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Патент USA US2128256

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Patented Aug. 30, 1938
,. 2,128,256;
PATENT OFFICE '
UNITED STATES
2,128,256
AZO DYESTUFFS
Hans Krzikalla and Hanns Ufer, Ludwigshafen
on-the-Rhine, Bernd Eistert, Mannheim,
and Gustav Klaproth, Ludwigshafen-on-the
Rhine, Germany, assignors to General Aniline
Works, Inc., New York, N. Y., a corporation of
Delaware‘
No Drawing. Original application December 18,
.1935, Serial No. 55,040. Divided and this appli
cation July 16, 1936, Serial No. 90,944. In Ger
many December 22, 1934
'7 Claims.
(01. 260-200)
The present invention relates to the produc
with dimethylamine and subsequent reduction of
tion of new azo dyestuffs. This application has
been divided out from our copending application
the nitro group.
By the reaction of > meta-nitro-omega-chlor
Ser. No. 55,040, ?led December ‘18, 1935.
acetophenone with ethylamine and subsequent
We have found that new valuable azo dyestuffs
are obtained if the coupling components and the
reduction of the nitro group, an amine is ob
5
tained having the formula:
diazo compounds employed in the preparation of
the new dyestuffs are so chosen that the molecule
of the dyestu? contains at least one sulphonic
acid group and at least one basic group of the
10
CIHI
general formula
N H:
From 1-brom-2-(dlethylamino)—ethane and
para-acetamino—thiophenol, a. sulphide is ob
15
in which R1 and R2 may be identical or different
15
tained having the formula:
and may be hydrogen or alkyh‘ cycloalkyl, hy
droxyalkyl or aralkyl radicles or members of a
saturated ring system and X is an aliphatic
20 radicle combined with an aromatic nucleus’ of.’
the dyestu? molecule either directly or by‘ means
of a non-basic bridge.v As non-basic bridges may
be mentioned for example —-O—-, -S—-, —CO-,
—SO2—--, —O—CO—, --NH—CO--, —SO2—NH-—
25 and -CO—NH--.
Dyestuffs of the said kind may also be pre
pared by introducing at least one basic group of
the said general formula ‘into ‘a ,dyestu?-‘which
does not yet contain such a basic group combined
3 O in the manner described above.
Thus for example a diazotizable amine having
the formula:v
35
"
‘ HmOom-pm-mom).
may be prepared by converting para-nitrophenyl
ethyl alcohol by means of thionyl chloride into
omoo-rvn-O-s-(omh-mcm.»
20
which may be saponi?ed as such to'form the
amine or may ?rst be oxidized to form the
sulphone having the formula:
omoo-NHOs-onronrmolnm
g \
-
25
30
and then saponi?ed.
The amines prepared according to the above
methods or by other known methods and having
external basic. groups are capable of diazotiza
35
tion in the same way as ordinary aromatic amines
and yield azo dyestuffs of the said kind by cou
pling with compounds‘ which are capable of
para - nitro - omega - chlorethyl - benzene, reacting
the latter with dimethylamine and reducing the
40 nitro group in the resulting amine.
coupling.
‘ ‘
Coupling ‘components having external basic
40
groups are obtained for example by reacting
An amine having the formula:
2—amino-8-hydroxynaphthalene-6-sulphonic acid
with chloracetyl chloride or a chlorpropionic
acid chloride and treating the resulting 2-(chlor
45
OH:
NH:
is obtainable for example by the reaction of meta
nitroaniline with .chloracetyl chloride, treatment
50
of the resulting chloracetyl-meta—nitro-anilide
acylamino) - 8 - hydroxynaphthalene - 6 - sulphonic
acid with piperidine, dimethylamine or other
nitrogen bases which have at least one reactive»
hydrogen atom. By reacting 2-acetoxy-3-naph
thoio acid‘ chloride with N-diethyl-ethylene
45
2f
_
2,128,256
_.
diamine and then splitting off the acetyl group,
a naphthol is obtained having the formula:
aminoacetyl) -amino-8-hydroxynaphthalene-3,6 -
disulphonic acid, yellower dyestu?s are in general
obtained.
Example 2
208 parts of p-amino-omega-diethylamino
CO-—NH—GHz—CHr-N(C:Ha)i
Further suitable coupling components are for
10
ties are obtained. By employing 1- (dimethyl
phenetol are diazotized in the presence of 350
examplejthe‘pyrazolone's'prepared from the above parts of concentrated hydrochloric acid and 1000
parts, of water with 69 parts of sodium nitrite.
amines by the usual methods, and also the aceto
10
acetyl or benzoyl-acetyl and 2-hydroxy-3-naphe.
These‘ The diazo solution thus obtained is added to an
ifaqiieous solution, containing such an amount of
thoyl compounds of the said amines.
coupling components may be coupled with ‘any. ~ sodium hydroxide to neutralize the hydrochloric
desired diazotized aromatic‘amines toyield dye-Z
acid; of 213 parts of the sodium salt of 1-amino
naphthaléne-7—sulphonic acid. The mono-azo
If the coupling component employed contains \dyestu? thus prepared is salted out, separated,
an amine group, the mono azo dyestuff prepared @dissolved" agai‘n'under the addition of acid and‘
may be diazotized and the diazo-v-compound' be, dia'zoti‘zed- with?sodium nitrite. The diazo solu
coupled with any desired coupling component. tion thus'obtained is added to an aqueous solu
20 Disazo dyestuffs are thus obtained with excellent tion, containing such an amount of sodium acetate
15
stuffs of the said kind.
"
i .
'
properties as regards levellingrpower. and fastness. " to-n'eutralize the'acid,'of 289 parts of the sodium
The introduction of the external basicradicle, salt offl:l-phenylaminonaphthalene-8-sulphonic
of the general formula
;_,facid.
disazo dyestuff is thus obtained which
'
/Rl
25
fxrl‘i
c
I
Bl‘
>
.
'
v
_
V
V
_
.
in‘ which X stands ,for an ialiphatic radicle into
aminoazo or hydroxyazodyestu?'s is e?ected in
30
a similar manner.
.
’
dyes wool beautiful blue shades of good fastness to '
washing ‘and ~fulling.
Instead of para-aminoromega-diethylamino
T
-
phenetol ‘other amines" containing externalfbasic
gl'qllpsmay beemployed. As amines of this kind
there may vbe mentioned ‘iraminobenzyl-di
methyl - amine, 3 - amino - 4 -. methylphenyl - l -
.
The azo dyestu?s obtainable according-to this
invention and having‘external basic groups are
distinguished by an excellent levelling power and
for the most part by good to very good fastness
omega -_(dimeth_ylamino'ethyl) -_ sulphone, 3,-, ami
compounds. ‘ Instead of ‘ lv-ramino-naphthalene?e
tain groups which are capable of being exchanged
by metals, they may be converted in substance
sulphonic acid or a mixture of these two acids.
When the dyestuffs con
or on the ?bre into their complex metal com
30
n'o 5f!- methoxyphenyl e omega -(_dimethylamino ethyl) -sulphone_ _ or the correspondingr'rdieethyl
sulphonic acid there may also. be employedas :the
?rst coupling component l-aminonaphthaleneg?
35 to washing and fulling.
25
35
Instead of 1 - phenylamino - naphthalene -8- sul
phonic acid there may be employed as the second
'40
how the said “invention may b'e'fjcarried? out ‘in
coupling component,’ the LOP-methylphenyl)
aminonaphthalene-8Jsulphonic acid.
practice but the invention‘is ‘not restricted "to
these examples. The parts are by weight.
diazo componentqalready contains a‘ sulphonic
" ,The following. examples/will ‘furtheyillustrete
_
_
_
acid; group;v 1-_-amino'-naphthalene maybe ~eme
ployed'as thel?rst coupling component in this
Examplél
107 parts of para-toluidine are diazotiz'ed in the
usual manner and the diazo solution is stirred into
50
a vsolution, rendered ‘alkaline with sodium carbon-v
ate, of 340' parts of 2-(dimethyl-amino-acetyl)A
amino -8- hydroxynaphthalenee?-sulphonic acid,
having the formula"
~
~ .If._the> amineused for-the preparationot-the
“
‘
‘
case“
~-
-
'
‘Whatwe claim is:—-:
"
V
e
'
-'
"
'
,
45
'
1:1. Azo' dyestu?s corresponding to the general
formulae"
.7
"
r‘
T
50
-
wherein' Ar stan'dsfor an aromatic radical; the
group,,..
H018
60'.
red'shades of good fastnesstqwashing;
- -
-
~
pounds dyestuffshaving a good levellingpower
and good fastness to washing. are obtained, giving
the following color shades: '
V
m
1-;aminonaphthalene._--2- sulphonic
‘
,
—N/
5
i
stands for 5. basic‘radical'selected from the group
consisting of —-NH2, primary and secondary alkyl,
. hyd'rox'y'alkyl,
v
_ aralkyl
and cycloalkyl
amino
groups and the radicals of hydrogenated hetero
cyclic ‘nitrogen compounds includingthe N atom,
_,
sulphanilic acid__'_'_;_____1_"_'__-___. Red.:
Aminoazobenzene sulphonic acid;; Bordeaux red.
l:.-cmethylj-3-‘ amino .-'6-'chlorben~-g_,,
70
'
and;the"mixtures ;worked up in the usual .manner.
The dyestuif obtained dyes wool uniformcarmine
By starting from-thefollowing diazotized come
65
.
V
c
cid—~.—.———-+?-;--:-~-_f?-f-r-f'ff' ~Blue-red' '
If, instead of "the ‘2-'(dimethylaminoacetyl) amino *8- hydroxynaphthalene '-6I- sulphonic ‘acid
the’ic’orresponding v3,6-disulp‘honic acid be em-v
75 ployed, dyestuffs ‘of similar 'shades'and proper
X stands for achain containing carbon atoms,
which is free from; a basic action, and, _B stands
for the radicle of an aromatic ‘a'zo compound,v ‘and
in which at least one of the radicles marked Ar
and B contains a sulphonic acid'gro‘up.
2. A20 dyestuifs corresponding to the general 70
V
formula
'_ iB——'N=N—Ar--X—N
.Y
:
'
‘ \
.
Br.
3
2,128,256
which is free from a basic action, and, B stands
for a radicle corresponding to the general formula
wherein Ar stands for an aromatic radical, the
group
“gag
-—N
\
Rl/
Ra
stands for a basic radical selected from the group
in which at least one of the naphthalene nuclei I
and 11 contains at least one sulphonic acid group 10
and in which R3 stands for hydrogen or a radicle
of the benzene series.
5. The azo dyestuff corresponding to the
formula
consisting of —-NI-I2, primary and secondary alkyl,
hydroxyalkyl, aralkyl and cycloalkyl amino groups
and the radicals of hydrogenated heterocyclic
nitrogen compounds including the N atom, X
stands for a chain containing carbon atoms,
which is free from a basic action, and, B stands
15
CaHs
15
N=NOO CHzCHiN/\
CzHs
20
S 0:11
6. Azo dyestu?s corresponding to the general
for a radicle corresponding to the general
formula:
HRN
formula
R1
OH
25
11035;
wherein Ar stands for an aromatic radical, the
group
‘S0311
in which the nucleus marked A contains at least
30 one substituent of the class consisting of halogen
atoms and nitro groups.
3. The azo dyestu?f corresponding to the
formula
i
R1
30
—-N
R:
stands for a basic radical selected from the‘group
35
GEN
o
Hm
1
olN—
OH
|
N=N
o
CaHn
\ ¢
S-CHaCHzN
/N=N
C 2H5
40
40
1103s
\SO3H
4. A20 dyestuffs corresponding to the general
formula
/R1
B—N=N--AI—X—N
45
R2
wherein Ar stands for an aromatic radical, the
groups and the radicals of hydrogenated hetero 45
cyclic nitrogen compounds including the N atom,
X stands for a chain containing carbon atoms,
which is free from a basic action, and, B stands
for the radicle of a condensation product of 1
molecular proportion of phosgene with 2 molecu 50
lar proportions of an amino-hydroxynaphthalene
group
50
—N
\
R2
stands for a basic radical selected from the group
55
consisting of —NH2, primary and secondary alkyl,
hydroxyalkyl, aralkyl and cycloalkyl amino
consisting of -—NI-I2, primary and secondary alkyl,
sulphonic acid and in which Y stands for a radicle
of the benzene series.
7. The azo dyestuif corresponding to the
55
formula
CH
0
011
0H
0
s-cmonm
/N=N
60
if
11101?
HO:S
0,135
\ %
03H!
\SOzH
H 11
hydroxyalkyl, aralkyl and cycloalkyl
amino
groups and the radicals of hydrogenated hetero
cyclic nitrogen compounds including the N atom,
X stands for a chain containing carbon atoms,
HANS KRZIKALLA.
HANNS UFER.
I BERN'D EISTERT.
GUSTAV KLAPRO'I'H.
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