close

Вход

Забыли?

вход по аккаунту

?

Патент USA US2118986

код для вставки
2,118,986
Patented May 31, 1938
UNITED STATES PATENT OFFICE
2,118,986
.
SOLID DIAZO SALTS
Karl Schnitzspahn and Wilhelm Koch, O?en
vbach-on-the-Main, Germany, assignors to Gen
eral Aniline Works, Inc., New York, N. Y., a cor
poration of Delaware
No Drawing. Application November 27, 1936, Se
rial No. 113,083. In Germany May 21, 1932
5 Claims.
(Cl. 260-69)
The present invention relates to new solid
diazo salts; more particularly it relates to diazo
salts containing a free amino group and corre
sponding probably to the general formula:
mono-diazotization of the diamines, with mono
diazo compounds in a stable form ready for use.
These new solid diazonium salts which may be
diluted with the usual admixtures and adjusted
to the usual commercial form, are of especial 5
value- in the ice color industry.
The following examples serve to illustrate the
invention, but they are. not intended to limit it
whenrein Y stands for halogen, n and p stands f or
10 one of the numbers 1 and 2, and wherein the
benzene nucleus may be further substituted.
This application is a continuation-in-part of
our col-pending U. S. patent application Serial
No. 671,590, ?led May 17, 1933 which has matured
15 into Patent 2,067,132.
The diazo salts may be obtained by diazotizing
unilaterally lA-diaminobenzenes, halogenated
thereto, the parts being by weight:
(1) 187 parts of 2-bromo-1,4-diaminobenzene 10
are diazotized in 145 parts of sulfuric acid of 78%
strength and 2800 parts of water at‘ 10° C. to
15° C. with a solution of 72 parts of sodium
nitrite in 300 parts of water. To the diazo solu
tion, there are added 740 parts of an aqueous 15
solution of 41% strength of free 1,5-naphthalene
disulfonic acid. The 1,-5-naphthalene disulfonate
in the nucleus and being free from sulfonic acid
or carboxylic acid groups, i. e. by treating the
separates in a crystalline form and is worked
said 1,4-diaminobenzenes with the quantity of
good stability.
mineral acid and nitrous acid, necessary for
diazotizing one amino group, and by precipitat
ing the diazo compounds, thus obtained, in the
form of the different kinds of arylsulfonates.
Morgan and Cleage (cf. “Journal of the Chem
N) 01
ical Society”, 113, (1918), pages 590 and 596)
have transformed 2,6-dichloro-lA-diaminoben
zene in dry acetone solution into 2,6-dichloroben
zene-4-diazo—1-imine by the action of nitrous
anhydride. The product, thus obtained, is very
unstable. It was not separated in a solid form
but, after its formation, it was at once acetylated
in the acetone solution and thereby identi?ed.
It could not be foreseen that halogenated 1,4
' diaminobenzenes
could be transformed in
a
up in the usual manner.
It possesses a very
20
By rep-lacing 1,5-naphthalenedisulfonic acid by
2,6-naphthalenedisulfonic acid, there is obtained
in an analogous manner the corresponding 2,6
naphthalenedisulfonate.
(2) 177 parts of 2,6-dichlo-ro-1,4-diaminoben
25
zene are diazotized in 270 parts of hydrochloric
acid of 32.1% strength and 3500 parts of water
at 10° C. to 15° C. with a solution of 72 parts of
sodium nitrite in 300 parts of water. To the
diazo solution, there is added a solution of 260 30
parts of the sodium salt of para-chlorobenzene
sulfonic acid in 500 parts of water of about 35° C.
Thereby, the diazonium-para-chlorobenzenesul
fonate separates and is worked up as usual.
It
corresponds probably to the following formula:
smooth reaction into aminodiazonium salts in
the presence of mineral acid and it could, fur
thermore, not be foreseen whether these mono
diazo compounds could easily be precipitated and
40 whether they would be stable enough for being
35
40
used on an industrial scale as dyeing salts.
As is known, it is not possible to perform the
mono-diazotization of para-phenylenediamine
in a technical manner. Biilow (cf. “Berichte der
45 Deutschen Chemischen Gesellschaft”, 29, (1896),
page 2285) describes the unilateral diazotization
of nitro-para-phenylenediamine; but it could not
be concluded from this literature reference that
it would be possible to transform halogenated
50 1,4-diaminobenzenes into a mono-diazo com
pound.
All these diazo salts possess a very good sta
bility, even at higher temperatures. It is, there
fore, possible to furnish the dyer, for whom it is
55 dif?cult or at least laborious to carry out the
It forms a feebly brown powder.
In an analogous manner, there may be pre
pared, for instance, the chloro-toluene-sulfonate,
the benzene-disulfonate, the chlorobenzene-di 45
sulfonate and the alpha-naphthalene-sulfonate.
(3) 156.5 parts of 2-chloro-5-methyl-1,4-di
aminobenzene are introduced into 1600 parts of
Water and 270 parts of hydrochloric acid of
20° Bé. and mono-diazotized by adding a solu 50
tion of 71 parts of sodium nitrite in 150 parts of
Water. To the diazo- solution thus obtained there
is added a solution of 248 parts of 1,3-nitroben
zenesodiumsulfonate in 420 parts of water. The
nitrobenzene sulfonic acid mono-diazonium salt 55
2
2,118,986
separates in the form of brownish yellow crystals
1 and 2, Y stands for halogen, Z for one of the
and is worked up as usual.
In an analogous manner there may be sepa
group consisting of hydrogen, halogen and alkyl
and R means a member of the group consisting
rated the monodiazonium compound of 2-chloro
of radicals of the benzene and naphthalene series,
being very stable and easily soluble in water.
3. The solid diazo salts corresponding to the
general formula:
S-methyl-1,4-diaminobenzene with para-chloro
benzenesulfonic acid, 1,5-naphthalenedisulfonic
acid or 2,6-naphthalene disulfonic acid.
The arylsulfonic acid diazonium salts of other
halogen-1,4-diaminobenzenes, such as of '210
,
chloro-1,4-diaminobenzene, 2,6-dibromo-L4-di
aminobenzene,
10
2,5-dichloro-1,4-diaminobenzene
or 2-chloro-6-bromo-lA-diaminobenzene may be
prepared in a manner analogous to that described
15
in the foregoing examples.
We claim:
1. The solid diazo salts corresponding to the
general formula:
l’
Z
25
I
wherein n and 10 stand for one of the numbers
1 and 2, Y stands for halogen, Z for one of the
group consisting of hydrogen, halogen and alkyl,
and R means a member of the group consisting
of radicals of the benzene and naphthalene series,
being very stable and easily soluble in water.
2. The solid diazo salts corresponding to the
30 general formula:
Y
wherein n and 1) stand for one of the numbers
1 and 2, and R means a member of the group
consisting of radicals of the benzene and naph
thalene series, being very stable and easily soluble
in water;
4. The solid diazo salt corresponding to the
formula:
20
7
Br
SOaH
\
HaNONr-SO:
being very stable and easily soluble in water.
5. The solid diazo salt corresponding to the
formula:
25
01
\
HINQNFSOBGCI
30
01
being very stable and easily soluble in water.
35
1
Z
n
wherein n and 11 stand for one of the numbers
35
KARL SCHNITZSPAHN.
WILHELM KOCH.
Документ
Категория
Без категории
Просмотров
0
Размер файла
194 Кб
Теги
1/--страниц
Пожаловаться на содержимое документа