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Патент USA US3057852

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.*
,
,_
.
v.
c.
3,057,846
Patented Oct. 9, 1962
1
2
the phenylene or naphthylene radical vB there may be
3,057,846
mentioned sulpho, carboxy, chloro, alkoxy for example
METALLEZED DI§AZO DYES CONTAHNENG A
MONOCHLOROTRIAZINE SUBSTITUENT
methoxy and ethoxy, alkyl for example methyl and ethyl
and acylamino for example acetylarnino and benzoyl
11$:iggwlggglaughgdcg?mfijoggg (gziatN?mzazlgsi,
is provided a process for the manufacture of the new azo
Ciaims Priority’ app?ca?m Great Britain Apr. 22, 1959
5 Claims_ (Cl. 260__146)
dyestuffs, as hereinbefore de?ned, which comprises dia
zotising an amine of the formula:
Herbert Francis Andrew and Alec Mee, Manchester, Eng- 5 amino_
land, assignol‘s t0 Imperial Chemical Industries Limited’
According to a further feature of the invention there
,
.
.
,
.
.
10
This invention relates to new azo dyestu?s and more
A_N=N< B > NH2
particularly it relates to new water-soluble azo dyestu?s
I
‘
which are valuable for colouring cellulose textile ma-
5'
terials.
‘\______/’
According to the invention there are provided the new 15
F
azo dyestu?s which, in the form of the free acids, are
‘\,
1
I
\
'
\
0mm a
represented ‘by the formula:
wherein A and B have the meanings stated above, and
On-lHZn-l
OH N-—-LG OA—-N=N—
<—>
B
I,
,
\
\ ____ _..I
L
N=N
‘I
/N
r a“ \?—X
R, JV1 N
\
\
It
\ /
o
Y
(S0311)m
wherein A represents a phenyl or naphthyl radical which 30 coupling the diazo compound so obtained with a coupling
may optionally be substituted by halogen atoms or by
component of the formula:
alkyl or alkoxy radicals containing not more than 4 car-
OMHBH
bon atoms or by hydroxy, sulphonic or carboxylic acid
groups,,R’ represents a hydrogen atom or an alkyl radi-
cal containing not more than 6 carbon atoms, X represents 35
OH
N
r
LOO“
N
a chlorine or a bromine atom, Y represents an amino
group or an aryl, aryloxy or an alkylamino radical or an
N
\ /
arylamino, sulphoarylamino or carboxarylamino radical
wherein the aryl residue contains not more than 12 carbon
atoms, In represents 1 or 2, n represents 1, 2, 3, 4 or 5, 40
p represents 1 or 2 and the phenylene or naphthylene
radical B can carry further substituents.
As examples of the alkyl or alkoxy radicals containing
not more than 4 carbon atoms which may be present in
%N\
\
I
Y
(503mm
Formula II
wherein R’, X, Y, m, n and p have the meanings stated
above.
may be mentioned methyl, ethyl, propyl, vbutyl, methoxy
This process of the invention may be conveniently car
ried out by adding sodium nitrite to a solution or sus
pension of the amine of Formula I in a dilute aqueous
and ethoXY-
solution of hydrochloric acid, adding the dia'zo solution
the phenyl or naphthyl radical represented by A there 45
_
_ _
AS examPles of the alkyl Tadlcal cont'fumng not more
or suspension so obtained to an aqueous solution of the
than'6 carbon atoms represented by R there may be
coupling component of Formula II, adding sodium car
mentloned methyl: ethyl, PYQPY1 §nd butyl50 bonate to maintain the pH of the mixture between 6.5
As examples of the aryl radicals represented by Y
and 7 and ?ltering off the azo dyeshl?g which is pre_
there may be mentioned phenyl and tolyl, as an example
cipitated.
of the aryloxy radicals represented by Y there_may bf:
ensure complete precipitation of all the azo dyestuif.
mentloned phenoxy: as examples ‘of the alk‘ylammo rad“
If desired sodium chloride can be added to
The amines of Formula I may themselves be obtained
cals represented by Y there _may be mentioned methyl- 55 by diazotising a primary amine of the formula: A__NH2
amino, dlmethylamino and d1‘(5‘hydr°XyethY1)am1n°’ as
wherein A has the meaning stated above, and coupling
examples of the arylamino radicals represented by Y there
the diam compound so obtained with a para coupling
may be mentioned naphthylamino, phenylamino and hymine of the formula:
droxyphenylamino, as examples of the carboxyarylamino
radicals represented by Y there may be mentioned 2-, 3- 60
B
NHI
or 4-carboxyphenylamino and as examples of the sulpho-
arylamino radicals represented by Y there may ‘be men
tioned 2-, 3- or 4-sulphophenylamino, sulphonaphthyl-
,
\
E;
\-----J’
amino and 3:5-disulphophenylamino.
wherein B has the meaning stated above. If desired the
As examples of substituents which may be present in 65 para coupling amine may be used in the form of the
3,057,846
a
I
w~methane sulphonate; this group being subsequently removed after coupling by treatment with alkali.
As examples of the naphthol sulfonic acids of Formula
HI which may be used to obtain the coupling components
As examples of the primary amines of the formula:
of Formula II used in this process of the invention there
A—NH2 Which may be used to obtain the amines of
may be mentioned 1-amino-8-naphthol-3:6-disulphonic
Formula I used in this process of the invention there may 5 acid, 1-(3'- or 4'-aminobenzoylamino)~8-naphthol 3:6-di
be mentioned aniline, orthanilic acid, metanilic acid, sulsulphonic acids, 1-N-ethylamino~8-naphthol - 3:6 - disul
phanilic acid, S-amino-Z-hydroxybenzoic acid, S-amino-Z-
phonic acid, l~N-butylamino-8-naphthol-3:6-disulphonic
hydroxy-B-sulphobenzoic acid, Z-naphthylamine 6- or 8acid, 1-amino-8-naphthol-4:6-disulphonic acid, l-Nebutyl
sulphonic acid, l-naphthylamine 4-, -5-, -6-, or -7-sularnino-8-naphthol-4:6-disulphonic acid, 1-(3’- or 4’-amino
phonic acid, l-amino-S-naphthol 3:6-disulphonic acid, 10 benzylamino)-8-naphthol-4:6-disulphonic acid, l-amino
2:S-dichloroaniline-4-sulphonic acid, 5-chlor0-4~methyl8-naphthol-4-sulphonic acid and 1-amino-8’naphthol-3
aniline-Z-sulphonic acid, 4-methoxyaniline-2-sulphonic
sulphonic acid.
acid, 3-chloro-4-methylaniline~2-sulphonic acid, 4-chloroAs examples of the triazines of Formula IV which may
aniline-Z-sulphonic acid, 4-chloro-3-methylaniline-6-sulbe used to obtain the coupling components of Formula
phonic acid, 4-chloroaniline-3-sulphonic acid, aniline-2:4- 15 II used in this process of the invention there may be
disulphonic acid, aniline-2:5-disulphonic acid, anthranilic
acid, 5-sulphoanthranilic acid, 4-sulphoanthranilic acid,
mentioned 2-phenyl-4z6-dichloro-lz3z5-triazine, Z-amino
4:6-dichloro-l:325-triazine, 2-methylamino-4:6-dichloro
Z-methoxy-l~naphthylamine-6-sulphonic acid, Z-ethoxy-l-
1:3:5-triazine, 2-diethy1amino-4:6-dichloro - 1:325 - triaz
naphthylamine-6-sulphonic acid, 2-naphthylamine 1:5-,
ine, 2-phenylamino-4:6-dichloro-1:3:5 -triazine, 2-(2’
3:6-, 4:8-, 5:7- or 6:8-disulphonic acid, 2-naphthylamine- 20 sulphophenylamino) - 4:6 - dichloro-1:3:5-triazine, 2-(3’
l-sulphonic acid, Z-naphthylamine 3:6:8-trisulphonic acid,
sulphophenylamino)-4:6-dichloro - 123:5 - triazine, 2-(4'
and 4—sulpho-2-aminoanisole.
sulphophenylamino) - 4:6 - dichloro-l :3 :S-triazine, 2-(2’
As examples of the para coupling amines which may
carboxyphenylamino)-4:6-dichloro-1z3z5-triazine, 2-(3’
be used to obtain the amines of Formula I used in this
carboxyphenylamino)-4:6-dichloro-1:3z5-triazine, 2-(4'
process of the invention there may be mentioned 2-meth- 25 carboxyphenylamino)-4:6-dichloro-1:3:5-triazine, 2 - (4’
oXy-5-methy1aniline, m-toluidine,
2:5-dimethoxyaniline,
hydroxy-3' - carboxyphenylamino) - 4:6 - dichloro-l :325
l-naphthylamine, 2-methoxy-1-naphthy1amine, aniline,
anthranilic acid, o-anisidine, 2-methoxy-l-naphthylamine-
triazine, 2-phenoxy-4z6-dichloro-1:325-triazine and 2
amino-4:6-dibromo-l:3z5-triazine.
6-su1phonic acid, 1-naphthylamine-6-sulphonic acid, 1According to a further feature of the invention there is
naphthylamine-7-sulphonic‘ acid, 4-acetylamino-2-arnin0- 30 provided an alternative process for the manufacture of
anisole, m-aminoacetanillde, 4-benzoylamino-2-amin0the new azo dyestuffs, as hereinbefore de?ned, which
anisole, 4-acetylamino-2-aminobenzoic acid, m-chlorocomprises treating an azo compound of the formula:
(En-111m»!
OH N foo-QN i
A N-NGN_N
._
__
L
_
H
R, Jr]
|
(SO3H)m
aniline, m-anisidine and 2-amino-4—methoxyphenoxyacetic _0
acid.
Formula V
0
The coupling components of Formula II may themwherein A, B, R’, m, n, and p have the meanings stated
selves be obtained by treating a naphthol sulphonic acid
above, with a triazine of Formula IV as hereinbefore
of the formula:
de?ned.
(IJn-rHZH
r
This alternative process of the invention may be con
OH
N
(00G 1
N
|
R'
H
"5 veniently carried out by adding an aqueous solution of
the azo compound of Formula V to a solution or suspen
sion of the triazine of Formula IV in Water or in a mix
ture of acetone and water, heating the resulting mixture,
preferably at a temperature between 40° and 50° C., add
9-1
60 ing sodium carbonate to maintain the pH of the mixture
between 5 and 7.5, and ?ltering off the azo dyestuti which
(502mm
is precipitated. If desired, sodium chloride can be added
Formula III
to ensure complete precipitation of all the azo dyestuif.
The azo compounds of Formula V used in this alterna
wherein R’, m, n, and p have the meanings stated above, 65 tive process of the invention may be obtained ‘by coupling
with a triazine of the formula:
a diazotised amine of Formula I, as hereinbefore de?ned,
%
with a naphthol sulphonic acid of Formula III, as here
/0\
inbefore de?ned.
N
70
‘Fig
(g_X
\N%
According to a further feature of the invention there is
provided a modi?ed process for the manufacture of the
new azo dyestuffs, as hereinbefore de?ned, wherein Y
represents an amino group or an aryloxy, alkylamino radi-,
Formula IV
wherein X and Y have the meanings stated above.
cal or an arylamino, carboxyarylamino or sulphoary1~
75 amino radical wherein the aryl residue contains not more
5
3,057,848
6
than 12 carbon atoms, which comprises treating an azo
dyestuff of the formula:
wherein A, B, R’, X, Y, m, n, and p have the meanings
stated above and Z represents a metallisable group.
As examples of the metallisable groups represented 1by
wherein A, B, R’, X, m, n, and p have the meanings 15 Z there may be mentioned hydroxy, car-boxy, methoxy
and carboxyethoxy, and as examples of metals there may
stated above, with a compound of the formula: HD
wherein D represents an amino group or an aryloxy or
be mentioned copper, nickel, cobalt and chromium, and
preferably copper.
alkylarnino radical or an arylamino, carboxyarylamino or
sulphoarylamino radical wherein the aryl residue con
According to a further feature of the invention there is
tains not more than 12 carbon atoms.
This modi?ed process of the invention may be con
20 provided a process for the manufacture of the new metal
containing azo dyestuffs, as hereinbefore de?ned, which
comprises treating an aminoazo compound of the for
mula:
veniently carried out by heating an aqueous solution of
a dyestuff wherein Y represents a halogen atom with one
Cit-113mm
Z
A—-N=N-
<,\
molecular proportion of a compound of the formula:
B
0H N MG]
N=N
R, Jr‘
J)
/\
'
(SOsH)m
Formula VII
H——D, as hereinbefore de?ned, at a temperature between
40° and 45° C., adding sodium carbonate to maintain
wherein A, B, Z, R’, m, n and p have the meanings stated
the pH of the mixture between 7.0 and 7.2, adding so
above, with a metallising agent and with a triazine of
dium chloride and ?ltering off the dyestuff which is 40 Formula IV, as hereinbefore de?ned.
precipitated.
The aminoazo compound may be treated with the tri
As examples of compounds of the formula: H-D
azine and then with the metallising agent, but it is pre
which may be used in ‘the modi?ed process of the inven
ferred to treat the amino azo compound with the metal
tion there may be mentioned phenol, ammonia, aniline,
lising agent and subsequently treat the metal complex
2-sulphoaniline, 3-s'ulphoaniline, 4~sulphoaniline, 2-car
boxyaniline, 3-carboxyaniline, 4-carboxyaniline, 3:5-disul
45 so obtained with the triazine.
This process of the invention may be conveniently car
ried out by heating an aqueous solution of the aminoazo
compound with an aqueous solution of the metallising
agent, adding an aqueous solution of the metal complex
phoaniline, N-methylaniline, 4-hydroxy-3-carboxyaniline,
2-naphthylamine-4:8-, 517-, 6:8- or 3:6-disulphonic acid,
metanilic acid and 1-naphthylamine-4-sulphon'ic acid, or
the alkali metal salts of these compounds.
50 so formed to a solution or suspension of the triazine in
The azo dyestuffs of Formula VI may themselves be
water or in an aqueous solution of acetone, maintaining
obtained by treating an azo compound of Formula V with
cyanuric chloride or cyanuric bromide.
the pH of the mixture between 6 and 7 by adding sodium
carbonate and ?ltering off the dyestuif which is precipi
A preferred class of the new azo dyestuffs, as herein
before de?ned, are those dyestuffs which contain a metal
lisable group in the phenylene or naphthylene radical rep
complete precipitation of all the dyestuff.
As examples of metallising agents which may be used
tated. If desired sodium chloride can be added to ensure
resented by B, the said metallisable group being in an
in the process of the invention here may be mentioned
ortho position to the azo bond which links B with the
naphthalene nucleus, as this preferred class of dyestuffs
copper sulphate, cuprammonium sulphate, copper acetate,
nickel acetate, cobalt sulphate and chromium formate,
but the preferred metallising agents are agents which
yield copper.
As examples of triazines of Formula IV which may be
yield metal complexes which, when applied to cellulose
textile materials, give dyeings which have excellent fast
ness to light.
According to a further feature of the invention there
are provided as new metal-containing azo dyestuffs the
metal complexes of the azo dyestuffs of the formula:
%
X life O_®
60
used in this process of the invention there may be men
tioned 2-phenyl-4 : 6-d-ich1oro-1 :3 : S-triazine, 2-phenoxy
4:6-dichloro-1 :3 :5 -triazine, 2-amino-4 : 6-dichloro-1 :3 :5
3,057,846
triazine, 2-di(/3-hydroxyethyl)amino-4:6-dichloro-l:315triazine, 2-phenylamino-4:6-dichloro-lz3z5-triazine, 2-(2'-
amino-8-naphthol-4-sulphonic acid and l-amino-8-naph
thol-3-sulphonic acid.
sulphophenylamino)-4:6-dichloro - 1:3:5 -triazine, 2-(3'sulphophenylamino) - 4:6 - dichloro-l :3 :S-triazine, 2-(4’-
According to a further feature of the invention there
is provided a modi?ed process for the manufacture of the
sulphophenylamino) - 4:6 - dichloro - 1:3:5 - triazine,
2-
5
new metal-containing azo dyestuifs, as hereinbefore de
amino-4z6-dibromo - 123:5 - triazine, 2-methylamino-4:6—
?ned, wherein Y represents an amino group or an aryloxy
dichloro-l:3 :S-triazine and 2-dimethylamino-4:6-dichloor alkylamino radical or an arylamino, carboxyarylamino
ro-lz3z5-triazine.
or sulphoarylamino radical wherein the aryl residue con~
The aminoazo compounds of Formula VII used in this
tains not more than 12 carbon atoms, which comprises
process of the invention may be obtained by diazotising 10 treating a metal complex of an azo dyestuff of the for
a primary amine of the formula: A-—-NH2, wherein A has
mula:
the meaning stated above, coupling the diazo compound 25
so formed with a para coupling amine of the formula:
Formula VIII
wherein A’ B, R,’ X’ Z, m’ n’ and I) have the meanings
stated above, with a compound of the formula: DH as
herein'before de?ned.
This modi?ed process of the invention may be con
30 veniently carried out by heating an aqueous solution of
the metal complex of an azo dyestutf of Formula VIII
with one molecular proportion of a compound of the
wherein B and Z have the meanings stated_a,b°ve> {e'di‘
formula: D—H, as hereinbefore de?ned, at a tempera
azotising and coupling under alkahne conditions with a
_ mm between 40° and 50° C_ adding Sodium carbonate
naphthol sulphonic acid of Formula III, as hereinbefore 3D to maintain the PH 0f the mixture between 7.0 and 7,2,
de?ned-
_
_
adding sodium chloride and ?ltering off the dyestutf which
As examples of primary amines of the formula:
A—NHz which may be used to Obtam the ammoazo
_
_ _
I _ there
,
compounds used
in this
process _of_ the_ invention
is precipitated_
The metal complex of an azo dyestuif of Formula VIII
may be obtained by treating an aminoazo compound of
may be mentloned aniline, orthamhc acld, metamhc acid, 40 Formula VII with a metallising agent and then with
sulphanilic acid, S-amino-Z-hydroxybenzoic acid, S-aminocyanuric chloride or cyanuric momma
2'hYdmXy'3'$u1Ph°l{enZ°i° acid, l'mflphthylamim 4': 5f’
The new azo dyestulfs and new metal-containing azo
6'_°1' 7'5u1P1}°m¢ acld; 2-naphthylamme 6'_ 01' s'sulphomc
amd’ 25éjdlchlm'oamhIPe'4'SQ1PhOmC and, 5_'_ch1°r°'4‘
dyestuffs, as hereinbefore de?ned, are valuable for colour
ing cellulose textile materials, for example cotton, viscose
meth¥1am!1ne'2'S‘-‘1Ph°m° acld, _ fl‘meth°XYam_hne'?'Su1' 45 rayon and linen textile materials. For colouring the cellu
Phomc acld, 3-chloro-4jmethylamhne-6-sulphonlc aclflg 4'
‘lose textile materials the new dyestuffs may be applied by
chloroaniline-2-sulphon1c acid, 4-chloro-3-rnethylamline-
either a dyeing or a printing method’ preferably in com
6-sulphonic acid, 4_-chlor‘o.aniline-3:sulphonic acid, anlllne'
ll4-dlsulphonlc 391d, anlllneaiidlslllphomc 301d’ anthF?’
junction with a treatment with an acid-binding agent, for
example by the methods disclosed in British speci?cation
nilic acid, 5-sulphoanthranilic acid, 4-sulphoanthran1l1c 50 NO_ 797,946 When so appued to Cellulose textile ma_
acid, Smitfoanthranilic acid, Z'mGthOXY“l'l}aphthylamm?‘
terials the new dyestuiis, as hereinbefore de?ned, yield
6'slllphonic acid, F'?thoxy-1'naphthylamme'?'sulphPmc
reddish-blue to greenish-blue shades possessing excel
acid, 2-naphthylarn1r1e-1:5-, 3:6-, 4:8-, 517- 0r 6I8-d1w1-
lent fastness to wet treatments such as washing and to
phonic acid, l-amino-8-naphthol-3:6-disulphonic acid, 2-
light
naPhthylamine'l'sulphonic acid and 4'sulpho'z'amlno' 55
amsole.
_
_
_
As examples of the Para couplmg ammes whlcl} may
A preferred class of the new dyestuffs of the invention
are the copper complexes of the azo dyestuffs which, in
the form of the free acids, are represented by the formula:
be used to obtain the aminoazo compounds used in this
process of the invention there may be mentioned 2:5-di
methoxyaniline, 2-methoxy-5-methylaniline, anthranilic 60
C H
acid, 2 - methoxy- 1 - naphthylamine-6-sulphonic acid, 2-
ethoxy-l-naphthylamine-6-sulphonic acid, o-anisidine, 4acetylamino-Z-aminoanisole, 4 - acetylamino-Z-aminoben-
zoic acid, 4-benzoylamino-Z-aminoanisole and 2-amino-4methoxyphenoxyacetic acid.
65
As examples of the naphthol sulphonic acids of Formula III which may be used to obtain the aminoazo com-
N
“" ’“"/ \
Z’
(‘)3 I?’
A'-'N=N‘<E>—N=N
“"m’
?-X
N
\O/
\
’,> 11035
<
?
N
'1‘
|
Y
T
pounds used in this process of the invention there may be
mentioned 1 - amino - 8 - naphthol-3:6_disulphonic acid,
1-(3’- or 4’-aminobenzoylamino)-8-naphthol - 3:6 - disul- 70
phonic acid, l-N-ethylamino-8-naphthol-3:6-disulphonic
wherein B, X, Y and n have the meanings stated above,
acid, 1-N-butylamino-8~naphthol - 3:6 - disulphonic acid,
1-amino-8-naphthol-4:G-disulphonic acid, 1-(3’- or 4’~
aminobenzoylamino) - 8- naphthol - 4:6—disulphonic acid,
1 -N- butylamino - 8 - naphthol-4:6-disulphonic acid, 1- 75
A’ represents a phenyl or naphthyl radical containing at
least one sulphonic acid group, Z’ represents a hydroxy
or methoxy group, and one T represents a sulphonic acid
group and the other T represents a hydrogen atom. In
3,057,846
9
this preferred class X preferably represents a chlorine
atom, Y preferably represents a sulphoanilino or disul
phoanilino radical and 11 preferably represents 1.
The invention is illustrated but not limited by the fol
lowing examples in which the parts and percentages are
water. 38 parts of a 10% aqueous solution of sodium
carbonate are then added and the mixture is heated for
2 hours at a temperature between 40° and 45° C., the pH
of the mixture being maintained at 7 by the addition of a
10% aqueous solution of sodium carbonate. 55 parts of
by weight:
sodium chloride are added and the dyestuif, which is
precipitated, is ?ltered off and dried. On analysis the
Example 1
dyestulf so obtained is found to contain 1.1 atoms of
10
Diazotised orthanilic acid is coupled with Z-methoxy-S
methylaniline and the aminoazo compound so obtained '
is diazotised and coupled under alkaline conditions with’
an equirnolecular proportion of l-aminoe8-naphthol-3z6
disulphonic acid. The aminodisazo compound so ob
tained is converted to the copper complex by heating with
an aqueous solution of cuprammonium sulphate for 20
hours at a temperature between 95° and 100° 0., adding
organically bound chlorine for each disazo molecule
present.
When applied to cellulose textile materials in conjunc
tion With a treatment with an acid-binding agent the dye
st-u? gives navy blue shades possessing excellent fastness
to washing and to light.
Example 4
salt and ?ltering off the precipitated copper complex.
Diazotised Z-naph-thylamine 4:8-disulphonic‘ acid is
A solution of 15.1 parts of the above copper complex
coupled with Z-methoxyaniline and the aminoazo com
in 300 parts of water is added with stirring to a suspension
pound so obtained is diazotised and coupled under talka
of 3.8 parts of 2-amino-4z6-dichloro-l23:5-triazine in a
line conditions with an equimolecular proportion of 1
mixture of 30 parts of acetone and 100 parts of water.
amino-S-naphthol 3:6-disulphonic acid. The aminodis
The mixture is then stirred for 2 hours at a temperature 25 azo compound so obtained is heated with an aqueous
of 50° C., the pH of the mixture being maintained at 7
solution of cuprammonium sulphate for 20 hours at 'a
by the addition of a 10% aqueous solution of sodium
temperature between 95° and 100° C., ‘salt is then added
carbonate. 80 parts of sodium chloride are added, the
and the copper complex which is precipitated is ?ltered
precipitated dyestu? is then ?ltered oil and dried at 30° C.
off and dried.
On analysis the dyestu? so obtained is found to contain 30
A solution of 10 parts of the above copper complex
1.0 atom of organically bound chlorine for each disazo
is added
stirring to a suspension of 3.6 parts of
molecule present.
2-(4'—sulphoanilino)-4: 6-dichloro-1 :3 :S-triazine in a mix
When applied to cellulose textile materials in conjunc
ture of 50 parts of acetone and 150 parts of water. The
tion with a treatment with an acid-binding agent the dye
stuff yields navy blue shades possessing excellent fastness
to washing and to light.
35 mixture is then stirred for 2 hours at a temperature of
45—50° C., the pH of the mixture being maintained at
7 by the addition of a 10% aqueous solution of sodium
carbonate. 10 parts of sodium chloride are then added
and the dyes-tuif which is precipitated is ?ltered off and
On analysis the dyestuif is found to contain 1.1
atoms of organically bound chlorine for each disazo mole
cule present.
When applied to cellulose ‘textile materials in conjunc
Example 2
40 dried.
In place of the 3.8 parts of 2-amino—4:6-dichloro->l:3 :5
triazine used in Example 1 there are used 4.7 parts of 2
phenoxy-4: 6-dichloro-l : 3 : S-triazine.
tion with a treatment with an acid-binding agent the
On analysis the dyestuff so obtained is found to con
dyestu?.’ yields blue shades possessing excellent fastness
to washing and to light.
tain 0.98 atom of organically bound chlorine for each
disazo molecule present.
When applied to cellulose textile materials in conjunc
tion with a treatment with an acid~binding agent the dye
Example 5
stuff yields navy blue shades possessing excellent fastness 50
In place of the 3.6 parts of 2-(4'-sulphoanilino)-4:6
to washing and to light.
dichloro-1:3:5~triazine used in Example 4 there are used
3.6 par-ts of 2-(3'-sulphoanilino)-4:6-dichloro-1:3:5~tri~
Example‘ 3
azine.
55
Diazotised orthanilic acid is coupled with Z-methoxy
aniline and the aminoazo compound so obtained is di
azotised and coupled ‘under alkaline conditions with an
equimolecular proportion of 1-amino-8-naphthol-3:6-di
On analysis the dyestulf so obtained is found to con
tain 0.83 atom of organically Ibound chlorine for each
disazo molecule present.
When applied to cellulose textile materials in conjunc
tion with a treatment with an acidebinding agent the
sulphonic acid. The aminodisazo compound so obtained 60 dyestuff yields blue ‘shades possessing excellent fastness
is converted to the copper complex by heating with an
to washing and to light.
aqueous solution of cuprammonium sulphate for 20 hours
The following table gives funther examples of the
at a temperature between 95° C, and 100° C., adding
shades obtained on cellulose textile materials from the
salt and ?ltering off the precipitated copper complex.
65
dyestuffs obtained by the method described in Example
A solution of 30 parts of the above copper complex in
3 above by diazo-tising the amine listed in the second
250 parts of water is added with stirring to a suspension
column of the table, coupling with the para coupling
of 7.6 parts of cyanuric chloride in a mixture of 80 parts
amine listed in the third column of the table, rediazotising
of acetone, 150 parts of ice and 150 parts of water, the
and coupling with the coupling component listed in the
70
temperature being maintained between 0° and 5° C. by
fourth column of the table, treating the resulting disazo
external cooling. The mixture is stirred for 1 hour and
compound with a coppering agent, condensing the result
23 parts of a 10% aqueous solution of sodium carbonate
ing copper complex with cyanuric chloride and .r?nally
are then added. To the solution so obtained is added a
reacting with the amino compound listed in the ?fth col
solution of 8.1 parts of sodium metanilate in 50 parts of 75 umn of the table.
3,057,846
ll
12
Shade ob~
Ex.
Amine
Para coupling amine
Coupling component
Amino compound
tained on
cellulose tex
tile materials
6____- Orthanilic acid ___________________ _. 2methoxyaniline .......... -_ l-alniélcesnaphthol 3i6-diS11lpll0l1lC Sodium sulphanilate“ Navy blue.
aci
.
7_.__. Metanilic acid ___________________ __ 2-methoxy-5-pqethyl?llilille?- ---__d0 ____________________________ __ Sodium metanilate-.- Blue.
s_____ 2-naphtl1ylamine 6:8‘disulphonic Z-rnethoXramlme.
---_.do
_____do _________ __
__ Dark blue.
ac
.
.
.
.
.
9_.__. Orthanilic acid ___________________ _- 2-methoxy-5-methy1anilme.._ l-a?ltlélo-s-naphthol-‘i:B-disulphonrc
an .
10_.__ Aniline 2zadisulphonic acid ___________ _.do ..................... -- l-amviéio-snaphthol3:6-disulphonlc
aci .
1L. _ Z'naphthyIamine 3:6:Hrisulphon-
__
do
-._
10 am .
12.- _ Sulphanilic
acid __________________ -_ 2-rnethoxyaniline
Example 13
Diazotised 2-naphthylamine-4:S-disulphonic acid is cou
do
Do,
Blue.
Do.
do
Sodium metanilate____ Navy blue.
salt of p~aminobenzoic acid. On analysis the dyestuif
so obtained is ‘found to contain 1.15 atoms of organically
bound chlorine for each disazo molecule present.
pled with 2:5-dimethoxyaniline and the aminoazo com
When applied to cellulose textile materials in conjunc
pound so obtained is diazotised and coupled under alka
tion with a treatment with an acid-binding agent the dye
line conditions with an equimolecular proportion of 1 20 stuff yields navy blue shades possessing excellent fastness
amino-8-naphthol-3:6-disu1phonic acid. The aminodis
to washing and good iastness to light.
azo compound so obtained is heated with an aqueous
Example 16
In place of the 7 .6 parts of cyanuric chloride used in Ex
and the copper complex which is precipitated is ?ltered 25 ample 3 there are used 13.1 parts of cyanuric bromide.
0n analysis, the dyestuff so obtained is found to contain
OE and dried.
A solution of 37.3 parts of the above copper complex
0.95 atom of organically bound bromine for each disazo
solution of cuprammonium sulphate for 20 hours at a
temperature between 95° and 100° C., salt is then added
in 280 parts of water is added with stirring to a sus
pension of 14 parts of 2—(2’-sulphoanilino)-4:6-dichloro
molecule present.
When applied to cellulose textile materials in conjunc
1:3 :5~triazine in a mixture of 50 parts of acetone and 100 30 tion with a treatment with an acid-binding agent the dye
parts of water. The mixture is then stirred for 1 hour
stuif yields blue shades possessing excellent fastness to
at a temperature of 45° C., the pH of the mixture being
washing and to light.
maintained at 7 by the addition of a 10% aqueous sodi
Example 17
um carbonate. 60 parts of sodium chloride are then
added and the dyestu?, which is precipitated, is ?ltered 35
oil and dried. On analysis the dyestu?i is found to con
tain 0.8 atom of organically bound chlorine for each
A solution of 20.9 parts of the disodium salt of l-N
butylamino-8-naphthol-3:6-disulphonic acid in 200 parts
of water is added with stirring to a suspension of 9.5
parts of cyanuric chloride in a mixture of 120 parts of
When appiled to cellulose textile materials in con
acetone, 100 parts of water and 100 parts of ice. The re
junction with a treatment with an acid-binding agent the 40 sulting mixture is stirred for 21/2 hours at a temperature
dyestuff yields blue shades possessing excellent fastness
between 0° and 3° C. and the pH of the mixture is then
raised to 7 by the addition of a 10% aqueous solution of
to washing and to light.
sodium carbonate. 4.7 parts of aniline are added and the
Example 14
disazo molecule present.
Diazotised orthanilic acid is coupled with Z-methoxy
S-methylaniline and the aminoazo compound so obtained
is diazotised and coupled under alkaline conditions with
an equimolecular proportion of 1-arnino-8-naphtho1-3:6
disulphonic acid.
A solution of 28.7 parts of the above aminodisazo com
pound in 250 parts of water is added with stirring to Y
a suspension of 7.6 parts of cyanuric chloride in a mix
ture of 80 parts of acetone, 150 parts of water and 150
parts of ice, the temperature of the mixture being main
tained between 0° and 5° C. by external cooling. The
mixture is stirred for 2 hours at a temperature between 40°
and 45° C., the pH being maintained at 7 by the addition
of a 10% aqueous solution of sodium carbonate. The so
lution is then cooled to a temperature between 0° and 10°
C., and an aqueous suspension of diazotised 4-amino-2
methyl-S-methoxy-l : 1’-azobenzene-2’ : 5'-disulphonic acid
(which is obtained by adding a solution of 22.2 parts of the
disodium salt of the above aminoazo compound and 3.8
parts of sodium nitrite in 200 parts of water to a mixture
of 24 parts of a concentrated aqueous solution of hydro
chloric acid and 200 parts of ice), is then added during 5
minutes while the temperature of the mixture is maintained
between 0° and 7° C. Sodium carbonate is then added,
during ten minutes, until the pH of the mixture is 7.5 and
the mixture is stirred for 3 hours at a temperature between
0° and 5° C. 150 parts of sodium chloride are then added
mixture is then stirred ‘for 1 hour and 23 parts of a 10%
aqueous solution of sodium carbonate are added. To
the solution so obtained is added a solution of 8.1 parts
of sodium metanilate in 50 parts of water. 23 parts of
a 10% aqueous sodium carbonate solution are then added
and the dyestuff which is precipitated is ?ltered off, washed
and the mixture is heated for 2 hours at a temperature 60 with 15 parts of a 10% aqueous solution of sodium chlo
between 40° and 45° C., the pH of the mixture being
ride and dried. On analysis the dyestu? so obtained is
maintained at 7 by the addition of a 10% aqueous solu
found to contain 1.1 atoms of organically bound chlorine
tion of sodium carbonate. 55 parts of sodium chloride
for each disazo molecule present.
are then added and the dyestul'f which is precipitated, is
When applied to cellulose textile materials in conjunc
?ltered off and dried. On analysis the dyestu? so ob
tion with a treatment with an acid-binding agent the dye
tained is found to contain 1.15 atoms of organically
stu?f yields violet shades possessing good fastness to wash
bound chlorine for each disazo molecule present.
ing and to light.
When applied to cellulose textile materials in con
Example 18
junction with a treatment with an acid-binding agent the
dyestu? yields navy blue shades possessing excellent fast 70 In place of the 30 parts of the copper complex used in
Example 3 there are used 35.7 parts of the chromium com
ness to washing and good fastness to light.
Example 15
plex which is obtained by coupling diazotised 2-naphthyl
amine-5:7-disulphonic acid with anthranilic acid in acid
medium, diazotising the aminomonoazo compound so ob
In place of the 8.1 parts of sodium metanilate used
in Example 14 there are used 6.4 parts of the sodium 75 tained, coupling the resulting diazo compound with 1
3,057,846
13
l4
amino-8-naphthol-3:6-disulphonic acid in alkaline medi
stu? so obtained is found to contain 0.91 atom of organ
ically bound chlorine for each disazo molecule present. '
um and heating the aminodisazo compound so obtained
with an aqueous solution of chromium acetate. On anal
ysis the dyestuif so obtained is found to contain 0.85 atom
of organically bound chlorine for each disazo molecule
When applied to cellulose textile materials in conjunc
tion with a treatment with an acid-binding agent the dye-_
stu? yields grey shades possessing good fastness to wash
ing and to light.
The following table gives further examples of the shades
present.
When applied to cellulose textile materials in conjunc
tion with a treatment with an acid-binding agent the dye
obtained on cellulose textile materials from the dyestuffs
stuif yields violet shades possessing good fastness to wash
obtained by the method described in Example 3 above by
diazotising the amine listed in the second column of the
table, coupling with the para coupling amine listed in the
third column of the table, rediazotising and coupling with
ing and to light.
Example 19
In place of the 30 parts of the copper complex used in
Example 3 there are used 37.0 parts of the nickel complex
the coupling component listed in the fourth column of the
table, treating the resulting disazo compound with a cop
which is obtained by coupling diazotised Z-naphthylamine
5 :7-disulphonic acid with anthranilic acid in acid medium,
pering agent, condensing the resulting copper complex with
cyanuric chloride and ?nally reacting with the amino
diazotising the aminomonoazo compound so obtained,
compound listed in the ?fth column of the table.
Ex.
Amine
Para coupling amine
Coupling component
Amino compound
Shade obtained
OIItCGItlIIIIOSG
ex 1 e
materials
21- - _
Orthanilic acid ____________________ __
o-Anisidine ________________________ __
Metanilic acid ______ __
Navy-blue.
Aniline ______________ __
Do.
2-methoxy-5-methy1aniline _____________ __d0 ...................... _-d0 _______________ -.
Do.
22." 2-naphthyiamine- 6:8- disulphonic _____do________
_____ ._
acid.
23.-. . 2-nap1hthylamine- 4:8- disulphonic
aci
1-amino<8-naphthol-4:6-
disulphonic acid.
disulphonie acid.
1-an.iiuo'8-naphtl_1ol-3:6~
.
24.- - 2-Impélthylamine-3z?z8-trisulphor1ic _____do __________________________________ __do _________________ ._ jp-Aminobenzoic acid._
ac1
25. _ -
Do.
.
Orthanilic acid _________________________ __do _____________________________ __
l-amino-8'naphthol-4z?-
Sulphanilic acid _____ __
disulphonic acid.
26. _ _ _____do _____________________________ __
l-amino-G-sulpho-2-naphthoxyacetic
acid.
i-amino-8-naphthol-3z6-
_
Metamlic acid ______ --
disulphonic acid.
coupling the resulting diazo compound with 1-amino-8
Do.
Greenish
blue.
The following table gives further examples of the shades
naphthol-3:6-disulphonic acid in alkaline medium and
heating the aminodisazo compound with an aqueous solu
tion of nickel sulphate. On analysis the dyestulf so ob
obtained on cellulose textile materials from the dyestuffs
obtained by the methods described in Examples 1 and 4
40 above by diazotising the amine listed in the second column
tained is found to contain 1.1 atoms of organically bound
of the table, coupling with the para coupling amine listed
chlorine for each disazo molecule present.
in the third column of the table, rediazotising and coupling
When applied to cellulose textile materials in conjunc
with the coupling component listed in the fourth column of
tion with a treatment with an acid-binding agent the dye
the table, treating the resulting disazo compound with a
stutf yields violet shades possessing good fastness to wash 45 coppering agent, and condensing the resulting copper com
ing and to light.
plex with the triazine listed in the ?fth column of the table.
Ex.
Amine
Para coupling amine
Coupling component
Triazine
Shade obtained
ontceltllililose
ex
e
materials
27___ Orthanilic acid ____________ __ 2-methoxy-54methyl
aniline.
28,..- _____do
____ __
o-Ani irline
1-amino-8-naphtho1-3:?adisulphonic acid.
__________ __do
2-(3’-sulphoani1ino)-4:G-dichloro1:3:5-tr1azine. I
2-(3’:5’-d1sulphoa.n1lino)-4:6-di-
Navy-blue.
Do.
chl0ro-1z3z5-triazine.
29. _ - 2-naphthylamine-4z8-disulphonic acid.
30- _ -
31.- _ 4-aminoanisoie-3-su1phonic
tnazine.
__ .__do ____________________ __do ___________________________ . .
_____do _______________ -_ l-amino-S-na hthol-4:6-disul-
acid.
32---
2-m§lih_0Xy-416-di0h10r0-1=3=5-
aniline.
3-chloro-4-methyiani1ine-6-
sulphonic acid.
2-methoxy-5-methyl
phonic aci .
Aniline-2:5-disulphonic acid. _____do _______________ __
. _
2-(3’ : 5’-disulph0anilmo)-4:6-di-
chloro-lz3z5-triazine.
2-(3’-su1pl1oamlmo)-4:G-dichloro-
Do.
Do.
1:3:5-tr1az1ne.
1-(3’-aminobenzoylamin0)-8- _
naphthol-az?-disulphonic acid.
Example 20
D0
._.-_d0 ___________________________ __
Greenish
blue.
The following table gives further examples of the
shades obtained on cellulose textile materials from the
In place of the 30 parts of the copper complex used in
Example 3 there are used 35.8 parts of the cobalt complex
which is obtained ‘by coupling diazotised 2-naphthylamine
dyestuffs obtained by the method described in Example
14 by diazotising the amine listed in the second column
of the table, coupling with the para coupling amine listed
5 :7-disulphonic acid with anthranilic acid in acid medium, 70 in the third column of the table, rediazotising and cou
diazotising the aminomonoazo compound so obtained,
pling with the coupling component listed in the fourth
coupling the resulting diazo compound with l-amino-8
column of the table, condensing the resulting aminodisazo
naphthol-3 :6-disulphonic acid in alkaline medium, and}
compound with cyanuric chloride and ?nally reacting with
heating the aminodisazo compound so obtained with an
the amino compound listed in the ?fth column of the
aqueous solution of cobalt acetate. On analysis, the dye- 75 table.
3,057,846
Shade obtained
Ex.
Amine
Para coupling amine
Coupling component
Amino compound
ontceltlillilose
ex e
material
33--- Orthanilic acid ______________ __ 2-methoxy-1-naphthylamine-
1-amino-8~naphthol-3:6-disu1
?-sulphonic acid.
34. _ -
2-nophthylamine-4 : B-disui-
phonic acid.
2 : 5‘dimcthoxyaniline _____________ ._do ____ _ .' ______ -; _________ __
phonic acid.
35___ _____do ____________________________ __do _______________________ __
36. _ -
2-nailphtihylag1ine-3z?z8'trlsulp on c ac
37---
_
2-methoxy-5-methylanillne. - __
Snlphanilic ................ __
Do.
p'Aminobenzolc acid ______ ._
Do.
Aniline-3:5disu1phonic acid-
Do.
.
Metam‘llc acid _ . _ _ _ _
. _ . ._rin
______ __
.
1-ar1nino'8-na(phtho1-4:6>disu1-
38“- ___._do ____________________________ __do _______________________ __
1-amino-8-naphthol-3:B-disul-
p oruc aci _
39- -_
2-aminophenol-4z6-dlsul-
Metunillc acid ____________ -_
phonic acid.
2:5-dimethoxyaniline _____________ ._do ............................ ..do ..................... __
Do.
Greenlsh
phonic acid.
blue.
sisting of sulfonated phenyl and naphthyl radicals on
What we claim is:
which any substituents are selected from the class
1. A compound selected from the class consisting
of azo dyestuffs of the formula:
00113
on
0n-1H2u-1/N
N
0/ \Q_X
I11
A__N:N_
consisting of chlorine, methyl, methoxy and hy
N=N
droxy;
20
R is selected from the class consisting of hydrogen,
ll
methyl and methoxy;
,
X represents a member selected from the class con
Y
Y represents a member selected from the class con
('3
R
,
\ /
sisting of chlorine and bromme atoms;
25
sisting of amino and methoxy, phenoxy and phenyl
amino on which any substituents are selected from
(80311)"
and the 1:1 copper-, 1:1-nickel-, 1:2-chromium and 1:2cobalt complexes thereof, wherein
the class consisting of sulfonic acid and carboxylic
acid radicals; ‘and,
n represents one of the numbers 1, 2, 3, 4 and 5.
A represents a member selected from the class con-
2.
01
NJ;
%
SOaH
0-—-0u-—(|) IIIH—O\N=0 /N
NH
'
H038
-s0;,H
I Q
SOZH
3.
(‘>1
N—-C
/
\
S0311
(')———-Cu-—(|) Ir’H-O
N=O
/N
NH-—
H038
SOzH
303K
4.
01
N_b\
SIOaH
0—-—Cu-—-(|J IfH-C
‘
I
QM
HOaS
N=O
M
H3
H033
/N
I
NE
SOaH
,
503B
5.
01
N_<l\
SlOsH
O-—-—Cu———~(|) IIIH—C\N==O /N
C>-N=NH3
N=N
11038
References Cited in the ?le of this patent
UNITED STATES PATENTS
2,396,659
Kaiser _____ .__' ________ __ Mar. 19, 1946
2,860,128
Gunst _______________ __ Nov. 11, 1958
2,945,021
Fasciati et a1 __________ _- July 12, 1960
I
NH
50311
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