close

Вход

Забыли?

вход по аккаунту

?

Патент USA US2131992

код для вставки
v2,131,992v
Patented Oct. 4, 1938
UNITED STATES
.
I
PATENT‘ OFFICE
2,131,992
DIAZO COMPOUND AND PROCESS OEMAK
ING SAME
Adolf Wirz, Basel, Switzerland, assignor to the
?rm Society of Chemical Industry in Basic,
7 Basel, Switzerland
No Drawing. Application March 4, 1937, Serial
No. 129,101. In Switzerland March 9, 1936
(Cl. 260-,-142)
This invention is based on the observation that manganous chloride on the diazonium chlorides
obtained by diazotizing the most various amino
diazonium salts of aromatic amines of the ben
zene and naphthalene series can be precipitated diphenyl ethers. Quite particularly valuable are
from their solutions by means of manganous salts the products which are formed when using as di-'
5 ' which are derived from hydrohalic. acids or by, azotizing bases an aminodiphenyl ether of the
"
‘
‘
manganous salts in presence of halogen ions, general formula '
10 Claims.
with formation of compounds containing man
ganese. In this manner there are obtained man
ganiferous products which can-probably be re
10 garded as double salts of manganese and di
azonium compounds, and which may be con
verted into valuable diazo preparations by inter
mixture with the usual auxiliaries, for instance
sulfate of alumina, chlorobenzene disulfonic acid,
15 naphthalene trisulfonic acid or Glaubers salt.
Among the diazo compounds which yield double
compounds with the hydrogen halide salts of the
bivalent manganese, there may be named quite
generally diazo compounds of the benzene and
20 naphthalene series which are precipitated by zinc
chloride. The precipitations with manganous
Y
Y
7 Y
Y
5
1.5
—NH:
01
salts have however the advantage over the pre
wherein four Y's stand for hydrogen and one Y is
cipitations with zinc chloride that they yield more
a member of the group consisting of chlorine and
hydrogen.
easily soluble double salts, so that the new method
25 of working is particularly valuable for precipitat
ing such diazonium salts which produce with zinc
chloride such diffncultly soluble precipitations that
they cannot be used in practice, or only to a lim
ited extent, for the manufacture of dyeings on
30 the ?ber. This applies for example to the di
azonium salts which are derived from aminodiaryl
ethers.
Analytical. investigations have shown that the
new products correspond very probably quite gen
3
Y
erally to the general formula
'
Similar precipitations are of course also formed
when using manganous bromide instead of man
ganous chloride, or when e?ecting the precipita
tions in the presence of salts of the hydrohalic
acids.
The following examples illustrate the invention,
the parts being by weight; the ratio between parts
39
by volume and parts by weight is that which ex
ists between the liter and the kilogram.
Example ‘1
35
88 parts’ of 4,-chloro-2-amino-l,1'-diphenyl
[ R—NEN
i 1 MIlCl:
C1
40
2
wherein R. represents an aryl radical of the ben
zene or naphthalene series. Among these prod
ucts those are particularly valuable which corre
spond to the general formula
'
wherein R1 and R2 represent‘ benzene nuclei.
50‘ These products are obtained by the action of
ether hydrochloride containing 75 per cent. of
free base are well stirred together with '75 parts
by volume of hydrochloric acid of 30 per cent. 40
strength and 90 parts of ice. Into this suspen
sion at 0—5° C. there is dropped in the course of
half an hour a solution of 24 parts of sodium
nitrite in 45 parts of water; when this operation
is complete the whole is stirred for 15-20 minutes 45
at 0-5° C. To the ?ltered diazo solution there
are added whilst stirring well and in the course
of 10-20 minutes 60 parts of ?nely powdered
manganous chloride (MnClz.4HzO) andthen 35
parts of common salt, and stirring is continued 50
2
.
V
.
2,131,992
.
for 3-4 hours at 0-5° C. to complete the reaction.
The yellow double salt which has separated is
?ltered with suction or centrifuged and dried at
45-50° C. in a vacuum with addition of a suit
5 able diluent (calcined Glaubers salt or aluminium
sulfate). 'The stabilized diazo salt is very easily
soluble in Water and the solution is neutral. The
product corresponds to the formula
or centrifuged and dried at 45-50° C. in a vacuum
with addition of a suitable diluent. This diazo
preparation from 4,2'-dichloro-2—amino--1,1'-di
phenyl ether and manganous chloride is very
easily soluble in water to a neutral solution.
The product corresponds to the formula
10
10
‘ M1101:
15
15
NEN
'
'
'1
'.
MnCh
01
01
20
t1
2 '
<
2
“As ,vpointedyout explicitly in the introduction,
20
the process can also be carried out with other
‘ diazo salts, for example other aminodiphenyl
Example 2
ethers, or'products which belong to quite differ
92 parts of 4,4’—diohloro-2-amino-1,1’-diphenyl
25 ether hydrochloride having a content of 82.5’ per - ent series, for example simple diazo compounds,
cent.v of- free base are well stirred together with 75 such as those of the a-naphthylamine or the 25
' parts byvolume of hydrochloric acid of 30 per {3-naphthylamine,v ' the l-amino-li-benzoylamino
cent. strength andQOparts of ice. In the course
2,5-‘die'thoxybenzene‘ or’ 2,5-dimethoxybenzene, or’
of 30‘ minutes and at 0-530. therejis run into the
still more complicated diazo compounds, such as
those'fro'm 4-amino-l,p1'-azobenzene, ‘ll-amino
mixture a nitrite solution containing v2f! partsof
sodium nitrite and 45 parts of water; in order to
2",3-dimethyl-1.1_'-azobenzene, 4-amino-3-meth
complete the reaction‘ stirring is continued for
15-20 minutes at 0-5° C. '60 parts of ?nely pow
dered manganous chloride (MnClzAHzO) and.
ox"y-1,p1»'( -azobenzene, ' 1-aminonaphthalene-4- (2’
methoxy~"o-'r '2'v-ethoxyleazobenzene, and the like.v
' ‘What'I claim is?
then 35 parts of common salt vare stirred into the ‘
it
_
'
“ l‘.- Process’for the manufacture of diazo salts,
?ltered diazo solution in the course of 10-20 min
comprising treating diazonium compounds of the 35
utes and stirring is continued for about 4 hours
at ~0-5° C. to complete the reaction. The yellow
double salt this obtained is ?ltered with suction
general formula _
Y
or centrifuged and then dried with addition of
r
Y
Y
Y-
Y
40'
a suitable diluent at 45-50" C. in a vacuum. The
double salt of manganous chloride thus obtained
is very easily soluble in water, yielding a neutral
solution. The product corresponds to the formula
is
30
V
(I).
45
-1|§IEN
01
a
01'
.
0
wherein‘ four Y’s stand for hydrogen and one Y
M11012
stands for a member of the group consisting of I
hydrogen and chlorine, with manganous chloride.
ITIEN'
'2. Process for the manufacture of a diazo
salt, comprising precipitating diazotized 4-chloro
2-amino-1,1'--diphenyl» ether' with 'manganous
o1
7
-
2 I
chloride.
60‘.
‘
>
V
' 3.v Process for ‘the manufacture of a diazo salt,
Example 3
> comprising precipitating diazotized 4,4'.--dichloro
"
87 parts of 4,2’-dichloro-2V-amino-1,1’-dipheny1
ether hydrochloride having a content of 87.6 per
cent; of free base are ‘well stirred together With
__ 75 parts by volume, of hydrochloric‘ acid of 30 per
65‘ cent. strength and 90 parts of ice. Into this
suspension at 0-5° Cjthere is dropped in the
course of 30 minutes a solution of 24 parts of
sodium nitrite in_45-parts of water. ‘ Stirring
,, is continued for 15-20 minutes. 'Into the’ ?l
70 tered diazo solution there are introduced whilst
2-amino-1,1'-dipheny1 ether with manganous
chloride.
4. Process for the manufacture of a diazo salt,
comprising precipitating diazotized 4,2'-dichloro
2-'amino-1,l'-diphenyl ether with manganous
chloride.
'
‘1
‘
'
'
.
-5. The double salts. from manganous halides
and-diazo compounds of the group consisting of
diazonium halides of they benzene andnaphtha
lene series.
stirring well 60v parts of manganous chloridei ' ' 6. The diazonium salts of the general formula
(MnClz.¢lHzO) and then 35 parts of common'salt,
and stirring'is'continued for 3-4 hours at '0-5" C.
7 in order. to‘ complete the reaction;
The diazo
salt which has'separated is ?ltered With suction‘ wherein R1 and R2 represent benzene radicals.
5o.
2,131,992
7. The diazonium salts of the general formula
9. The diazonium salts of the formula
Y
5
Y
0
0
I0
Much
I
N_=_N
.
MnCh
1O
“NEN
(In
01
C1
>
2
01
2
15
15 in which Y stands for a member of the group
consisting of hydrogen and chlorine, and in which
not more than one Y represents chlorine.
8. The diazonium salts of the formula
20
10. The diazonium salts of the formula -
O1
O1
MnCln
25
25
blTEN
Cl
M11012
NEN
_
30
1
1
2
30
ADOLF WIRZ.
Документ
Категория
Без категории
Просмотров
0
Размер файла
270 Кб
Теги
1/--страниц
Пожаловаться на содержимое документа