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Патент USA US2135008

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Patented Nov. 1, 1938
2,135,008
UNITED STATES
PATENT OFFICE
2,135,008
WATER-INSOLUBLE AZO DYESTUFFS
, Helmut Kleiner, Cologne-Mulheim, Otto Bayer,
Leverkusen-I. G. Werk, and Wilhelm Kunze,
Frankfort-on - the - Main - Fechenheim,
Ger
many, assignors to General Aniline Works,
Inc., New York, N. Y., a corporation of Dela
ware
No Drawing. Application March 18, 1936, Serial
No. 69,588. In Germany March 22, 1935
'5 Claims. (Cl. 260-207)
The present invention relates to new water
insoluble azodyestuffs suitable for dyeing cellu
lose esters, such as cellulose acetate silk, and to
the materials dyed therewith, more particularly
5
the invention relates to water insoluble azo
dyestu?s which may be represented by the gen
eral formula:
It
ester group stands in para position to the azo
group, by a distinct deepening of color. More
over the dyeings obtained with the new dye
stuffs can be discharged to a pure white.
The invention is illustrated by the following
examples, without being restricted thereto:
Example 1.—165 parts by weight of p-amino
benzoic acid ethyl ester are diazotized with 69
parts by weight of nitrite, and the diazotization
mixture is added to a hydrochloric acid solution 10
of 195 parts by weight of dihydroxy ethyl
wherein R stands for the radical of a diazotized
aromatic amine, bearing as substituent at least
15 one esteri?ed carboxylic acid group, and wherein
R’ stands for an aromatic radical, which has
been coupled in para position to
m-toluidine. Neutralization is e?ected with so
dium acetate and, as soon as the coupling is
complete, the solution is rendered alkaline with
sodium carbonate. ‘The dyestuff, having the fol
lowing formula:
20
CH3
:1: stands for a mono- or polyhydroxyalkyl group, is ?ltered with suction, washed, pasted with a
dispersing agent and dried under mild condi
which may be etheri?ed or esteri?ed, and which >
may be attached to R’ in ortho position to the
nitrogen atom, and :1; stands for hydrogen, alkyl
or hydroxyalkyl. As diazotization components
there may be mentioned by way of example
amines of the benzene series, bearing at least
30 once as substituent an esteri?ed carboxylic acid
group, such as an alkyl ester, hydroxyalkyl ester,
alkoxyalkyl ester, a phenyl ester, a benzyl ester,
and which may bear further ‘substituents, such
as halogen, the nitro group, a hydroxy group,
16 CH which may be esteri?ed or etheri?ed, it being
understood that the free sulfonic acid or the
free carboxylic acid group is excluded. As cou
pling components there are mentioned by way of
example mono- or polyhydroxyalkyl substituted
40' aromatic amines of the benzene or naphthalene
series, including such amines in which the nitro
gen atom forms part of a ring system, especially
tions. It is a brick-red powder dyeing acetate
arti?cial silk vivid orange ‘shades, which can be 25
discharged to a pure white.
'
-
The analogous dyestuiT without the ester group
dyes acetate‘ arti?cial silk yellow shades, and is
distinctly inferior as regards fastness to wash
ing and water.
30
By using instead of the ethyl ester of the
p-amino benzoic acid the corresponding methyl
or n-butyl ester, dyestuffs of similar properties
are obtained. .
Example 2.--165 parts by weight of p-amino
benzoic acid ethyl ester are diazotized, as de
scribed in Example‘l, and the diazotization mix
ture is added to 252 parts by weight of the hydro
chloric acid salt of 3,7-dihydroxy-tetrahydro
benzoquinoline of the formula:
H2
II
of a six-membered ring system, such as a tetra
hydrobenzoquinoline compound, the said cou
45 pling component being capable of further sub
EN
/o\ /H
7
o
45
stitution in the manner indicated above.
The dyestu?s obtained in this manner are
especially suited for the dyeing of cellulose esters,
such as acetate arti?cial silk, and it is useful to
50 - employ them- with the addition of a dispersing
agent.
The dyeings obtained with these dye
stuffs are distinguished from such obtained with
analogous dyestuffs, which contain no carboxylic
acid ester groups, by an improved fastness to
washing and to water, and, especially when the
H
dissolved in water. Coupling begins at once
with separation of the dyestu?- formed and is
quickly complete after the addition of sodium
acetate. The dyestu?, worked up as described
50
65
2
2,135,008
in Example 1, corresponds to the following for
mula:
,
with a hydrochloric acid solution of 125 parts
by weight of dihydroxyethylaniline.
The hy
drochloric acid is neutralized with sodium ace
Hz
tate, whereby the formation of the dyestuff is
completed. The dyestu? corresponding to the
HN/ <‘l\o/H
following formula:
.
noomomooo-OrrmG-momomomi
10
It is a violet black powder and dyes acetate
arti?cial silk clear and bluish Violet shades,
which can be discharged to a pure white.
The corresponding dyestuff without the ester
group only dyes acetate arti?cial silk ruby-red,
and is inferior to the above dyestu? as re
gards washing, fastness to water, and discharge
ability.
\ .
Example 3.-209 parts by weight of aniline-2,4
10
is isolated by ?ltering with suction from the
acetic acid solution. It can be pasted with the
usual dispersing agents and dyes acetate arti
?cial silk vivid yellowish-orange shades of good
fastness properties, which can be discharged to
a pure white.
When using for example hydroxyethylmethyl
aniline, hydroxyethyl-m-toluidine, or N-hydroxy
ethyl-m-toluidine as coupling components, dye
stuffs of similar shades and qualities are ob
tained.
Example 6.-l95 parts by weight of 4-amin'o
dicarboxylic acid dimethyl ester are diazotized in benzoic acid-,B-methoxyethylester '
a suspension of aqueous hydrochloric acid with
69 parts by weight of nitrite, whereby the whole
25
passes into solution. There is-then added there
are diazotized in the usual manner with 69 parts
to a solution of 195 parts by weight of l-dihy
by weight of sodium nitrite and coupled with a
droxyethylamino-B-methyl benzene in dilute hy
hydrochloric solution of 155 parts by weight of
drochloric acid, neutralization is effected with hydroxyethylmethylaniline. Coupling begins al
ready in the hydrochloric acid solution and is 30
30 sodium acetate, and, after the coupling is com
plete, the solution is rendered alkaline with sodi-é ‘ completed by neutralizing with sodium acetate.
um carbonate. The dyestuff separated is ?l
The dyestuff corresponding to the following for
tered with suction, washed, pasted with a dis
mula:
persing agent, and carefully dried. It corre
OHs
sponds to the following formula:
‘Oi
35
N:
OH:
CHzCHaOH
401
40'
and forms a dark red powder, which dyes ace-~
tate arti?cial silk reddish orange shades. The
dyeings can be discharged to a pure white. They
have a deeper shade than those obtained with
the dyestuff from the corresponding aniline‘
monocarboxylic acid ester.
Example 4.-210 parts by weight of 3-nitro-4
amino-l-benzoic acid ethyl ester are. dissolved
in some glacial acetic acid, and concentrated
hydrochloric acid in the quantity necessary for
the diazotization is added. The diazotization is
effected with 69 parts by weight of nitrite, and
the solution is diluted with ice water. After
the ?ltration, a solution of 181 parts by weight
' 'of dihydroxy ethyl aniline in. dilute hydrochloric
acid is added, and neutralization is effected with
sodium acetate. After the coupling is complete,
the dyestuff, which corresponds to the following
60
formula:
e
O O CHzCHaO CH:
is ?ltered with suction and washed. When
pasted with a~ dispersing agent it yields on ace
tate arti?cial silk strong yellowish-orange shades
of good fastness properties.
Example 7.—210 parts by weight of 4-amino
benzoic acid-glycerinmonoester‘
50
are dissolved in acetate and aqueous hydrochloric
acid, diazotized with 69 parts by weight of .sodié
um nitrite and coupled with a hydrochloric solu
tion of 200 parts of tetrahydro-3-hydroxybenzo- .
quinoline.
The dyestuff corresponding to the
following formula:
'
,
'
H2C-_'CHOH
/
N=N—
>CH1
NH
60
'
NO:
is separated and worked up in the usual man
ner. It dyes acetate arti?cial 'silk yellowish red
shades, which can be discharged well.
The corresponding dyestuff without ester group
only dyes orange,‘ and is, in washing and in
fastness to water, distinctly inferior.
Example 5.—l8l parts by weight of 4-amino~
benzoic acid glycolmonoester are diazotized in a
ooocniononomon
is separated from the acetic acid solution and
pasted withga dispersing agent; it yields on ace
tate arti?cial silk strong pink shades.
Example 8.—-226 parts by weight of 3-nitro-4
aminobenzoic acid-glycolester are dissolved in‘
glacial acetic acid and a sufficient quantity of
hydrochloric acid in the usual manner with a’ concentrated hydrochloric acid, diazotized with
solution of 69 parts by weight of sodium nitrite.
75-;‘The clear diazo solution thus obtained is coupled
69 parts by weight of sodium nitrite and thinned
with ice water. The diazo solution is ?ltered'a'nd '
70
.
3
112,136,008
coupled
a hydrochloric solution of 15.5 parts
by weight of hydroxyethylmethylaniline.
The
R" stands. for an aromatic radical, which has
been coupled in. para position to
.
.
dyestu?, which corresponds to the following for
mula:
2‘
\
CH]
i '
'
N
CEaOHiOH
OzN
:2: stands for a member selected from the group
consisting of mono- and polyhydroxyalkyl 10
10
groups, etheri?ed and esteri?ed mono-V and
OOCHaCHaOH
is worked up and pasted with a dispersing agent.
, It yields on acetate arti?cial silk vivid and strong
yellowish-red shades of good fastness properties.
When using 5-nitro-2-aminobenzoic acid gly
colester, a dyestu? of a similar shade is obtained;
when using B-methoxy-é-aminobenzoic acid gly
colester
or 4-amino-2-chlorobenzoic acid glycol
20 ester, a yellowish orange dyeing more strongly
is obtained, which has good fastness properties
polyhydroxyalkyl groups, and such derivatives
thereof, which are attached to R’ in ortho-posi
tion to the nitrogen atom, and y stands for a
member selected from the group consisting of 15
hydrogen, alkyl and hydroxyalkyl.
'
2. Water insoluble azodyestu?s of the general
formula:
20
(alkO 0 0+. R—N=N—R'—-N/
\
:1
and can be discharged to a pure white.
The following table contains a number of fur
ther combinations manufactured according to
wherein alk stands for a member selected from
the process, and their shades on acetate arti
the group consisting of alkyl and hydroxyalkyl,
?cial silk:
R stands for the radical of a diazotized aromatic
»
Diazotizing components
Coupling components
Shade
30
30
p-Aminobenzoic acid-n-butyl-(or ethyl-)ester ____ __. ________ __
Do__
Do_ _ _
DihydroxyethyI-m-toluidine ........ ._
Orange
‘__ Dihydroxy-ethyl aniline __________ _.
Do.
__
Do.--
35
Dihydroxyethyl-m-chloramlme
Do.
Hydroxyethyl-methylanilinen _
Do.-Do
Do.-Do---
_ . . _.
______ __ n-Hydroxyethyl-butyljm-toluid e
Hydroxyethyl-p-cresidme ...... _.
' Dihydroxyethyl-p-cresidine__ _
._ n-Hydroxyethyl-butyl-p-cresid}ne--___
Do
__ 3 - hydroxytetrahydtobenzoqumoline
Do.
Do.
Reddish orange.
Do.
Do. _
35
Bluish pink.
of the formula:
H:
ll
H
/C /
40
40
@?ll?z
HN 0H
45
m-Aminobenzoic acid ethyl ester .......................... ._ Dihydroxyethyl-m-toluidine ........ __
Do__
'
Dihydroxyethyl-m-chloraniline _____ __
Do ___________________________________________________ __ 3, 71; dihydroxytetrahydrobenzoquin-
Reddish yellow.
Do.
Bluish red.
0 me.
50
o-Aminobenzoic acid ethyl ester __________________________ __ Dihydroxyethyl-m-toluidine ______ _;-_
Do___--
'
3, 71; dihydroxytetrahydrobenzoquin-
Reddish yellow .
50
Reddish violet.
0 me.
3.5-dinitro-2-amino-benzoic acid-n-butyl-(or ethyl-)ester__-.. Dihydroxyethyl-m-toluidine ........ __ Ruby.
Do
>
Dihydroxyethyl-m-chloraniline_ _
1-amino-2.4»dicarboxylic acid dimethylester _______________ __
Do ................... _.‘ _________________________ ._
55
Wine red.
Dihydroxyethylaniline ______________ -_
__ 3, 7]; dihydroxytetrahydrobenzoquin-
3-amino-4-metl1oxybenzoic acid methylester ________ --
0 me.
Dihydroxyethyl-m-toluidine ________ -_
B-nitro-é-aminobenzoie acid ethylester ............. ._‘.
3, 7r- dihydroxytetrahydrobenzoquin-
ReddIsh. orange.
Violet grey.
Reddish orange.
Greenish blue.
0 me.
5-nitro-2'aminobenzoic acid-n-butyl-(or ethyl-)ester _______ __
Do- _ _
__
p-Aminobenzoic acid ethylester ___________________________ _-
Do__
'
Dihydroxyethyl-aniline _____________ __
Saturated red.
Dihydroxyethyl-m-toluidine. _
Bluish red.
___
N-di-(?-methoxyethyD-aniline ....... _.
Orange.
._ N-ethyl-B-acetohydroxy-ethyl-aniline__
Do.
60’
The dyestuffs indicated in the table have good
a?inity for the ?ber. All the dyeings obtained
with them can be discharged to white.
We claim:
65
1. Water insoluble azodyestu?s of the general
formula:
amine, R’ stands for an aromatic radical, which
has been coupled in para position to
'
2:
N/
65
*
:0 stands for hydroxyethyl, 1/ stands for a mem
ber selected from the group consisting of hydro
gen, alkyl and hydroxyalkyl, and n stands for one
of the numbers 1 and 2.
70
3. Water insoluble azodyestu?s of the general
wherein R stands for the radical of a diazotized
aromatic amine, bearing as substituent at least
75 one esteri?ed carboxylic acid group, and wherein
formula:
‘
.
(alkOOC—)-,.R—N=N—-R’—N(CHgCHgOH):
wherein alk stands for an alkyl group of at most 75
4
2,135,008
four carbon atoms, R and R’ stand for’ a radical
of the benzene series and n stands for one of the
numbers 1 and 2.
5. The dyestu? of the following formula:
4. Water insoluble azodyestu?s 0f the general
formula:
CHgCHzOH
dyeing cellulose acetate‘ silk reddish orange
OHaCHnOH
shades.
:
"
HELMUT :KLEINER.
wherein R‘ stands for a radical of the benzene
OTTO BAYER.
series.‘
WILHELM KUNZE.
'
10
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