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Патент USA US2406972

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Patented Sept. 3, 1946
’
2,406,972
PROCESSES FOR PRODUCTION’QEPQY-RIDINE‘
‘
3-SULPHONIG ACID AND‘lI-TS SAIiTS’f
Edmond'Ti'?Tiszajand‘Bernard F. Duesel, Yonkers,
NE SE, assi-gnors -‘ to Pyridium Corporation,
Yonkers; NJ Y1, incorporation of New York
No; Drawings ‘Application’. February- 24>, 194%}
'
’
Seri'al‘lNo. 4763908?
40mins;
‘
(01. 260-290i
1;‘ >
'Our invention relates to improvements‘ in; the‘.
process of sulphonating, pyridine andrefers' par=
ticul-arlyin processes‘ for obtaining pyridine 3
sulphoni‘eiacid and its salts.
The 'sulphonationl of. pyridine takestplacez acaw
cordingitoithexfollowingiormula;
‘
While the sulphonation of‘many aromatic com
pounds‘of" the benzene series is easily) accom
pli‘sh'e'd“ by treating them with concentrated’ sull
phuric acid‘ or‘ oleum at'relatively low tempera
tures,‘ the yield, being almost quantitative; pyri;
dine‘ and" its derivatives offer considerable resist
ance' to sulphonation" by the processes adapted
forv the. sulphonation‘ of‘ members of‘ the benzenev
series:
'
r
‘
It; is- 1 evident- ‘from this» equation :-that peachsmolj
of ‘ pyridine? (in; wt? 79'), liberates; one; mola oii wa-t
ter-MB) duringsulphonationt
I
We ‘have-found that .thissliberatedtwater-z dilutes?
the ‘ sulphuric < acid to such‘ amextentt as ; to s-ma-ke,
itttooaweak for the“sulphonationttoany consid
‘
Numerous attempts have been made to over
come" the" dif?culties present‘: in the sulphonation
erable -' degree- and that the presence of‘. a; dehy-e
drating; agent.‘ in su?icient; quantity» to‘ take. up :
the-i water: results. in; increased; yieldst
ideal,»
dehydrating: agent-for. thistpurpose is fuming sul-.-~
of ‘ pyridine‘, but they have all'resulted'ih the use
of‘ex'cessive amounts of‘the: sulphonating‘ com
pound; prolonged'heatingat highly elevatedlteni
perature's' and of‘ comparatively small‘ yields.‘
The following'are amongithe previous ‘attempts
to sulphonate pyridine:
phuric'; acid, it the‘ S03 —- oi?‘ which; forms- sulphuric.
acid With‘the water.“ Using an oleumicontaining~v
20%;- S03; ?ve-parts areirequired‘. theoretically to
take care of the producediwater.‘
>
One process consisted‘ in heating the‘ pyridine
It must, be considered, however; that-‘when; pyw
with excessive proportions of’sulphuric acid and‘
ridinehis? added- to the,» oleum,. some, 0t the-S93; Yes?
sulphuric anhydride" at 3I3‘O°'-’-350°“ C. for‘ sixty‘
capes from: the:oleum duringgthea' heating: oil the‘:
hours; the-sulphuric acid which was distilled'off" 25 sulphonating process, and, hence; increased yields!
at these" high temperatures" being replaced from"
are‘ obtained by; employingT an- . amount 4 in‘. excess”.
time to time: In addition tothe large amounts
of‘ the sulphonating chemicals; and‘ the’ l'engthrof’
o?thetheoreticatquantityt
time employed, the yieldswere‘verysmall.
We have now found, that we=cantincreaseithea
yield’ of pyridine 3-sulphonic acid considerably
Attempts“ have been made“ to‘ produce the'sul- 30 by adding oleum tethereaction mixture at in
phonati'on» by ‘heating pyridine withconcentrated“
tervals. We; have: ‘found; also that it: isiadvisable
to: :add': a;.f.urther."smalhquantity 0ft: catalyst with“:
sulphuric‘ acid sealed‘ tubes‘ to the' boiling‘point“
of‘ the- mixture; 320°'-330°‘ 0., for" thirty >' or"i"orty*
hours without‘ satisfactory results?
Further attempts have been madeby‘ adding
a: catalyst, mercurysulpha-te; vanadiumsul‘phate,
aluminum‘ sulphate‘ or. magnesium sulphate; to"
the" pyridine; sulphuric a-cid‘and' sulphuric" anhy
dfi‘i-de; heating’ to 330°'-350°" C, for'forty to‘ sixty‘
hours‘ and‘replacing" the distilled sulphuric acid“
with additional amounts of'the acid; Whileth'is"
process increased the" yield‘ above“ that" obtained‘
eachsa-dditiorr OfZEOlGlll'l'lL.
‘
With. periodical: additi'onsz'oflf oleuma and? proper?
35 catalysts‘i‘ we‘ have: practically" doubled-L the‘ yield}
of: pyridine 3:-sulphoni'ci aci'dc. ‘compared: with‘;
yields obtainedrby =the§previonsly< described meth'-_
O'd‘S‘L- For:instance;.: using: mercury‘or its-salts~ as;
catalysts, the. yield‘ i‘s137'%, our>yie1dris:»abouti
75% ;: using: magnesiumz. as scatalystltby i the usual?‘
method; the; yield: is: 14%,‘- by" our method‘: the: .
yieldi isaw about. 23%;‘ usings aluminum; _
catalyst";
in‘ the- absence of‘ the catalyst; it“ still possessed"
by the usual method, the yield isA12i%l,‘ ounfyield:
is about 22%.
gards". the : amounts ‘of 'sulphonatingmaterials"em; 4.7151? An object‘ of this invention, therefore,.. is to
the" disadvantages of“ the‘ former‘ " processes"
ployed.
re‘;
increase the? yield’. of pyridine 3.-sul’p'honi‘c‘ acid,‘
’
Our invention presents. processes for the pro-‘
while: at" the‘ same .timeureducingj the'xamountfof”
duction ofipyridine3¢su1phonic acid in which the
the‘ sulp‘honating agent‘ and‘ijthe‘ time‘ of‘ opera- _
amountofchemicals and‘ the time of procedure
tion'.
‘
are materially decreased, and the yield is con 50
Another object is to prevent the undue dilu
siderably increased over those of the described
tion of the sulphonating agent by the periodical
processes, these advantageous results being ob
addition of a dehydrating agent.
tained by the particular steps of procedure of our
Further objects of this invention will be evi
processes which are not present in the prior proc
esses.
'
dent from the herein described processes and
.55 the results produced thereby.
2,406,972
3
~
Among the catalysts suitable for application in
our processes are mercury, aluminum, magnesi
um and vanadium and their salts, but we do not
limit ourselves to these catalytic metals, as other
suitable catalytic metals may be employed.
These catalysts dissolve in the hot sulphuric acid
as the corresponding sulphates, and therefore,
the sulphates may be added to the sulphonating _
4
310°-320° C. After heating for one hour, 0.5
part aluminum and 16 parts oleum are added.
This is repeated after the second and third hour
of heating, and then the heating is continued for
eight more hours.
The sulphonation mixture is
then cooled and added to water and worked up
for the sodium salt in the usual way.‘:1 -12'.7 parts
of sodium salt was obtained representing a yield
' of 21.6%.
mixture.
Example IV
Our preferred method of sulphonation can be 10
clearly seen from the following illustrative ex
A pyridinium sulphate solution in 75 parts of
amples. All parts referred to in these examples
oleum is prepared from 25 parts pyridine as de
are given by weights.
scribed in Example I. Two parts of mercury
sulphate are added to the solution and heated to
Example I
' 15
270° C. After an hour heating 16 parts of oleum
250 parts of pyridine are run as a ?ne stream
into 750 parts of oleum (fuming sulphuric acid,
20% S03) under stirring and cooling, taking care
that the temperature does not rise over 75° C.
The mixture now consists of a solution of pyri
dinium sulphate in oleum. Three parts of mere
cury are added to the solutionv and heated to
about 250°-270° C. under constant stirring.
After an hour heating 160 parts of oleum and 1.5
parts of mercury are added. vThe heating is con
tinued, and after the second and third hour
heating, each time the same amount of mercury
and oleum is added thereto. The heating is then
continued for two more hours and then cooled
down to room temperature.
p and 1 part of mercury sulphate are added.
The
heating is continued, and the addition is repeat
ed after an hour of heating. The heating is then
continued and the reaction mixture is worked up
as in Example I. The yield obtained is 68% of
the theoretical.
,
_
It will be noted from the foregoing that our
invention broadly comprises the periodical addi
tion ofoleum and a catalyst to a mixture of
pyridinium, oleum and a catalyst, whereby in
creased yields are obtained over former processes,
with decreased amounts of materials and at lower
temperatures.
As already mentioned other metals than those
The mixture is now 30 described in the examples, may be used as cata
added to 7500 parts of Water and neutralized
with ?nely pulverized calcium carbonate.
‘ The calcium sulphate formed is ?ltered off and
washed with hot water. ‘The ?ltrate now con
tains calcium 3-pyridine sulphonate and the un
reacted pyridine, which pyridine may be recov
ered.v Sodium or potassium carbonate is now
added to the solution till it becomes alkaline to
lyst in the sulphonation of pyridine without de
parting from the invention or sacri?cing the ad
vantages thereof. Therefore, we do not limit
ourselves to the speci?cally mentioned times,
temperatures, quantities, chemicals, or steps of
procedure as these are given simply to describe
our invention as set forth in our speci?cation
and claims, and they may be varied without going
phenolphthalein, the calcium carbonate is ?l
. beyond the scope of our invention.
tered off and the solution is evaporated to dry 40
What we claim is:
ness. By using 130'parts of sodium carbonate,
1. In a process of sulphonating pyridine in the
442 parts of sodium 3-pyridine sulphonate is ob
3 position, the step which comprises the periodi
tained which represents 77% yield. If the free
S-pyridine sulphonic acid is required, the cal
cal additions of oleum and a member of the group
of catalysts consisting of mercury, aluminum,
magnesium and vanadium and their sulphates
cium is removed from the calcium salt by the 45
addition of the theoretical amount of sulphuric
to a solution of pyridine sulphate in oleum under
acid, the calcium sulphate is ?ltered off, and the
sulphonating temperatures and recovering the
solution is evaporated to dryness.
3 pyridine sulphonic acid.
Example II
2. In a process of sulphonating pyridine in the
50 3 position, the step which comprises the periodi
A pyridinium. sulphate solution in 50 parts
cal additions of oleum and mercury to alsolution
oleum is prepared from 25 parts of pyridine as
of pyridine sulphate in oleum at temperatures
described in Example I. 1.5 parts of magnesium
between 250°—320° C. and recovering the 3 pyri
turnings are added to the solution and heated
to 270°—300° C. After heating for one hour, 0.375 , dine sulphonic acid.
3. In a process of sulphonating pyridine in the
part of magnesium and 16 parts oleum are added.
3 position, the step which comprises the periodi
This is repeated after the second and third hour
cal additions of oleum and magnesium to a solu
of heating, and then the heating is continued
tion of pyridine sulphate in oleum at tempera
for nine more hours.‘ The sulphonation mixture
is then cooled and added to water and worked 60 tures between 250°—320° C. and recovering the 3
pyridine sulphonic acid.
_up for the sodium salt in the usual way. 13.5
4. In a process of sulphonating pyridine in the
parts of sodium salt were obtained, representin
3v position, the step which comprises the periodlé
~
cal addition of oleum and mercury sulphate to a
Example III
solution of pyridine sulphate in oleum at temper
A pyridinium sulphate solution in 75 parts 65 atures between 250°-320° C. and recovering the 3
oleum is prepared from 25 parts pyridine as de-,
pyridine sulphonic acid.
EDMOND T. TISZA.
a yield of 23.5%.
scribed in Example I. 1.5 parts aluminum turn-v
ings are added to the solution and heated to
BERNARD F. DUESEL.
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