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Патент USA US2112405

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2,112,405
Patented Mar. 29, 1938
UNITED STATES PATENT OFFICE _'
2,112,405
POLYAZO-DYESTUFFS
Bertram Mayer and Ernst Alfred Henzi, Basel,
Switzerland, assignors to the ?rm of Society
of Chemical Industry in Basle, Basel, Switzer
land
I
No Drawing. Application December 28, 1936, Se
rial No. 117,970. In Switzerland January 9,
1936
9 Claims.
(Cl. 260—44.2)
In Patent No. 1,667,327 there is described a
series of valuable polyazo-dyestu?s which are
made by causing to react on 1 mol. of resorcinol in
any order 1 mol. of diazotized dehydrothio
in which R1 stands for a radical of a yellow com
ponent selected from the ‘group consisting of
5 toluidine sulfonic acid and 1 mol. of a diazotized
toacetic acid, D stands for a radical of the di
phenyl series the two azo-groups being linked at
the 4- and 4’-position,\R2 stands for an aromatic
nucleus selected from the group consisting of aro
para-aminoazo-dyestu? of the general formula
R1—N:N—R2-~NH2, in which R1 and R2 are the
same or different aromatic nuclei free from hy
droxyl groups.
.10
The dyestuffs obtained in the above manner
dye cotton valuable tints which are characterized
by their general good properties of fastness. On
the other hand their affinity for vegetable ?ber is
not quite satisfactory.
15
‘
The present invention relates to the manufac
ture of other dyestuffs also containing a thiazole
radical which are characterized by an equally
good levelling capacity and an essentially en
hanced a?inity for vegetable ?ber. The manu
facture consists in causing to act on resorcinol in
20
any order 1 mol. of diazotized sulfonic acid of the
thiazole series, such as diazotized dehydrothio
toluidine sulfonic acid, diazotized primuline or di
azotized para-aminophenylnaphthothiazole sul
25 fonic acid and 1 mol. of a diazotized para-amino
azo-dyestuff of the general formula
monohydroxy derivatives of the benzene series,
1-phenyl-5-pyrazolones, and arylides of the ace- I
matic nuclei of the benzene and naphthalene
series, the two azo-groups being linked at the
1- and 4-position, and R3 stands for a radical se
lected from the group of radicals consisting of sul
fonic acids of the p-phenyl benzthiazol and
,u-phenyl-naphthothiazolseries,the azo-groups be- '
ing linked at the n-phenyl radical, but not in ore
thoposition to the n-carbon atom, in which iur~
ther at least one of the two radicals R1 and R2 con-
tains at least one sulfonic acid group, which prod‘
ucts are dark powders dissolving in water to brown
solutions and in sulfuric acid to red-violet and
green solutions, and dye cotton, viscose rayonand
leather brown tints, and which dyestu?s, when
being dyed on union fabrics consisting of cotton
and acetate arti?cial silk, leave the latter ?ber 25
undyed.
'
3.
The following examples illustrate the invention,
the parts being by weight:in which R2 is the radical of a so-called middle
3 O component, for example a middle component of
the benzene series, such as para-xylidine, 1
amino-2-ethoxy-3-methy1benzene or l-amino
2 :5-diethoxybenzene,0r amiddle component of the
naphthalene series, such as l-aminon-aphthalene,
l-aminonaphthalene-G- or 'Y-sulionic ‘acid, 1
amino-2-methoxynaphthalene and the 6-sulfonic
acid thereof, and R1 is the radical of a so-called
intermediate product from 1 mol. of a 4:4’
tetrazo-‘compound of the diphenyl series and 1
40 mol. of a yellow component, for instance phenol,
salicyclic acid, 1-phenyl-3-methyl-5-pyrazolone
30
Example‘ 1
18.4 parts of 4:4’-diaminodiphenyl are tetrazo
tized in the usual manner'and coupled with 15
parts of salicylic acid in a solution alkaline with 35
sodium carbonate. When coupling is complete a
solution of 24.5 parts of sodium-l-aminonaphtha
lene-6- or 7-sulfonate are added.
When coupling
is complete the dyestuff which has been formed
is ?ltered, stirred with water, further diazotized
with nitrite and hydrochloric acid and coupled in
or acetoacetic acid anilide or a sulfonic acid
a solution alkaline with sodium carbonate with
thereof.
The new dyestu?s correspond therefore to the
general formula
the monoazo-dyestuff from diazotized primuline
no-
on
and 1:3-dihydroxybenzene. This monoazo-dye
stuff is produced by diazotizing 58.6 parts of 45
primuline (sulfonated ‘primuline base), adding
the diazo-compound to an aqueous solution of 11
parts of 1:3~dihydroxybenzene, and after pro
longed stirring neutralizing the mineral acid with 50
‘
’
'
2,112,405
dilute sodium carbonate solution.
When cou~
pling is complete the dyestuff of the formula
parts of sodium-l-aminonaphthalene-G- or '7
sulfonate. When coupling is complete there is
(I) O O H
HO-—
N=N
10
I
l
III
I
—OH
—N=N—primuline
10
(in which one :1: stands for H and the other ac for
added a solution of 27.6 parts of the sodium salt
S0313) is salted out at 60-70"
of 1 - (4=’-sulfophenyl) -3-methyl - 5 - pyrazolone.
?ltered and
‘When coupling is complete the dyestuff thus
brown solution and in concentrated sulfuric acid ‘formed is salted out in alkaline solution, ?ltered,
15
to a violet solution. It dyes cotton or leather ‘stirred with water, further diazotized with ni
dried.
It is a dark powder soluble in water to a
brown.
' trite and hydrochloric acid and coupled in solu
Similar dyestuffs are obtained when the sali
tion alkaline with sodium carbonate with the
cylic acid is exchanged for another. yellow compo
intermediate dyestuff described in Example 1
from 58.6 parts of primuline and 11 parts of
20 nent, for instance one of the S-cresotinic acids,
para-cresol or xylenol and the primuline is ex
resorcinol. When coupling is complete the dye
changed for another thiazole derivative, for in
stuff of the formula
stance dehydrothiotoluidine sulfonic acid. The
4:4’-diamincdiphenyl may be exchanged for an
25
other diphenyl derivative, for instance 4:4’- dia
25
mino-S :3 ’ -dimethyldip_henyl.
Example 2
18.4 parts of 4:4’-diaminodiphenyl are tetrazo
tized in the usual manner and coupled in solu
30
tion alkaline with sodium carbonate with 15
parts of salicylic acid. When coupling is com
plete the compound is further coupled with 13.7
35
510
45
30
parts of l-amino-Z—methoxy-5-methylbenzene in
neutral solution. When coupling is complete the
dyestu? formed is ?ltered, stirred with water
and further diazotized with nitrite and hydro
chloric acid and then coupled in solution alka
line with sodium carbonate with the intermedi
ate dyestuff described in Example 1 from 58.6
parts of primuline and 11 parts of resorcinol.
When coupling is complete the dyestuff of the
formula
40
(in which one :1: stands for H and the other 2:
stands for SOsH) is salted out at 60-70" C., ?l
tered and dried. It is a dark powder which dis
solves in Water to a yellowish brown solution
and in concentrated sulfuric acid to a red-violet
I
Coon
solution. It dyes cotton yellowish brown.
A similar dyestuif is obtained by substituting
dehydrothiotoluidine sulfonic acid for the primu
line. Similar products are produced when the
4:4'-diaminodiphenyl is exchanged for 4:4'—di
.50
amino-3 : 3'-dimethyldiphenyl
3:3’-dichlorodiphenyl.
or 4 : 4’ -diamino
The yellow component
may be exchanged for another yellow component,
for instance sulfonic acid of acetoacetic acid
55
anilide. Finally, also the l-aminonaphthalene-G
or 7-sulfonic acid may be exchanged for 1-ami
nonaphthalene.
is salted out at 60-'70° 0., ?ltered and dried. It
is a dark powder which dissolves in water to a
yellowish brown solution and in concentrated sul
furic acid to a red-violet solution. It dyes cot
ton yellowish brown.
7
Similar dyestu?s are produced when the sali
cylic acid is exchanged for 1-phenyl—3-methyl
5-pyrazolone-4’-sulfonic acid, and the l-amino
2-methoxy-5-methylbenzene is exchanged for
other middle components of the benzene series,
such as for example para-xylidine or l-amino
70 2 : 5~dimethoxybenzene.
Example 3
18.4 parts of 4:4’-diaminodiphenyl are tetrazo
tizyed in the usual manner and coupled in solu
75 tion alkaline with sodium carbonate with 24.5
Example '4
18.4 parts of 4:¢l'-diaminodiphenyl are tetrazo 60
tized in the usual manner and coupled in solu
tion alkaline with sodium carbonate with 15
parts of salicylic acid. When coupling is com
plete there is added a solution of 24.5 parts of
sodium-1-aminonaphthalene-6- or 7-sulfonate.
When coupling is complete the dyestu? thus
formed is ?ltered, stirred with Water and fur
ther diazotized with nitrite and hydrochloric acid
and coupled in presence of sodium carbonate
with the monoazo-dyestuff from 1:3-dihydroxy 70
benzene and the thiazole derivative obtainable by
condensing sodium-2-amino-5-hydroxy-7-naph
thalene sulfonate with l-nitro-B-benzaldehyde
and sodium polysul?de.
This monoazo-clyestuff is produced by diazotiz 75
2,112,405
ing 37.2 parts of the above named thiazole deriv
radicals of sulfonic acids of the ,u-phenyl-benz
ative of the vIormula
thiazole and n-phenyl-naphthothiazole series,
the azo-groups being linked at the u-phenyl
radical, but not in ortho-position to the ,u-carbon
atom in which further at least one of the two 5
radicals R1 and R2 contains at least one sulfonic
S—@-<:> ‘
IlTHz
10
3
acid group, which products are dark powders dis
solving in water to brown solutions and in sul
furic acid to red-violet and green solutions, and
dye cotton, viscose rayon and leather brown tints,
and which dyestuffs, when being dyed on union
fabrics consisting of cotton and acetate arti?cial
silk, leave the latter ?ber undyed.
2. The polyazo-dyestu?‘s- of the general for
mula
15
with nitrite and hydrochloric acid, adding the
diazo-compound to an aqueous solution of 11
parts of 1:3-dihydroxybenzene and gradually
neutralizing the mineral acid by means of a di
lute solution of sodium carbonate. When cou
pling is complete the dyestu? is salted out, ?l
tered and stirred with water. When the coupling
of the ?nal dyestuff of the formula
OOOH
25
25
30
35
It
SOQH
40
40
(in which one :0 stands for H and the other :1:
in which R1 stands for a radical of a yellow
stands for SOsH) is complete the latter is salted
out, ?ltered and dried. It is a dark powder
soluble in concentrated sulfuric acid to a blue
green solution and in water to a reddish brown
component selected from the group consisting of
monohydroxy derivatives of the benzene series,
1-phenyl-5-pyrazolones, and arylides of the
aoetoacetic acid, D stands for a radical of the
solution.
It dyes cotton brown.
I
Similar products are obtained when the 1
aminonaphthalene-?- or 7-sulfonic acid is ex
50 changed for another middle component of the
‘ diphenyl series, the two azo-groups being linked
at the 4- and 4'-position, R2 stands for an arc
naphthalene series, for example the l-amino-Z
methoxynaphthalene-G-sulfonic acid, or when
the benzidine is exchanged for 4:4’-diamino-3:3'
dimethyldiphenyl or 4 : 4’ -diamino--3 :3’ -dimeth
oxydiphenyl or 4 : 4'-diamino-3 : 3’-dichlorodi
matic nucleus of the naphthalene series, the two
azo-groups being linked at the 1- and ll-position,
a
and R3 stands for a radical selected from the
group consisting of the sulfonated radicals of
the formulas
phenyl.
What we claim is:
1. The polyazo-dyestuffs of the general for
mula
60
HO-
OH
in which R1 stands for a radical of a yellow '
65 component selected from the group consisting of
85
monohydroxy derivatives of the benzene series,
1-phenyl-5-pyrazolones, and arylides of the,
aceto-acetic acid, D stands for a radical of the
diphenyl series, the two azo-groups being linked
70 at the 4- and 4’-position, R2 stands for an aro
matic nucleus selected from the group consisting
of aromatic nuclei of the benzene and naph
thalene series, the two azo-groups being linked
at the 1- and 4-position, and R3 stands for a
75 radical selected from the group consisting of the
in which further at least ‘one of the two radicals
it
4
v2,112,405
R1 and R2 containsat- least one sulfonic
group, which products are dark powders‘
solving in water to brown solutions and in
furic acid to red-violet solutions,,and dye
acid
dis
sul
cot
hydrogen atom and theother actor a SQsI-hgroup,
and R3 stands for a radical selected from the
group consisting of the sulfonated radicals of
the formulas
ton, viscose‘rayon and leather brown tints,_and
which dyestuffs, when being dyed on union fab,
rics consisting of cotton and ‘acetate arti?cial
silk, leave the latter ?ber undyed.
'
3. The polyazo-dyestuffs of. the general for
mula
-
,
no?
Q/
I
\s
-on
g,
G\s—
CH3
an
20
in which R1 stands for a radical of a yellow
component selected from the group consisting of
monohydroxy derivatives of the benzene series,
1—phenyl-5-pyrazolones, and arylides of the
aceto-acetic acid, D stands for a radical of the
diphenyl series, the two azo-groups being linked
at- the 4- and 4’-position, one :1: stands for a
hydrogen atom and the other :0 for a SO3H-group,
and R3 stands for a radical selected from the
15
which products are dark powders dissolving in
water to brown solutions and in sulfuric acid to
red-violet solutions, and dye cotton, viscose rayon
and leather brown tints, and which dyestuffs,
when being dyed on union fabrics consisting of ~
cotton and acetate arti?cial silk, leave the latter
?ber undyed.
5. The polyazo-dyestuffs of the general for
mula
so
30
35
03 Cl
group consisting of sulfonated radicals of the I in which R1 stands for a hydroxycarboxylic acid
of the benzene series, one at stands for a hydrogen
formulas
atom and the other x for a SOaH-group, and R3 40
stands for a radical selected from the group con
40
sisting of sulfonated radicals of the formulas
CH3
45
C Ha
an d
50
-
g“
/
s
55
-o\N_
N
\S/
—CH:
which products are dark powders dissolving in
water to brown solutions and in sulfuric acid to
red-violet solutions, and dye cotton, viscose
rayon and leather brown tints, and which dye
stuffs, when being dyed on union fabrics con
and
- sisting of cotton and acetate arti?cial silk, leave
the latter ?ber undyed.
4. The poWazo-dyestuffs of the general for
mula
65
which products are dark powders dissolving in
water to brown, solutions and in sulfuric acid
79
‘
12
I
in which R1 stands for a hydroxycarboxylic acid of
the benzene series, D stands for a radical of the
diphenyl series, the two azo-groups being linked
15,
at- the 4- and-4’-position,v one .a: stands for a
to red-violet solutions, and dye cotton, viscose
rayon and leather brown ‘tints, and which dye
stuffs, when being dyed on union fabrics con
sisting of cotton and acetate arti?cial silk, leave
75
the latter ?ber undyed.
5
2,112,405
6. The polyazo-dyestu?s of the general for
mula
10
inwhich one :0 stands for a hydrogen atom and
COOH
15
15
the other x for .a sOsH-group, and R3 stands for
the sulfonated radicals of the formulas
in which one a: stands for a hydrogen atom and
the other :c for a SOsI-I-group, and R3 stands for
a radical selected from the group consisting of
the sulfonated radicals of the formulas
/N\
20
\S/
\s
--cm
25
and
_
30
Q of
\S
——CHa
35 and
which products are dark powders dissolving in
water to brown solutions and in sulfuric acid to
red-violet solutions, and dye cotton, viscose rayon
and leather brown tints, and which dyestuffs, 40
when being dyed on union fabrics consisting of
cotton and acetate arti?cial silk, leave the latter
fiber undyed.
8. The polyazo-dyestuffs of the general for
mula
40
45
which products are dark powders dissolving in
water to brown solutions and in sulfuric acid to
50
55
55
in which one :1: stands for a hydrogen atom and
the other a: for a SOsH-group, and R3 stands for
red-violet solutions, and dye cotton, viscose rayon
and leather brown tints, and which dyestuffs,
60
when being dyed on union fabrics consisting of
cotton and acetate arti?cial silk, leave the latter
?ber undyed.
'7. The polyazo-dyestuffs of the general for
65 mula
the sulfonated radical of the formula
65
HO
70
60
OH
70
HO
COOH
33
75
Z
75
6
2,112,405
which products are dark powders dissolving in
Water to brown solutions and in sulfuric acid to
red-violet solutions, and dye cotton, viscose
rayon and leather brown tints, and which dye
stuffs, when being dyed on union fabrics con
sisting of cotton and acetate arti?cial silk, leave
the latter ?ber undyed.
9. The polyazo-dyestu?s of the general for
mula
in which one an stands for a hydrogen'atom and
the other as for a SOaH-group, which products
are dark powders dissolving in Water to brown
solutions and in sulfuric acid to green solutions,
and dye cotton, viscose rayon and leather brown or,
tints, and which dyestu?s, When being dyed on
union fabrics consisting of cotton and acetate
arti?cial silk, leave the latter ?ber undyed.
10
10
soar?
OH
OH
15
’ HO_ON=NOON=N_
COOH
20
BERTRAM MAYER.
ERNST ALFRED HENZI.
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