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Патент USA US2133780

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Patented Oct. 18, 1938
2,133,780
UNITED STATES PATENT OFFICE
2,133,780
CHROMABLE DYESTUFFS OF THE TRIARYL
METHANE SERIES‘ AND PROCESS OF PRE
PARING THEM
Wilhelm Eckert and Karl Schilling, Frankfort
on-the-Main-Hochst, Germany, assignors to
General Aniline Works, Inc., New York, N. Y.,
a corporation of Delaware
No Drawing. Application March 19, 1937, Serial
No. 131,936. In Germany March 2'7, 1936
12 Claims.
(Cl. 260—335)
The present invention relates to chromable
dyestuifs of the triarylmethane series and to a
process of preparing them.
According to the present invention very clear
1
dyestu?s of the triarylmethane series capable of
being chromed are made by condensing 1 molecu
lar proportion of 5-hydroxy-benzene-1,2,4-tri
carboxylic acid or 3-hydroxybenzene-1,2,4-tri
carboxylic acid (hydroxy-trimellitic acid) or the
equivalent amount of the corresponding anhy
dyestu?s may also be chromed in substance
whereby they are transformed into the corre
sponding chromium complex compounds which
dye the ?ber from an acid bath very clear shades
which possess without after-chroming good fast
ness properties.
COOH
10
'
dride with 2 molecular proportions of a cyclic
OH
coon
meta-dihydroxy-compound having a reactive
hydrogen atom, for instance, by melting the re
agents at a temperature between about 150° C.
and about 200° C. The dyestuffs may also be
made by condensing, for instance, by melting at
OH
~
The formation of the dyestufi probably occurs,
for instance, as follows:
OH
\
/
HOOC—
,
15
(|)H
/OH
VOH\
00
OH
00011
+
OH
\
/
I
0
\C/
,___>
'
I
\0
,
HOOC/
OH
\
_-co
3000/
H
OH
a temperature between about 150° C. and about
200° C., one molecular proportion of a benzoyl
The dyestuffs, obtainable according to the
process of the present invention are new. There
benzoic acid, which is obtainable by condensing
are, for instance, obtained dyestuifs of the fol
one molecular proportion of one of the said
lowing probable formula:
‘
hydroxy-trimellitic acids with only one molecu
lar proportion of a cyclic meta-dihydroxy com
C3 01
pound‘ having a reactive hydrogen atom, or of
a halogenation product of such benzoylbenzoic
35
acid, with one mol. of a cyclic meta-dihydroxy
compound having a reactive hydrogen atom. In
this operation there may be used condensing
40 agents as, for instance, concentrated sulfuric
acid or para-toluenesulfonic acid, whereby a
lower reaction temperature, for instance, be
tween about 70° C. and about 140° C. may be
applied. The product may be halogenated sub
45
sequently.
The new dyestuffs dye animal ?bers in an acid
bath very clear yellow to red tints; by after
chroming them the properties of fastness are
considerably enhanced. The dyestuffs are also
suitable for chrome printing on cotton. The
wherein the nuclei B may contain substituents
as, for instance, hydroxy, ' methoxy, halogen,
45
carboxy or sulfo or a condensed, benzene nucleus
in the positions X and wherein one Y represents
hydroxy and thezother Y hydrogen.
50
2
2,133,780
The same dyestu?s may be characterized by
a quinoide constitution as follows:
HO
X
\ R
0W0
hanced by after-chroming.
V
RI r X
I
C
10
a large quantity of water until neutral to Congo
paper. The dyestu? may be recrystallized from
a large quantity of hot glacial acetic acid or
aqueous alcohol. It dyes wool in an acid bath
orange-yellow tints the fastness of which is en
(3) 39 parts of the dyestu? described in Ex
ample 1 are suspended in 200 parts of glacial
X
X
acetic acid and a solution of 68 parts of bromine
Y—
coon
in 100 parts of glacial acetic acid is added drop 10
by drop while stirring. When the bromine has
been absorbed, the dyestuff is isolated and puri
H000
?ed as indicated in Example 2. The dyestuff has
I
probably the following constitution:
Y
15
15
wherein the values R, X and Y have the above
Br
indicated meaning.
HO
It is also possible that isomerides of
the above-mentioned compounds are formed
OH
/O
It is not known with certainty whether the
hydroxy-trimellitic acids react in the manner
20 presumed.
Br 7
20
/
having the constitution:
25
25
H000
H
or represents an isomeride thereof or a mixture
30
of isomerides. It dyes wool in an acid bath a 30
very clear yellowish red tint the fastness prop
erties of which are considerably enhanced by
after-chroming.
(4) 21 parts of 5-hydroxy-trimellitic anhydride,
31 parts of beta-resorcylic acid and 14 parts of 35
anhydrous zinc chloride are triturated and heated
35
or
the
corresponding
quinoide
constitution,
wherein the values R, X and Y have the above
indicated meaning, or that the products are
Ill)
mixtures of isomerides of the said formulae.
The following examples serve to illustrate the
invention but they are not intended to limit it
thereto; the parts are by weight:
(1) 21 parts of 5-hydroxy-1, 2, 4-trimellitic an
hydride and 22 parts of resorcinol are ?nely
triturated and melted together. '7 parts of an-,
hydrous zinc chloride are introduced into the
mass, while stirring, and the whole is heated at
180° C. to 190° C. for 4 to 5 hours. During this
50 time the melt solidi?es. The mass is cooled and '
~?nely pulverized and then digested with 100 parts
of hot vhydrochloric acid of about 5 per cent
strength for some time. The undissolved yellow
residue is ?ltered with suction while hot, dis
solved in caustic soda solution, the solution is
?ltered and the yellow dyestuff is precipitated
from the orange-red ?ltrate‘ by means of dilute
hydrochloric acid. For further puri?cation the
dyestuff may be recrystallized from aqueous
alcohol. By dissolution in water with the neces
sary quantity of sodium bicarbonate and evapor
at 180° C. in an oil bath for several hours until
the melt solidi?es. After cooling, the crude prod
not is pulverized and boiled with 200 parts of hy
drochloric acid of 5 per cent strength; the un
40
dissolved yellow dyestuff is ?ltered with suction
while hot. ‘It is dissolved in dilute sodium carbo
nate solution, yielding an orange-red solution
with a green ?uorescence; the solution is ?ltered
and the dyestuff is precipitated by means of a 45
dilute acid.
For further puri?cation the dye- -
stu? may be recrystallized from aqueous alcohol.
4_=0 parts of this dyestuff are suspended in 160
parts of alcohol and 64 parts of bromine are grad
ually added at ordinary temperature, while stir 50
ring. After standing for several hours the whole 7
is diluted with double the volume of water, the
precipitated red dyestu? is ?ltered with suction,
washed until neutral to Congo paper and trans
formed into the sodium salt by dissolution in so
dium bicarbonate solution and evaporation. The
dyestuff has probably the following constitution:
ation, the easily soluble orange-red sodium salt
is obtained.
'
-
The dyestuff dyes animal ?bers in an acid bat
65
a very clear yellow tint; its properties of fastness
are considerably enhanced by after-chroming.
(2) 39 parts of the yellow dyestu? described
in Example 1 are suspended in 200 parts of glacial
acetic acid and a solution of 34 parts of bromine
in 100 parts of glacial acetic acid is added, drop
by drop, while stirring. When the bromine has
been absorbed, the orange-yellow dyestu?” is
?ltered with suction. washed with a small quan
75 tity of glacial acetic acid and then’ washed with
Br
HOOC/
H
wherein the number and the position of the bro
mine atom or atoms are unknown. Perhaps it is
an isomeride thereof or a mixture of isomerides.
The dyestu? dyes animal ?bers in an acid bath
70
3
2,183,780
very clear yellowish red tints; its fastness proper
ties are considerably enhanced by after-chrom
solution.
The dyestu?f probably possesses the
following constitution:
mg.
,
on
(5) 28 parts of 4-chloro-resorcinol, 20 parts of
5-hydroxy-trimellitic anhydride and 7 parts of
OH
HO
anhydrous zinc chloride are ?nely triturated and
heated at 180° C. in an oil bath until the melt
solidi?es, which occurs after about 5 hours. The
pulverized melt is puri?ed by boiling it with dilute
Br/
0
0H
0/
Br
5
\O\CO »
10 hydrochloric acid, dissolving the undissolved resi
due in dilute caustic soda solution and reprecipi
tating it. For further puri?cation the precipitate
is dissolved by boiling it with barium hydroxide
10
nooo/
solution, the solution is ?ltered and the dyestu?
H
15 is precipitated from the ?ltrate by acidi?cation _
15
with dilute hydrochloric acid. The dyestu? dyes
or is an isomeride thereof ‘or a mixture of isom
wool in an acid bath yellow tints which, by after
chroming, become darker and faster.
(6) 16 parts of 1.3-dihydroxy-naphthalene, 10
erides. The dyestuff dyes wool in an acid bath
wine-red shades. The after-chromed dyeings are
violet and possess essentially better fastness prop
erties than the non-chromed dyestu?.
20
20 parts of 5-hydroxy-trimellitic anhydride and 4
parts of anhydrous zinc chloride are melted together as described in Example 5. The dyestu? is
puri?ed by boiling it with dilute hydrochloric
acid, dissolving the insoluble residue in 250 parts
25 of bicarbonate solution of 5 per cent. strength,
?ltering the solution and adding 60 parts of sodi
(9) 32 parts of 2’, 4'-dihydroxy-2-benzoyl-or
thohydroxy-carboxy-l-benzoic acid having the
following constitution:
HO
OH
'- HO
OH
um chloride to the ?ltrate. After stirring for one
hour the resulting dark precipitate'is ?ltered with
suction and the dyestuff is precipitated from the
30 ?ltrate by means of dilute hydrochloric acid,
OO
l
7
oo
COOH
‘
coon
.
or
‘
'30
washed with water and dried.
The dyestu? dyes animal ?bers in an acid bath
brown-red tints; the fastness properties are im
11000
proved by after-chroming.
at 190° C. to 200° C. for 3 to 4 hours while exclud
The pulverized melt is recrystallized
from aqueous alcohol.
The dyestuff thus obtained has probably the
following constitution:
'
OH
HO\
OH
/0
/OH
0/
\
H0
OOOH
011
('7) 25 parts of pyrogallol, 21 parts of 5-hy
droxy-trimellitic anhydride are melted together
ing air.
/
0\
~00
or a mixture of both isomerides (obtainable by
condensation of one molecular proportion of
5-hydroxy-benzene-l,
2,
4-tricarboxylic
acid
with one molecular pro-portion of resorcinolor
by treating the dyestuff of Example 1 with
about 80 per cent. of caustic soda solution at about
150° C. for about one hour) are melted together
with 20 parts of resorcinol for 4 to 5 hours
at 180° C. The yellow melt is pulverized after
cooling and dissolved in dilute caustic soda
solution. The solution is heated to boiling 45
and acidi?ed with dilute hydrochloric acid.
The yellow precipitate obtained is ?ltered with
suction after cooling, washed until neutral and
dried. The dyestu? may be recrystallized, if de
sired, from aqueous alcohol. On dissolution in 50
dilute alkalies and evaporation of thesolution the
easily soluble sodium salt of the 'dyestuff is ob
H000
tained.
011
'
'
The dyestu? dyes the animal ?berin an acid
bath yellow shades. The fastness properties are 55
It may also be an isomeride of the above formula
in which the positions of the ortho-situated hy
droxyl and carboxyl groups are exchanged. The
60 dyestu? dyes wool in an acid bath red shades,
which on after-chroming become violet and pos
sess very good fastness properties.
(8) 42 parts of the dyestu? obtainable by con-,
densation of 2 molecular proportions of pyrogallol
with 1 molecular proportion of 5-hydroxy-trimel
litic anhydride are suspended in 200 parts of gla
cial acetic acid.
While quickly stirring, a solution of 32 parts of’
bromine, in 100 parts of glacial acetic acid, is
added drop by drop. After consumption of the
bromine the dyestuff is precipitated by means of _
Water and recrystallized for puri?cation from
acetic acid of 50 per cent strength. It forms a red
powder, which dissolves in bicarbonate solution
75 to a red, and in caustic soda solution to a blue
essentially enhanced by after-chroming.
Instead of resorcinol there may also be used '
other meta-dihydroxy-compounds having a re
active hydrogen atom, as, for instance, chloro-,
bromo-, methyl-resorcinol or resorcinolmonoe
methyl ether and so on.
'
(10) By bromination of the dyestu? of Example
9, as indicated in Example 2, a dyestu? is ob
tained which possesses similar properties as de
scribed therein. If the bromination is conducted 65
as described in Example 3, a dyestu? is obtained
which dyes wool in an acid bath very clear yel
lowish red shades, the fastness properties of which
are essentially enhanced by after-chroming.
(11) 32 parts of 2’, 4’-dihydroxy-2-benzoyl~ 70
orthohydroxy-carboxyl-l-benzoic acid (cp. Ex
ample 9) and 17 parts of beta-resorcylic acid are
introduced into 20 parts of’ concentrated sulfuric
acid and heated at 70° C. to 80° C. for 6 hours,
while stirring. Thereupon the mixture obtained
4
2,133,780
is introduced into about 100 parts of water','the
solution is saturated by means‘of sodium chloride
and the yellow precipitate obtained is ?ltered with
suction. In order to eliminate any unchanged 2’,
4' -dihydroxy-2-benzoyl-ortho-hydroxy-carboxy
l-benzoic acid from the yellow residue, it is stirred
with about 25 parts of slaked lime and 250 parts
of water and boiled again. After cooling the
di?icultly soluble calcium salt of the dyestu? is
10 ?ltered with suction, washed with water and the
yellow dyestuff is freed therefrom by means of
dilute acids. With the condensation there occurs
simultaneously sulfonation and the dyestuff pos
sesses probably the following constitution:
15
HO
\/\/O
‘/
Uyy \
HOaS
20
[\ O
OH
,
parts of para-toluene-sulfonic acid are heated at
120° C. to 130° C. for 3 to 4 hours. The pul
verized melt is stirred With about 100 parts'of
water and the dyestuff is ?ltered with suction
from the solution containing toluenesulfonic
acid. The dyestuff is dissolved in sodium car
bonate solution, ?ltered, the red solution obtained ll)
is boiled with 1 part of animal charcoal, ?ltered,
and the dyestuff is precipitated from the cooled
solution by means of dilute hydrochloric acid.‘
It dyes wool in an acid bath orange-yellow
shades. On after-chroming essentially faster
brown dyeings are obtained.
(15) 95 parts of 2’,4’-dihydroxy-3',Sf-dibromo
2-benzoyl- (ortho-hydroxy - carboxy) - 1 - benzoic
acid, which is obtainable from the bromine-free
OOOH
compound (cp. Example 9) by bromination in 20
alcohol with the necessary quantity of bromine,
30'parts of pyrogallol and 150 parts of para
toluene sulfonic acid are melted together at
Q00
120° C. to 130° C. for 4.hours while excluding
H000
26
>(14) 24:par_ts of’ 2',4'-dihydroxy+2-benzoyl
(orthoj-hydroxy- carboXy)-1-benzoic acid (cp.
Example 9), 10%.; parts of phloroglucin and 22
5H
or is an isomeride thereof or a mixture of
isomerides. The dyestuff dyes W001 in an acid
bath yellow shades. The fastness properties are
30 essentially enhanced by after-chroming.
On after-broming in alcohol or glacial acetic
acid there are obtained dyestuffs the Shades of
which turn gradually red pari pas'su with the
number of bromine atoms absorbed.
(12) 16 parts of 2',4’~dihydroxy-2-benzoyl
35
(ortho - hydroxy - carboxy) -1-benzoic acid
(cp.
Example 9) and 7.5 parts of pyrogallol are melted
together at 160-170° C. for 4 hours while exclud
ing air and stirring.
The pulverized melt is dissolved in sodium
40
carbonate solution of 5 per cent strength and
?ltered. The red solution is heated to boiling
and acidi?ed with dilute hydrochloric acid until
the reaction becomes feebly acid to Congo paper.
45 After standing for several hours the precipitated
dyestu?' is ?ltered with suction, washed with
water several times and dried. The dyestu? dis
solves in sodium carbonate or bicarbonate solu
tion to a red, and in dilute caustic soda solution
to a green solution. It dyes wool in an acidbath
air. The cooled pulverized melt is stirred in 1000
parts of water and the dyestuff is ?ltered with
suction. The brown-black residue is dissolved in
sodium carbonate solution. The solution ob
tained is ?ltered and the dyestu? is precipitated
therefrom by means of dilute hydrochloric acid. 30
For further puri?cation it may be recrystallized I
from acetic acid of 50 per cent strength. The
dyestuff dyes wool in an acid bath. On after
chroming it becomes blackand the fastness
. properties are enhanced.
(16) 32 parts of 2’,4’-dihydroxy-2-benzoyl—
(ortho-hydroxy-carboxy)-1-benzoic acid and 16
parts of 4-chloro-resorcinol are melted together
at 160° C. to 170° C. for ?ivhours. It is further
worked up as described in the foregoing example. 40
The dyestuff dyes wool in an acid bath orange
yellow tints. The after-chromed dyeing is
brown and essentially faster.
We claim:
1. A member of the group consisting of com 45
pounds of the general formulae:
x
HO
1
x
0
I
\
\
X/
C/
\1%
X
grey or deeply black shades, the fastness of which
chromed dyeings.
Y
(13) 40 parts of 2’,4'-dihydroXy-2-benzoyl
acid
animal charcoal.
The dyestu? is precipitated
from the hot ?ltered yellow-red solution with
65 dilute hydrochloric acid. Aftercooling entirely
the dyestuff is isolated in the usual~manner.
For further puri?cation it may be recrystallized
from a large quantity of glacial acetic acid or
dioxane. The dyestu? forms a yellow-red, in
70 distinct crystalline powder. It dissolves in bi
carbonate solution to a yellow-red solution hav
ing a yellow, ?uorescence. It dyes‘ wool in an
acid bath clear ‘golden-yellow shades. The
chromed dyeings are brown. and show enhanced
15
fastness
properties.
1
'
-
55
I
thalene are heated at 150° C. to 160° ‘C. for 4
boiled for half-an~hour with about.1 part of
00
HOOC
(cp.
Example 9) and 20 parts of 1,3-dihydroxynaph
60 hours. The pulverized melt is dissolved in bi
carbonate solution and the solution obtained is
\X
\O \
is considerably enhanced compared with the non
(ortho-hydroxy-carboxy) - 1 - benzoic
OH
50
brown-red shades. The after-chromeddyeings
show, according to the strength of the dyeing,
55
35
Y
and
'
~ HO
o
OH
\[I
U
(IQ/l
65
11000
\/Y_
75
2,133,780
and
boxy and sulfonicacid, and the chromium com
plex compounds of these-compounds.
I
3. Compounds of the general formula:'
10
15
HOOC/ I
OH‘
wherein X represents a member of the group
consisting of hydrogen, hydroxy, halogen, car
boxy and sulfonic acid and one Y represents hy
droxy and the other Y hydrogen, and the chro
mium complex compounds of these compounds.
where X represents a member of the group con
sisting of hydrogen, hydroxy, halogen, carboxy
and sulfonic acid and the chromium complex
compounds thereof.
4. The compound of the formula:
Br
2. A member of the group consisting of com
pounds of the general formulae:
X
O
\
OH
\
/
X
HO
O\
/OH
Br/
30
\G< 0
'Br
—OO
/
X
C
X
I
X
\‘r
O\
———CO
35
HOOC
I
/
OH
being a dyestuff which dyes wool from an acid
bath very clear yellowish red shades, the fast
ness properties of which are essentially enhanced
5. The compound of the formula:
and
\
HOOC/
by after-chroming.
OH
H0
Br
HO
0
£41)
OH
} KO
O\
O—co
HOOC/ I
OH
and
X
HO
O
OH
\
3000/
on
wherein X means that the compound is bro
minated, being a dyestuff which dyes the animal
?ber from an acid bath clear yellowish red shades,
the fastness properties of which are essentially
enhanced on after-chroming.
6. The compound of the formula:
OH
CO
OH
65
HOOO/
OH
wherein X represents a member of the group
76 consisting of hydrogen, hydroxy, halcgen, car
70
being a dyestuff which dyes wool from an acid
bath red shades, which on after-chroming be
come violet and possess very good fastness prop-_
erties.
75
6
2,138,780
'7; The process which comprises causing one
mol of a hydroxy-trimellitic anhydride of the
formula:
mol of 5-hydroxy-trimel1itic anhydride of the
formula:
00-o
to
CO~O
X
CO
HOOC
_
11000
OH
1%
10
to react with two mols of resorcin by melting at 10
wherein one X represents hydroxyr and the other ‘about 180° C. to about 190° C. for about 4 to 5
hours a mixture of the reagents in the presence
X hydrogen, to react with two mols of a cyclic
of anhydrous zinc chloride, separating the dye
m-dihydroxy' compound which contains a re
stu? thus obtained and brominating it at room
active
hydrogen
atom,
by
melting
the
reagents
at
temperature in glacial acetic acid.
15
16
a temperature of between about 150° C. and
11. The process which comprises causing one
about 200° C.
mol of 5-hydroxy-trimellitic anhydride of the
8. The process which comprises causing one
mol of a hydroxy-trimellitic anhydride of the formula:
00~0
formula:
20
00-0
CO
00
25
HOOC
I
E000
OH
25
to react with two mols of beta-resorcylic acid by
H
to react with two mols of a cyclic m-dihydroxy
compound which contains a reactive hydrogen
30 atom, by melting the reagents at a temperature
of between about 150° C. and about 200° C.
9. The process which comprises causing one
mol of a hydroxy-trimellitic anhydride of the
formula:
00-0
melting at about 180° C. for about 5 hours a mix
ture of the reagents in the presence of anhydrous
zinc chloride, separating the dyestuff thus ob
tained and brominating it at room temperature
in alcohol.
12. The process which comprises causing one
mol of ?-hydroxy-trimellitic anhydride of the
formula:
35
00-0
00
0
E000
H000
40
H
to react with two mols of a cyclic m-dihydroxy
compound which contains a reactive hydrogen
atom, by melting the reagents at a temperature
45 of between about 150° C. and about 200° 0., and
brominating the compounds thus obtained.
10. The process which comprises causing one
H
to react with two mols of pyrogallol by melting
While excluding air, at about 190° C. to about
200° C. for about 3 to 4 hours a mixture of the
45
reagents.
WlLHELM ECKERT.
KARL SCHILLING.
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