Note: Descriptions are shown in the official language in which they were submitted.
lQ4~999
The present invention relates to soluble trisazodyestuffs of the
general formula I
OH NH2
A-N=N ~ N=N-Z-N-N-B
tS~3H)
wherein Z denotes the radical
~ N
or
R
X s _N-, -S- or -O-,
R = H, alkyl having 1 to 4 C atoms, phenyl or benzyl;
A tenotes the radical of a diazo component;
B denotes the radical of a coupling co~ponent;
n denotes the number 1 or 2,
and the nuclei I and/or II can carry further substituents and/or the sulpho
groups can also be present in the salt form.
The present invention also relates to a process for the production
of a trisazo dyestuff as defined in claiml hhich comprises either:-
ta) coupling a diazotised disazo dyestuff which, in the form of thefree acid, corresponds to the general formula II:
~( ~
10~999
OH NH2 1
~_N=N~X N-N-Z-N2 6)~ 1~ 3 11
t 3H)n
.
wherein Y ~ represents an anion and wherein A, Z and n are as deflned in
claim 1 with a coupling component of the formula III
B _ H III
wherein B is as defined in claim l; or
b) diazotising and coupling a diazo component of the formula YII
A - NH2 YII
wherein A is as defined in claim 1 with a disazo dyestuff which, in the form
of free acid, has the formula VIa
~H NIH2
N=N-Z-N2N-B
VI~
(S03H)
Nherein 8, Z and n are 85 defined in claim 1.
Thc radical A of thé diazo component can be derived
-r-~
~ ' -1j9- '
~ Ref. 3008
.. ! 104~999
from an aromatic or heterocyclic diazo component A-N~I2, for
example a diazo componcnt of the benzene or naphthalene series,
and the diazo components can also additionally carry other
substituents which are customary in dyestuff chemistry.
Examples of suitable radicals A of aromatic diazo components
are, therefore, the phenyl radical or the - or ~-naphthyl
radical. ~hese radicals ca~ be monosubstituted or polysub-
stituted, for example by the following substituents: alkyl,
alkoxy or alkylthio, in each case especially having 1 to 4 C
atoms; hydroxyl, cyano, nitro, sulpho, carboxyl, halogen,
particularly chlorine or bromine, or alkoxycarbonyl, especially
- - having 1 to 4 C atoms in the alkoxy radical; acyl, especially
having 2 to 5 C atoms, such as, for exanple, acetyl or butyr~l;
aroyl, such as particularly, for exampl~, benzoyl; carbox~lic
acid amide or s~lphonic acid amide, both Or which can be mono-
substituted or disubstitu-ted, for example by alkyl having 1 to
4 C atoms; alkylamino, especially havin~ 1 to 4 C atoms i~ the
alkyl radical; or arylamino, especially having 6 to 12 C atoms
i~ the aryl radical.
Examples Or suitable radicals ~ of heterocyclic diazo
components are the benzthiazolyl-(2) radical or a radical
which is derived from 2-(4'-aminophenyl)-6-methyl-benzthiaZole
(also called dehydrothiotoluidine). These radicals can also
additionally contain other substituents, such as, for exampie,
alkyl groups having 1 to 4 C atoms, sulpho, nitro and the
like.
The radical B can be derived from a custonary coupling
component, particularly ef the aromatic or heterocyclic series,
Ref 3008
161 4t~999
~l~h can also additionally carry o~her substituents
customary in dyestuff chemistry. .In particular, the radical
B is ~erived rrom a coupling component of the benzene or
~aphthalene series. Examples of suitable radicals B are, ..
therefore, radicals of coupling compon~nts of the hydroxy-
phenyl, dla~inophenyl, aminohydroxyphenyl, dihydroxyphenyl,
hydroxynaphthyl, aminonaphthyl or acetoacetic acid arylamide
~eries. Suitable heterocyclic coupling components from which
the radical B can be derived, belong? for example, to the
pyrazolone, 6-hydroxypyridone-(2) or 2,~-diaminopyridine
8eries. Preferred aromatic radicals B are a~ - or ~- -
naphthyl radical, particularly a phenyl radical, which is mono-
substituted or disubstituted by amino and/or hydroxyl, and
one amino group can also be monosubstituted or disubstituted
by alkyl, especially having 1 to 4 C atoms, or by ar~l,
especially having 6 to 12 C atoms, for example phenyl or
. tolyl, or can be monosubstituted by acyl, especially having
2 to 5 C atoms, or can be disubstituted by aryl and alkyl,
or acyl and alkyl, it being possibl~ for the - -
aryl, alkyl and acyi groups to contain, in particular, the
number Or C atoms indicated abo~e. ~he amino groups can also
be monosubstituted by carboxyalkyl or sulphoalkyl, in each
ca-~e especially having 1 or 2 C atoms in the alkyl radical.
~urthermore, the radic~ B can, for example, additionally-
contain the following substituents: alkyl, alkoxy or alkyl-
thio, in each case especia ly havi~g 1 to 4 C atoms; hydroxyl;
cyano; nitro; sulpho; carboxyl; or halo~en, particularly
chlorine or bromine; alk~xycarbon~l, especially having 1 to
_ 3 _
.
Ref. 3008
. ; - 1048999
C atoms in the alkoxy radical; acyl, especially having 2 to
5 C atoms, such as, for example, acetyl or butyryl; or aroyl,
such as, for example, benzoyl.
~ he nucleus I can, in particular, caxry one or two
me~hyl, chlorine or bromine substituents. The nucleus II can,
in particular, carry one or two substltuents rrom the series
alkyl having l to 4 C atoms, alkoxy having 1 to 4 C atoms,
chlorine or bromine. : . -
. Within the scope of the present invention, those dye-
8tuf~s of the formula I are preferred in which A represen~s a
radical of a diazo component of the naphthalene series, but
~articularly Or the benzene series,. it being possible for the
naphthalene radical,.but particularly the phenyl radical,
-- also to be monosubstituted by nitro, chlorine, sulpho, carboxyl,
alkyl having 1 to 4 C atoms, particularly 1 to 2 C atoms,
alkoxy having 1 to 4 C atoms, particularly 1 to 2 C atoms, or
acylamino having 2 to 5 C atoms, particularly acetamino, or to
be disubstituted by chlorine and/or nitro and/or sulpho and/or
alkyl having 1 to 2 C atoms, or to be trisubstituted by
chlorine, B represents a radical of a coupling component of
the hydroxynaphthyl or aminonaphthyl series, but particularly
Or the hy~roxyphenyl, diaminophenyl, dihydroxyphenyl or amino-
hydroxyphenyl series~ it bein6 possible for the said radicals,
ln particular, of the coupling component of the phenyl series
~lso to be additionally monosubstituted by alkyl having 1 to
4 C atoms, particularly 1 to 2 C atoms, alkoxy having 1 to 4
C atoms, particularly 1 to 2 C atoms, carboxyl, sulphot
chlorine or nitro, and for amino groups which may be present
. _ 4 _
.
Ref. 3008
.
104~999
also to carry a sulphoethyl, sulphomethyl, carboxyethyl,
earboxymet}lyl, acetyl, phenyl or tolyl substituent or two
d~methyl or diethyl substituents, and X represents the ~roup
-N-, -0- or -S-, particularly -NH-.
In particular, the dJestuffs according to the inven-
tion can be present in the form of sodium salts.
~ he dyestuffs according to the invention, of the
general formula I, can be manufactured by coupling a diazo-
tised disazo dyestuff which, in the form of the free acid,
eorrespo~ds to the ~eneral formula II
'' '0~ NH
J~ ~N=N-z-Nel Y (~)
(S3~)n
wherein Y~ represents an anion, preferably an anion of a
mineral aeid, for example hydrochloric or sulphuric acid,
with a coupling component of the formula III
B ~
The eoupling Or the compou~d II with the coupling
eomponent III is earried out in a manner which is in itself
known i~ an aqueous medium, which ean, however, also contain
org~nie solve~ts, sueh as, for example, alcohols, such as
methanol or ethanol, at temperatures from -10 to +30 C, pre-
ferably 0 to 20 C, in a p~I ran~e from 6 to-12, preIerably 8
to 10.
In the manufacture of the dyestuffs accordin6 to the
Rer. 3008
~ 04~999
invention, the starting components are chosen in such a way
that the final dyestuffs have an adequate solubility in the
dyeing liquor
.~he compound of the general formula II which is
required can b.e manufactured by tetrazotising a heterocyclic
diamine of the general formula IV
: . .
~U-z-ux2 = ~2N ~ N ~ 5 2 IV
in a manner which is in itself k~own, and coupling it, on
: cne side, with a l-amino-8-hydroxy-naphthalenesulphonic acid
of the formula ~ . .
~: ~ 2 V
: .(S03~) ~
This gives a monoazo dyestuff which, in the form of the free
acid, has.the formula VI:
(S03H)~
.
A diazo compone~t of the formula VII
. A NH2. VII
i8 then diazotised and coupled with t~e monoazo dyestuff of
6 -- .
.
~ Ref 3008
- ~04~3999 .
the formula VI, the required product of the ~eneral fo~mula
II bein~ thus obtained.
~he diazotisation of the compound VII and the tetrazo-
tisation of the heterocyclic diamine IV are carried out in a
manner which is in itself known. The couplings are carried
out i~ an aqueous medium, which can also contain organic sol-
vents, such as, for example, ethanol, at temperatures from
-10 to +30 C, preferably at 0 to 20 C. The one-sided coupling
o~ the tetrazotised heterocyclic diamine of the general
formula IV with the l-amino-8-hydroxy-naphthalenesulphonic
acid of the formula V is carried out in a~ acid pH range,
preferably àt p~ values from 1 to 3. The coupling Or the
diazotised diazo component with the monoazo dyestuff of the
~eneral formula VI is carried out at weakly acid or alkaline
pH values, prefe.ably at pH values from 4 to 12. 7
~ In the abovementioned coupling reactions, the reactants
are combined in a molar ratio of 1:1. It can be appropriate
to carry out the couplings in the presence of coupling
accelerators whlch are in themselves known, such as, for
example, pyridine or urea.
~he new trisazo dyestuffs of the formula I can,
furthermore, also be manufactured by diazotising a diazo com-
ponent of the formula VII
A NH2 VII
and coupling with a disazo dyestuff which, in the form of the
free acid, has the 6eneral formula VIa
04 N~
~ - N=N-Z-N-N-~ VIa
(S0311)n
7 ~
Re r . 300
; - 104~99
The diazotisation Or the diazo compo~ent VII is
carried out in a manner which is in itself known. The
coupling with the diqazo dyestuff VIa is carried out in an
aqueous medium, but which can al50 contain organic solvents,
~uch as, for example, ethanol, at temperatures from -10 to
+30 C, preferably at 0 to 20 C. The couplin~ can also be
carried out in the pre.sence of couplin~ accelerators which
are in themselves known, such as, for example, pyridine or
urea. The pH value during the coupling is normally 4 to 12.
~he disa20 dyestuff Or the formula VIa which is required can
----- be manufactured by tetrazotising the heterocyclic diamine IY
and coupling it on one sido with a l-amino-8-hydroxy-naphthalene-
sulphonic acid V, the monoazo dyestuff VIb being thus formed.
.
.' 0~ .
N=N-Z-N-N ~ vrD
(S03~)~
The coupling is carried out in the p~ range from 1 to 3.
Thi~ monoazo dyestuff VIb is then coupled with a
coupling co~ponent III (B-~) at pH values from 4 to 12, the
disazo dyestufr VIa being formed. ~hese couplings can
also be carried out in an aqueous medium, if appropriate in
the presence Or organic solvents,such aq ethanol, and/or
of couplin~ agents Or the kind already mentioned. The
coupling Or the tetrazotised heterocyclic diamine IV with the
l-amino-8-hydroxy-naphthalenesulphonic acid V is carried out
at temperatures from -10 to +30 C, preferably O to 20C, as
-- 8 --
I~ef. 300~
- ! :1048999
. is the subsequent coupling to ~ive the.disazo dyestuff VIa
Coupling accelerators of tne kind already.mentioned can be
added in the coupling reactionq.
In the case of the heterocyclic diamines of the
formula IV, the amino ~roup in the nucleus II can be in the
5-position or 6-position of thé heterocyclic system, which
iQ éxpressed in the formulae by marking the amino group bet~een
the 5-position and the 6-position. EXamples of suitable
diamines Or the formula IV are: 2-(4'-aminophenyl)-5- (or 6)-
amino-beQzimidazole, l-methyl-2-(4'-aminophenyl)-6-amino-
benzimidazole, l-methyl-2-(4'-aminophenyl)-5-aml.no-benzimi-
dazole, l-ethyl-2-(4'-aminophenyl)-5-amino-benzimidazole, 1-
propyl-2-(4'-aminophenyl)-5-amino-benzimidazole, 1-butyl-2-
- (4'-aminophenyl)-5-amino-benzlmidazole, 1-phenyl-2-(4'-amino-
phenyl)-5-amino-benzimidazole, l-benzyl-2-(4~-aminophenyl)-5
amino-benzimidazole, 2-(4'-aminophenyl)-4-methyl-5-amino-
benzimidazole (identical with 2-(4'-aminophenyl)-6-amino-7-
methyl-benzimidazole), 2-(4'-aminophenyl)-5-amino-6-methyl-
benzimidazole (identical with 2-(4'-aminophenyl)-5-methyl-6-
amino-benzimidazole), 2-(4'-aminophenyl)-5-amino-6-chloro-
benzimidazole (identical with 2-(4'-aminophenyl)-5-chloro-
6-amino-benzimidazole), 2-(4'-aminophenyl)-5-amino-7-chloro-
benzimidazole (identical with 2-(4'-aminophenyl)-4-chloro-6-
amino-benzimidazole), 2-(4'-a~inophenyl)-5-amino-6-ethoxy-
benzimidazole (identical with 2-(4'-aminophenyl)-5-etho~y-6-
ami~o-benzimidazole), 2-(2'-methyl-4'-aminophenyl)-5- (or 6)-
amino-benzimidazole, 2-~3'-methyl-4'-aminophenyl)-5- (or 6)-
amino-benzimidazole, 2~'-chloro-4'-aminophenyl)-5- (or 6)-;
g _- .
Ref. 3~
. .
. . . .
104~3999
amino-benzimidazole, 2-(3'-chloro-~ ~ninophenyl)-5- (or 6)-
amino-benzimidazole,.2-(~'-arnino~henyl)-5-amino-benzoxazole,
2-(4'-aminophenyl)-6-amino-benzoxazole, 2-(4'-amino-2'-
chloro-phenyl)-5-arnino-benzoxazole, 2-(~'-arninophenyl)-4-
methyi-5-amino-benzoxazole, 2-(4'-a~inophenyl)-5-amino-
benzthiazole, 2-(4'-aminophenyl)-6-amino-benzthiazole, 2-
(4'-aminophenyl)-6-methyl-5-amino-benzthiazole, 2-(4'-amino-
phenyl)-5-methyl-6-amino-benzthiazole and 2-(4'-aminop~enyl)-
5-chloro-6-amino-benzthiazole - ` ~
- In the case of the benzimidazoles having X = -NH-,
tautomerism is possible so that, for example, it is not ..
possible to distinguish between the 5-position and the .6-
position. If rurther substituents are present in the nucleus
II, two different methods Or numbering become possible, and
this has been taken into consideration in the preceding text.
I~sofar as the heterocyclic diamines Or the formula
IV are not already described in the literature, they can be
manufactured by various proce~ses which are in themselves
known: benzimidazoles (X = -N-) and benzoxazoles (X = -O-)
Or the general formula IV can, for example, be manufactured
as rOllOws:
Usin6 suitably substituted p-nitrobenzoic acids of
the formula VIII, the intermediate products X (anilides or
phenyl esters of p-nltrobenzoic acid)
O~J~C02}~ ~ ~{X'~) ~ O~I~C-X~
VIII IX X .-
-, - 10-
Rer. 3008
104~999
(X' denotes ~ or -0-) are manufactured by reaction with
suitably substituted anilines or phenols of the formula IX.
The anilides or phenyl esters of p-nitrobenzoic acid, Or the
formula X, which can be sllbstituted in the nuclei I and II
as mentioned initially, are nitrated, the trinitro compounds
Or the formula XI being thus obtained:
2~ C-X~ ~ N02 XI
2
.
Diami~es of the benzimidazole or benzo~azole series, Or the
formula XII
H~N ~ N ~ -N~2 XII
'
can be manufactured by su~sequent reduction Or the ~e nitro
groups and a cyclising condensation. The above reaction
sequence is described in DRP 70,862; 0. ~ym: Ber. dtsch.
chem. Ges. ~2, 1427 to 1432 (1899) and ~ 178 to 2180 (1899).
Examples of suitable ~itrobenzoic acids VIII are: 4-
nitrobenzoic acid, 2-chloro-4-nitrobenzoic acid, 3-chloro-4-
nitrobenzoic acid, 2-bromo-4-nitrobenzoic acid, 3-bromo-4-
nitrobenzoic acid, 2-methyl-4-nitrobenzoic acid and 3-methyl-
4-nitrobenzoic acid.
B~ using substituted 4-~itrobenzoic acid derivatives,
diamines of the rormula XlI which are correspondingly sub-
stituted in the rin~ I, can be manufactured.
Suitable starti~g compounds Or the formula IX are,
.-- 11 -- , .
. ~
Ref. 300~
. .
! 104~999 jJ
besides the compounds which are u~substituted in the nucleus,
also the derivatives which are substitu-ted in the 2-, 3- and
5-position of the benzene ring, for example: aniline, 2-
methylaniline, 3-methylaniline, 2-methoxyaniline, 2-methyl-
5-methoxy-aniline, 2,5-dimethoxy-aniline, 2-chloroaniline,
3-chloroaniline, 5-chloro-2-methylaniline, N-methyla~iline,
N-~thylaniline, N-propylaniline, N-butylaniline, ~I-benzyl-2-
chloroaniline, phenol, 2-methyl-phenol, 3-methoxy-phenol and
3-chloro-phenol. ~ ~
In thiR w~y substituents can be introduced into the
4~ ? 6- or 7-position of the ring II of the heterocyclic
diamines XII.
It is also possible to react suitably substituted p-
nitrobenzoic acid chlorides Or the formula XIII with 2,4- or
2,5-dinitro-aniline, 2,4- or 2,5-dini~rophenol or 2,4- or
2,5-dinitrothiophenol of the for~ula XIV, which compounds
can be further substituted in the nucleus II, if appropriate,
to give the trinitro compounds XV,
OyN ~ C ~ HX ~ ~ ~ 2N ~ C X ~ N02
~2 0
XIII XIV XV
.
and the trinitro compounds XV can be conYerted into the
heterocyclic diamines of the for~ula IV by reduction and
cyclising condensation. ~his manufacturing process is des-
cribed in 0. ~ym; Ber. dtsch. chem. Ges. 32, 1427 to 1432
;1899) and Chem. Abstr. 52, 17240 (1958) (B.A. Porai-~oshitq
- 12 - -
. Ref. 300~
.
! 1C1 4~999
and Ch. Frankowskii, Zhur. Obshch~i Khim. 2~, 928 (195~).
Examplcs of nitrobenzoic acid chlorides ~III which
can be employed are: 4-nitrobenzoic acid chloride, 2-chloro-
4-nitrobenzoic acid chloride, 3-chloro-4-nitrobenzoic acid
chloride, 2-bromo-4-nitrobenzoic acid chloride, 3-bromo-4-
nitrobenzoic acid chloride, 2-methyl-4-nitrobenzoic acid
chloride and 3-methyl-4-nitrobenzoic acid chloride
Examples of suitable dinitro compounds of the general
formula XIV are; 2,4-dinitroaniline, N-methyl-2,4-dinitro-
aniline, N-phenyl-2,4-dinitroaniline, 5-chloro-2,4-dinitro-
aniline, 5-bromo-2,4-dinitroaniline, N-phenyl-5-chloro-2,4-
dinitroaniline, 6-chloro-2,4-dinit~oaniline, 5,6-dichloro-
2,~-dinitroaniline, 2,5-dinitroaniline, N-methyl-295-dinitro-
aniline, N-propyl-2,5-dinitroaniline, 4-chloro-2,5-dinitro-
aniline, 4-bromo-2,5-di~itroaniline, 6-chloro-2,5-dinitro.-
aniline, N-phenyl-4-bromo-2,5-dinitroaniline, 2,4-dinitro-
phenol, 3-chlo.ro-~,4-dinitrophenol, 5-chloro-2,4-dinitrophenol,
6-chloro-2,4-dinitrophenol, 2,5-dinitrophenol, 4-chloro-2,5-
dinitrophenol, 4,6-dinitro-3-hydroxy-toluene, 2,5-dinitro-4-
hydroxy-toluene and 2,4-dinitrothiophenol.
The 5-isomers Or the heterocyclic diamines of the
general for~ula IV can also be obtained by reacting suitably
substituted derivatives o~ p-aminobenzoic acid XVI with
suitably substituted 2,4-diamino derivatives of aniline, phenol
or thiophenol XVII, in the presence of polyphosphoric acid, to
~ive the 5-isomers IXX:
. .
,
- 13 -
e~. 300a
i0 4~9 99
. .
b~. H2N¢~LNI~ H2N~c" ~N~2
xyr XV~I IXX
compare J. Preston, W. DeWinter and W.L. Xofferberth Jr., J.
Heterocycl. Chem. 1~2~ 6 (1), 119, and ~ ~. Bogert and M. G.
Sevag, J. Am. Chem. Soc. 53, 660 ~193~); F.~. Stephens and
D.G. Wibberley, J. Chem. Soc. 1950, 3336; M.T. Bogert and W.
S. Taylor, Collection Czechoslov. Chem. Comm. ~, 480 (1931).
The heterocyclic diamines of the general f~rmula IV
can be manufactured by yet another process, in which a suit-
ably substituted p-nitrobenzoic acid chloride XIII is reacted
with suitably substituted 4-nitro or 5-nitro derlvatives of
o-phenylenediamine, o-aminophenol or o-aminothiophenol of the
formula XX: , ,
.
Nl~} 2 ~ ~J~<~
XIII XX . XXI
,
~he heterocyclic dinitro compounds XXI which can thus be
obtained are then subsequently reduced to the heterocyclic
diamino compounds IV, compare Muttelet, Annales de ~himie et
Physique ~7] 14, 415; B.N Feitelson, P. Mamalis, R.J. .
Monalim, V. Petrow, 0. Stephenson and B. Stur~eon J. Chem.
- 14 - .
Re r . 300
- 1048999
... ; . l
Soc~ , 2389; Cllem Abstr. 67, 91987 b (1967), compare 1`
also H Hauser, I~elv. Chim. ~cta 11, 19~ (192~) a~d French
Patent 854,156.
Examples of 4-nitro or 5-nitro compounds of the
formula XX are: 4-nitro-1,2-diaminobenæene, Nl-phenyl-~-
nitro-1,2-diaminobenzene, 4-nitro-2-amino-phenol, 5-nitro-2-
amino-phenol, 6-chloro-4-nitro-2-amino~phenol, 4-nitro-2-
amino-thiophenol and 5-nitro-2-amino-thiophenol. ~~
In this way it is possible to manufacture both 5-
isomers and 6-isomers of the heterocyclic diamines IV. The
compounds of the formula XIII which have already been men-
tionedcan also be employed in these manufacturing ~rocesses.
- qhe heterocyclic diamines IV have an unsymmetrical
structure. When a tetrazotised heterocyclic diamine IV is
coupled with 2 1 -2m' no-8-hydroxy-naphtha'er.esulphcr c acid V,
the couplin~ takes place in the ortho-position to the amino
group Or the naphthalene nucleus, and two alternatives can
arise, dependin~ on which side of the tetrazotised diamine
attaches itself. Corresponding to these two alternatives,
the followi~g two structures are given for the fi~al dye-
stuffs I:
N~2 .-
A-N=N ~ N= ~ ~ -5- N=N-B Ia
(S03H~
. ~ N~2 .
~-N-N ~ N-N-~ ~ N/ ~ N-N-B Ib
(S:~)u '
~ Rer. 3008
1048999
~he trisazo dyestuffs I, manufactured in the manner mentioned,
are mixtures of the two components Ia and Ib. It can be
assumcd that the dyestuff Ia predominates in the mixture.
Examples of suitable diazo components A-NH2 of the
formula VII are: aniline, 2-, 3- and 4-chloroaniline, 2-, 3-
and 4-methylaniline, 2,5- and 2,4-dimethylaniline, 2- and 4-
méthoxyaniline, 2- and 4-ethoxyaniline, 2-methyl-5-methoxy-
aniline, 4-chloro-2-methylaniline, 5-chloro-2-methylaniline,
2,3-, 2,4- and 2,5-dichloroaniline, 2-, 3- and 4-nitroaniline,
2-chloro-4-nitroaniline, 2-methyl-5-nitroaniline, 2-nitro-4-
methylaniline, 4-aminobenzoic acid, 4-aminobenzoic acid amide~
?-~ 3- and 4-amino-benzenesulphonic acid, 4-aminobenzene-1,3-
disulphonic acid, 2-amino-5-nitro-benzenesulphonic acid, 4-
nitro-4'-amino-diphenylamine-2-sulphonic acid, 4-aminobenzene-
sulphonic acid amide, l-amino-naphthalene, l-amino-naphthalene-;
4~sulphonic acid, 1-amino-naphthalene-3,6-disulphonic acid,
2-amino-naphthalene-5-sulphonic acid, 2-amino-naphthalene-
3,6-disulphonic acid, dehydrothiotoluidine, 2-aminobenzthia-
zole, 2,4,5-trichloroaniline and dehydrothiotoluidine
sulphonic acid.
Examples of suitable l-amino-8-hydroxy-naphthalene-
sulphonic acids of the formula V are: l-amino-8-hydroxy-
naphthalene-3,6-disulphonic acid, 1-amino-8-hydroxy-naphthalene-
4,6-disulphonic acid and 1-amino-8-hydroxy-naphthalene-4-
~ulphonic acld.
Example~ of suitable coupling components B-H of the
~ormula III are: phenol, 2-methylphenoll 4-methylphenol, 3-
chlorophenol, 3-methoxyphenol, 1,3-dihydroxybenzene, l-amino-
3-hydroxybenz~ne, 1-a~ino-3-hydroxy-~-chlorobenzene, 1-(2'-
- 16 -
~er. ~oo~
1C3 48999 .
!
methyl-phenylamino)-3-hydro~y-ben~ene, 1,3-diaminobenzene~
1~3-diamino~ methyl-benzcne, 1,3-diamino-4-chloro-benzene,
1~3-diamino-4-nitro-benzene, 1-amino-3-dimethylamino-benzene,
l-acetylamino-3-diethylamiIio-benzenc, l-amino-3-carboxymethyl-
~mino-benzene, l-amino-3-carboxyethylamino-benzene, l-amino-
3-sulphomethylamino-benzene, 1-amino-3-sulphoethylamino-
benzene, 1,3-diaminobenzene-4-sulphonic acid, 2-hydroxybenzoic
acid, 2-hydroxybenzenesulphonic acid, 2-hydroxy-naphthalene,
2-hydroxy-naphthalene-3-carbc~ acid, 2-hydroxy-naphthalene-
6-sulphonic acid, 2-amino-5-hydroxy-naphthalene-7-sulphonic
acid, 2-amino-8-hydroxy-naphthalene-6-sulphonic acid, f-phenyl-
3-methyl-pyrazolone-(5), ~,4-dihydroxyquinoline, 5-cyano-6-
hydroxy-pyridone-(2), acetoacetic acid anilide and 4-methyl-
5-cyano-6-hydroxy-pyridone-(2).
The ne~ trisazo dyestuffs are outstandingly suitable
for dyeing and printing natural or synthetic ~ibre materials
containing hydroxyl groups or containing nitrogen, particularly
cotton and regenerated cellulose, as well as ~ool, ~lool-cotton
union, silk, polya~ide, leather and paper. The dyeing and
printin~ is carried out by the customary processes. Blue,
green and black dyeings uith ~ood fastness properties are
obtained on the substrates mentioned. ~he new dyestuffs are
distinguished particularly by good fastness properties to
washing and perspiration. If X ~ -N-R-, particularly -NH-,
the new dyestuffs normally do not need to be salted out during
their manufacture and pr~vide manufacturing effluents con-
taining Yirtually no dyestuff. ~.~en dyein~ by the exhaustion
process, they are also very largely absorbed onto the fibres
-- 17 - .
R~f. 3008
.
104~999
to be dyed, so that a nearly clear residual iiquor is
obtained. The new dyesturfs are particularly suitable for
dyeing linin~s made of cotton and re~enerated cellulose, and
for dyein~ polyamide.
In the examples which follow, parts denote parts by
weight and percentages dcnote percenta~es by weight; the
temperatules are quoted in degrees centi~rade.
Example 1
30 parts of 1-amino-8-hydroxy-naphthalene-3,6-
disulphonic acid are dissolved in 100 parts of water by addinB
sodium carbonate to such an extent that the so~ution has a pH
value of 6.5.
22.4 parts of 2-(4'-aninophenyl)-5- (or 6J-amino-
benzimidazole in a mixture of 200 parts of water and 50 parts
of ~ stren~th aqueous hydrochloric aci~ are tetrazotised,
while adding ice at 0 to 5C, with a solution of 13.8 parts
of sodium nitrite in 50 parts o~ water.
After the a~dition of the sodium nitrite solution,
the mixture is fur'her stirred for approx. 1 hour at O to 5C
and excess nitrous acid is then removed by means of amido-
sulphonic acid. ~he solution of the l-amino-8-hydroxy-
naphthalene-3,6-disulphonic acid is then added dropwise to
the solution of the tetrazo component, the pH of which has
been raised to 2 using 10% stren~th sodium carbonate solution,
and the one-sided coupling is completed by stirring at 10 to
15 C and adding l~o strength sodium carbonate solution until
the pH value i9 2.5. A benzenediazoniwn salt solution,prepared
at O-C in a known manner from 8.45 parts of aniline, 25 part~
- 18 -
ner. 300~
1048999
Or 30~o strength aqueous hydrochloIic acid and a solution of
6.3 parts Or sodiu~ nitrite in 20 parts Or water is then
added to the suspension, cooled by means Or ice to 0-5 C,
of the diazotised monoazo dyestuff, and the p~ value is
adJusted to 8.5 to 9 with l~/o strength sodium carbonate
solution. A solution Or 10.3 parts of 1,3-diaminobenzene in
100 parts of ~ater is ad2ed to the resulting suspension of
the green, diazotised disazo dyestuff. Stirring is continued
for 3 hours at 5 to 10 C and the p~ value is then adjusted to
7.5 with 3~,o stren~th hydrochloric acid, as a result Or which
the dyestuff is precipitated. The dyestuff is filtered off
and dried.
A solution of 0.2 part of sodium carbonate and 4
parts of sodium sulphate decahydrate is prepared, at 40 C, in
200 parts of water in a dye bealcer placed in a bath which can
be heated.
0.2 part of the dyestuff which has been prepared are
then added. 10 g of a cotton fabric are kept in continuous
motion in the ready-to-use dyeing liquor, the temperature is
raised to 95 C and dyeing is carried out for a further 45
minutes at this te~perature. The dyed cotton fabric is then
withdrawn from the residual liquor, which is now only slightly
coloured, and the liquor still adherin~ is removed by wringing
out. The dyed material is then rinsed with cold water and
dried at 60 C.
~ his gives a deep n_ack dyeing with ~ood fastness
propertiea, particularly good fastness to washing and perspira-
tion~ -
19
,
; Ref 300~
1~4~999
. . . .
22.4 parts of 2~ aminophenyl)-5- (or 6)-amino-
benzimidazole in a mixture of 200 parts of water and 50 parts
Or 30~o stren~th aqueous hydrochloric acid are tetrazotised,
while addin6 ice at 0 to 5 C, using a solution of 13.8 parts-
of sodium nitrite in 50 parts Or water.
. . After the addition of the ~odium nitrite solution,
stirring is continued for about 1 hour at 0 to 5 C and-excess
nitrous acid is then removed with amidosulphonic acid.
A solution Or 30 parts of 1-amino-8-hydro~y-naphthalene-
3,6-disulphonic acid in 100 parts.of water, which is adjusted
to pH 6.5 with sodium carbonate, is then added dropwise over
the course of 1/2 hour to the solution of the tetrazo com-
ponent, the pH of which has previously been raised to 2 using 10%
stren6th sodium carbonate solution. The one-sided coupling
lS completed by stirrin~ at 10 to 15 C and adding 105~ strength
aqueous sodium carbonate solution until the pH vzlue is 2.5.
A solution of 10.3 parts Or 1,3-diaminobenzene in
100 parts of water is then added, the p~ value of the mixture
is raised to ~.5 to 9 using l~io stren~th aqueous sodium car-
bonate solution and the mixture is stirred for a further hour
in order to complete the coupling reaction; A benzene~azon;l~m
salt solution, prepared at 0C in a known manner from 8.45
parts of aniline, 25 parts Or 3~ stren~th aqueous hydro-
chloric acid and a solution Or 6.3 parts of sodium nitrite in
~n parts Or water, is then added to the ~ixture of the resulting
disazo dyestuff, the p~l value of the mixture is adjusted to
8.5 to 9 usin~ stren~th aqueous sodium carbonate solution
- 20 -
~ Ref. 3008
.
104~999
and stirrin~ is continued for sevcral hours at this pH value.
After the coupling iq complete , the tri6azo dyestuff
is isolated - after adjusting the pH value to 7.5 using 30%
strength aqueous hydrochloric acld - a~d is dried.
The product obtained in this way is identical with
the trisazo dyestuff obtained in accordance with ~xample l.
The structural composition Or other dyestuffs which
can be prepared in accordance with Ex~ples 1 and 2, can be
~een from ~ables I and II.
~ le following dataare given in the tables:
In column l. the diazo component A-NH2 used.
In column 2: the l-amino-8-hydroxy-naphthalene-
sulpnonic acid of the formula
q~ ~ 2
,~, ;'.', '-.
3 )n
used, only the number and the position
Or the sulphonic acid groups being given
in the table.
In column 3: the heterocyclic diamine used, hetero-
cyclic diamines of the formula
~2~ ~ \N ~ NH2
5l 6' 3 4
that is to say the $-isomers, being
listed in ~able I and heterocyclic
: diamines of the formula
- 21 ~
,
Re r . 300
104t~9S'5~
3~ 2~ I 7 - '
H2 ~ - <`N ~ ~'H
, ~ that is to say the 6-isomers, being
listed in 'rable II. The meanin~ of -X-
is indicated in the first part of
column 3. Additionally, column ~ alsv
lists possible substituents and their
position in the molecule, the numbering
being put first. The entry ll_NX_, 4-CH~"
in column 3 o~ Table I therefore denotes,
ror example, the compound
2 ~ ~ ~H~ H2N ~ H ~ ~H2
CH~ C~3
Owing to the possibility of tautomerism,
thi~ compound can be designated as 4-
methyl-2~ '-aminophenyl)-5-amino-
benzimidazole or as 7-methyl-2-(4'-
aminophenyl)-6-aminob,enzimidazole.
In column 4: the coupliIIg component BH used.
In colun~l 5: the colour shade of the dyestuff on
cotton. ' '
.
.
'
-- 22 -- .
Rc ~ . 300
1048999
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Rcr. 300
1048999
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- 26-
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104~999 Ref, 3008
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~ 27 -
