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Патент USA US2130322

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5
Patented Sept. 13, 1938
UNITE
2,130,322
STATES 'ATENT OFFIQE
2,130,322
STABILIZATION OF HYDROXY BENZENOID
COMPOUNDS AND TETRAVALENT SUL
PHUR COMPOUNDS AGAINST IWETAL OAT
ALYSTS
Morris S. Kharasch, Chicago, Ill., assignor to Eli
Lilly and Company, Indianapolis, Ind., a corpo
ration of Indiana
No Drawing. Application May 14, 1934,
Serial No. 725,483
32 Claims. (Cl. 223-250)
It is the fundamental object of my invention to
stabilize more effectively than has heretofore been
done certain very easily oxidized benzenoid com
may be added to the benzenoid compounds re
pounds, particularly those containing two nega
tetravalent-sulphur salts, such as sodium sulphite,
sodium hyposulphite (Na2SzO4, commonly known
tive substituents in ortho and para positions on
the aromatic nucleus.
By “negative substituents,” I mean amino
1.5
2:0
I
I have discovered both how to stabilize known
others; and also how to produce certain inherent-v
produce an e?'ective and relatively permanent
stabilization of the easily oxidized benzenoid com
duce certain stabilized and stable tetravalent-sul
pounds above referred to.
phur salts, by which term I include sulphites and
ly stable tetravalent-sulphur salts, both sulphites
and hyposulphites, which are new. By such sta
bilized or stable tetravalent-sulphur salts I can
I
V
i _
Stabilized and stable tetravalent-sulphur salts
hyposulphites; which in turn will serve as stabil
and their production are included in the generic
izers for the benzenoid compounds above referred
to and for other things, in addition to being stable
themselves for such uses as they may serve.
It is well known that certain benzenoid com
subject-matter of my copending application Serial
No. 725,482, ?led May 14, 1934; and the present
application is directed to them speci?cally; as well
as to the stabilization of benzenoid compounds‘by
pounds, such as o-aminophenol, p-aminophenol,
them.
catechol,
hydroquinone,
metal, and epinephrin, oxidize very rapidly under
certain conditions, especially in solution, and
25 more especially in neutral and alkaline solution
and indeed at any pH on the alkaline side of
about pH 6; and that the oxidation increases
under the action of heat and light. This oxida
tion is due to oxygen of the air. No water solu
30 tions which are stable at room or elevated tem
peratures have been prepared of these compounds.
It is also known that a certain stabilization of
such benzenoid compounds, even in water solu
tion, can be obtained by adding sodium sulphite,
which preferentially takes up the oxygen. Sodi
um sulphite, however, is very sensitive to catalytic
oxidation by oxygen in the presence of certain
metal ions; chie?y copper, but also manganese
and iron in the order named. Since it is substan
1
sulphite or hyposulphite or by the production of '
an inherently stable sulphite or hyposulphite, is
by having an aliphatic 1,2-diamine present, either
as a-separate added ingredient, in addition to the
sulphite or hyposulphite, or as the “basic” part of
so
and either diamines per se or parts of compounds
which contain such diamines, or may be initially
part of the tetravalent-sulphur salt, as by being
in combination therewith.
However, I deem it
preferable that the diamines, whether present per
se or as part of a co-present compound, shall be
separate ingredients added to the tetravalent
to that preferred embodiment. Therefore, when
itself into the production of a stabilized or stable
50 sulphite; so that such stabilized or stable sulphite
2-5
the sulphite or hyposulphite or of some co-present
substance. That is, from a generic standpoint,
the aliphatic diamines may be either added in
gredients initially separate from the tetravalent
sulphur salts, such as the sulphite or hyposulphite,
or the benzenoid compounds free from these metal
catalysts, which are cataiytically eiTective in in
Thus one way of achieving stabilization of the
benzenoid compounds mentioned above resolves
go
valent-sulphur salts, whether of an alkali-metal
sulphur salts, and some of my claims are directed
temporary.
155
Broadly speaking, my stabilization of tetra
tially impossible to prepare either sodium sulphite
?nitesimal amounts, the value of sodium sulphite
45 in stabilizing these benzenoid compounds is only
5
in the trade as sodium hydrosulphite), and
groups or alkyl_ or aryl-substituted-amino
groups, or hydroxy groups, or radicals containing
characteristic groupings of one or more of these
groups.
It is a further object of my invention to pro-.
p-phenylenediamine,
40
ferred to, to stabilize them in turn.
v4.0
in my claims I state merely that a diamine is
present in the solution I intend to include all of
these situations, because they are in effect in the 45
same generic class; and when I intend to specify
that the diamine is a separate added ingredient
I specifically so state.
Various aliphatic diamines, unsubstituted or
substituted, may be used for obtaining the stabi1~ 50
n
;
a
(OZ. iAJWlI’UOHlUNZiY
M’ “Mr
2
“Minus UHRJU
2,130,322
iz'ed or stable tetravalent-sulphur salts. Among
them are the following:
a. 1,2-ethylenediamine;
b. 1,2-propylenediamine;
TABLE II
Relative effects of copper, manganese, and iron on
.
c. N-ph'enylethylenediamine, represented
rate of oxidation of sodium sulphite, alkalin
ized with sodium hydroxide and with 1,2-ethyl
by
the formula:
enediamine respectively
Concentration of sodium sulphite——l: 1000.
Concentration of sodium hydroxide, when used,
is to give pH 9.
Concentration of ethylenediamine, when used,
d. 1,2-butylenediamine;
e. 1,3~propylenediamine;
f. Condensation products of such diamines with
aldehydes; and
10"
is 5 drops per 500 cc., which gives in excess of
g. Salts of such diamines, especially with weak
acids.
Of these various aliphatic diamines, I prefer the
15
pH 9.
.
Iodine titre is given in cc. of 0.015N iodine solu
tion per 5 cc. of sodium-sulphite solution. The
accuracy of the iodine titrations is 10.2 cc.
1,2-diamines, especially 1,2-ethylenediamine and
1,2-propylenediamine.
Iodine titre
Added metal ions
20
Sodium sulphite solution
Original
With added NaOH.
2. 43
0.10
With added ethylenediamme.
4. 59
4. 00
With added N e011.
4. 30
0. 06
None.
_
25
After 20 hours
‘
Cu++ I:200,000.
20
_
25
_
With added ethylenediamine.
'
4. 45
4. 30
(After 67 hours)
With added NaOH.
3. 41
1. 13
With added ethylenediamine.
4. 37
3. 87
Mn" 11200.000.
With added NaOH.
2. 70
0. 96
With added ethylenediamine.
4. 34
4. 31
Fe’r+ 1:50.000.
35
The measure of deterioration of sulphites, by
reason of oxidation, can be followed by their loss
in iodine titre; and the measure of stabilization
The stabilization of sodium sulphite by added 35
1,2-propylenediamine and by added N-phenyl
ethylenediamine, in contrast to that produced by
by relative constancy in iodine titre.
The stabilization of sodium-sulphite solutions
40 against metal catalysis by added 1,2-ethylenedi
ethanolamine (which also has some stabilizing
effect), is shown‘in the following Table III:
40
amine is shown in the following Tables I and II:
TABLE D1’
TABLE I
Stabilization of sodium sulphite solutions by the
addition of ethanolamine, 1,2-p1opylenedi
amine, and N-phenylethylenediamine
'
Stabilization of sodium sulphite solutions by the
addition of 1,2-ethylenediamine
45
Concentration of sodium sulphite-—1:1000.
Concentration of added copper ions, when cop
per is added—1:200,000.
Iodine titre given in cc. of 0.015N iodine solu
50 tion per 5 cc. of sodium-sulphite solution. The
accuracy of the iodine titrations is $0.2 cc.
Concentration of sodium sulphite-'-1: 1000.
Concentration of added copper ions, when cop
per is added--1:200,000.
45
'
Iodine titre given in cc. of 0.015N iodine solu
tion per 5 cc. of sodium-sulphite solution. The ac
curacy of the iodine titrations is :0.2 cc.
50
Iodine titre
55
Ethylenediamine added
Solution
Sodium sulphite.
60
Orig-
Later—aiter
After
the]
time indicated
10 days
4. 54
None.
2.91 (2 hrs.)
0.00 (3 days)
______ ._
...... __
Sodium sulphite-l-copper sulphate.
4. 45
0.30 (8 hrs.)
Sodium sulphite+Na0H to give
3. 74
1.68 (2 hrs.)
pH 9.
0.00 (2 days)
N one.
55
60
...... __
'
Sodium sulphite+Na0H to give
3.28
Sodium
4. 33
pH 9+copper sulphate.
65
sulphite+N H4011
(5
drops per 500 00.).
None.
0.00 (2 days)
______ ..
3.86 (4 hrs.)
2.27 (22 hrs )
______ _.
l 71 (4 hrs.)
______ __
65
‘
.
Sodium
sulphite+NH40H
(5
2. 77
drops per 500 cc.)+copper sul-
0 26 (22 hrs)
phate.
Ethylenediamino to give pH 9.
Ethylenediamine in excess (5
drops per 500 00.).
Sodium sulphitc.
4. 50
4.37 (3 days)
3. 89
Sodium sulphite+copper sulphate.
4. 45
3.30 (3 days)
1.01
Sodium sulphite.
4. 41
4.43 (3 days)
4. 41
Sodium sulphite+copper sulphate.
4. 45
4.30 (3 days)
4. l9
70
75
3
2,130,322
Concentration of diamine-aldehyde concentra
Concentration of added stabilizer-5 drops
per 500 cc.
tion products—1 : 1000.
Iodine titre
Added stabilizer
Solution
Original ?ggleirrs iéiiéiirs hours
‘3281
10
N
Sodium sulphite+NaOH to give pH 9.
4. 65
0. 21
Sodium sulphite+NaOH to give p11 9
2. 23
1. 10
Sodium sulphite.
4. 05
4. 33
4. 25
4. l2
Sodium sulphite+copper sulphate.
4. 46
3. 35
1.71
0.00
10
one.
+ copper sulphate.
15
Ethanolamine.
1. ‘2-propylene-diamine.
20
N -phenylethylene diamine.
25
Sodium sulphite.
4. 50
4. 53
Y 4. 37
4. 25
Sodium sulphite-l-copper sulphate.
4. 48
4. 50
4. 33
4. 10
Sodium sulphite.
4. 67
3. 92
3. l0
1. 73
Sodium sulphite+copper sulphate.
4. 40
3. l6
1. 99
0. 56
Similar effects are obtainable _ on other sul-
Iodine titre given in cc. of 0.015N iodine solu
phites.
The
stabilization
of
sodium
20
25
tion per 5 cc. of sodium-sulphite solution. The ac
curacy of the iodine titrations is :0.2 cc.
hyposulphite
(Na2SzO4) by ethylenediamine in the presence
30 of copper ions is shown by the following Table
Iodine titre
IV:
TABLE IV
_
E?‘ect of copper on rate of oxidation- of sodium
hyposulphite alkalinized with sodium hydrox
ide and with ethylenediamine respectively
Solution
30
'
Sodium sulphite ______________________________ __
Origi-
After 20
nal
hours
4. 20
0. 10
5. l0
4. 75
4. 90
4. 34
Sodium sulphite+condensation product 01’ ethyl
enediamine with acetaldehyde............... __
Sodium sulphite-l-condensation product of pro
pylenediamine with salicylic aldehyde ______ __
Concentration of sodium _sulphite—l:1000.
Concentration of added copper ions--1:200,000.
40
Such condensation products of 1,2-diamines 40
Iodine titre given in cc. of 0.015N iodine solu
tion per 5 cc. of sodium sulphite solution. The
with aldehydes may be obtained in various ways.
A convenient way is by treating an ether solu
accuracy of the iodine titrations is —l__—0.2 cc.
45
45
Iodine titre
Solution
O? b
50
nagl
After bubbling air
through—
After
_
standing
For 2
For 5
hours.
hours
Sodium hyposulphite-l-CuSOvl-NaOH to
55
'
give pH 9.6 ____________________________ --
4. 05
3‘ 80
0. 10
4. 08
4.07
4.0%
Sodium hyposulphite+CuSO4+ethylene-
This effect of aliphatic 1,2-diamines in stabilizing compounds against these metal catalysts
persists in condensation products of such dia
mines with aldehydes—such as acetaldehyde,
vanillin, salicyclic aldehyde, isobutyraldehyde,
65 etc.
This stabilization effect on sodium sulphite
by these condensation products is illustrated in
the following Table V.
TABLE V
55
4. 16
tion of the aldehyde with the desired diamine; 60
such as ethylenediamine.
In some cases a solid
separates out, as in the case of propylenediamine
with salicyclic aldehyde. This last-mentioned
compound is a bright yellow solid, which melts at
118°-123° C. Ethylenediamine and salicyclic al 65
dehyde also yield a bright yellow solid, which
melts at about 125° C. Ethylenediamine and
acetaldehyde yields a white solid, which melts
at about 108° C.
Stabilization of sodium sulphite solutions by con
densation products of 1,2-diamines and alde
hydes
0.10
_
diamine to give pH 9.6 ________________ __
60
50
18 hours
.
Concentration of sodium sulphite—>l:1000.
Concentration of added copper ions-—1:200,000.
In all of these stabilizations, the alphatic dia 70
mine probably exerts its inhibiting or stabiliz-y'
ing action by forming extremely stable complexes
with the metallic ions, as of copper, manganese,
and iron, and by thus preventing such ions from
exerting their catalytic e?ect.
75
an
4
A sulphite or hyposulphite; thus stabilizedwith
observation. Moreover, if the colored solution of
an aliphatic diamine is effective to produce the
desired stabilization of the easily oxidized ben
zenoid compounds the stabilization of which is
catechol was treated with stabilized sodium sul
phite, the color disappeared, and did not reappear
during the periodof observation.
The following Table VI summarizes these three
examples.
the fundamental object of the present invention.
All that
oxidized
a small
phite or
one needs to do to stabilize. those easily
benzenoid compounds is to add thereto
quantity of the stabilized sodium‘ sul
stabilized sodium hyposulphite, or of a
10 stable diamine sulphite.
.
compounds
The following three examples indicate the
stabilizing action on some benzenoid compounds
15
‘
mThe‘ extent" of‘ discoloration indicates the
extentrof decomposition.
by a sodium ‘sulphite stabilized with ethylenedi- ’
'
~
diamine on certain easily oxidized benzenoid
'
amine.
TABLE VI
E?ect of sodium sulphite stabilized by ethylene
-Observations after standing in the light at
.
room temperature.
Example 1.--A solution of 0.1 g. p-phenylene
15
diamine in 100 cc. of water.. The solution turned
dark pink within ?ve minutes; and upon stand
ing three or four days became intensely red, and
a dark brown precipitate had settled. By con
Solution
With ordinary NazSO;
.
20 trast, in an identical solution of'0.1 g.’ of p
.-
p-I’henylenedia-
phenylenediamine in 100 cc. of water in which
there was also dissolved 0.4 g. of stabilized sodi
um sulphite (stabilized with ethylenediamine)
'
"n'iin'e.
'
'
ethylenediamine
Dark pink to red.
‘
'
'
With NazSOa sta
bilizcd with 1, 2
S u bst a n tia ll y
'
colorless.
Hydroquinone ____ ..
Dark brown.
Faint brown tinge.
Catechol __________ ._
Yellow.
Colorless.
the initially colorless solution ~Wasyfound to re
25 main substantially colorless throughout the en— .l:.;. The following .Table'VII-illustrates the stabi; 25
lization of p-phenylenediamine by sodium sul
tire period of observation, here ten, days; -More erphitez-stabilized by propylenediamine against the
over, if the solution of p-phenylenediamine in
cited; of copper:
water was ?rst prepared without the stabilized
sodium sulphite, and discoloration occurred, that
30 disooloring could be removed by adding the sta
bilized sodium sulphite later, up to at least four
E?‘ect of
35
7
sulphite stabilized ‘by propylene-I"
diamine on p-phenylenediamine in the presence
hours later; and the solution so produced was
free of any appreciable color throughout a ten
day period of observation.
.
Concentratiomof sodium sulphite-41100055
1 ‘Concentration iof. pephenylenediamine—-'1r1000. 1*
_
Example 2.—A solution of 0.1 g. hydroquinone
in 100 cc. of water. The solution turned dark
Added diamine
Concentration of added copper ions, when cop
35
per is added--1:200,000.
Solution
Original appearance
Aégeiolbiagflg Agfagtgggrlgg
"40
40
’
plPhenylenediamine + so'
None.
Colorless.
Pink.
Pink.
Colorless.
Dark pink.
Brown.
Colorless.
Colorless.
ldiur?’s'ulpl'zlte. ”
-
p-Phenylenediamine
+ so~
dium sulphite + copper sul
phate.
45
.
p-Phenylenediamine
dium sulphite-
.
+
50-
.
Colorless.
.
_
.
.
.
.
Propylenediaminc (l
drop per 100 cc.).
_
p-Phenylenediamine- + ' so.diurn sulphite + copper sul-
phate.
within ?ve minutes; and upon standing three. or
four days became very dark brown. By contrast,
in an identical solution of 0.1 g. of hydroquinone
in 100 cc. of water in which there was also dis
55 solved OA g. of stabilized sodium sulphite (here
again stabilized with ethylenediamine) the. solu
tion showed only a very faint brown tinge,~and
did not become darker or otherwise change in
M60
color during the ten days of=ob5?vation _- More
over, if the darlgcolored solution ,of ' hydro~
quinone, darkened ‘by reason of; the absencemf
any stabilized sodium sulphite, was ‘later-treated
with stabilized sodium sulphite, up to atwleastA
hours later, the discoloration almost disappeared,
65 and the solution became ‘only faintly tingedwith
brown, with no furthur change in color during the
period of observation.
-
.
b
_
'.
--
.
Example 3.—A solution of 0.1 g. catechol‘ in
100 cc. of Water“; The solution lturnedvyellow
on standing overnight. By contrast, in an identi
cal solution of 0.1 g. of catechol in 10000. of‘
water in which there was also dissolved.- 0.4:g..>_ of
Pale purple: iron} copperpropylenedlamine com-
plex formed.
Substantially
colorless.
‘
Substantially
colorless.
:It isdesirable' in the case of many of the ben
zenoid compounds whichrare easily oxidized that
their solutions be capable of remaining colorless;
and- this has heretofore been di?icult ‘and in
many casesimpossible to effect, because the oxi
dation caused discoloring. The foregoing Tables
VI and VII illustrate how discoloration can be
largely if not wholly prevented. The same .free
dom from:rdiscoloratiomimay be obtainedwitn
-many othersv of ,these benzenoid compounds ‘by 60
having: present my diamine-stabilized:solution of
an alkali-metal tetravalent-sulphur salt. This
includes not only solutions of sodium. sulphite
and of sodium hyposulphite with added diamines,
as considered in Tables I, II, III, IV, VI, and VII,
but also such solutions of- either sodium sulphite
or sodium hyposulphite stabilized with condensa
tion products of the diamines with aldehydes, as
considered in Table V, as’ well as solutions of
stable sulphites and hyposulphites described 70
hereinafter.
It is of especial advantage in photography to
stabilized sodium sulphite -(her_e~ againstabilized
have a colorless; solution, as for a developer.
with ethylenediamine) the solution wascolorless,
‘When. an ordinary 'developer containing p
phenylenediamine or hydroquinone and sodium 75
and remained colorless for the ten-day period of
5
2,130,322
sulphite is allowed to stand in the air, it quickly
turns brown; due to the fact that sodium sulphite
is used up at a great rate, and oxidation of
p-phenylenediamine or the hydroquinone takes
place. If instead of ordinary sodium sulphite,
my stabilized sodium sulphite (containing a small
amount of ethylenediamine for instance) is used,
no such change in color takes place, and the so~
lution can be kept in the light for days without
10 undergoing any perceptible change in color.
In the preceding Tables I to VII inclusive, and
in the preceding Examples 1 to 3 inclusive, the
stabilization has been initially of an existing sul
phite or hyposulphite with a diamine which was
15 not part of the saltmolecule. It is possible,
however, to prepare a new and inherently stable
type of tetravalent-sulphur salt—-sulphite and or
hyposulphite—from
the
aliphatic
diamines,
whereby the diamine enters into the salt mole
20 cule; and to use such inherently stable diamine
tetravalent~sulphur salts to produce the desired
stabilization of the easily oxidized benzenoicl
compounds. These diamine tetravalent-sulphur
salts are stable even in the presence of the metal
25 ion catalysts of copper, manganese, and iron, and
even in a solution which is neutral or slightly
alkaline—a property which is unique for tetra
valent-sulphur salts.
These diamine salts may be prepared in var
30 ious ways. The diamine sulphites may be pre
pared by causing the desired diamine‘ to react
with sulphur dioxide or sulphurous acid; and
the diamine hyposulphites by electrolytic reduc
tion of the diamine sulphites.
35
An example of these diamine salts is ethylene
diamine sulphite. It is perhaps most simply pre
pared by passing sulphur dioxide into either an
absolute or aqueous alcoholic solution of 1,2
ethylenediamine or into an acetone solution of
such diamine; upon which the salt separates in
solid form.
Ethylenediamine sulphite melts at 173-175" C.,
with decomposition. It is white, and quite sol
uble in water. The water solution is about pH
6.7. The analysis of the salt for nitrogen and
sulphur indicates that it contains one mole of
ethylenediamine to one mole of sulphurous acid.
It is quite stable against metal catalysis, and is
very e?ective as a stabilizer of those easily oxi
60 dizable benzenoid compounds which are unstable
in the presence of ions of copper, manganese, or
iron. It probably has the following formula:
55
Another example is propylenediamine sulphite.
It may be prepared analogously to ethylenedi
60 amine sulphite; and is similar thereto in most
respects. It melts at 162° C., with decomposi
tion. It also is quite stable against metal cataly
sis, and effective as a stabilizer of these benze
noid compounds.
65
_
Ethylenediamine hyposulphite may be ob
tained by reducing ethylenediamine sulphite.
These inherently stable sulphites or hyposul
phites act substantially like my stabilized sodium
sulphite and hyposulphite, to stabilize such ben
70 zenoid compounds as epinephrin, amino-phenols,
p_-phenylenediamine, etc. I have tried ethylene
diamine sulphite for all the combinations which
I have enumerated for obtaining stabilization by
the use of my stabilized sodium sulphite; and
75 ?nd that such ethylenediamine sulphite is of
substantially the same effectiveness as my stabi
lized sodium sulphite.
This action is illustrated by the following ex
amples:
Example 4.—-A 1:10,000 solution of epinephrin
was divided into two parts, and one part was
treated with three moles of ethylenediamine
sulphite, and the other part used for a control.
On heating for ten hours at 100° C., the part
containing ethylenediamine sulphite remained
colorless, while the control became quite dark.
Ethylenediamine sulphite has a marked ad
vantage in stabilizing epinephrin, because it per
mits the epinephrin or epinephrinchloride solu
tion to be neutral or even slightly alkaline, in
stead of acid. This unique proper of maintain
ing epinephrin preparations stable and colorless
is quite important, for it is frequently desirable
to use an epinephrin which is not at the acid pH
at which, for the sake of stability, it is usually 20
necessary to maintain it.
Erample 5.—-Wl1en 0.1 g. of p-phenylenedi
amine was dissolved in 100 cc. of water the solu
tion turned pink within a few minutes, and upon
standing for ?ve days a dark brown precipitate 25
settled out and the solution became intensely
red and quite opaque. But when 03 g. of solid
ethylenediamine sulphite was added to 0.1 g. of
solid p-phenylenediamine, and the whole was dis
solved in 100 cc. of water, a solution was ob 30
tained which was not only initially colorless but
which remained colorless during the two weeks
of observation.
‘
Example 6.-—Instead of using ethylenediamine
sulphite as in Example 5, I may use 1,2-propyl- ‘
enediamine sulphite, and get the same results
as indicated in Example 5 in the stabilization of
p-phenylenediamine.
Example 7.——When 0.1 g. of p-amino phenol
and 0.3 g. of ordinary (unstabilized) sodium sul
phite were dissolved in 100 cc. of water, the solu
40
tion become dark brown immediately. However,
if instead of using such unstabilized sodium sul
phite I use ethylenediamine sulphite, I avoid dis-_
coloration substantially completely; for on add 45
ing 0.1 g. of solid p-amino phenol to 0.3 g. of
solid ethylenediamine sulphite, and dissolving the
whole in 100 cc. of water, I get only a slight dis
coloring of the solution, and no additional dis
coloring during the period of two weeks during 50
which observations were continued.
Similar re—
sults were obtained with N-methyl-p-amino
phenol (commonly known as metal).
Example 8.-—When a strong alkaline solution
of hydroquinone plus unstabilized sodium sulphite 55
(such as is used in ?ne grain developers) is al
lowed to stand in the air, it rapidly assumes a
black color; and when it is used in developing, the
bath becomes practically un?t for use after about
the third time. On the other hand, if instead of 60
unstabilized sodium sulphite I employ either my
stabilized sodium sulphite or 1,2-ethylenediamine
sulphite or 1,2-propylenediamine sulphite, a solu
tion is obtained which not only remains light
colored for weeks but which may also be used 65
ten or twelve times as a developing bath.
The
stabilizing effect of the stable diamine sulphite
is even more pronounced than that of sodium
sulphite stabilized with ethylene diamine.
The various examples given of benzenoid' com~ 70
pounds have in general been hydroxy-substituted
or amino-substituted benzenoid compounds, with
the substitution in the ortho position and/or in
the para position; but these examples are not in
tended to limit the broad aspect of my invention.
2,130,322
For instance, pyrogallic acid, which is oxidizable
adding to such solution 1,2-ethylenediamine sul
but not as readily so as some of the other sub
stances discussed, can readily be made more
stable by the use of my stabilized or stable sul
phite.
10. The process of stabilizing a solution of a
hydroxy benzenoid compound which is easily
oxidized by oxygen of the air, which consists in
phites. So can naphthalene-substituted prod—
ucts. So also can certain derivatives of epine
phrin and of ephedrine, such for instance as
nor-epinephrin or 3,4~dioxy-nor-ephedrine, the
adding to such solution 1,2-propylenediamine
sulphite.
11. A composition of matter, comprising a water
solution of a tetravalent-sulphur salt, in which
water solution there is present an aliphatic 1,2 10
diamine.
12. A composition of matter, comprising a water
structural formulas of which are as follows:
10
Nor-epinephrin:
(3)
HO
solution of a sulphate, in which water solution
there is present an aliphatic 1,2-dia1nine.
13, A composition of matter comprising a water
solution of a hyposulphite, in which water solution
there is present an aliphatic 1,2-diamine.
14. A composition of matter, comprising a water
solution of a sodium tetravalent-sulphur salt, in
which water solution there is present an aliphatic
LZ-diamine as an added ingredient uncombined
with the tetravalent-sulphur salt.
15. A composition of matter, comprising a water
solution of sodium sulphite, in which water solu
tion there is present an aliphatic 1,2-diamine as
an added ingredient uncombined with the sodium
Ht
SA-dioxy-nor-ephedrine:
(4)
20
|
H0
In other words, the examples which are given
are intended to illustrate and not to limit the
broader aspects of my invention.
N, C21
I claim as my invention:
1. The process of stabilizing a solution of a
sulphite.
hydroxy benzenoid compound which is easily ox
idized by oxygen of the air, which consists in
adding to such solution a tetravalent-sulphur
salt which has an aliphatic 1,2-diamine present
16. A composition of matter, comprising a water
solution of sodium hyposulphite, in which water
solution there is present an aliphatic 1,2-diamine 3O
with it.
2. The process of stabilizing a solution of a
as an added ingredient uncombined with the
sodium hyposulphite.
hydroxy benzenoid compound which is easily
oxidized by oxygen of the air, which consists in
1'7. A composition of matter, comprising a solu_
tion of a hydroxy benzenoid compound which is
easily oxidized by oxygen of the air, in which solu
tion there is a tetravalent-sulphur salt which has
adding to such solution a sulphite which has
an aliphatic 1,2-diamine present with it.
3. The process of stabilizing a solution of a
an aliphatic 1,2-diamine present with it.
18. A composition of matter, comprising a solu
hydroxy benzenoid compound which is easily
oxidized by oxygen of the air, which consists in
tion of a hydroxy benzenoid compound which is
easily oxidized by oxygen of the air, in which solu 40
tion there is a sulphite which has an aliphatic
40 adding to such solution a hyposulphite which
has an aliphatic 1,2-diamine present with it.
4. The process of stabilizing a solution of a
1,2-diamine present with it.
hydroxy benzenoid compound which is easily
oxidized by oxygen of the air, which consists in
45 adding to such solution a sodium tetravalent
sulphur salt which has present with it an ali
phatic 1,2-diamine as an added ingredient un
combined with the tetravalent~sulphur salt.
1,2-diamine present with it.
.
A composition of matter, comprising a solu
tion of a hydroxy benzenoid compound which is
5, The process of stabilizing a solution of a
50
_ _
19. A composition of matter, comprising a solu
tion of a hydroxy benzenoid compound which is
easily oxidized by oxygen of the air, in which solu
tion there is a hyposulphite which has an aliphatic
hydroxy benzenoid compound which is easily
oxidized by oxygen of the air, which consists in
easily oxidized by oxygen of the air, in which solu
adding to such solution sodium sulphite which
tion there is a sodium tetravalent-sulphur salt
which has present with it an aliphatic 1,2-diamine
has present with it an aliphatic 1,2-diamine as
an added ingredient uncombined with the sodium
as an added ingredient.
55 sulphite.
,
6. The process of stabilizing a solutionpf a
hydroxy benzenoid compound which‘ is easily
oxidized by oxygen of the air, which consists in
adding to such solution‘ sodium hyposulphite
60 which has present with it an aliphatic 1,2-di
amine as an added ingredient uncombined with
the sodium hyposulphite.
’
7. The process of stabilizing a solution of a
hydroxy benzenoid compound which is‘ easily
65 oxidized by oxygen of the air, which consists in
50
21. A composition of matter, comprising a solu
tion of a hydroxy benzenoid compound which is
easily oxidized by oxygen of the air, in which solu
tion there is sodium sulphite which has present
with it an aliphatic 1,2-diamine as an added in
gredient.
22. A composition of matter, comprising a solu 60
tion of a hydroxy-benzenoid compound which is
easily oxidized by oxygen of the air, in which solu
tion there is sodium hyposulphite which has pres
cut with it an aliphatic 1,2-diamine as an added 65
ingredient.
adding to such solution an aliphatic 1,2-diamine
tetravalent-sulphur salt.
8. The process of stabilizing a solution of a
hydroxy benzenoid compound‘ which is easily
oxidized by oxygen of the air, which consists in
adding to such solution an aliphatic 1,2-diamine
sulphite.
9. The process of stabilizing a solution of a
hydroxy benzenoid compound which is easily
75 oxidized by oxygen of the air, which consists in
o
23. A composition of matter, comprising a solu
tion of a hydroxy benzenoid compound which is
easily oxidized by oxygen of the air, in which solu
tion there is an aliphatic 1,2-diamine tetravalent~ 70
sulphur salt.
24. A composition of matter, comprising a solu
tion of a hydroxy benzenoid compound which is
easily oxidized by oxygen of the air, in which solu
75
tion there is an aliphatic 1,2-diamine sulphite.
2,180,322
25. A composition of matter, comprising a solu
tion of a hydroxy benzenoid compound which is
easily oxidized by oxygen of the air, in which solu
tion there is 1,.2-ethylenediamine sulphite.
26. A composition of matter, comprising a solu
tion of a. hydroxy benzenoid compound which is
easily oxidized by oxygen of the air, in which solu
tion there is 1,2-propylenediamine sulphite.
27. A composition of matter, comprising a solu
10 tion which includes as solutes hydroquinone and
a tetravalent-sulphur salt which has an aliphatic
1,2-diamine present with it.
28. A composition of matter, comprising a solu
tion which includes as solutes hydroquinone and a
sulphite which has an aliphatic 1,2-diamine pres
ent with it.
29. A composition of matter, comprising a solu
tion which includes as solutes hydroquinone and
a hyposulphite which has an aliphatic 1,2-di
20 amine present with it.
30. A composition of matter, comprising a solu
7
tion which includes as solutes a benzenoid com—
pound of the class consisting of o-aminophenol,
p-aminophenol, p-phenylenediamine,' catechol,
hydroquinone, metol, and epinephrine, and a
tetravalent-sulphur salt which has an aliphatic 5
1,2-diamine present with it.
31. A composition of matter, comprising a solu
tion which includes as solutes a benzenoid com
pound of the class consisting of o-aminophenol,
p-aminophenol, p-phenylenediamine, catechol,
10
hydroquinone, metol, and epinephrine, and a sul
phate which has an aliphatic 1,2-diamine present
with it.
'
32. A composition of matter, comprising a solu
tion which includes as solutes a benzenoid com
pound of the class consisting of o-aminophenol,
p-aminophenol, p-phenylenediamine, catechol,
hydroquinone, metol, and epinephrine, and a
hyposulphite which has an aliphatic 1,2-diarnine
present with it.
MORRIS S. KHARASCH.
15
252. tvwiomwliiu
.
' l
1\
'4'. _ ‘35:0
_
i
"Q 1'" I"
‘"{ii’i‘vi
'
CERTIFICATE OF CORRECTION.
Patent No. 2,150,522..
September 15,- 1958.
MORRIS S. KHARASCH .
It is hereby certified that error appears ‘in the, printed speci
ficat ion of the above numbered patent requiring ‘correction as fol
lows: Page 1‘, first column, line 25, for the word} "metal" read metol;
page 2, first column, line 1, beginning with the syllable and words
"ized or stable" strike out all to and including "sodium" in line
75, second column of page )4, and insert instead the following —
ized or stable tetravalentesulphur salts. Among
'them are the following:
a. 1,2-ethylenediarnine;
b. 1,2-propylenediamine;
c. N —ph'enylethylenediamine, represented by
the formula:
d. 1,2-buty1enediainine;
- e. 1,3-propylenediamine,‘
f. Condensation products of such diamines with
aldehydes; and
g. Salts of such diamines, especially with weak
acids.
or these various aliphatic diamines, I prefer the
1,2-diamines, especially 1,2-ethylenediamine and
1,2-propylenediamine.
The measure of deterioration of sulphites, by
reason of oxidation, can be followed by their loss
in iodine titre; and the measure of stabilization
by relative constancy in iodine titre.
'
-
The stabilization of sodium-sulphite solutions
against metal catalysis by added 1,2-ethylenedi
amine is shown in the following Tables I and II:
TABLE I
Stabilization of sodium' sulphite solutions by the
addition of LZ-ethylenediamine
Concentration of sodium sulphite—-1:,1000.
Concentration of added copper ions, when cop
per is added-£200,000.
Iodine titre given in do. of 0.015N iodine solu
tion per 5 cc. of sodium-sulphite solution. The
accuracy of the iodine titrations is _-i;0.2 cc.
Iodine titre
Ethylenediaimne added
'
'
Solution
Sodium sulphitc.
orig‘
Lam_aner
After
inal
time indicated
10 days
It 54
2.91 (2 hrs.)
0.00 3 days)
None.
_
.
4. 45
Sodium sulphite-l-NaOH to give
' 3. 74
pH 9.
None.
Sodium sulphite+Na0H to give
pH 9+oopper sulphate.
3. 28
Sodium
4. 33
sulphita-i-NIhOH
.
'
Sodium
Etbylenediamine to give pH 9. ‘
Ethylenediemine in am (5
drops per 500 00.).
‘
suiphite+NH40H
(5
-
_
(l5
drops per 500 cc.)+copper 3111-
V phate.
-
0.30 (8 hrs.)
1.68,
'
drops per 500 cc.).
None.
______ __
'
Sodium sulphite+copper sulphate.
2. 77
-
______ ._
hrs.)
0.00 (2 days)
...... -_
0.00 (2 days)
‘
______ __
3.86 (4 hrs.)
v
2.27 (22 hrs.)
______ ..
_1.71.(4 hrs.)
...... __
006(22 hrs.)
'
Sodium sulphite.
4, 50-
4.37 (3 days)
Sodium sulphite-l-copper sulphate.
Bodlum sulphite.
4. 45
4. 41
3.30 (3 days)
4.43 (3 days)
4. 41
4. 45
4.30 (3 days)
4. 19
_
3. 89
1.01
‘
Sodium sulphite+copper sulphate.
- Relative ejects of copper, manganese, and iron on
'rate of oxidation of sodium sulphite, alkalin
ized with ‘sodium hydroxide and with 1,2-eth1/l
enediamz'ne respectively
Concentration of sodium sulphite—1:1000.
. Concentration of sodium hydroxide, when used,
is to give pH 9.
-
Concentration of ethylenediamine, when used,
isH59drops-per
500 00., which gives in excess of
p
.
Iodine titre is given in cc. of 0.015N iodine solu
tion per 5 cc. of sodium-sulphite solution. The
accuracy of the iodine titrations is :0.2 cc.
Added metal ion;
f
_
Iodine titm
Sodium sulphite solution
Original
_
With added NBOH.
None.
'
Alter 20 hours
a 43
0. 10
With added ethylenediamine.
‘ 4. 69
4. 60
With added NaOH.
7 4.30 ‘
Cu" 1:200,000.
.
'
With added ethylonediamino.
'
With added NBOH.
Mn" 1200.000.
'
'
‘
'
.
a u‘
With added othylonediamino.
.
.
4. 30
(Aim 67 hours)
"
_
1‘ 13
4. 37
With addod N OH.
Fe" 1:50.000.
0 06
4. 45
3. 87
.
8
2 7o
0‘ 96
With added othylanodiamine. ’
4. s4
4. 31
The stabilization of sodium sulphite by added
1,2-propylenediamine and by added N-phenyl
ethylenediamine, in_ contrast to that produced by
ethanolamine (which also has some stabilizing
effect), is shown in the following TableIII:
TABLE I11
' Stabilization of sodium sulphite solutions by the
addition of ethanolamine, 1,2-propylenedi
amine, and -N-phenylethylenediamine
Concentration of sodium sulphite-1r1000.
Concentration of added copper ions, when cop
per is added—1:200,000.
Iodine titre given in cc. of 0.015N iodine solu
tion per 5 cc. of sodium-sulphite solution. The ac
curacy ot the iodine titrations is :0.2 cc.
Concentration of added stabilizer-4 di'oPB
per 500 cc:
‘
Iodine um
Added stabilizer
J
'
Solution
.
'
-None.
Original m“ 4"" “1%”
24 hours 48 hours hours
Sodium
'
sdmmmmonwme
.
_pH 0. .
4 as
. a 2i
‘Sodium sulphite-i-NaOH togive pH 0 .
2. 23
l. 10
+ oopperimiphow.
Sodium sulphite.
Ethanolamine.
Sodium sulphitai-oopper sulphate.
1. 2~propyleno-_diamina.
'
N -phenylethylene diamine.
Sodium sulphite.
'
..... .Q ____
______________ _
4 65
l 4. 33
' _ 4. 46
3. 35
4. 25,
1. 71
4. 12
0.00
4. 50
4. 53
4. 37
4. 25
4. l0
Sodium sulphite+oopper sulphate.
4. 48
4. 50 I
4. 33
Sodium sulphite.
4. 67
3.92 '
3. l0
1. 73
4. 40
3. 16
1. 99
0. 58
_ Sodium sulphite+copper sulphate.
xi
252..
" con/wosmoms.
I
g‘étij’f
in‘,5.“ I
t
Similar eifects are obtainable on other sul
phites.
'
The stabilization
of sodium 'hyposulphite
(Na2S2O4) by ethylenediamine in the presence
of 1’ copper ions is shown by the following Table
IV:
TABLE IV
E?ect of copper on rate of oxidation of sodium
.hyposulphite alkalinized with sodium hydrox
z‘de and with ethylenedz'amine respectively
Concentration of sodium sulphite—l:l000.
Concentration of added copper ions-1:200,000.
Iodine titre given in cc. of 0.015N iodine solu
tion per 5 cc. of sodium sulphite solution. The
accuracy of the iodine titrations is $0.2 cc.
Iodine titre
I
i
Arte: bubbling air
,through-
Solution
Alter
0:51‘ \ standing
For 2
For 5
hours
hours
18 hours
Sodium hyposulphite-i-CuSOi+NaOH to
give pH 9.6 ____________________________ _Sodium
>hyposulphite-i-CuSprl-othylene
4.05
3.80
0.10
0. 10
diamine to give pH 9.6 ________________ .i
4. 08
4. 07
4. 04
4.16
This e?'ect of aliphatic 1,2-diamines in sta
bilizing compounds against these metal catalysts
persists in‘oondensation products of such dia
minesc with‘ aldehydesésuch as acetaldehyde,
vaniliin, salicylic ' aldehyde, isohutyraldehyde,
etc. This stabilization effect on sodium sulphite
by these condensation products is illustrated in
the following Table V.
TABLE V
Stabilization of sodium sulphite solutions by con
densation products of 1,2-diamines and alde
hydes
'
'
Concentration 01' sodium sulphite—-1:1000.
Concentration of added copper ions-1:200,000. '
Concentration of diamine-aldehyde concentra
tion products-#1000.
Iodine titre given in cc. of 0.015N iodine solu
tlon per 5 cc. of sodium-sulphite solution. The ac
curacy of the iodine titrations is :0.2 cc.
Iodine titre
Solution
.
Origi11
Sodium sulphite .............................. . .
After 20
hours
4. 20
0. 10
enediamiua with acetaldehyde
5. i0
4. 75
pylenediaminc with salicylic aldehyde ______ _.
4. 90
4. 34
Sodium sulphite+condensstion product oiethyl
Sodium sulphitell-oondeusation ‘15651565 b'r'b'rbl'
zézgvcolv;Positions.
a
N .
Such condensation products of 1,2-diamines
with aldehydes may be obtained in various ways.
A convenient way is by treating an ether solu
tion of the aldehyde with the desired diamine,
such as ethylenediamine. In some cases a solid
separates out, as in the case of propylenediamine
with salicylic aldehyde. This last-mentioned
compound is a bright yellow solid, which melts .at
118°¢-123° C. Ethylenediamine and 581102110 al
dehyde also yield a bright yellow solid, which
melts'at about 125° C. Ethylenediamine and
acetaldehyde yield. a white solid, which melts
at about 108° C.
In all of these stabilizations, the aliphatic'dia
mine probably exerts its inhibiting or stabiliz
ing action by ‘forming extremely stable complexes
with the metallic ions, as or copper, manganese,
and iron, and by thus preventing such ions from
exerting their catalytic effect.
A sulphite or hyposulphite thus stabilized with
an aliphatic diamine is e?ective to produce. the
desired stabilization of the easily oxidized ben
zenoid compounds the stabilization-of which isv
the fundamental object of the present invention.
All that one needs to do to stabilize those easily
oxidized benzenoid compounds is to add thereto
a small quantity of the stabilized sodium sul
phite or stabilized sodium hyposulphite, or of a
stable diamine sulphite.
.
The following three examples indicate the
stabilizing action on some benzenoid compounds
by a sodium sulphite stabilized with ethylenedl
amine._
Example 1-.7-A solution of 0.1 g. _p~phenylene
diamine in 100 cc. of waterl The solution turned
dark pink within ?ve minutes; and upon stand
ing three or four days became intensely red, and
a dark brown precipitate had settled. By con
trast, in an identical solution of 0.1 g. of p
phenylenediamine in 100 cc. of water in which
there was also dissolved 0.4 g. of stabilized sodi
um sulphite (stabilized with ethylenediamine)
the-initially colorless solution was found to re
main substantially colorless throughout the en
tire period of observation, here ten days. More
over, if the solution of p-phenylenediamine in
water was ?rst prepared without the stabilized
sodium sulphite, and discoloration occurred, that
discoloring could be removed by adding the sta
bilized'sodium sulphite later, up to at least four
hours later; and the solution so produced was
free of any appreciable color throughout a ten
day period of observation.
»
Example 2.--A solution of 0.1 g. hydroquinone
in 100 cc. of water.
The solution turned dark
within ?ve minutes; and upon standing three or
four days became very dark brown. By contrast,
in an identical solution of 0.1 g. of hydroquinone
in 100 cc. of water in which there was also dis
solved 0.4 g. of stabilized sodium sulphite (here
again stabilized with ethylenediamine) the solu_
tion showed only a very faint ‘brown tinge, and
did not become darker or otherwise change in
color during the ten days of observation. More
over, if the dark-colored solution of hydro
quinone, darkened by reason of the absence of
any stabilized sodium sulphite, was later treated
with stabilized sodium-sulphite, up to at least 4
hours later, the discoloration almost disappeared,
and the solution became only faintly tinged with
brown, with no furthur change in color during the
period of observation. .
4&3
252.. @QMPQSUUNZ‘F.
QFQSS (5)
, Example 3.?A solution of 0.1 g. catechol in
_100 cc. of .water.
The solution turned yellow
on standing overnight. By contrast, in an identi
cal solution of 0.1 g. of .catechol in 100 cc. of
water in which there was also dissolved 0.4 g. of
stabilized sodium sulphite '(here again stabilized
with ethylenediamine) the solution‘was colorless,
andremainedcolorless for the ten-day period of
observation. Moreover, if the colored solution of
cateohol was treated with stabilized sodimn sul
phite, the color disappeared, and did not reappear
during the period of observation.
.
v
The following Table VI summarizes these three
examples.
E?‘ect of sodium sulphite stabilized by} ethylene
‘
diamine on certain easily oxidized benzenoid
compounds
’
The extent of discoloration indicates the
extent of decomposition.
Observations after standing in the light at
room temperature.
Solution
p-Phenylenedia-
-
With NmSOz sta
With ordinary NmSO:
bllized with 1,- 2
ethylenediamine
Dark pink to red.
Substantially
mine.
colorless.
Hydroquinone ____ _.. Dark brown.
Catechol_-_._
-. Yellow.
'
Faint brown tinge
Colorless.
‘The following Table VII illustrates thestabi
.iization of p-phenylenediamine by sodium‘ sul
phite stabilized by propylenediamine against .the
eilfeet of copper:
.
TABLE VII
E?‘ect of sodium sulphit'e stabilized, by propylene
diamine on p-phenylenediamine in the presence
of copper
Concentration of sodium sulphlte-4: 1000.
,
Concentration of p-phenylenediamine-l: 1000.
Concentration of added copper‘ ions, when cop
per is added-—1:200,000.
Added diamine
.
Solution
Original appearance
p-Phenylenediamine
+
so~
dium sulphlto.
None.
Agegolsiasfxg Ag?gtggglfgg
Colorless.
Pink.
‘
piPhenylenediamlne + so-
' Pink.
~
Colorless.
‘ Dark pink.
Brown.
' dium sulphite + copper sul
phate.
.
.
p-Phenylenodlamine + sodium sulphite.
~
Colorleé.
Propylenediamine (1
drop per 100 cc.).
'
Colorless.
.
p-Phenylenedismine + so- Pale purple: iron} oopper- Substantially
dium sulphite + copper sulpropylenediamme oomcolorless.
phate.
plex formed.
It is desirable in the case of many of the ben
zenoid compounds which are easily oxidized that
their solutions be capable ‘of remaining colorless;
and this has heretofore been di?icult and in
many cases impossible to effect, because the oxi
dation caused discoloring'. The foregoing Tables
VI and VII illustrate how discoloration can bev
‘
,
_
largely if not wholly prevented.
The same free-4
dom from discoloration may be obtained with
many others of these benzenoid compounds by
having present my diamine-stabilized solution of
Colorless.
.
_
Substantially
colorless.
252. COMPOSITEONS,
402
Qrcss Refers-‘x6e
it)
an alkali-metal tetravalent-sulphur salt.
m W,
3-.
This
includes not only solutions of sodium sulphite
and of sodium hyposulphite with added diamines,
as considered in Tables I, II, III, IV, VI, and VII,
but also'such solutions of either sodium sulphite
or sodium hypo'sulphite stabilized with condensa
tion products of the diamines with aldehydes, as
considered in Table V, as well as solutions of
stable sulphites and hyposulphites described
hereinafter.
‘
It is of especial advantage in photography to
have a colorless solution, as for a developer.
When an ordinary developer containing p
phenylenediamine or hydroquinone and sodium
,
page 5, first column, line 17, strike out "and" before "or";1ine
55, ,in the formula, for " a " read
line 16, for "proper" read property;- line 1L2, for. "become" read
became; line 55, for "metal" read metol; page 6, second column, line
15, and page 7, second column, line 1].‘?12, claims l23and 51v respec- '
tively, for "sulphate" read sulphite; and that the said Letters Pat
ent should be read with this correction therein that the same may
conform to the record of the case in the Patent Office.
Signed and sealed this 2lith day of January, A.D. 1959.
Henry Van Arsdaile
(Seal)
Acting Commissioner of Patents.
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