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Patented Sept. 17, 1946
2,407,704
UNITED STATES PATENTOFFICE;
2,407,704
ANTHRAQUINONE ACID DYESTUFF
Jean G. Kern, Orchard Park, N. Y., assignor to
Allied Chemical & Dye Corporation, New York,
N. Y., a corporation of New York
No Drawing. Application January 1, 1944,
Serial No. 516,728
16 Claims. (01. 260-346)
1
2
This invention relates to anthraquinone acid
animal or other proteinic ?bers (e. g., W001, silk,
dyestuffs; It relates more particularly to dye
Aralac, soybean, etc.).
‘
i
‘
stu?s of the l,‘l-diamino-anthraquinone acid
i In the form of the salts of metals other than
those of the ?rst group of the periodic table (for
class, and especially which are derivatives of 1,4~
diamino-anthraquinone-Z-sulfonic acid, in which 5 example, barium, tin, lead, aluminum, calcium,
a hydrogen atom of the 4-amino group is re
placed by an aryl radical.
The dyestu?s of the present invention are de
rlvatives of 1,4-d-iamino-anthraquinone acids in
which an amine radical is present in the 1-posi
strontium, magnesium; copper, chromium, nickel,
tion and a hydrogen atom of the ?l-amino group
are unusually brighter and clearer than those
is replaced by a heterocyclic ortho-biphenylene
.ztc.) which, for convenience are termed “lakes,”
they are insoluble or dif?cultly soluble in Water;
but their aqueous ‘dispersions dye animal ?bers
and nylon, especially the latter, shades which
obtained with‘ the corresponding water-soluble
radical (referred to hereinafter as “a heterocyclic
The l-position of the anthraquinone nucleus
o-biphenylene radical”) ; that is, a radical formed
of two benzene nuclei linked to each other di 15 of the dyestuffs may be occupied by an unsubsti
tuted amino radical or by any of a number of
rectly at one nuclear carbon atom of each nu‘
cleus and linked through an inorganic atom or
substitutedamino radicals, all of which are in
cluded herein within the generic term “an amine
radical at an adjacent carbon atom of each nu
radical.” Thus, one or both of the hydrogens of
cleus. They include the free acids and salts
thereof. Preferably they contain a carboxyl or 20 the NH2 group in the 1-position may be replaced
modi?cations.
‘
,
‘
sulfonic acid group (in the free acid or salt form)
by an alkyl, aryl, aralkyl, hydroaryl, cycloalkyl,
in the 2-position of the anthraquinone nucleus.
or heterocyclic radical.
In the form of the sodium salts they are blue
to green solids, soluble in water, and dyeing ani
mal ?bers and nylon from acid and neutral dye
baths in level, bright blue to green shades. Their
neutral solutions, particularly those containing
sodium sulfate or other similar salt, dye animal
?bers, nylon and related substances strong, uni
form and fast shades of blue to green. (It will
The heterocyclic o-biphenylene-amine radical
in the 4-position of the vanthraquinone nucleus
may be any of various amino derivatives of the
heterocyclic o-biphenylenes, whether containing
additional substituents in the ‘phenyl nuclei or
not (that is, derivatives of amino heterocyclic
o-biphenylenes in which one or both of the ben
zene nuclei [of the biphenylene radical are fur
be understood that the term “nylon,” as em
ther substituted or unsubstituted) .
ployed herein, includes synthetic ?ber-forming
Thus, the dyestuffs of the present invention in
clude compounds which, in the form of the free
acids, correspond with the following formula:
linear polyamides, such as are described in
United States Patents 2,071,250, 2,071,253,
2,130,523, 2,130,948, and British patent 495,790, 35
in the form of masses, sheets, rods, ?bers, tex
tiles, or otherwise.)
‘
The dyestuffs of the present invention are par
ticularly valuable by virtue of their ability to
produce strong and even dyeings on the afore
said ?bers when applied from a neutral dye bath
containing sodium sulfate.- ‘Hence, in and for
dyeing mixed fabrics, e. g., nylon-rayon, nylon
cotton, etc., the new dyestuffs may be employed
simultaneously in a single dye bath with direct
dyestu?’s for rayon or cotton‘ or other dyestu?s
which are applicable only from a neutral or
slightly alkaline dye bath. The dyestuffs of the
present invention, when applied from a neutral
dye bath, are also valuable for producing union
shades on mixed fabrics composed of nylon and
wherein R.’ is a member selected from the class
consistingof hydrogen and alkyl, aralkyl, cyclo
alkyLaryl, hydroaryl, and heterocyclic radicals,
B” is a member selected from the class consist
ing‘of hydrogeniand alkyl, aralkyl, cycloalkyl,
aryl, hydroaryl, and heterocyclic radicals,
2,407,704
3
4
X is a member selected from the class consisting
of halogen, the carboxyl group and the sul
fonic acid group,
Z is a member selected from the class consisting
of hydrogen, the carboxyl group and the sul
lecular amounts of the anthraquinone compound
and about one molecular amount of a diamino
heterocyclic o-biphenylene (preferably with a
slight excess of the anthraquinone compound),
an acid-binding agent (such as sodium carbonate,
sodium acetate, etc.), and a catalyst (such as
a carboxyl group or a sulfonic acid group,
powdered copper, cuprous or cupric salts, etc.),
m is one of the integers 1 and 2, and
cuprous salts (e. g., cuprous chloride) being pre
R'” is a member selected from the class consist
ferred. The reaction mixture also may contain a
ing of heterocyclic o-biphenylene radicals cor— 10 Water-soluble organic solvent (e. g., methyl or
fonic acid group, at least one of X and Z being
responding with the following formula and
ethyl alcohol, diethylene glycol, dioxan, etc.) ;
their alkyl, alkoxy, aryl, halogen, and sulfo
(e. g., sulfonic acid, sulfonamide, substituted
sulfonamide, etc.) derivatives, attached through
a nuclear carbon atom of the hetero‘cycl-ic o
and, when ‘employing a vdiamino,‘het‘erocyclic o
biphenylene, the reaction mixture preferably in
cludes a water-soluble solvent to ensure conden
15 sation of more than one mol of the anthraqui
biphenylene radical to the nitrogen atom of
the amino group represented by I-IN.—-:
none compound with each mol of the diamino
I heterocyclic o-biphenylene. After the condensa
tion is completed; the resulting dyestuff is recov
ered in the form of the free acid by acidifying the
V20 reaction mixture, followed by ?ltration. It is
' preferably puri?ed by washing with dilute acid or
Y
hot‘saline solution. It may also be puri?ed by
repeated dissolution in water and/or alcohol or
wherein Y is a, member of the class consisting
of O, S, NH, N-alkyl, S02 and SO.
other appropriate solvent and crystallization in
'Those'dyestuffs are of particular importance
which containan —NH2 group in the‘ 1-position
25 the form of the sodium salt.
of the anthraquinone nucleus, a sulfonic acid
acted in aqueous solution with a water-soluble
salt or other compound of ametal of the type re
ferred to above, and the resulting precipitate, re
group vin the 2-position of the vanthraquinone nu
cleus, and an amino heterocyclic o-biphenylene
radical (especially, one which contains no water
covered by ?ltration.
solubilizing group) in the 4-position of the an
thraquinone nucleus.‘
_
I
r
heterocyclic o-biphenylene with an anthraqui
none acid (such as an anthraquinone sulfonic
acid or an anthraquinone carboxylic acid) hav
ing an amine rdical in the 1-position of the
anthraquinone nucleus and a halogen atom in the
4-position of the anthraquinone nucleus, with the
aid of a copper condensationcatalyst. The an
,
. The invention will be illustrated by the follow
ing speci?c examples, but it is to be understood
The dyestuffs of the present invention can be
prepared by condensing a mono- or di-amino
1
For the production of’ the dyestuif “lakes”.of
the present invention, the dyestuff maybe re
35
that it is not limited to the details thereof and
that changes may be made Without departing ‘
from the scope of the invention. The tempera
tures are in degrees centigrade and the parts
and percentages are by Weight.
40
'
Example 1.—-A mixture of 5 parts of 2,-amin0
dibenzofuran, 5 parts of soda ash, 0.5 part of '
cuprous chloride, and 250 parts of water is heated
to 75° until homogeneous, after whichlo parts
thraquinone sulfonic acid dyestuffs may also be
of sodium 1-amino-4-brom-anthraquinonee2
obtained by condensing a mono- or diamino
heterocyclic o-biphenylene with a dihalogen 4-5 sulfonate are added over a period of 10 to 15 min
utes. The mixture is agitated at 75° to 85° ‘for
aminoanthraquinone having an amine radical in
about 6 hours to complete the condensation.
the 1-position of the anthraquinone nucleus, a
During the ?rst few hours, 1 part of cuprous
halogen atom in the 4-position of the anthraqui
chloride is added to the’ reaction mixture in 5
none nucleus and another halogen atom‘ in an
equal
portions at equal intervals. The resulting
other position (preferably the 2-position) of the 50
reaction mass is rendered slightly-acid to Congo
anthraquinone nucleus, with the aid of a copper
red test paper with hydrochloric acid and ?ltered.
condensation catalyst, followed by conversion of
The filter cake is washed with dilute hydro
the resulting ' amino-halogen-anthraquinone
chloric acid until the ?ltrate appears colorless.
amino heterocyclic o-biphenylene to the corre
The dyestuif is further puri?ed by dissolving it
sponding sulfonate by treatment with a sul?te or
in water andadding soda ash and salt to the
bisul?te.
solution to isolate the dyestuff as the sodium salt.
In the production of the dyestuffs of the pres
The resulting product is a blue crystalline solid
ent invention, in accordance with the preferred
which is sparingly soluble in cold water and solu
method of procedure, an amino heterocyclic o
. , ble in hot water, and which dyes wool, silk and
biphenylene is reacted with an alkali metal salt 60
nylon, from acid and neutral dye baths, level
of l-amino-4=-brom-anthraquinone - 2 - sulfonic
bright blue shades of good tinctorial strength
acid (so-called “bromamin-e acid”), or an alkali
and fastness to light and washing. , In the form
metal salt of 1-amino-4-bromo-anthraquinone
of the free sulfonic acid, it corresponds with the
2-carboxylic acid, in' an aqueous reaction me
dium containing an acid binding agent and a cop 65 formula:
0
NH2
per catalyst of the type usually employed in con
densation reactions of thistype, preferably at a
temperature of about 70° to about 100° C. and
especially at temperatures of 75° to 85° C.
Thus the reaction may be carried out‘ by heat
ing an aqueous reaction mixture containing about
equimolecular amounts of the anthraquinone
compound and a monoamino heterocyclic 0-bi
phenylene (preferably with ,a small excess of the
amino "heterocyclic o-biphenylene), or two mo
2,407,704
5
6
Example 2.—5 parts of 3-amino-2-methoxy
dibenzofuran‘are employed in place of‘the 2
amino-dibenzofuran in the foregoing example,
the procedure being otherwise the same.
previously heated to 80°, are added 55 parts of
10% aqueous sodium carbonate, 05 part of cu
prous chloride, and 8 parts of sodium l-amino
el-brom-anthraquinone-2-sulfonate. The result
The resulting product is a green-blue crystal
line solid which'dyes silk, wool and nylon from
acid and neutral dye baths strong, uniform green
shades, which possess excellentfastness to light
and washing. In the form of the free sulfonic
1,0
acid, it corresponds with the formula:
0
II
NHz
|
/\
'
803B
,
,
ing reaction mass is further treated in the same
manner as the reaction mass in Example 3.
The resulting product, sodium 1-amino-4 (3’
dibenzo-furan-8’-sulfon-diethylamide) amino
anthraquinone-z-sulfonate, is a blue ‘crystalline
solid which dyes wool, silk and nylon from a
neutral dye bath uniform blue shades of good
strength, brilliance and fastness to light and
washing. In the form of the free sulfonic acid
it corresponds with the formula:
1
‘ '
15
0
0 CH3
N H:
II ,
(I) HN
—S_0aNa
0
/
Emdmple 3.—To a mixture of 5 parts of 3
amino-dibenzo-furan, 175 parts of water and 110
parts of diethyleneglycol, previously heated to
80°, are added 55 parts of 10% aqueous sodium
carbonate, 0.5 part of cuprous chloride, and 10
parts of sodium 1-amino~4-brom-anthraquinone
20
l
0
Calls
N
—-S O2—N
H
(12H!
25
Example 5.-—The procedure described in Exam
‘ ple 3 is employed, but with 5 parts of B-amino
carbazole substituted for the B-amino-dlibenzo
2-sulfonate. The resulting reaction mass is
furan.
stirred at 80° to 85°, with heating until no fur
The resulting product is a greenish-blue crys
ther color change is observed (a period of about 30
talline solid which , dyes wool, silk and nylon
7 hours). During the ?rst few hours, 1 part of
from acid and neutral dye baths strong bluish‘
cuprous chloride is added to the reaction mass
green shades of good levelness and fastness prop
in 5 equal portions at equal intervals. After cool
ing, the reaction mixture is diluted with 300 parts 35 erties. In the form of the free sulfonic acid,
it corresponds with. the formula:
of water and rendered acid to Congo red paper
with hydrochloric acid. The resulting precipi
tate of the desired coloring matter is ?ltered oil
at about 80°. The ?lter cake is washed with
about 1000 parts of warm (60°) 1 per cent hydro 40
chloric acid, and thereafter with hot (80°) water
until a colorless ?ltrate is obtained. The result
ing ?lter cake is boiled with 500 parts of water,
and the hot mixture is made slightly alkaline to
Brilliant Yellow with aqueous sodium carbonate.
The resulting mixture is cooled and salted lightly
‘ with common salt to isolate the dyestu? as the
sodium salt, which is separated by ?ltration,
washed alternately with warm aqueous solutions
of common salt and sodium carbonate (1 per 50
cent and 0.1 per cent concentrations, respective
ly) until colorless ?ltrates are obtained, and then
dried.
The resulting product, sodium l-amino-4 (3'
dibenzo - furan)
- amino - anthraquinone - 2
sulfonate is a blue crystalline solid which dyes
wool, silk and nylon from a neutral dye bath
(H)
NHi
—SO:§H
Y
0
EN
GO
\N/
H
Example 6.—5 parts of 3,6-diaminocarbazole
are dissolved in 85 parts of diethyleneglycol at
about 50°. To the resulting solution are added
20 parts of urea, 125 parts of a 10% aqueous
solution of sodium carbonate, 0.5 part of cuprous
chloride, and 125 parts of water, and the mass
is agitated until homogeneous. 27.5 parts of
“bromamine acid” (containing 88% of sodium 1
containing sodium sulfate bright blue shades,
amino - 4 - bromanthraquinone-2-sulfonate) are
which possess good strength, clarity, levelness
introduced into the batch, which is then heated
and fastness to light and washing. In the form 60 with agitation to 75° and agitated for 5 hours
of the free sulfonic acid, it corresponds with the
at that temperature until condensation is com
formula:
plete. During the ?rst four hours of said period
of condensation 2.5 parts of cuprous chloride are
added in portions. The resulting reaction mass
is diluted with 300 parts of water, rendered acid
to Congo red paper with hydrochloric acid, heated
to 80°, and ?ltered at that temperature. The
?lter cake is washed twice with 500 parts of warm
(60°) 1% hydrochloric acid, and then With hot
70 (80°) water until the ?ltrate is substantially col
orless. The ?lter cake is suspended in 1500 parts
of water, and the slurry is heated to boiling,
Example 4.—>To a mixture of 6 parts of 3
cooled to 80°, and aqueous sodium carbonate is
amino-dibenzo-furan-S-suIfQn-diethylamide, 175
added until the mixture is alkaline to Brilliant
parts of water and 110 parts of diethyleneglycol, 75 Yellow paper. The mixture is then allowed to
2,407,704
'2’
8
coolslowly tosroomxtempe'rature while adding a
The resulting product,‘ they sodium salt of’ 1
small 'amount'of common saltito promote crys
amino - 4(3‘l-dibenzofuran) — amino - anthraqui
tallization.
none-Z-carboxylic acid, is a blue crystalline solid,
which is somewhat less soluble in hot and cold
The resulting crystals of dyestuff
are ?ltered o?, washed with a slightly alkaline
1% solution of sodium chloride until the ?ltrate CR water, but exhausts more completely from a neu
is colorless, and dried.
traldye bath, than the corresponding dyestuff
The dyestu? thus obtained is a blue-green
of Example ‘3. It dyes nylon from a neutral'dye
crystalline solid, which dyes wool, silk and nylon
bath blue shades, which possess good strength,
from acid and neutral dye baths blue-green
uniformity and fastness properties, and are
shades, which. are bluerithan, but otherwise sim 10 brighter than dyeings similarly obtained‘ with
‘ ilar in properties to, theshades obtained with the
the corresponding sulfonic acid dyestuff of Ex
dyestu? of Example 5. In the form'of the free
ample 3. In the form of the free carboxylic
sulfonic acid, the dyestuff corresponds with the
acid, the dyestu? corresponds with the formula:
following formula:
‘a? 17H:
15
A
POOH
\Q
20
0 EN
u
O,
It Will be realized’by those skilled in‘ the art
25 that‘ the invention is not limited to the details of
the foregoing examples andthat changes can
be made without departing from the scope of the
invention.
Example 7.—6 parts of 2,7-diamino—3,6-di
niethylcarbazole are employed in pla_ce_of ‘the
Thus, instead of thePbromamine acid” and 1
amino-4-bromo~anthraquinone-2-carboxylic acid
3,(i-diaminocarbazole in Example 5, the proce
dure being otherwise the same.
7
employed in‘ the above examples; other anthra
,
quinone-sulfonic vand -carboxylic acids, or mix
' The resulting product (disodium salt) is a blue
solid which dyes wool, silk and nylon from acid
and neutral dye baths blue-green shades, In the
form of the free sulfonic acid it is represented
by the formula:
'
tures thereof, having an amino radical in the
i-position and a halogen atom in the 4-position
may be employed, for example:
1~amino-4-chloro-anthraquinone - 2 - carboxylic
acid
'
1-amino¢4-chloro-anthraquinone-2r-sulfonic acid
40 l-methylamino~4-brommanthraquinone -, 2 - sul
fonic acid
7
1-methylamino-(i-brorno-anthraquinone,- 2 - car
boxylic acid
,
'1-dimethylamino-4r-bromo-anthraquinone-2-sul
fom'clacid
V
1-ethylamino-4-bromo7anthraquinone-Z:sulfohic
acid
1-benzylamino~4-bromo-anthraquinone g 2- - sul- l
fonic acid
Example 8.—A mixture of 40 parts of l-amino
4-bromo-anthraquinone—2-carboxylic acid, 3'7
parts of 3-amino-dibenzo-furan, 30/ parts of soda
ash, 4 parts of copper sulfate, 2 parts of cuprous
chloride, and 500 parts of'water is heated to 90°
to 95° until foaming subsides (about 1 hour), and 55
is then refluxed for about 4 hours to complete
1-phenylamino~4-bromo-anthraquinone - 2 - sul
fonic acid
,
,
1-cyclohexylamino-4-bromo - anthraquinone - 2 -
sulfonic acid
1ralpha-furfurylamino-llebromo-anthraquinone
.
2-su1fonic acid
the condensation. After cooling to room tem
perature, the reaction mass is ?ltered. The ?lter
l-dibenzofuranamino - 4 — bromo~anthraquinone
2-sulfonic acid
'
l-hydroxyethylamino - 4 - bromoranthraquinone
cake is washed with a cold 5% aqueous solution
of sodium chloride, and then stirred into a mix 60
ture of 1000 parts of water and 175 parts of 20°
l-amino-2,4-dibromo-anthraquinone - 5 - sulfonic
acid
j
Bé. hydrochloric acid. The resulting slurry is
heated to 90° to 95°, agitated at that temperature
2~sulfonic acid
1-amino-2,4-dibromo—anthraquinone - 6 - sulfonic
acid
for one hour, and ?ltered hot, and the ?lter cake
1-amino-2,4-dibromo-anthraquinone ,- 7 - sulfonic
is Washed free from acid with hot water. The 65
acid
.'
'
l
cake of crude dyestu? thus obtained is slurried
1-amino-2,4-dibromo-anthraquinone - 8 - sulfonic
with 3000 parts of hot water, and the mixture is
acid
,
,
rendered alkaline to Brilliant Yellow with soda
1-amino-4~bromo-anthraquinone r 2,5 - disulfonic
ash. . ‘The mass is then ?ltered at 85° and the
?lter cake is washed with hot water until a col
orless ?ltrate is obtained. The combined ?ltrates
acid
'
~
'
‘
1~amino-4-bromo-anthraquinone - 2,6 - disulfonic
acid
,
are cooled to room temperature and salted with
common salt to precipitate the dyestu?‘, which is
1-amino-4-brom0—anthraquinone - 2,7 - disulfonic
separated by ?ltration, washed with cold water
1-amino-4-bromo-anthraquinone - 2,8 Qdisulfonic
acid
acid
yndxdried.
'
'
.
._
'
.
..
'
‘
.
__
2,407,764
10
Further, instead of the amino heterocyclic,
nylon from acid and neutral dye baths in level,
o-biphenylenes employed in the above examples
bright blue to green shades.‘
I
'
1 ‘ i' ‘
i2.‘ Anthraquinone acid dyestuffs of the 1,4
or the modi?cations thereof referred to above,,.
other amino heterocyclic o-biphenylenes may be~
diamino-anthraquinone acid class, saiddyestu?s,
employed, for example:
in the free acid ,form, corresponding ‘with the
‘
3-amino-2-ethoxy-dibenzofuran
‘
formula:
‘
V
i
z
‘
3-amino-2-methoxy-7-methyl-dibenzofuran
3-amino-2,7 ~dimethoxy-dibenzofuran
3-amino-2~methoxy-7-chloro-dibenzofuran
l-amino-dibenzofuran
ll-amino-dibenzofuran
3-amino-4-methoxy¢dibenzofuran
2,7-diamino-3,6-dimethoxy dibenzofuran
4-amino-6,7,8,9-tetrahydro-dibenzofuran
,OHN
2~aminocarbazole-7-sulfonic acid
R!!!
m
3-amino-N-ethyl-carbazole '
wherein R’ is a member selected from‘the class
Z-amino-dibenzothiophene
4-amino-bipheny1-2,2'-sulfone
consisting of hydrogen and alkyl, ’ aralkyl,
_
cycloalkyl, aryl, hydroaryl, and heterocyclic
2-aminocarbazole-7-sulfon-N-methylanilide ,
radicals,
'
‘
.
'
“
i
R" is a member selected from the class consist‘
ing of hydrogen and alkyl, aralkyl, cycloalkyl,
aryl, hydroaryl, and heterocyclic radicals,
CH3
——SO2N
X is a, member selected from the class consisting
of halogen, the carboxyl group and the sulfonic
CoHs
l-amino - carbazole - 3,6,8 - trisulfonhexaethyltria
acid group,
amide
C2116
02135
N 0 :S
—S O 2N
02H;
,
30
02115
N
NH:
(32H:
S OzN
'
one,
>
>
T
‘
Z is a member selected from the class consisting
of hydrogen, the carboxyl group and the sul
fonic acid group, at least one of X and Z being
,
While the condensation ‘is preferably carried
out at temperatures of about 70° to about 100°
0., and especially at temperatures of 75° to 85°‘
0., other temperatures may be used; ,for example,
temperatures between 60° and 115‘? C.
a
r
r to
The dyestuffs of the present invention may be
a carboxyl group or a sulfonic acid group,
m is one of the integers 1 and 2, and
R’” is a member selected from the class con
sisting of heterocyclic o-biphenylene radicals
corresponding with the following formula and
their alkyl, alkoxy, aryl, halogen, and sulfo
derivatives, attached through a nuclear carbon
atom of the heterocyclic o-biphenylene radical
to the nitrogen atom of the amino group repree
sentediby HN-—:
‘
"
‘
-
'
employed in conjunction with diluents and as
sistants (such as, dextrine, sugars, sodium chlo
ride, sodium hexametaphosphate), dispersing
agents (e. g., higher alkyl aryl sulfonates, di-i
arylmethane sulfonates, etc.), and they may be
marketed in the form of powdered ‘compositions
comprising mixtures of said dyestuffs with dilu
ents‘ and/or assistants ancl/or‘idispersingiagents.
wherein Y is a member of the class consisting of
O, S, NH, N-alkyl, S02 and SO,
said dyestuffs being, in the form of the sodium
salts, blue to green solids, soluble in water, and
dyeing animal ?bers and nylon from acid and
The sodium salts of those dyestu?s of i the 50 neutral dye baths in level, bright blue to green
shades.
.
j
present invention which contain only one water
3. Anthraquinone sulfonic acid dyestuffs ofl‘the
solubilizing group (namely, a carboxyl group or
1,4 - diamino - anthraquinone sulfonic acid class,‘
a‘ sulfonic acid group) in the molecule are par
said dyestuffs having an amine radical in the 1-~ _
ti'cularly suited ~for dyeing nylon from a neutral
dye bath, but they are dif?cultly soluble in cold‘ ' position of the anthraquinone nucleus, an amino;
heterocyclic o-biphenylene radical in the: 4-posi
water and only" moderately soluble in hot water
tion of the anthraquinone nucleus, and a sulfonic
and hot dye baths. Their dissolution or dis
acid radical at least in the 2-position of the
persion in cold and hot water can be improved
anthraquinone nucleus, said dyestu?s being, in
and dyeing facilitated by adding a small amount
the form of the sodium salts, blue to green solids,
(1% to 5%, or more, based on the weight of the
soluble in water, and dyeing animal ?bers and
dyestu?) of a dispersing agent (e. g., a formalde
nylon from acid and neutral dye baths in level,
hyde condensation product of naphthalene sul
bright blue to green shades.
fonic acid, “Tamol NNO”, a mixture of alkyl
4. Anthraquinone sulfonic acid dyestuffs of the
benzene sodium sulfonates derived from kerosene,
1,4-diamino-anthraquinone-2-sulfonic acid class
etc.) to such dyestuffs (as well as to other dye
stuffs of this invention) .
in which‘ a hydrogen’ atom of the e-amino group
anthraquinone nucleus and an amino heterocyclic
is replaced by a heterocyclic o-biphenylene radi
cal, said dyestu?s being, in the form of the
sodium salts, blue to green solids, soluble in water,
and dyeing animal ?bers and nylon from acid
and neutral dye baths in level, bright blue to
o-biphenylene radical in the 4-position of the
green shades.
I claim:
1. Anthraquinone acid dyestu?s of the 1,4
diamino-anthraquinone acid class, said dyestu?s
having an amine radical in the 1-position of the
anthraquinone nucleus, said dyestuffs being, in
the form of the sodium salts, blue to green solids,
5. Anthraquinone sulfonic acid dyestu?'s which
are sodium salts of 1,4-diamino-anthraquinone
Soluble in water, and dyeing animal ?bers and 75 2-sulfonic acids in which a hydrogen atom of the
151‘
12
4-amino group is replaced by a heterocyclic
a neutral dye bath containing sodiumlsulfate
V
o-biphenylene radicaL-rsaid dyestuffs being blue
bright blue shades which possess good strength,
to green solids, soluble in Water, and dyeing ani
clarity,'levelness and fastnes’s to-rlight and Wash‘
mal ?bers and nylon fromacid and neutral dye
baths in level, bright blue to green shades.
6. Anthraquinone sulfonic acid dyestuffs which
mg.
the 1,4-diamino-anthraquinone carboxylic acid
class, said dyestuffs having an amine radicalin
the l-position of the anthraquinone nucleus, an
amino heterocyclic o-biphenylene radical in the
are sodium saltsof 1,4-diamino-anthraquinone
2-sulfonic acids in which a hydrogen atom of the
4-amino group is replaced by a dibenzofuran rad
ical, said dyestuffs being blue to green solids, sol
‘
12. Anthraquinone carboxylic acid dyestuffs of
10 4-position of the anthraquinone nucleus, and a
uble in water, and dyeing animal ?bers and nylon '
carboxyl radical at least in the 2-position of the
from acid and neutral dyebaths in‘ level, bright
anthraquinone nucleus, said dyestuffs being, in
blue to green shades.
- the form‘ of the sodium salts, blue to green sol
7. Anthraquinone sulfonic acid dyestuffs of the
ids, soluble in. Water, and dyeing animal ?bers
1,4-diamino-anthraquinone-z-sulfonic acid class 15 and nylon from acid and neutral dye baths in
in which a hydrogen atom of the 4-a1nino group
level, bright blue to green shades.
is replaced by a heterocyclic'o-biphenylene radi
13. Anthraquinone carboxylic acid dyestuffsof
cal which contains no water-solubilizing group,
the 1,ll-diamino-anthraquinone-Z-carboxylic acid
saidgdyestuifs being,‘ in the form of the sodium
class in which a hydrogen. atom of the 4-amino
salts, blue to green solids, soluble in water, and 20 group is replaced by a heterocyclic o-biphenylene
dyeing animal ?bers and nylon from acid and
radical, said dyestuffs being, in ‘the form of the
neutral dye baths in level, bright blue to green
sodium salts, blue to green solids, soluble in
Water, and dyeing animal ?bers and, nylon from
shades.
8. Anthraquinone sulfonic acid dyestuffs of
acid and neutral dye baths in level, bright blue
to green shades.
.
the 1,4-diamino-anthraquinone sulfonic acid
' l4. Anthraquinone vcarboxylic acid dyestu?s of
class, said dyestuffs having an amine radical in
the l‘-position of the anthraquinone nucleus and
the 1,4-diamino-anthraquinone-2-carboxylic acid
an amino heterocy'clic 'o-biphenylene radical
class in which a hydrogen atom of the ,ll-amino
containing an oxygen, atom in‘ the heterocyclic
group is replaced by a heterocyclic .o-biphenylene
nucleus, in the lleposition of the anthraquinone
radical which contains no water-solubilizing
nucleus, said dyestuifs being, in theform of the
group, said dyestuffs being, in the form of the
sodium salts, blue to green ‘solids, soluble in
sodium salts, blue to green solids, soluble in
water, and dyeing animal ?bers and nylon from
water, and dyeing animal ?bers and nylon from
acid and neutral dye baths in level, bright blue
acid and neutral dye baths in level, bright blue
to green shades.
35
to green shades.
~
'
.
'
9. vAnthraquinone sulfonicacid dyestuffs of the
15; Anthraquinone carboxylic acid dyestuffs of
. 1,4-diamino-anthraquinone-2-sulfonic acid class
the lA-diamino-anthraquinone carboxylic acid
in which a hydrogen atom of the ll-amino group
class, said dyestuffs having an amine radical in
the 1-position' of the anthraquinone nucleus and
is replaced by a dibenzofuran radical, said dye
stu?s being, in the form of the sodium salts, blue
to green solids, soluble in water, and dyeing ani
mal ?bers and nylon from acid and neutral dye
baths in level, bright blue to green shades.
10. Anthraquinone sulfonic acid dyestuffs of
an amino heterocyclic o-biphenylene radical con
taining an ‘oxygen ‘atom in the heterocyclic nu
cleus, in the 4—position of the anthraquinone'nu
cleus, said dyestuffs being, in the form of theqsoj
dium/ salts, blue to green solids, soluble in ‘water,
the' 1,4-diamino-anthraquinone-2-sulfonic acid 45 and dyeing animal ?bers and nylon from acid
class in which a hydrogen atom of the 4-amino
and neutral dye baths in level, bright blueto
group is replaced by the dibenzofuran radical,
green'shades.
said dye-stuffs being, in the form of the sodium
16. Anthraquinone carboxylic acid ‘dyestuffs of,
salts, blue solids, soluble in water, and dyeing
the lA-diamino-anthraquinone-2ecarboxylic acid
animal ?bers and nylon from acid and neutral
dye baths in level, bright blue shades.
11. Anthraquinone
sulfonic
acid
dyestuffs
which are l-amino-4 (3’-dibenzofuran)-amino-
anthraquinone-Z-sulfonates, said. dyestuffs be
ing, in the form of the sodium salt, a blue crys
talline solid which dyes wool, silk and nylon from
class in which a hydrogen. atom of the? Zl-amino
group is replaced by the dibenzofuran radical,
said dyestuffs being, in the form of the sodium
salts, blue solids, soluble in water,_ and-dyeing
7 animal ?bers and nylon from acid and neutral
dye baths in level, bright blue shade-s. _
if
Y
JEAN G. KERN.
.
Certi?cate of Correction
Patent No. 2,407,704.
September 17, 1946.
‘
JEAN G. KERN
Ira-1:5‘
It is hereby certi?ed that errors appear in the printed speci?cation of the above
numbered patent requiring correction as follows: Column 3, line 39, for “rdice"?l’~i_read<11i*'
radical; column 6,.11ines 21 to 25 inclusive, Example 4, for that portion of the formula“ ‘
reading
11:
HO reed $0
and that the said Letters Patent should be read with these corrections therein that
the same may conform to the record of the case in the Patent O?ice.
-
Signed and sealed this 24th day of December; A. D. 1946.
[M]
LESLIE FRAZER,
First Assistant Commissioner of Patents.
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