOs + EC1
-- »
CE3 CCEs )lsCOOCE(C7Els)£ + EG1
|
To 30 g* (*25 moles) of thionyl chloride was added in
small portions 62 g. (*23 moles) of stearic acid*
After
the reaction was complete, air was drawn through the liquid
| to remove any excess thionyl chloride*
Finely ground
| di-n-heptylcarbinol (50 g., *22 moles) was added to the
J stearyl chloride*
i
The reaction mixture was heated on a
steam bath until no more hydrogen chloride was evolved*
The total amount of material obtained from the above
! reaction was placed in a Claisen flask and heated on a salt
!bath in order to decompose the ester into stearic acid and
ji
I the olefin, 7 -pentadecene*
With a bath temperature of 300°,
jmost of the olefin distilled at 210°•
jj
Redistillation of the olefin gave two fractions.
!
i
j
fraction
|
1
2
n
pressure
8 mm*
8 mm*
weight
120-122°
123-125
13 g.
22 g*
! This gives a total amount of 35 g* or a 75# yield of the olefin*
|
A sample of 7-pentadecene was found to react readily
with the D*S. reagent and a white barium salt was isolated*
Eowever, due to the complexity of the product (See Sulfonation
of 2-Pentene) the investigation was abandoned*
SUMMARY
SI
i
l
||
i
ji
A study has been made of the reaction of dioxane
;!sulfotrioxide with ethylene, propylene, 1-pentene, cyclo-
|
J hexene, styrene, and 1-pentadecene.
j
It was found that reaction may occur either by
addition or substitution, the former leading to the
j formation of hydr oxy sulf onat es, the latter to unsaturated
j sulfonic acids.
!
j
The reaction of ethylene with dioxane sulfotrioxide
occurs readily at 50° to yield methionic acid and a major
product of uncertain structure.
Propylene reacts with dioxane sulfotrioxide readily at
||5-10° to produce an unstable solid which is thought to be a
jjhomolog of carbyl sulfate coordinated with one or more
|moles of ethylene chloride.
Both the solid and filtrate on
jhydrolysis with barium hydroxide produce barium 2-hydroxyl
| propane-1-sulfonate contaminated with an unsaturated product
| thought to be a barium propene-1-sulf onate.
i
2-Chloropropane-l-
sulf onyl chloride and a propene-1-sulf onyl chloride have
jbeen prepared.
1-Pentene sulfonates normally to give on hydrolysis
2-hydroxypentane-l-sulfonic acid contaminated with an unsaturated salt.
Cyclohexene reacts with dioxane sulfotrioxide at low
|temperatures, 5-10°, to produce a white unstable solid
jsimilar to that obtained from propylene.
The solid is
|suspected of being the sulfuric-sulfonic anhydride co­
ilordlnated with ethylene chloride.
ii
Both the solid and filtrate
ij
Ion hydrolysis with barium hydroxide give barium 2-hydroxycyclohexane-1-sulf onate contaminated with some unsaturated
material.
I
|
j has
The sulf onat ion of styrene at 5° produced a solidwhich
been Identified as the
!phenylethane-l-sulfonlc acid.
sultone of 2-hydroxy-2The filtrate on hydrolysis
I
!yielded barium 2 -phenylethylene-1-sulfonate.
This was
!converted to 2-phenylethylene-1-sulfonyl chloride and
2 -phenyle thylene-1-sulf onamide .
j|
1-Pentadecene is sulfonated readily by the dioxane
,
1
jsulfotrioxide reagent at 10° to give on hydrolysis with
Isodium hydroxide, sodium 2-hydroxypentadecane-l-sulf onate.
|
!This is reported to possess very good detergent properties.
I
| Sodium 2-acetoxypentadecane-1-sulf onate was prepared by
ijthe action of acetic anhydride on the hydroxysulf onate.
m*>rthw#etern
**tv*rst*y
69 «
Library
BIBLIOGRAPHY
1*
2.
3.
4.
5*
6.
7.
8.
9.
10.
11.
12.
13.
14.
15*
16.
17.
18.
19.
20.
21.
22.
23.
24.
25.
26.
27.
28.
29.
30.
31.
32.
33.
34.
35.
36.
Evans, Ph.D.Thesis, Northwestern University, 1955#
Keifer, M.S.Thesis, Northwestern University, 1937#
Suter, Evans and Kiefer, J.Am.Chem.Soc. ,60, 538 (1938).
Malkemus, Ph.D.Thesis, Northwestern University, 1939*
Suter, U.S.Patent 2,098,144.
Suter, U.S.Patent 2,135,358.
Regnault, Ann.. 25. 32 (1837).
Huber, Ann.. 223. 198 (1884).
Plant and SIdgwick, J.Soc.Chem.Ind., 40, 14 (1921).
WIeland and Sakellarios, Ber.. 53. 203 (1920).
Michael and Weiner, J•Am.Chem.Soc•, 58, 294 (1936).
Kohler, Am.Chem.J., 19, 728 (1897).
Kohler, ibid., 20, 680 (1898).
Kolker and Lapworth, J.Chem.Soc., 127. 313 (1925).
Kharasch, May and Mayo, J.Org.Chem.,3, 175 (1938).
Quilico and Eleischner, Atti.accad.Lincei, 6 , 7, 1050 (1929);
C.A., 2$, 1628.
Ashworth and Burkhardt, J.Chem.Soc., 1791 (1928).
Suter, Unpublished Review, Northwestern University, 1937.
Dobryanskii, Neftyanoe Khozyaistro, 9, 565 (1925);
C.A., 20, 1576 (1926).
Mutuszak, Ind. Eng. Chem., Anal .Ed., 10. 354 (1938).
Brooks, The Non-Benzenoid Hydrocarbons, 1922, p. 143.
Malkemus, This Laboratory, Private Communication.
Whitmore, Organic Chemistry, 1937, p.35.
McAllister, Private Communication, The Procter and
Gamble Company, Ivorydale, Ohio.
Lowry, J.Chem.Soc., 822 (1923).
Kharasch and Reinmuth, J.Chem.Ed., 8^ 1703 (1931).
Drogin and Rosanoff, J.Am.Chem.Soc., 38, 711 (1916).
Cook and Cook, Ind.Eng.Dhemi* (Anal.Ed.T/ 5, 186 (1933).
Kistiakowsky, Ruhoff, Smith and Vaughan, J.Am.Chem.Soc.,
57. 877 (1935).
Hurd, Goodyear and Goldsby, J.Am.Chem.Soc., 58, 235
(1936).
w0rganic Synthesis w, Coll. Vol., 1, 1932, p.421.
Kharasch, Walling and Mayo, J.Am.Chem.Soc., 61, 1559
(1939) .
Lucas and Prater, J.Am.Chem.Soc., 59, 1683 (1937).
Wilkinson, J.Chem.Soc., 3057 (193l7V
Kozaclk and Reid, J.Am.Chem.Soc., 60, 2436 (1938).
Kipping, J.Chem.Soc., 455 (1893).
70.
VITA
James Marion Holbert
Born:
November 17, 1914 at Chattanooga, Tennessee
Education:
B.S., University of Chattanooga, Chattanooga, Tennessee,
1932-1936.
M.S., University of Tennessee, Knoxville, Tennessee,
1936-1937.
Positions Held:
Assistant in Chemistry, University of Chattanooga,
1934-1936.
Assistant in Chemistry, University of Tennessee,
1936-1937.
Assistant in Chemistry, Northwestern University,
1937-1940.
Affiliations:
Sigma Xi
Phi Lambda Ups lion
Gamma Sigma Epsilon
American Chemical Society
Документ
Категория
Без категории
Просмотров
0
Размер файла
3 557 Кб
Теги
sdewsdweddes
1/--страниц
Пожаловаться на содержимое документа