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Патент USA US2127371

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Patented Aug. 16, 1938
Ulti'l‘h
STATES
PATET OFFHQE
2,127,371
AROMATIC COMPOUNDS 0F TRIVALENT AN -
TIMONY AND PROCESS OF PREPARING
THE SAME
Hans Schmidt, Wuppertal-Vohwinkel, Germany,
assignor to Winthrop Chemical Company, Inc,
New York, N. Y., a corporation of New York
No Drawing. Application May 15, 1933, Serial
No. 671,286. In Germany May 19, 1932
31 Glaims.
This invention relates to neutral, water-soluble
complex compounds of trivalent antimony of the
aromatic series and'to a process of preparing the
same; more particularly it relates to complex
5“com.pounds of arylstibine oxides with benzene
(01. 260-367)
zoxazolonestibineoxide and the benzimidazolone
stibine oxides of the following formulae:
derivatives containing at least two hydroxyl
groups in ortho-position to each other and at
least one acid group capable of forming salts,
H
‘ and to a process of preparing such complex com
10“ pounds.
10
c
'
The primary organic compounds of the triva
lent antimony of the general formula
11!)
wherein R stands for an aromatic radical, are
‘ Pyrocatechin and pyrogallol carboxylic and sul
ionic acids are preferably used as the acid de~~
rivative containing at least 2 hydroxy groups in 15
ortho-position to each other, but it may be men~
known as relatively unstable compounds. They
tend to transform into compounds of the general.
tioned that also acid derivatives of other polyhy
droxy benzenes containing at least 2 hydroxyl
formula
groups in ortho-position to each other, and also
compounds containing other acid groups, for in 20
stance, the arsenic acid radical, may be em
(R2319) 20
while splitting oil antimony. Such a transforma
tion process is favored by the presence of tar
taric, lactic and malic acids which are known
n.
I
as complex forming compounds of the aliphatic
series (compare Annalen der Chemie 421 (1920),
page 215, and 429 (1922), page 131).
In accordance with the present invention neu
tral, water-soluble complex compounds of mon
v arylstibine oxides are obtainable without splitting
"off antimony from the arylstibine oxide by re
acting upon the mono~arylstibine oxide with a
benzene derivative containing at least two hy~
droxy groups in crtho-position to each other
a. ‘and at least one acid group capable of forming
salts, such as the carboxylic, sulfonic and arsenic
acid group. while rendering the reaction mix
ture neutral by the addition of a base.
In the above indicated reaction the arylstibine
4,91 compounds may be used in the form of stibine
oxides or in the form of freshly precipitated ox
ides, i. e., in the hydrated form, as prepared for
instance by treating the corresponding halides
with caustic alkalis. The said arylstibine oxides
risiinay be substituted in the benzene nucleus by
halogen atoms, preferably chlorine and bromine,
allryl groups, such as the methyl, ethyl, propyl,
ployed.
A ?nally neutral reaction is eiiected by the ad
dition of an alkali metal-, magnesium or cal
cium hydroxide, ammonia or an aliphatic amine,
such as dimethyl- and diethyl-amines, piperidine
and ethanoLamine; the use of sodium and cal
cium hydroxides, diethylamine and diethylamino
ethanol has. proved particularly advantageous.
The reaction is performed in the presence of 30
a solvent; advantageously aqueous alcohols, such
as methyl and ethyl alcohol are used.
The re~
action temperature may be normal temperature,
sometimes‘ cooling is advisable. From the reac
tion mixture the complex compound formed is
advantageously separated by pouring the reac
tion mixture into excess alcohol while stirring.
In the above reaction two, three or four mole
cules of the acid hydroxy benzene derivative may
be caused to react upon 1 molecule of the aryl 4:0
stibine oxide. It is not necessary to use the
reacting components in stoichiometric propor
tions, since also neutral complex compounds
which are suitable for practical use are obtain
able if the reacting components are combined 45
in other proportions. In this connection it may
be emphasized that the present invention does
isopropyl groups, or O-—R—~COOH groups, fur~
not relate to the manufacture of complex comtheir by amino and substituted amino groups, such ‘ pounds which are characterized by de?nite struc
50, as all<yl.-, hydroxyalkyl- and acyl-arnino groups tural or empirical formulae which would be of
for instance, the methyl-amino, ethyl-amino, mere scienti?c interest, but the invention tends
acetyl-amino and carbethoxyamino groups. The
said substituted amino groups may also be com
bined with another substituent of the benzene
551 nucleus to a ring, as, for instance, in the ben
to transform the arylstibine compounds which
hitherto could not be employed in therapy into
neutral, water-soluble complex compounds which
can be used therapeutically without causing any
2
harm.
2,127,371
The usefulness of such complex com.
is combined with two molecules of sodium pyro
pounds in therapy has proved to be independent
catechinsulfonate and the R—Sb0 type is main
to a marked extent on the proportions of the
tained in the reaction.
arylstibine radical and the complex-forming acid
hydroxy benzene component.
following formula:
The compound obtained corresponds to the
10
10
15
SOgNa
In the above described manner. whitish to
weakly colored complex compounds of the tri
valent antimony are obtained which are insoluble
in alcohol, but dissolve in water to neutral solu
tions. In the said complex compounds the an
timony is. partly linked to a carbon atom of
a benzene nucleus contained in the arylstibine
compound used as starting material. Other
valences of the antimony are linked to the hy
25 droxyl oxygen atoms of the benzene derivative
containing at least 2 hydroxyl groups standing in
ortho-position to each other and at least one acid
group capable of forming salts, which benzene
derivative has been used as complex-forming
301 component in the above described reaction. The
new complex compounds are neutral by a con
tent of a basic component as above speci?ed.
As to the composition of the new complex com
pounds it has
necessary that
the arylstibine
droxy benzene
been stated above that it is not
the complex compounds contain
component and the acid polyhy
component in a de?nite propor
tion. Obviously, the structure of the new com
plex compounds is often of a complicated nature
40 and, therefore, I am not able to give the structural
formulae of the new complex compounds in all
cases.
The analysis of the new compounds shows that
the neutral, water-soluble products obtainable in
45 accordance with the above described process may
have various compositions, this depending on the
quantities of the reacting components used in
the reaction; for instance, complex compounds
containing upon 1 arylstibine radical 2 or 3 radi
cals of the acid polyhydroxy benzene component
have been obtained.
The new antimony complex compounds are in
tended to be used in therapy, particularly in the
treatment of infectious diseases. The neutral
aqueous solutions may be used for injection.
The invention is further illustrated by the fol
lowing examples, but it is not limited thereto:
Example 1.——A solution, suspension respectively
of 6.5 grams of para-acetylaminophenylstibine
("20 chloride dissolved in methyl alcohol is poured
into an ice cooled solution of 14 grams of the
bibasic sodium salt of pyrocatechindisulfonic acid
while stirring. A solution of 2 normal diethyl
aminoethanol is simultaneously added until the
reaction is neutral or about neutral. The solu
tion is ?ltered and the complex salt formed is
precipitated by pouring into alcohol while stirring.
After separating and drying in the exsiccator,
an almost colorless powder which is readily solu
ble in water with neutral reaction is obtained.
On adding hydrogen sul?de the acidi?ed solution
yields the light yellow precipitate which is char
acteristic of the organic antimony compounds.
According to analysis in the new product one
molecule of para-acetylaminophenylstibineoxide
S OzNa
15
On using milk of lime for effecting the neutral
ization, likewise a neutrally soluble complex salt
which contains calcium is obtained. Similarly
magnesium hydroxide, ammonia and ethanola
20
mine may be used as the neutralizing agent.
."1
analogous manner neutral complex salts
are obtained when using, for instance, meta
chloro - )imra -~ acetylaminophenylstibinechloride
hydrochloride, or meta—para-benzimidazolesti
bincchloride~hydrochloricle. On the other hand, 25
also the sodium salt of pyrocathechin sulfonic
acid. the sodium salt of pyrogalloldisulfonic acid,
or the corresponding potassium salts, further
more, gallic acid, pyrocatechincarboxylic acid and
30
pyrocatechinarsonic acid may be used.
Example 2.~--5 grams of meta-amino-para
carbamidophenylstibinechloride-hydrochloride in
methylalcoholic suspension are introduced into
a solution of 1.0 grams of the bibasic sodium salt
of pyrocatechindisulfonic acid while simultane 35
ously adding a solution of dilute caustic soda until
the reaction is neutral. The solution is ?ltered,
diluted with methyl alcohol and the complex salt
formed is precipitated by pouring into ethyl al
001101 while stirring. After separating the precipi
40
tate and drying in the exsiccator the sodium salt
of meta-amino-para-carbamidophenylstibineox
ide-pyrocatechindisulfonic acid is obtained as a
whitish powder which is readily soluble in Water
with neutral reaction. The aqueous solution 45
yields no precipitate on the addition of dilute
hydrochloric acid. The hydrochlorid acid solu
tion yields a light yellow precipitate on the addi
tion of hydrogen sul?de. The said product con
tains 1 molecule of the stibine component com 50
bined with about 2 molecules of pyrocatechindi
sulfonic acid.
On using 15 grams of the bibasic sodium salt
of pyrocatechindisulfonic acid, a complex salt of
analogous properties is obtained. It contains 1 55
molecule of. the stibine component combined with
about 3 molecules of the pyrocatechin derivative.
Example 3.-4 grams of 4-hydroxyacetic acid
3~aminophenylstibinechloride-hydrochloride, ob
tainable by reduction of 4-hydroxyacetic acid-3
60
nitrophenylstibinic acid, are mixed up and added
to a solution of ill grams of the bibasic sodium
salt of pyrogalloldisulfonic acid in water. There
upon a solution of dilute diethylamine is added 65
until. the reaction is neutral. The solution is ?l
tered and the complex salt formed is precipi
tated by pouring the solution into alcohol while
stirring. After separating the precipitate and
drying a faintly colored powder is obtained which 70
readily dissolves in water with neutral reaction
and light yellow color. The solution acidi?ed
with dilute hydrochloric acid yields a light yellow
turbidity on the addition of hydrogen sul?de.
In an analogous manner a complex compound 75
3
2,127,371
is obtainable when starting with benzimidazo
lonestibine oxide of the probable formula:
small quantity of methyl alcohol and introduced
into an ice cooled solution of 12 grams of the bi
basic sodium salt of pyrogallol disulfonic acid in
0 Sb
MNH
60 cos. of water. The solution is neutralized with
a dilute solution of diethylaminoethanol, ?ltered
\oo
_NH/
which latter is obtainable by reduction of ben
zimidazolonestibinic acid.
and the complex salt formed is precipitated by
pouring the solution into alcohol while stirring.
After separating the precipitate and drying a
faintly colored powder which is readily soluble
Example 4.—Benzoxazolonestibineoxide, pre-,
pared fom 6 grams of benzoxazolonestibonic acid
of the probable formula:
in water is obtained. The acidi?ed solution yields 10
a yellow precipitate on the addition of hydro
gen sul?de.
In an analogous manner, for instance, a solu
ble complex salt'of the 4-acetylamino-2-methyl
15
by reduction with sulfurous acid is mixed up as
freshly precipitated paste with a solution of 14
grams of the bibasic sodium salt of pyrocatechin
disulfonic acid while adding a small quantity of
methyl alcohol and a solution of dilute caustic
soda until the reaction is almost neutral. The
25 solution thus obtained is ?ltered and the ?ltrate
is poured into alcohol while stirring. After sep
arating the precipitate and drying in vacuo a
faintly colored powder which is readily soluble
in water with neutral reaction is obtained. The
solution acidi?ed with dilute hydrochloric acid
yields a light yellow turbidity on the addition of
hydrogen sul?de.
‘
In an analogous manner a complex salt of, for
instance, the‘ para-ethylamino- or para-ethyl
35
acetylaminophenyl
or
of
hydroxyalkylamino
phenyl-stibineoxides may be obtained.
Ewample 5.—3.2 grams of para-acetylamino
phenyl-stibinechloride are dissolved in methyl
alcohol. The solution is added to a solution of
40
8 . grams
of
calcium-sodium
calcium-pyro
catechindisulfonate (compare U. S. Patent No.
1,879,533) of the formula:
or Z-ethyI-phenyl-stibine oxide may be obtained. 15
I claim:
1. The process which comprises reacting upon
pyrocatechindisulfonic acid compound with an
amino phenylstibine-chloride in the presence of
20
water, a water-soluble alcohol and such a quan
tity of a base selected from the group consist
ing of sodium and calcium hydroxides, am
monia, diethylamine and‘ diethylaminoethanol,
that the ?nal reaction is neutral. ’
,
2. The process which comprises reacting upon 25
sodium pyrocatechindisulfonate with para
acetylamino phenylstibinechloride in the pres
ence of water and methyl alcohol while neutral—
izing the reaction mixture with diethylamino
ethanol.
‘
'
30
'
3. Neutral, water-soluble complex. compounds
of trivalent antimony in which the antimony is
partly‘ linked to the benzene nucleus of a ben
zene derivative and partly to hydroxyl oxygen
atoms of an ortho-polyhydroxybenzene contain- 35
ing at least one acid group capable of forming
salts, in which antimony complex compounds the
acid groups are neutralized by a basic radical
selected from the group consisting of alkali
metal, calcium, magno" 1m, ammonium and ali~ 40
phatic amines, and which complex compounds
are whitish to ‘faintiyycolored substances which
are insoluble in alcohol, ‘but dissolve in water
to neutral solutions and are suitable for thera
peutic purposes.
45
45
C
4. Neutral, water-soluble complex compounds
of trivalent antimony in which the antimony is
s03 ---- ?og ---- --o,s
partly linked to the benzene nucleus of a benzene
Z-normal milk of lime is added until the reaction
50 is neutral, the solution is ?ltered and precipitat
ed by pouring into alcohol while stirring. After
separating the precipitate and drying in vacuo,
the complex salt formed is obtained as a faintly
colored powder, which is readily soluble in water
with neutral reaction.
7
Example 6.--A solution of 3.2 grams of para
acetylaminophenylstibinechloride in methyl al
derivative and partly to hydroxyl oxygen atoms
of ortho-polyhydroxybenzene containing at least 50
one acid group selected from‘ the group con
sisting of carboxylic andsulfonic acid groups, in
which antimony complex compounds the acid
groups are neutralized by a basic radical selected
fromv the group consisting of alkali metal, cal 55
cium, magnesium, ammonium and aliphatic
amines, and which complex compounds are whit
cohol is added to an aqueous solution of 8 grams ‘ ish to faintly ‘colored substances which are in
of the sodium salt of pyrogalloldisulfonic acid.
60 Neutralization is effected by means of dilute caus
tic soda, the solution is ?ltered and precipitated
by pouring into alcohol while stirring. After
separating the precipitate and drying in vacuo
a faintly colored powder, which is readily solu
L ble in water with neutral reaction, is obtained.
Example 7.——Chlorobenzoxazolonestibinechlo
ride obtained by reduction of chlorobenzoxazo~
lonestibonic acid of the probable formula:
soluble in alcohol, but dissolve in‘w‘ater to neutral
solutions and are suitable‘ for’ therapeutic pur
poses.
‘
60
‘
5. Neutral, water-soluble complex compounds
of trivalent antimony in which the antimony is .
partly linked to a benzene nucleus substituted by
a member of the group consisting of an amino 65
group, a substituted‘amino group and a substi
tuted amino group which is a member of a heter
ocyclic nucleus combined with the benzene nu
cleus, and partly to the hydroxyl oxygen atoms of
pyrocatechindisulfonic acid, in which antimony 70
complex compounds the acid groups are neutral
ized by a basic radical selected from the group
consisting of alkali metal, calcium, magnesium,
ammonium and aliphatic amines, and which com
in hydrochloric acid solution, is dissolved in a
plex compounds are whitish to faintly colored
4
2,127,371
substances which are ‘insoluble in alcohol, but
dissolve in water to neutral solutions and are
suitable for therapeutic purposes.
6. Neutral, water-soluble complex compounds
of trivalent antimony in which the antimony is
partly linked to the benzene nucleus of an amino
phenyl radical and partly to the hydroxyl oxygen
atoms of pyrocatechindisulfonlc acid, in which
antimony complex compounds the acid groups
10 are neutralized by a basic radical selected from
the group consisting of sodium, calcium, am
monium, diethylamine and diethylaminoethanol,
and which complex compounds are whitish to
faintly colored substances which are insoluble in
15 alcohol, but dissolve in water to neutral solutions
and are suitable for therapeutic purposes.
7. The neutral, water-soluble complex com
pound of trivalent antimony in which the anti;
mony is partly linked to the benzene nucleus of
20 the para-acetylaminophenyl radical and partly
to the hydroxyl oxygen atoms of pyrocatechindi
sulfonic acid, which antimony complex com
pound is neutral by the content of sodium and
diethylaminoethanol and which complex com
25 pound contains one antimony atom combined
with about two molecules of pyrocatechindi
sulfonic acid and about one molecule of acetyl
aminobenzene radical and forms a whitish pow
der which is insoluble in alcohol but dissolves in
30 water to a neutral solution and is suitable for
fonic‘iacid, which antimony complex compound
is neutral by the content of sodium and di
ethylaminoethanol and which complex compound
contains one antimony atom combined with
about two molecules of pyrogallol disulfonic acid
and about one molecule of acetylamino ben
zene and forms a faintly colored powder which is
insoluble in alcohol but dissolves in water to a
neutral solution and is suitable for therapeutic
purposes;
an ortho-polyhydroxybenzene containing at least
one acid group capable of forming salts, with an
arylstibine compound selected from the group
consisting of the oxide and the hydrated oxide, 15
in the presence of a solvent and such a quantity
of a base selected from the group consisting of
alkali metal bases, calcium bases and magne
sium bases, ammonia and aliphatic amines, that
20
the ?nal reaction is neutral.
l3. Neutral, water-soluble complex compounds
of trivalent antimony in which the antimony is
partly linked to a benzene nucleus substituted
by a. member of the group consisting of an amino
group, a substituted amino group and a substi 25
tuted amino group which is a member of a
heterocyclic nucleus combined with the benzene
nucleus, and which is further substituted by a
substituent. selected from the group consisting
of halogen, alkyl, alkoxy and carbethoxy groups
therapeutic purposes.
8. Neutral, water~soluble complex compounds
of trivalent antimony in which the antimony is
rocatechindisulfonic acid in which antimony
partly linked to the benzene nucleus of an amino
tralizedby a basic radical selected from the
35 carbamido-phenyl radical and partly to the hy
droxyl oxygen atoms of pyrocatechindisulfonic
acid, which antimony complex compounds are
neutral on account of containing a component
selected from the group consisting of sodium,
calcium, ammonium, diethylamine, and diethyl
aminoethanol, and which complex compounds
are whitish to faintly colored substances which
are insoluble in alcohol, but dissolve in water
to neutral solutions and are suitable for thera
peutic purposes.
9. Neutral, water-soluble complex compounds
of trivalent antimony in which the antimony is
partly linked to the benzene nucleus of an amino-‘
carbamido-phenyl radical and partly to the hy
droxyl oxygen atoms of pyrocatechindisulfonic
acid, which antimony complex compounds are‘
neutral on account of sodium, and which com
plex compounds are whitish to faintly colored
substances
which are insoluble in alcohol, but
55
dissolve in water to neutral solutions and are
suitable for therapeutic purposes.
10. Neutral, water-soluble complex compounds
of trivalent antimony in which the antimony is
partly linked to the benzene nucleus of an amino
phenyl radical and partly to the hydroxyl oxy
gen atoms of pyrogallol disulfonic acid, in which
antimony complex compounds the acid groups
are neutralized by a basic radical selected from
the group consisting of sodium, calcium, am
monium, diethylamine and diethylaminoethanol,
and which complex compounds are whitish to
faintly colored substances which are insoluble in
alcohol, but dissolve in water to neutral solu
tions and are suitable for therapeutic purposes.
.11. The neutral, water-soluble complex com
pound of trivalent antimony in which the anti
mony is partly linked to the benzene nucleus of
the paraacetylaminophenyl radical and partly to
the
hydroxyl oxygen atoms of pyrogallol .disul
75
10
12. The process which comprises reacting upon
30
and partly to the hydroxyl oxygen atoms of py
complex compounds the acid groups are neu
group consisting of sodium, calcium, ammonium, 35
diethylamine and diethylaminoethanol and which
complex compounds are whitish to faintly col
ored substances which are insoluble in alcohol
but dissolve in water to neutral solutions and
are suitable for therapeutic purposes.
40
14. Neutral, water-soluble complex compounds
of trivalent antimony in which the antimony is
partly linked toa benzene nucleus substituted by
a member of the group consisting of an amino
group, a substituted amino group and a substi
tuted amino group which is a member of a hetero
cyclic nucleus combined with the benzene nucleus
and which is further substituted by a substituent
selected from the group consisting of halogen,
alkyl, alkoxy and carbethoxy groups and partly
to the hydroxyl, oxygen atoms of pyrogallol di
sulfonic acid in which antimony complex com
pounds the acid groups are neutralized by a basic
radical selected from the group consisting of so
dium, calcium, ammonium, diethylamine and
55
diethylaminoethanol and which complex com
pounds are whitish to faintly colored substances
which are insoluble. in alcohol, but dissolve in
water to neutral solutions and are suitable for
therapeutic purposes.
15. Neutral, watersoluble complex compounds
of trivalent antimony in which the antimony
is partly linked to a benzene nucleus which is
substituted by a substituent selected from the 65
group consisting of amino, alkylamino, hy
droxyalkylamino, acylamino, carbethoxyamino,
O—R—COOH (R being an aliphatic radical),
carbamido and a substituted amino group which
is a member of a heterocyclic nucleus combined 70
with the benzene nucleus, and partly to hydroxyl
oxygen atoms of an o-polyhydroxybenzene con
taining at least one acid group capable of form
ing salts in which antimony complex compounds
the acid groups are neutralized by a basic radical 75
2,127,371
5.
selected from the group consisting of alkali metal,
calcium, magnesium, ammonium and aliphatic
19. Neutral, watersoluble complex compounds
of trivalent antimony in which the antimony is
amines and which complex compounds are whit- _
partly linked to a benzene nucleus-which is sub
stituted by a substituent selected from the
ish to faintly colored substances which are in
soluble in alcohol, but dissolve in water to neutral
solutions and are suitable for therapeutic pur
poses.
l6. Neutral, watersoluble complex compounds
of trivalent antimony in which the antimony
10 is partly linked to a benzene nucleus which is
substituted by a substituent selected from the
group consisting of amino, alkylamino, hy
droxyalkylamino, acylamino, carbethoxyamino,
O—-R—COOI—I (R being an aliphatic radical),
carbamido and a substituted amino group which
is a member of a heterocyclic nucleus, combined
with the benzene nucleus, and partly to hydroxyl 10
oxygen atoms of pyrocatechindisulfonic acid in
group consisting of amino, alkylamino, hy
which antimony complex compounds the acid
droxyalkylamino, acylamino, carbethoxyamino,
groups are neutralized‘ by a basic radical selected
O-—-R-—COOH (R being an aliphatic radical),
from the group consisting‘of alkali metal, cal
15 carbamido and a substituted amino group which
is a member of a heterocyclic nucleus combined
with the benzene nucleus and which is further
substituted by a substituent selected from the
group consisting of halogen and alkyl groups
'20 and partly to hydroxyl oxygen atoms of an
o-polyhydroxybenzene containing at least one
acid group capable of forming salts in which
antimony complex compounds the acid groups
are neutralized by a basic radical selected from
the group consisting of alkali metal, calcium,
magnesium, ammonium and aliphatic amines and
which complex compounds are whitish to faintly
colored substances which are insoluble in alcohol,
but ‘dissolve in water to neutral solutions and are
30 suitable for therapeutic purposes.
17. Neutral, watersoluble complex compounds
of trivalent antimony in which the antimony
is partly linked to a benzene nucleus which is
substituted by a substituent selected from the
35 group consisting of
amino, alkylamino, hy
droxyalkylamino, acylamino, carbethoxyamino,
O-—R—-COOI-I (R being an aliphatic radical),
carbamido and a substituted amino group which
is a member of a heterocyclic nucleus cbmbined
with the benzene nucleus, and partly to hydroxyl
oxygen atoms of an o-polyhydroxybenzene con
taining at least one acid group selected from the
group consisting‘of pyrocatechindisulfonic acid
and pyrogallol disulfonic acid in which antimony
complex compounds the acid groups are neu
tralized by a basic radical selected from the
group consisting of alkali metal, calcium, mag
nesium, ammonium and aliphatic amines and
which complex compounds are whitish to faintly
colored substances which are insoluble in alcohol,
but dissolve in water to neutral solutions and are
suitable for therapeutic purposes.
18. Neutral, watersoluble complex compounds
of trivalent antimony in which the antimony
is partly linked to a benzene nucleus which is
substituted by a substituent selected from the
cium, magnesium, ammonium and aliphatic 15
amines and which complex compounds are whit
ish to faintly colored substances which are in
soluble in alcohol, but dissolve in water to neu
tral solutions and are suitable for therapeutic
purposes.
20. Neutral, watersoluble complex compounds
of trivalent antimony in which the antimony is
partly linked to a benzene nucleus which is sub
stituted by a substituent selected from the
group consisting of amino, alkylamino, hy
droxyalkylamino, acylamino, carbethoxyamino,
25
O-—R——COOH (R being an aliphatic radical),
carbamido and a substituted amino group which
is a member of a heterocyclic nucleus combined
with the benzene nucleus, and which is further 30
substituted by a substituent selected from the
group consisting of halogen and alkyl groups and
partly to hydroxyl oxygen atoms of pyrocatechin
disulfonic acid in which antimony complex com
pounds the acid groups are neutralized by a basic 35
radical ‘selected from the group consisting of
alkali metal, calcium, magnesium, ammonium
and aliphatic amines and which complex com
pounds are whitish to faintly colored substances
which are insoluble in alcohol, but dissolve in 40
water to neutral solutions and are suitable for
therapeutic purposes.
21. The process which comprises reacting upon
an o-polyhydroxybenzene selected from the. group
consisting of pyrogallol disulfonic acid and pyro
‘catechindisulfonic acid with an arylstibine com
45
pound selected from the group consisting of the
oxide and the hydrated oxide in the presence of
a solvent and such a quantity of a base selected
from the group consisting of alkali metal bases, 50
calcium bases and magnesium bases, ammonia
and aliphatic amines that the ?nal reaction is
neutral.
22. The process which comprises reacting upon
an o-polyhydroxybenzene selected from the group 55
consisting of pyrogallol disulfonic acid and pyro
catechindisulfonic acid with a phenylstibine com
group consisting of amino, alkylamino, hy
pound selected from the group consisting of the
droxyalkylamino, acylamino, carbethoxyamino,
O—R—COOH (R being ‘an aliphatic radical),
oxide and the hydrated oxide the benzene nucleus
of which is substituted by a substituent selected 60
carbamido and a substituted amino group, which
is a member of a heterocyclic nucleus combined
with the benzene nucleus, and which is further
substituted by a substituent selected from the
from the group consisting of the amino, alkyl
65 group consisting of halogen and alkyl groups,
and partly to hydroxyl oxygen atoms of an
amino, hydroxyalkylamino, acylamino, carbeth
oxyamino, O--R—COOH (R being an aliphatic
radical), carbamido and a substituted amino
group which is a member of a heterocyclic nucleus 65
combined with the benzene nucleus, in the pres
o-polyhydroxybenzene containing at least one' ence of a solvent and such a quantity of a base
acid group capable of forming salts, in which selected from the group consisting of alkali metal
antimony complex compounds the acid group bases, calcium bases and magnesium bases, am
70 consisting of alkali metal, calcium, magnesium,
ammonium and aliphatic amines and which com
plex compounds are whitish to faintly colored
substances which are insoluble in alcohol, but
dissolve in water to neutral solutions and are
75 suitable for therapeutic purposes.
monia and aliphatic amines that the ?nal re 70
action is neutral.
23. The process which comprises reacting upon
an o-polyhydroxybenzene selected from the group
consisting of pyrogallol disulfom'c acid and pyro
catechindisulfonic acid with a phenylstibine com
75
6
2,127,371
pound selected from the group consisting of the
oxide and the hydrated oxide the benzene nucleus
of which is substituted by a substituent selected
from the group consisting of the amino, alkyl
amino, hydroxyalkylamino, acylamino, carbeth
chloride the benzene nucleus of which is sub
stituted by a substituent selected from the group
consisting of the amino, alkylamino, hydroxy
alkylamino, acylamino, carbethoxyamino,
oxyamino, O—-R—COOH (R being an aliphatic
radical), carbamido and a substituted amino
group which is a member of a heterocyclic nuc
leus combined with the benzene nucleus, and
which benzene nucleus is further substituted by
a substituent selected from the group consisting
of halogen and alkyl groups, in the presence of
a solvent and such a quantity of a base selected
from the group consisting of alkali metal bases,
calcium bases and magnesium bases, ammonia
and aliphatic amines that the ?nal reaction is
neutral.
'
24. The process which comprises reacting upon
an o-polyhydroxybenzene containing at least one
acid group capable of forming salts with a phen
ylstitbine chloride the benzene nucleus of which
is substituted by a substituent selected from the
group consisting of the amino, alkylamino, hy
droxyalkylamino, acylamino, carbethoxyamino,
O—R—COOH (R being an aliphatic radical) ,car
bamido, and a substituted amino group which
is a member of a heterocyclic nucleus combined
with the benzene nucleus, in the presence of
a solvent and such a quantity of a base selected
30 from the group consisting of alkali metal bases,
calcium bases and magnesium bases, ammonia
and aliphatic amines that the ?nal reaction is
neutral.
25. The process which comprises reacting upon
an o-polyhydroxybenzene containing at least one
acid group capable of forming salts with a
phenylstibine chloride the benzene nucleus of
which is substituted by a substituent selected
from the group consisting of the amino, alkyl
40 amino, hydroxyalkylamino, acylamino, carbeth
oxyamino, O—R—COOH (B. being an alphatic
radical), carbamido, and a substituted amino
group which is a member of a heterocyclic nu
cleus combined with the benzene nucleus, and
45 which benzene nucleus is further substituted by
a substituent selected from‘the groupconsisting of
halogen and alkyl groups, in the presence of a
solvent and such a quantity of a baseselected
from ‘the group consisting of alkali metal bases,
calcium bases and magnesium bases, ammonia
and aliphatic amines that the ?nal reaction is
neutral.
26. The process which comprises reacting upon
an o-polyhydroxybenzene selected from the group
consisting of pyrogallol disulfonic acid and
pyrocatchindisulfonic acid with a phenylstibine
chloride the benzene nucleus of which is sub
stituted by a substituent selected from the group
consisting of the amino, alkylamino, hydroxy~
alkylamino, acylamino, carbethoxyamino,
(R being an aliphatic radical), carbamido, and a
substituted amino group which is a member of a
heterocyclic nucleus combined with the benzene
nucleus, and which benzene nucleus is further
substituted by a substituent selected from the
group consisting of halogen and alkyl groups, in
the presence of a solvent and such a quantity of a
base selected from the group consisting of alkali .15
metal bases, calcium bases and magnesium bases,
ammonia and aliphatic amines that the ?nal re
action is neutral.
28. The process which comprises reacting upon
a pyrocatechindisulfonic acid compound with a
amino, alkylamino, hydroxyalkylamino, acyl :25
amino, carbethoxyamino, O-—R~COOH (R being
an aliphatic radical), carbamido, and a sub
stituted amino group which is a member of a
heterocyclic nucleus combined with the benzene
nucleus, in the presence of a solvent and such a 430
quantity of a base selected from the group con
sisting of alkali metal bases, calcium bases and
magnesium bases, ammonia and aliphatic amines
that the ?nal reaction is neutral.
29. The process which comprises reacting upon :35
a pyrocatechindisulfonic acid compound with a
phenylstibine compound selected from the group
consisting of the oxide and hydrated oxide the
benzene: nucleus of which is substituted by a sub~
stituent selected from the group consisting of the ;
amino, alkylamino, hydroxyalkylamino, acyl
amino, carbethoxyamino, O-R-COOI-I (R being
an aliphatic radical), carbamido, and a sub
stituted amino group which is a member of a
heterocyclic nucleus combined with the benzene '
nucleus, and which benzene nucleus is further
substituted by a substituent selected from the
group consisting of halogen and alkyl groups, in
the presence of a solvent and such a quantity of a
base selected from the group consisting of alkali ,50
metal bases, calcium bases and magnesium bases,
ammonia and aliphatic amines that the ?nal re
action is neutral.
30. The process which comprises reacting upon
a pyrocatechindisulfonic acid with a phenylstibine
chloride the benzene nucleus of which is sub
stituted by a substituent selected from the group
consisting of the amino, alkylamino, hydroxy
alkylamino, acylamino, carbethoxyamino,
(R being an aliphatic radical), carbamido, and
(R being an aliphatic radical), carbamido, and a
I, a. substituted amino group which is a member of
substituted amino group which is a member of a
' a heterocyclic nucleus combined with the benzene
7.9
heterocyclic nucleus combined with the benzene 65
quantity of a base selected from the group con
nucleus, in the presence of a solvent and such a
quantity of a base selected from the group con
sisting of alkali metal bases, calcium bases and
magnesium bases, ammonia andaliphatic amines
sisting of alkali metal bases, calcium bases and
magnesium bases, ammonia and aliphatic amines
nucleus, in the presence of a solvent and such a
‘ that the ?nal reaction is neutral.
27. The process which comprises reacting upon
an o-polyhydroxybenzene selected from the group
consisting of pyrogallol disulfonic acid and
. pyrocatechindisulfonic acid with a phenylstibine
v. 20
phenylstibine compound selected from the group
consisting of the oxide and hydrated oxide the
benzene nucleus of which is substituted by a sub
stituent selected from the group consisting of the
70
that the ?nal reaction is neutral.
31. The process which comprises reacting upon
a pyrocatechindisulfonic acid with a phenylstibine
chloride the benzene nucleus of which is sub
stituted by a substituent selected fromthe group 75
2,127,371
‘
7
consisting of the amino, alkylamino, hydroxy
alkylamino, acylamino, carbethoxyamino,
substituted by a substituent selected from the
(R being an aliphatic radical), carbamido, and a
metal bases, calcium bases and magnesium bases,
substituted amino group which is a member of a
‘ heterocyclic nucleus combined with the benzene
ammonia and aliphatic amines that the ?nal re~
action is neutral.
nucleus, and which benzene nucleus is further
group consisting of halogen and alkyl groups, in
the presence of a solvent and such a quantity of
a base selected from the group consisting of alkali
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