Us 4230618

United States Patent [191
[11]
4,230,618
Gauthier
[45]
Oct. 28, 1980
[54] AZO DYESTUFFS CONTAINING AN AMINO

OR ACYLATED AMINO NAPHTHOL
DI-SULFONIC ACID RADICAL AND AT
LEAST ONE REACTIVE PHOSPHORIC OR
PHOSPHONIC ACID GROUP
_
Inventor:
Donald R. Gauthier, Somerset, Mass.
[73] Assignee:
ICI United States, Inc., Wilmington,
[75]
[57]
ABSTRACT
Azo dyestuffs of the formula:

OH
R6
R2
R3
Del.
[21] Appl. No.: 837,625

[22] Filed:
Sep. 27, 1977
[51]
wherein A is a phenylene or naphthalene nucleus con~
Int. Cl.2 .................... .. C09B 62/82; D06P l/ 384;
DO6P 3/66
[52]
US. Cl. .................................. .. 260/187; 260/ 188;
260/ 190; 260/191; 260/194; 260/ 198; 260/199;

260/205; 260/206; 260/208
[58]
Field of Search ............. .. 260/ 187, 191, 190, 194,
3,947,435
of 2 to 8 carbon atoms, at least two of R1R6 being
References Cited
SO3H and at least one being NHQ, provided that

when the dyestuff is monoazo, then Q is an acyl group
of 3 to 8 carbons and when the dyestuff is clisazo, Q is
U.S. PATENT DOCUMENTS
hydrogen or an acyl group of 2 to 8 carbon atoms. The
260/198, 199, 188
[56]
taining at least one phosphoric or phosphonic acid

group; R1 and R2 are hydrogen or SO3H; and R3-R6
are hydrogen, SO3H, or NR7Q wherein R7 is hydro
gen or lower alkyl and Q is hydrogen or an acyl group
3/1976
Pechmeze et al. ................. .. 260/ 190
FOREIGN PATENT DOCUMENTS

2324809 12/1973 Fed. Rep. of Germany ......... .. 260/191
2618670 11/1976 Fed. Rep. of Germany ......... .. 260/ 191
dyestuff may be used to reactively dye cellulosic materi

als, e.g., cotton or cotton/polyester blends. The dye
stuffs are particularly useful in dyeing mixed fabrics of
cellulose and synthetics together with disperse dyes

from a single bath.
Primary Examiner-Floyd D. Higel

Attorney, Agent, or FirmCushman, Darby & Cushman
13 Claims, No Drawings
4,230,618
3 to 8 carbons and when the dyestuff is disazo, Q is

AZO DYESTUFFS CONTAINING AN AMINO OR
ACYLATED AMINO NAPHTHOL DI-SULFONIC
ACID RADICAL AND AT LEAST ONE REACTIVE
PHOSPHORIC OR PHOSPHONIC ACID GROUP
hydrogen or an acyl group of 2 to 8 carbon atoms.
Preferably, A is a phenyl or naphthyl group which,

apart from the phosphoric or phosphonic acid group or
groups, is either unsubstituted or substituted with, for
example, one or more halogen, alkyl, alkoxy, nitro,
cyano, acetylamino, sulfonic acid or carboxylic acid
BACKGROUND OF THE INVENTION
groups. Typical halogen values include chlorine and

bromine
while the alkyl and alkoxy substituents will
amino or acylated amino naphthol di-sulfonic acid radi 0
usually contain up to 6 carbon atoms, although longer
cal and at least one phosphoric or phosphonic acid
chain lengths may also be used.
group and which are suitable for reactively dyeing
It is also contemplated that the dyestuffs of the pres
cellulosic materials, e.g., cotton and cotton/polyester
ent invention include those wherein A stands for a radi
blends.
cal of azo benzene, azonaphthalene or phenylazonaph
A process for reactively dyeing a hydroxy-sub
This invention relates to dyestuffs which contain an
stituted organic polymer, such as cellulose, is described

by Stanford Research Institute in German Pat. No.
2,324,809, published Dec. 20, 1973. The process so de
scribed involves treating the cellulosic material with a
5 thalene series which, if desired, may be substituted as
noted.
The dyestuffs of the invention may be prepared using

conventional methods for preparing azo dyestuffs in
volving the preparation of a diazonium salt from a pri
dye containing a phosphonic acid group in the presence

of a carbodiimide, e.g., dicyandiamide, in such a way
that the dye is ?xed to the cellulose in the form of a
cellulose ester of phosphonic acid. The process can be
illustrated by the following reaction:
mary amine followed by coupling. See, for example,

Vogel Practical Organic Chemistry (1951) or Ger
man Pat. No. 2,324,809. Thus, an aromatic primary
amine containing at least one phosphoric or phosphonic
acid group may be converted into its diazonium salt
25 followed by coupling the diazonium salt with an acy
lated amino naphthol mono-sulfonic acid which has a
removable hydrogen attached to a carbon atom of the
naphthalene ring. The diazonium salt of the aromatic

primary amine may be prepared in any known way, e. g.,
by reacting the parent amine with sodium nitrite in the
wherein R is a chromophore group, ROH represents

cellulose, CDI is the carbodiimide and CDIM is a resi
due or side product of carbodiimide. A similar mecha
presence of HCL at low temperatures (such as 0~l5
C.). Coupling of this salt can be carried out by, for

example, mixing an aqueous solution of the salt with the
naphthol disulfonic acid component at 0l5 C. The
nism applies for dyestuffs containing phosphoric acid

groups. Cellulose materials so dyed exhibit good color
stability when subsequently treated with alkaline deter
gents.
resulting dyestuff can be recovered by precipitating the

same and ?ltering or by using other conventional sepa
ration techniques.
It is a primary object of the present invention to pro

The new dyes can be isolated as solid products by
vide new ?ber reactive dyestuffs which are especially
conventional means such as spray-drying or by precipi
suitable for coloring cellulose-based textile materials in 40 tation and ?ltration. They are preferably isolated in the
the manner described in the above-mentioned German
acid form or in the form of an ammonium salt or partly

in one of these forms and partly as an alkali metal, e. g.
patent.
Still another object of this invention is to provide
dyestuffs which may be employed in acid, neutral or
alkaline baths to color cellulose materials.
These and other objects of the present invention will
Li, Na or K salt. These salts can be obtained by adding

a halide e.g. the chloride of the desired alkali metal or
45 ammonium halide or ammonia to the completed reac
tion mixture before isolation. Alternatively by addition
be apparent from the following description.
of an alkanolamine e. g. diethanolamine to the com
pleted reaction mixture, a highly soluble form of the
DESCRIPTION OF THE INVENTION

The azo dyestuffs of the invention may be illustrated
dyestuff is obtained which can be used as a total liquor
for the dyeing in printing process.

Aromatic primary amines containing a phosphonic
by the formula:
OH
acid group which may be converted to diazonium salts

for use in preparing the dyestuffs of the invention may
R6
be described by the following formula:

55
wherein A is a phenylene or naphthalene nucleus con
taining at least one phosphoric or phosphonic acid

group; R1 and R2 are hydrogen or SO3H; and R3-R6
are hydrogen, SO3H, or NR7Q wherein R7 is hydro
gen or lower alkyl and Q is hydrogen or an acyl group
of 2 to 8 carbon atoms, at least two of R14, being
SO3H and at least one being NQ, provided that

when the dyestuff is monazo, then Q is an acyl group of
wherein:
R is a phenyl or naphthyl radical, unsubstituted or
substituted:
R1 is hydrogen or alkyl of l to 4 carbon atoms; and
n is O or an integer of l to 4, but preferably 0.
If substituted, the phenyl or naphthyl radical may

contain at least one halogen (e.g. bromine or chlorine)
nitro, alkyl of l to 4 carbon atoms, alkoxy of l to 4

carbon atoms, or phenoxy substituent.
4,230,618
Typical examples of phosphonic acid amines which

can be diazotized for use herein include the following:
meta-aminophenyl phosphonic acid;

para-aminophenyl phosphonic acid;
meta-aminobenzyl phosphonic acid;
para-aminobenzyl phosphonic acid;
2,4,6-tribromo-4-aminophenyl phosphonic acid;

3-nitro-4-aminophenyl phosphonic acid;
3-amino-4-chlorophenyl phosphonic acid;
3-amino-4-methylphenyl phosphonic acid;
3-amino-4-phenoxyphenyl phosphonic acid;
R2
3-amino-4-hydroxyphenyl phosphonic acid;

3-amino-4-orthochlorophenoxyphenyl
phosphonic 15
R2
R3
acid;
3-amino-4-bromophenyl phosphonic acid;

3-amino-4-methoxyphenyl phosphonic acid;
2-hydroxy-5-aminobenzyl phosphonic acid;
4-amino-l-naphthyl phosphonic acid;
4-amino-8-methyl-l-naphthyl phosphonic acid; and
4-amino-3-chloro-l-naphthyl phosphonic acid.
Aromatic primary amines containing a phosphoric
wherein:
n is O or an integer from 1 to 4;
R2 is hydrogen or halogen;
20
R3 is hydrogen or nitro; and

R4 is hydrogen, halogen, lower alkyl of 1 to 4 car
bons, methoxy, phenoxy or RNH where R is
alkyl of 1 to 4 carbon atoms, hydroxy alkyl of 1 to
4 carbon atoms having a terminal sulfonic acid
25
acid group which may be converted to diazonium salts

for use in preparing the dyestuffs of the invention may
group; provided further that A is coupled to the

naphthalene coupling component by a diazo link
age at R3 or R4.
If desired, any of the above amines may be coupled

with such amines as p-xylidine, Peri acid, cresidine at a
be described by the following formula:
pH of about 3 to 5. Also, one may use either aniline or
meta-toluidine by way of the methane sulfonic acids.
The resulting amino-monazo compounds may then be

diazotized and coupled with the desired coupling com
ponent. Thus, suitable amino-monazo compounds in
35 clude:
wherein:
R" is a phenyl or naphthyl radical, unsubstituted or
substituted; and
n is O or a whole number from 1 to 4, but preferably

0.
When substituted the phenyl or naphthyl radical may 40
contain one or more halogen (e. g. bromine or chlorine),
nitro, alkyl of l to 4 carbon atoms, alkoxy of l to 4
(Hob?
ll
carbon atoms or phenoxy substituents.
OCH3
Typical examples of phosphoric acid amines which 45

can be diazotized for use herein include the following:
meta-aminophenyl phosphoric acid;

para-aminophenyl phosphoric acid;
meta-aminobenzyl phosphoric acid;
para-aminobenzyl phosphoric acid;
2,4,6-tribromo-4-aminophenyl phosphoric acid;

3-nitro-4-aminophenyl phosphoric acid;
3-amino-4-chlorophenyl phosphoric acid;
3-amino-4-methylphenyl phosphoric acid;
3-amino-4-phenoxyphenyl phosphoric acid;
3-amino-4-hydroxyphenyl phosphoric acid;
3-amino-4-orthochlorophenoxyphenyl phosphoric acid;
3-amino-4-brornophenyl phosphoric acid;
3-amino-4-methoxyphenyl phosphoric acid;
Z-hydroxy-S-aminobenzyl phosphoric acid;
4-amino-l-naphthyl phosphoric acid;
4-amino-8-methyl-l-naphthyl phosphoric acid; and
4-amino-3-chloro-l-naphthyl phosphoric acid.
In a most preferred embodiment, A may be repre
sented by the formulae:
50
(?oh?
CH3
R.
55
(Ploh?
NHZ
CH3
where R' is hydrogen
60
or methyl;
N=N
NH;
; and
65
(H0)2?
s03
4,230,618
The invention is illustrated but not limited by the
continued
following examples wherein parts are by weight unless

otherwise stated.
EXAMPLE 1
An aqueous solution of the diazonium salt of meta

(HO)2P
phosphanilic acid and lamino-8-naphthol-2,4-disul
fonic acid (Chicago acid) was maintained at a pH of

about 7 to 8, and a temperature of 05 C. for coupling.
where Z = H or CH3
R" = OCH3, CH3 or H.
Upon completion of the coupling reaction, the solution
Typically, the naphthol component used to make the

present dyestuffs is one of the following:
was heated to 50 C. and then salted 10% w/v of ammo

nium chloride. The solution was then cooled to 20 C.
and ?ltered. A reactive red disazo dyestuff was ob
8-amino-l-naphthol-3,6-disulfonic acid (H-acid);

S-amino-l-naphthol-5,7-disulfonic acid (Chicago acid);
6-amino-l-naphthol-3,8-disulfonic acid (l-sulfo-J-acid);
15
tained in 70.5% yield having the formula:
OH
8-amino-l-naphthol-3,5-disulfonic acid;
8-amino-1-naphthol-4,6-disulfonic acid (B-acid);
6-amino-l-naphthol-3,5-disulfonic acid;
NH;
N=N
SO3H
lamino-6-naphthol-3,8-disulfonic acid; and
7-amino-1-naphthol-3,6-disulfonic acid,
wherein the amino group has been acylated to NHQ
wherein Q contains 2 to 8 carbon atoms, and is prefera 25
bly an alkyl group containing 2 to 4 carbons or an aryl
(H0)2P
ll
50;}!
EXAMPLE 2
group, e. g.
3-aminobenzene phosphonic acid was coupled with

cresidine and the resulting monazo amine treated to
30
form the diazonium salt. The resulting diazonium salt

was then coupled with Chicago acid at a pH of 7-8, and
a temperature of 0-5 C. After salting the coupling
mixture 30% W/v ammonium chloride, no precipitate
The lower alkyl amino counterparts of the naphthols
was observed. Acidi?cation with hydrochloric acid to a
referred to above may also be used to give acylated

derivatives wherein the amino hydrogen in NHQ is
uct was isolated by the addition of 1 liter of ethanol and
pH of 1.5 produced only a slight precipitate. The prod
replaced by lower alkyl.
?ltering at 10 C. The product yield was 70.3% of the

ory of a reactive blue dyestuff having the formula:
The new dyestuffs are soluble in water owing to the
presence of phosphoric or phosphonic acid groups. In

many cases, there may also be sulfonic acid groups
present to increase their solubility. They can be used, in
general, for the coloration of textile materials which can
be dyed by dyes solubilized by anionic groups, e.g.,

natural and synthetic polyamide materials, e.g., wool,
CH3
N=N
45
silk, polyhexamethylene adipamide and polycaproi

mide, but more especially, natural or regenerated cellu
lose textile materials, e.g., cotton, linen and viscose
rayon; in the case of cellulose textile materials, they are
preferably ?xed on the ?ber by baking at a temperature 50
of from 95205 C. in the presence of a carbodiimide,
e. g., cyanamide, dicyandiamide, as described in German
Pat. No. 2,324,809.
(noh?
OH NH;
N=N
00113
so 3H
$03},
EXAMPLE 3
The diazonium salt of the product resulting from the
coupling of 3-aminobenzene phosphonic acid and cresi
dine was coupled with acetyl-H-acid in an aqueous

solution having a pH of 7-8 and a temperature of O-5
The new dyestuffs are particularly suitable for appli
C. The coupling mixture was salted with ammonium
55
cation to mixed fabrics of cellulose and synthetics, e.g.,
chloride 10% w/v and isolated at a temperature of 10
polyester materials, together with disperse dyes from a
C.
The mixture was ?ltered and 94.2% yield of theory
single dyebath or printing paste. In this respect, the new
of a reactive violet diazo dyestuff was obtained having
dyestuffs show an advantage over most conventional
reactive dyes which are normally applied in the pres 60 the formula:
ence of alkaline ?xing agents. The latter lead to ?occu
lation of the majority of disperse dyes, so that the range

of the latter which can be applied together with con
ventional reactive dyes in single dyebaths or printing

pastes is very limited. In contrast, the acid ?xing condi 65
tions used for the new dyes have no effect on disperse
dyes, and the two classes of dyes can be used together
without dif?culty.
H035
4,230,618
7.
adding hydrochloric acid until the pH of the reaction is
EXAMPLE 4
0.5 the dyestuffs described in any of the preceding Ex

amples may be obtainedin their free acid form.
Para-xylidine was coupled with 3-aminobenzene

phosphonic acid and the resulting monazo amine re
EXAMPLE 6
acted to form the diazonium salt which was then cou

pled with acetyl-H-acid. Coupling was carried out at a
pH of 7-8 and a temperature of 0-5 C., after which the
By omitting the addition of ammonium chloride in

the procedure of Example 4 and including the step of
adding hydrochloric acid and heating to 50-70 C., the

product was salted with 10% w/v ammonium chloride.
dyestuff of Example 4 may be isolated in its free acid
The product was ?ltered at 5 C., yielding 70.7% yield
of theory of a reactive red dyestuff having the formula: 10 deacylated form. If desired, the deacylated free acid
may be converted to the ammonium salt by dissolving
with ammonia to pH 7-8, followed by salting out with
ammonium chloride and filtration.
NHCCHg
CH3
on
ll
0
N=N
(?oh?
EXAMPLES 7-51
15
Monazo dyestuffs are prepared by diazotizing an
H035
CH3
aromatic phosphonic or phosphoric acid amine (I) and

coupling at O-5 C. and pH 6-8 into an aminonaphthol
SO3H
disulfonic acid (II) previously N-acylated with an acyl
20 anhydride or halide (III) as outlined in Table A below.

EXAMPLE 5
By omitting the addition of ammonium chloride in

the procedure of Example 1 and replacing it by step of
TABLE A
EXAMPLE
7
8
9
10
H
I 12
13
14
15
l6
17
18
19
20
2l
22
23
24
25
26
27
II
S-Aminophenyl-phosphonic
l-Amino-8-naphthol-3,6-
acid
disulfonic acid
3-Aminophenyl-phosphonic
acid
disulfonic acid
acid
disulfonic acid
4-Aminobenzyl-phosphonic
acid
disulfonic acid
3-Amino-4-methyIphenyl-Zphosphonic acid
l-Amino-8-naphthol-3,6disulfonic acid ,
8-Amino-l-naphthol-3,5-
acid
acid
acid
disulfonic 'acid
8-Amino-l-naphthol-3,5disulfonic acid
acid
8-Amino-l-naphthol-3,S-
acid
acid
disulfonic acid
7-Amino-l-naphthol-3,6-.
acid
disulfonic acid
disulfonic acid .
acid
J-Aminophenyl-phosphonic
acid
disulfonic acid
acid
disulfonic acidv
acid
disulfonic acid
acid
disulfonic acid
Butyric anhydride
"
Propionic anhydride
"
"
"
"
Butyric anhydride
"
Propionic anhydride
"
"
"
"
Orange
Red
Butyric anhydride
Red
Propionic anhydride
"
"
"
Butyric anhydride
"
Propionic anhydride
"
Butyric anhydride
"
"
"
Propionic anhydride
"
l-Amino-6naphthol-3,8
acid
disulfonic acid
"
v
8-Amino-l-naphthol-4,6~ .
acid
disulfonic acid
28
acid
disulfonic acid
29
3-Amin0-l-napl'lthol74,'6-:
acid
disulfonic acid
30
31
acid
32
acid
3-Amino-4-methylphenyl-2~
disulfonic acid
'
'
Red
"
acid
COLOR
'
acid
Ill
Propionic anhydride
"
"
Butyric anhydride
"
"
"
8-Amino-l-naphthol-4,6--
Propionic anhydride'
"
disulfonic acid .
8-Amino-l-naphthol-4,6- -
"
"
"
"
4,230,618
10
TABLE A-continued
EXAMPLE
33
34
II
III
COLOR
"
Orange
6-Amino~l-naphthol-3,8-
Butyric anhydride
"
acid
disulfonic acid
phosphonic acid
disulfonic acid
acid
35
"
"
36
acid
disulfonic acid
Propionic anhydride
"
acid
disulfonic acid
6~Amino-l-naphthol-3,8-
"
"
acid
disulfonic acid
"
"
37
38
3-Amino-4-methylphenyl-2-
phosphonic acid
disulfonic acid
39
acid
l-Amino-8naphthol-2,4disulfonic acid
"
Red
40
l'Amino-8-naphthol-2A-
Butyric anhydride
"
acid
disulfonic acid
Propionic anhydride
Butyric anhydride
"
41
42
l-Amino-Smaphthol-ZA-
acid
disulfonic acid
l-Amino-S-naphthol-ZA-
acid
disulfonic acid
43
l-Amino8~naphthol-2,4-
"
"
44-
acid
Propionic anhydride
"
acid
disulfonic acid
l-Amino-8naphthol-2,4disulfonicacid
"
Butyric anhydride
"
"
"
45
46
47
S-Aminophenyl-phosphonic
6~Aminolnaphthol~3,S
acid
disulfonic acid
B-Aminophenyl-phosphonic
?-Amino-l-naphtholdj-
acid
disulfonic acid
6~Amino-l-naphthol-3,5~
acid
disulfonic acid
48
4-Aminobenzybphosphonic
acid
6Amino-l-naphthol-3,5*
disulfonic acid
Propionic anhydride
"
49
4-Aminophenyl~phosphonic
6Amino-l-naphthol-3,5-
"
acid
disulfonic acid
50
Butyric anhydride
"
acid
disulfonic acid
"
"
51
3-Amino-4~mcthylphenyl-2-
-Amino- l-naphthol-B,5-
phosphonic acid
disulfonic acid
The dyestuffs of examples 7-51 may be converted to

amine (I) and coupling into aromatic amines (IV) capa
and isolated as the deacylated free acids by heating with
ble of undergoing coupling at 0l0 C. and pH 4-5
hydrochloric acid to pH 0.5-2.0 at 5070 C. after
such as p-xylidine, cresidine and Peri acid or aniline via
coupling is complete, followed by cooling to 1020 C.
the omega methane sulfonic acid as outlined in Table B
and ?ltering. If desired, the ammonium salts of the 40 below. The resulting Monazo compound may be iso
deacylated dyestuffs may be obtained by neutralizing
lated by salting or used directly as a diazo component
by diazotization at 020 C. and coupling at pH 6-9
the hydrolyzed coupling mass to pH 7-8 with ammonia,
followed by salting with ammonium chloride and ?lter
into an aminonaphthol disulfonic acid (II) previously
N-acylated with an acyl anhydride (III). The dyestuffs
mg.
45
EXAMPLES 52-130
may be isolated by salting with ammonium chloride at

020 C. and ?ltering.
Acylated Disazo dyestuffs as in Example 4 may be

prepared by diazotizing an aromatic phosphonic acid
TABLE B
EXAMPLE
III
COLOR
Cresidine
l-Amino8-naphthol-
Propionic Anhydride
Bluish
53
phosphonic acid
3-Aminophenylphosphonic acid
m-Toluidine
3,6-disulfonic acid
l-Amino-S-naphthol3,6-disulfonic acid
Acetic anhydride
Red
Red
54
3-Aminophenyl~
Peri Acid
l-Amino-8-naphthol-
"
Blue
"
"
"
Red
"
"
"
"
"
"
Propionic anhydride
"
Acetic Anhydride
"
"
Violet
52
3-Aminophenyl
IV
phosphonic acid
55
3-Aminophenyl-
3,6-disulf0nic acid
l,7~Cleaves Acid
phosphonic acid
56
3-Aminophenyl3-Aminophenyl-
o-Anisidine
4-Aminobenzyl-
p-Xylidine
3-Aminophenyl-
"
60
3-Aminophenyl-
m-Toluidine
"
3-Aminophenyl-
6-Amino~l-naphthol-
3,8-disulfonic acid
Cresidine
phosphonic acid
62
?-Amino-l-naphthol-
3,8-disulfonic acid
phosphonic acid
3-Aminophenyl-
l-Amino-8~naphthol-
3,6-disulfonic acid
phosphonic acid
61
l-Amino-8-naphthol-
3,6-disulfonic acid
phosphonic acid
59
l4Amino~8-naphth0l-
3,6-disulfonic acid
phosphonic acid
58
l~Amino-B-naphthol~
3,6-disulf0nic acid
phosphonic acid
57
II
?Amino-l-naphthol-
3,8-disulfonic acid
Peri acid
6-Aminoal-naphthol-
'4,230,6 l 8
'12
TABLE B-continued
EXAMPLE
IV
phosphonic acid
63
3-Amin0phenyl
1,6-Cleaves Acid
o-Anisidine
6-Amino-l-naphthol
phosphonic acid
64
3-Aminophenyl
phosphonic acid
65
66
4-Aminophenyl
Peri acid
69
3,8-disulfonic acid
4-Aminophenyl
?-Amino-l-naphthol
1,6-Cleaves Acid
71
4-Aminophenyl
p-Xylidine
6-Amino-l-naphthol
4-Aminophenyl
o-Toluidine
3,8-disulfonic acid
4-Aminobenzyl
6-Amino-l-naphthol
Peri Acid
?-Amino-l-naphthol
1,6-Cleaves acid
6Amin0-l-naphthol
3,8-disulfonic acid
6-Amino~l-naphthol
73
phosphonic acid
4-Aminobenzyl
phosphonic acid
o-Anisidine
6-Amin0-1-naphthol
74
4-Aminobenzyl
p-Xylidine
6-Amino-l-naphthol
75
4-Aminobenzyl
o-Toluidine
G-Amino-l-naphthol
Cresidine
S-Amino-l-naphthol
3,8-disulfonic acid
3,8-disulfonic acid
phosphonic acid
3,8-disulfonic acid
phosphonic acid
3,8-disulfonic acid
S-Aminophenyl
phosphonic acid
3-Aminophenyl
Peri Acid
m-Toluidine
3-Aminophenyl
o-Anisidine
3-Aminophenyl
1,6-Clcaves acid
o-Toluidine
Aniline
3-Aminophenyl~
p-Xylidine
85
4-Aminobenzyl
86
4-Aminobenzyl
Peri Acid
4-Aminobenzyl
4~Aminobenzyl- .
89
phosphonic acid
4-Aminobenzyl
phosphonic acid
90
3-Aminophenyl
3-Aminophenyl
3-Aminophenyl
I Aniline
m-Toluidine
Peri Acid
7-Amino-l-naphthol
3,6-disult'onic acid
1,7-Cleaves acid
7-Amino-l-naphthol
7-Amino-1-naphthol
3,6-disulfonic acid
7-Amino-1-naphthol
o-Anisidine
7-Amino-l-naphth0l
3,6-disulfonic acid
m-Toluidine
Peri Acid
p-Xylidine
3-Aminophenyl
phosphonic acid
3,6-disulfonic acid
_ Red
7-Amino-1-naphthol
Blue
7-Amino-l-naphthol
Violet
3,6-disulfonic acid
m-Toluidine
phosphonic acid
. 102
7-Amino-l-naphthol
Blue
Black
Bluish
3,6-disulfonic acid
phosphonic acid
3-Aminophenyl
7-Amino-l-naphthol
3,6-disulfonic acid
phosphonic acid
101
Red
Violet
Bluish
Red
Violet
3,6-disulfonic acid
1,6-Cleaves acid
phosphonic acid
4~Aminobenzyl
o-Toluidine
phosphonic acid
100
7-Amino-1-naphthol
3,6-disulionic acid
phosphonic acid
4-Aminobenzyl
Blue
Black
Blue
Black
Blue
3,6-disulfonic acid
phosphonic acid
99
Violet
3,6-disulfonic acid
Aniline
4-Aminobenzy1
S-Amino-l-naphthol
7-Amino-I-naphthol
phosphonic acid
98
BlueViolet
Red
S-Amino-l-naphthol
p-Xylidine
phosphonic acid
3-Aminophenyl
4-Aminophenyl
8-Amino-l~naphthol
3,5~disulfonic acid
94
97
B-Amino-l-naphthol
Bluish
Red
Blue
3,5-disulfonic acid
p-Xylidine
4-Aminophenyl
3,5-disulfonic acid
B-Aminophcnyl
96
8-Amino-l-naphthol
3,5-disulfonic acid
1,6-Cleaves acid
93
4-Aminophenyl
Blue
p-Xylidine
phosphonic acid
95
S-Amino-lmaphthol
3,5-disulfonic acid - _
phosphonic acid
92
Red-Violet
S-Amino-l-naphthol
phosphonic acid
91
8-Amino-l-naphthol
o-Anisidine
phosphonic acid
88
Violet
3,5-disulfonic acid
phosphonic acid
87
8-Amin0-1-naphthol
3,5-disulfonic acid
phosphonic acid
phosphonic acid
Red
Blue
B-Amino-l-naphthol
3,5-disult'onic acid
phosphonic acid
4-Aminobenzyl
Bluish
3,5-disulfonic acid
3-Aminophenyl
phosphonic acid
84.
B-Amino-l-naphthol
3,5-disulfonic acid
I
phosphonic acid
83
Violet
3,5-disulfonic acid
phosphonic acid
82
8-Amino-l-naphtl1ol
3,5-disulfonic acid
phosphonic acid
3-Aminopheny1
B-Amino-l-naphthol
3,5-disulfonic acid
3-Aminophenyl
phosphonic acid
SI
Bluish
Red
Blue
3,5-disulfonic acid
phosphonic acid
80
Violet
3,8-disulfonic acid
m-Toluidine
79
Red
3,8-disulfonic acid
4-Aminobcnzyl
phosphonic acid
4-Aminobcnzyl
4-Aminobenzyl
78
Red Violet
6-Amino-1-naphthol
phosphonic acid
72
77
1:
3,8-disulfonic acid
phosphonic acid
76
Violet
3,8-disulfonic acid
phosphonic acid
7O
G-Amino-l-naphthol
phosphonic acid
phosphonic acid
68
Red Violet
3,8-disulfonic acid
phosphonic acid
67
COLOR
II
3,8-disulfonic acid
6-Amino- l-naphthol
3,8-disulfonic acid
Aniline
S-Amino- l-naphthol
4,6-disulfonic acid
8-Amino~l-naphthol
4,6-disulfonic acid
Red
u
4,230,618
13
14
TABLE B-continued
EXAMPLE
103
3-Aminophenyl-
IV
Peri Acid
phosphonic acid
104
3-Aminophenyl3-Aminophenyl-
1,7-Cleaves acid
3-Aminophenyl-
o-Toluidine
3-Arninophenyl-
Cresidine
3-Aminophenyl-
p~Xylidine
4-Aminobenzyl-
110
4~Aminobenzyl-
111
4aAminobenzyl~
o-Anisidine
"
1,6-Cleaves acid
1 l4
4~Aminobenzyl-
4-Aminobenzyl-
m-Toluidine
Aniline
3-Aminophenyl-
3-Aminophenyl-
Peri Acid
3-Aminophenyl-
o-Anisidine
S-Aminophenyl-
Aniline
3-Aminophenyl-
Bluish
B-Amino-l-naphthol-
"
Bluish
"
Blue
Red
8-Amino-l-naphthol-
Red
8~Amino-l-naphthol-
Blue
8-Amino-1-naphthol-
Violet
"
Blue
S-Amino- l-naphthol-
"
Red
S-AminoJ-naphthol-
S-Amino- l-naphthol-
"
"
"
1-Amino-8-naphthol~
Violet
l-Arnino-B-naphthol-
"
Blue
l-Amino-S-naphthol-
"
Violet
1-Amino-8-naphthol-
"
Bluish-Red
"
Blue
"
Violet
2,4-disulfonic acid
Cresidine
phosphonic acid
121
8-Amino-l-naphthol-
2,4-disulfonic acid
phosphonic acid
120
Violet
2,4-disulfonic acid
phosphonic acid
119
"
2,4-disulfonic acid
phosphonic acid
1 18
S-Amino-l-naphthol-
4,6-disulfonic acid
"
phosphonic acid
117
Blue
4,6-disulfonic acid
o-Anisidine
phosphonic acid
3-Aminophenyl-
4,6-disulfonic acid
phosphonic acid
116
S-AminoJ-naphthol-
4,6-disulfonic acid
phosphonic acid
1 l5
Red
4,6-disulfonic acid
phosphonic acid
4-Aminobenzyl-
"
4,6-disulfonic acid
Cresidine
phosphonic acid
113
8Amin0-1-naphthol-
4,6-disulfonic acid
Peri Acid
phosphonic acid
4-Aminobenzyl-
Blue
Violet
4,6-disulfonic acid
phosphonic acid
112
"
4,6-disulfonic acid
phosphonic acid
109
S-Amino-l-naphthol-
4,6-disulfonic acid
phosphonic acid
108
Blue
4,6-disulfonic acid
phosphonic acid
107
COLOR
4,6-disulfonic acid
phosphonic acid
106
III
4,6-disulfonic acid
phosphonic acid
105
11
S-Amino-lmaphthol-
l-Amino-8-naphthol-
2,4-disulfonic acid
m-Toluidine
phosphonic acid
1-Amino-8~naphthol-
2,4~disulf0nic acid
122
3-Aminophenyl-
1,6-Cleaves acid
l-Amino-8-naphthol-
"
Blue
123
phosphonic acid
3-Aminophenylphosphonic acid
p-Xylidine
2,4-disulfonic acid
l-Amino-8-naphthol2,4disulfonic acid
"
Violet
Violet
124
4-Aminobenzyl-
Peri acid
l-Amino-S-naphthol-
Blue
"
Red-Violet
"
Blue
"
Bluish
"
Blue
"
Violet
"
Phosphonic acid
125
4~Aminobenzyl-
2,4-disulfonic acid
m-Toluidine
Phosphonic acid
126
4-Aminobenzyl-
Cresidine
Phosphonic acid
127
4-Aminobenzyl-
4-Aminophenyl-
129
4<Aminophenyl-
Aniline
Peri acid
l-Amino-S-naphthol-
Red
2,4-disulfonic acid
m-Toluidine
phosphonic acid
4-Aminophenyl-
l-Amino-B-naphthol-
2,4~disulfonic acid
phosphonic acid
130
l-Amino-S-naphthol-
2,4-disulfonic acid
phosphonic acid
128
l-Amino-S-naphthol-
2,4<disulfonic acid
1-Amino-8-naphthol-
2,4-disulfonic acid
p-Xylidine
phosphonic acid
l-Amino-S-naphthol-
2,4-disulfonic acid
The dyestuffs illustrated by examples 52-130 may be

converted to the free acid deacylated form by hydroly-
OH
sis with hydrochloric acid at pH 0.5-2.0 at 5070 C.
after completion of coupling, followed by cooling to

0~20 C. and ?ltering. The deacylated dyestuffs may be 55
R"
A N_N
obtained as ammonium salts by neutralizing the cou-
R5
R1
pling after deacylation with ammonia, followed by salt-
R4
R2
R3
ing with ammonium chloride and ?ltration.

It will be appreciated that various modi?cations may
wherein A is a phenylene or naphthalene radical con
be made in the invention described herein without de- 60 taining at least one phosphonic or phosphoric acid
parting from the scope thereof. It is intended herein that
group having the formula:
reference to the dyestuffs and formulae refer to both the
free acid and salt form. Furthermore, the invention may
comprise, consist, or consist essentially of the hereinbe
fore noted substituents and steps. Hence, the scope of 65
the invention is de?ned in the following claims wherein:
I claim:
R is a phenyl or naphthyl radical, unsubstituted or
1. An azo dyestuff of the formula:
substituted;
4,230,618
15
16
n is 0 or an integer of 1 to 4;
R1 and R2 are hydrogen or SO3H; and R3-R6 are
hydrogen, --SO3H, or NR7Q wherein R7 is hydro

gen or lower alkyl and Q is hydrogen or an acyl
N=N
NHZ;
group of 2 to 8 carbon atoms, at least two of R1R6 Lll
being -SO3H and at least one being -NHQ, pro
vided that when the dyestuff is monazo, then Q is a
(Hoh?
carbonyl group of 3 to 8 carbons and when the
dyestuff is disazo, Q is hydrogen or a carbonyl

group of 2 to 8 carbon atoms.
OCH3
1 .10
2. An azo dyestuff according to claim 1 wherein A is

a phenyl radical including at least one phosphonic acid
group; and one of R1-R6 is
N=N
15
(HO)2P
NHCCH3.
NR2
CH3
9)
II
R...
3. A monazo dyestuff according to claim 1 wherein Q

is a carbonyl group containing 3 to 8 carbon atoms.
20
I
derived from a diazotized amine selected from the
group consisting of
_
N_N
(Hon?
'
CH3
ll
meta-aminophenyl phosphonic acid;
para-aminophenyl phosphonic acid;
NH2
h d
25
where: msthy?, rogen
meta-aminobenzyl phosphonic acid;
'
para-aminobenzyl phosphonic acid;

2,4,6-tribromo-4-aminophenyl phosphonic acid;
N=N
N142
3-nitro-4-aminophenyl phosphonic acid;
. and
3-amino-4-chlorophenyl phosphonic acid;
30
(Hoh?
503B
3-amino-4-phenoxyphenyl phosphonic acid;

3-amino-4-hydroxyphenyl phosphonic acid;
3-amino-4-orthochlorophenoxyphenyl phosphonic
acid;
35
N=N
NHz
3-amino-4-methoxyphenyl phosphonic acid;

Z-hydroxy-S-aminobenzyl phosphonic acid;
40
(Hoh?
4-amino-l-naphthyl phosphonic acid;
4-amino-8-methyl-l-naphthyl phosphonic acid; and
Where Z = H or CH3
4-amino-3-chloro-l-naphthyl phosphonic acid.
R" = OCH" CH3 or H

derived from a diazotized amine selected from the 45
group consisting of
7. An azo dyestuff according to claim 1, wherein A

has the formula:
meta-aminophenyl phosphoric acid;

para-aminophenyl phosphoric acid;
meta-aminobenzyl phosphoric acid;

para-aminobenzyl phosphoric acid;
50
2,4,6-tribromo-4-aminophenyl phosphoric acid;

3-nitro-4-aminophenyl phosphoric acid;
3-amino-4-chlorophenyl phosphoric acid;
3-amino-4-phenoxyphenyl phosphoric acid;

3-amino-4-hydroxyphenyl phosphoric acid; '
3-amino-4-orthochlorophenoxyphenyl
acid;
RZ'
R3
55
.
phosphoric
"
(HO)2P(CH3),,
3-amino-4-bromophenyl phosphoric acid;

3-amino-4-methoxyphenyl phosphoric acid;
60
3-amino-4-methylphenyl phosphoric acid; '
2-hydroxy-5-aminobenzyl phosphoric acid;
wherein:
4-amino-l-naphthyl phosphoric acid;
H is as de?ned in Claim 17;
4-amino-8-methyl-l-naphthyl phosphoric acid; and

4~amino-3-chloro-l-naphthyl phosphoric acid.
derived from a diazotized amine selected from the
group consisting of:
R1 is hydrogen or halogen;
65
R3 is hydrogen or nitro; and

R4 is hydrogen, halogen, lower alkyl of l to 4 car
bons, methoxy, phenoxy or R'NH where R is
alkyl of l to 4 carbon atoms, or hydroxyalkyl of l
4,230,618
17
18
to 4 carbon atoms having a terminal sulfonic acid
group.
CH,
CH N??c?l
8. A disazo dyestuff according to claim 1 wherein A

is phenylazonaphthalene or azobenzene and Q is hydro- 5
gen or a carbonyl group containing from 2 to 8 carbon
atoms.
N=N
N
CH
(Ho) P
2
1%
N
H035
son:
9. A dyestuff according to claim 1 having the for

mula
10
CH3
N=N

mula:
on NH-?CH;
N
0H
15
(?oh?
NH:
OCH} H035
N=N
s03}!
SO3H
(50):?
10. A dyestuff according to claim 9 having the for- 20

mula:
503}!

mula:
CH
(noh?
OH NH;
QN=NQ'N=NVSOJH
0cm
25
01-1
NH;
N=N
S03
SOBH
30
(HO)2P
gl)
S03

mula:
35
40
45
50
55
60
65
UNITED STATES PATENT AND TRADEMARK OFFICE

CERTIFICATE OF CORRECTION
PATENTNO. ;
4,230,618
DATED
October 28, 1980
|NVENTOR(S) :
Donald R. Gauthier
It is certified that error appears in the above-identified patent and that said Letters Patent
are hereby corrected as shown below:
'
Column 3, delete line 18.

Column 16, line 63 delete "claim 17" insert - claim 1
Column 17, - line 8 delete "claim 1'' insert -- claim 8 '
Column 17, line 20 delete "claim 9" insert -- claim 8 -
Column 17, line 32 delete _"claim 9" insert - claim 8
Signed and Sealed this

Twenty-third Day of June 1981
[SEAL]
Anal:
RENE DQTEGTMEYER
Arresting O?if_
Acting Commissioner of Patents and Trademarks
UNITED STATES PATENT AND TRADEMARK OFFICE

CERTIFICATE OF CQRREQTIQN
PATENT N0.
DATED
:
1
INVENTOR(S) :
4,230,618
October 28, 1980
Donald R. Gauthier
It is certified that error appears in the above-identified patent and that said Letters Patent
are hereby corrected as shown below:
Column 3, delete line 18.

Column 16, line 63 delete "claim 17" insert -- claim 1
Column 17, line 8 delete "claim 1" insert claim 3 "

Column 17,
line 20 delete "claim 9" insert claim 8 -
Column 17, line 32 delete "claim 9" insert claim 8 -
Signed and Sealed tis

Twenty-third Day of June I98!
[SEAL]
T Arrest:
RENE D. TEGTMEYER
Arte-?ing O?icer
Acting Commissioner of Patent: and Trademarks

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United States Patent [191

Oct. 28, 1980

[54] AZO DYESTUFFS CONTAINING AN AMINO

Donald R. Gauthier, Somerset, Mass.

ICI United States, Inc., Wilmington,

Azo dyestuffs of the formula:

[21] Appl. No.: 837,625

wherein A is a phenylene or naphthalene nucleus con~

Int. Cl.2 .................... .. C09B 62/82; D06P l/ 384;

US. Cl. .................................. .. 260/187; 260/ 188;

260/ 190; 260/191; 260/194; 260/ 198; 260/199;

Field of Search ............. .. 260/ 187, 191, 190, 194,

of 2 to 8 carbon atoms, at least two of R1R6 being

SO3H and at least one being NHQ, provided that

U.S. PATENT DOCUMENTS

hydrogen or an acyl group of 2 to 8 carbon atoms. The

260/198, 199, 188

taining at least one phosphoric or phosphonic acid

Pechmeze et al. ................. .. 260/ 190

FOREIGN PATENT DOCUMENTS

dyestuff may be used to reactively dye cellulosic materi

cellulose and synthetics together with disperse dyes

Primary Examiner-Floyd D. Higel

3 to 8 carbons and when the dyestuff is disazo, Q is

hydrogen or an acyl group of 2 to 8 carbon atoms.

Preferably, A is a phenyl or naphthyl group which,

BACKGROUND OF THE INVENTION

groups. Typical halogen values include chlorine and

stituted organic polymer, such as cellulose, is described

5 thalene series which, if desired, may be substituted as

The dyestuffs of the invention may be prepared using

dye containing a phosphonic acid group in the presence

illustrated by the following reaction:

mary amine followed by coupling. See, for example,

naphthalene ring. The diazonium salt of the aromatic

by reacting the parent amine with sodium nitrite in the

wherein R is a chromophore group, ROH represents

presence of HCL at low temperatures (such as 0~l5

C.). Coupling of this salt can be carried out by, for

nism applies for dyestuffs containing phosphoric acid

resulting dyestuff can be recovered by precipitating the

It is a primary object of the present invention to pro

the manner described in the above-mentioned German

acid form or in the form of an ammonium salt or partly

These and other objects of the present invention will

Li, Na or K salt. These salts can be obtained by adding

tion mixture before isolation. Alternatively by addition

be apparent from the following description.

of an alkanolamine e. g. diethanolamine to the com

pleted reaction mixture, a highly soluble form of the

DESCRIPTION OF THE INVENTION

dyestuff is obtained which can be used as a total liquor

for the dyeing in printing process.

acid group which may be converted to diazonium salts

be described by the following formula:

wherein A is a phenylene or naphthalene nucleus con

taining at least one phosphoric or phosphonic acid

SO3H and at least one being NQ, provided that

If substituted, the phenyl or naphthyl radical may

nitro, alkyl of l to 4 carbon atoms, alkoxy of l to 4

Typical examples of phosphonic acid amines which

meta-aminophenyl phosphonic acid;

2,4,6-tribromo-4-aminophenyl phosphonic acid;

3-amino-4-hydroxyphenyl phosphonic acid;