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Патент USA US2117745

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Patented May 17, 1938
2,117,745
UNITED STATES PATENT OFFKIE
2,117,745
AZO DYES
Gustav Reddelien, Leipzig, and. Georg Mat
thaeus, Wolfen, Kreis Bitterfeld, Germany, as
signors to General Aniline V‘Jorks, Ina, New
York, N. Y., a corporation of Delaware
No Drawing. Application July 28, 1937, Serial
No. 156,142. In Germany August 26, 1936
8 Claims. (Cl. 260-497)
Our present invention relates to a process for ble in water to a red-brown solution. Chrome
manufacturing new azo dyes and more particu
calf is treated in the dye bath in the usual man
larly tolsuch dyes which are especially useful in ner and is thus dyed brown.
dyeing leather.
U:
Further objects of our invention are the new
azo dyes obtainable according to this‘ process.
We have found that azo dyes dyeing leather
Valuable brown tints _mostly of very good fast
ness to light, are obtained when diazotizing an
10 amine of the general formula
'
Y
/
wherein X is any negative substituent, such as
N02, Cl, SO3H and so on, Y is a positive group,
such as O-alkyl and alkyl which may optionally
contain a substituent lending solubility in water
20 and coupling the diazo compound with a di
phenylamine of the general formula
Z
Z
Z being hydrogen or groups lending solubility
in water, for instance, --COOI-I or -—SO3I—I, of
which one Z must be such a group.
:3
These dyes are characterized by the especial
ly beautiful tints of the dyeings they produce
on leather and the very good fastness to light,
acid and alkali of such dyeings. Among these
easily soluble dyes are those which render possi
35 ‘ble a thorough dyeing throughout of the leather
so that the surface dyeing and the dyeing in
the section show equal tone strength. As com
pared with the red-brown tints of the known
dyes from 2-chloro-4-nitro-l-aminobenzene and
40 diphenylamine-‘l-sulfonic acid the dyes of the
above constituents yield tints which are more
on the yellow side.
The following examples illustrate the inven
45
tion, the parts being by weight:-—
Example 1.--231 parts of 2-methyl-6-bromo
é-nitro-l-aminobenzene or 186.5 parts of 2
methy1-6-chloro-4-nitro-l-aminobenzene are di
azotized in the known manner by means of ni
trosyl sulfuric acid and the aqueous diazo-solu
50 tion is added to a solution of 315 parts of di
phenylamine—2-carboxy-2’-sulf0nic acid and an
excess of sodium acetate in water. The dye pre
cipitates in a smeary condition but after pro
longed stirring becomes pulverulent and easily
55 capable of ?ltration. It is a brown powder solu
Example 2.—311 parts of 2-amino-3-bromo
5-nitro-l-benzyl-sulfonic acid are dissolved in 5
1000 to 3000 parts of water and diazotized in
the usual manner. The ?nished diazo-solution
is added gradually to a solution of 315 parts of
diphenylamine - 2 - carboxy - 2'-sulfonic acid in
about 5000 parts of water. After prolonged stir- 10
ring the mixture is neutralized with sodium hy
droxide solution and evaporated to dryness.
Chrome calf is dyed by this dye brown tints very
fast to light.
Example 3.—311 parts of 2-amino-3-brom0- l5
5-nitro-l-benzyl-sulfonic acid is diazotized as
described in Example 3 and the solution is added
to one of the sodium salt of 260 parts of di
phenylamine-2.2’-dicarboxylic acid in water con
taining 250 parts of crystallized sodium acetate.
When coupling is complete the dye is salted out,
?ltered with suction, washed and dried. This
freely water-soluble dye dyes chrome calf red
brown, the dyeing being very fast.
Example 4.—186.5 parts of 2-methyl-6-chloro- 25
4-nitro-1-aminobenzene are diazotized in the
known manner by means of nitrosyl sulfuric
acid. The aqueous solution of the diazo com
pound is added to a solution of 343 parts of
sodium-3-amino - 2 - methyl - 4’ -lnitrodiphenyl- 30
amine-2'-sulfonate. When coupling is complete
the dye is ?ltered, washed, dissolved by addition
of an alkali and again separated by a common
salt. It forms a dark brown powder dyeing
leather dark-brown tints.
35
Example 5.-186.5 parts of 2-methyl-6-chloro
4- nitro - l — aminobenzene are diazotized in the
known manner by means of nitrosyl sulfuric acid.
The aqueous solution of the diazo compound is
gradually added to a solution of 328 parts of the 40
sodium salt of 4-acetaminodiphenylamine-2-sul
fonic acid. After prolonged stirring the dye is
separated by addition of common salt, ?ltered,
washed and dried. It forms a dark powder which
dyes leather brown tints of very good fastness.
Example 6.-333 parts of the sodium salt of l
amino~4-nitro-6-bromo~2-benzy1sulfonic acid are
diazotized in the usual manner and the diazo
solution is slowly added to one containing 328 50
parts of the sodium salt of the ll-acetamino-di
phenylamine-Z-sulfonic acid. When coupling is
complete the solution is neutralized by means of
caustic soda and dried under diminished pressure
at about 40 to 50° C. The dye thus obtained has 55
‘A
2
,
2,117,745
an especially good solubility and dyes leather
beautiful brown tints of good fastness.
What we claim is:-—
1. The dyes which correspond to the general
formula
said dyes dyeing leather valuable brown tints of
very good fastness to light.
5. The process which comprises diazotizing an
amine of the general formula
NH:
'
10
l
wherein X is a negative substituentyof the group
consisting of —NO2, halogen, —SOsH, Y is a
positive substituent of the group consisting of
alkyl, O-alkyl, alkyl—SOsI-I and D is the radicle
of a diphenylamine substituted in at least one
ortho-position to the —NH—- group by a substitu
ent lending solubility of the group consisting of
—SO3H and —COOH, said dyes dyeing leather
valuable brown tints of very good fastness to
20
light.
2. The dyes which correspond to the general
formula
X
wherein X is a negative substituent of the group
consisting of —NO2, halogen, —SOsH and Y is
a positive substituent of the group consisting of
alkyl, —-O—alkyl, alkyl--SO3H, and coupling the
diazo compound with a diphenylamine bearing in
at least one ortho-position to the —NH— group a
substituent lending solubility of the group con
20
sisting of —SOaI-I and —COO-H.
6. The process which comprises diazotizing an
amine of the general formula
NH:
Y
/
—halogen
25
halogen
wherein Y is a positive substituent of the group
30 consisting of alkyl, O——alkyl, alky1—SO3I-I and D
is the radicle of a diphenylamine substituted in at
least one ortho-position to the —NH— group by
a substituent lending solubility of the group con
sisting of -——SO3H and —-COOH, said dyes dyeing
35 leather valuable brown tints of very good fast
ness to light.
3. The dyes which correspond to the general
formula
/
40
llToz
30
wherein Y is a positive substituent of the group
consisting of alkyl, —~O—alkyl, alkyl-SOxI-I, and
coupling the diazo compound with a diphenyl
amine bearing in at least one ortho-position to the
—NH- group a substituent lending solubility of
the group consisting of -—SO3H and —COOI-l.
7. The process which comprises diazotizing an
amine of the general formula
CH:
40
H5O
—halogen
halogen
wherein D is the radicle of a diphenylamine sub
45 stituted in at least one ortho-position to the
—NH—- group by a substituent lending solubility
of the group consisting of —SOaH and —COOH,
said dyes dyeing leather valuable brown tints of
very good fastness to light.
4. The dyes which correspond to the general
formula
N02
and coupling the diazo compound with a di
phenyl-amine bearing in at least one ortho-posi
tion to the —NH— group a substituent lending
solubility of the group consisting. of —SOaI-I and 50
—COOI-I.
8. The process which comprises diazotizing a 1
amino-2—halogeno—4-nitro-6-methy1benzene and
coupling the diazo compound with 3-amino-2
OnN
—QNHQNO:
halogen Nén
CH:
SOQH
45
methyl-4'—nitrodiphenylamine-2'-sulfonic acid.
GUSTAV REDDELIEN.
GEORG MATTHAEUS.
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