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Патент USA US2404198

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~ Patented July '16, 1946
2,404,198
" I ~ UNITED": STATES. PATENT OFFICE <
2,404,198
DISAZOJAND POLYAZO BENZIDINE TYPE
DYESTUFFS
.
'
Fritz Straub, Kaiseraugst, near Basel, and Jakob
Brassel, Basel, Switzerland, .assignors to Society
of Chemical Industry in Basle, Basel, Switzer
»
-
land, a Swiss ?rm
No Drawing. Application August 23, 1943, Serial
Nc.">499,707.
'. 1942v
In Switzerland September 3,
1'
~15 Claims. (Cl. 260-159)
l
.
The present invention is?conce'rned with disazo
and polyazo'dyestuifs, more particularly those of
r
2
a
" ,The'tetrazotization of the 3-hydroxybenzi'dine
‘may be conducted in known manner, for .in
stance in a hydrochloric acid solution.
the direct dyeing (i. e. substantive) series. Still
v‘more particularly it is. an ‘object of thepresent
‘For the coupling with the tetrazotized 3-hy
vinvention to provide new dyestuffs capable. of
forming‘ complex metal compounds, especially
such dyestuffs ‘of the saidseries,[_the complex
-- droxy-benzidine there may be usedtwo molec
ular proportions of the same or different cou
pling components of which, however,.at least one
metal compounds of which are substantially ,in
must be a pyrazolone.
‘soluble in normal baths used for textile treat
Further azo components to be united with
ments, whereas the parent dyestuffs free from .10 the tetrazotized 3-hydroxybenzidine may belong,
complex bound metal iareper?fectly. solublewand
for instances. to the benzene, or naphthalene se
- . can be dyedin-thwsual waywTheréis ‘a stwng
_. .demand for such dyestuffs," especially since the
;simple and effective-dyeing method of 'U. S. Pat
.1 -ent.2,148,659 (ct-also French Patent;80,9',893) has
; become known’, .Especially dyestuffs dyeing vred
.ri_es,;>;po_ssess_ a heterocyclic system, '-or_ contain
5.
a. carbon atom capable “of coupling __in an open
chain-There may- for. instance be mentioned
phenols and particularlysalicylic' acids, resorci
, shades, such asare obtainable according tothe
nol, naphthols, naphthol-mono- and -dis'ulfonic
acids, aminonaphthols and the sulfonic‘ acids
Nt'his‘invention, numerous dyestuffs derived (from
- thereof. Among the pyrazolones'there come par
- ticularly into consideration such products which
present invention, are highly. valued. “Prior to
s
.. benzidine-and dianisidine havebecome known. 20 arevsubstituted in known‘manner, for instance,
Due to the lack of complex-forming groups ‘in
by an aryl radical in l-position and/or .bya
ortho-position to the azo-groups in the ben
.methyl or carboxyl group in 3-position. In. this
zidine dyestuffs, these are not capable of form
case {also the aryl nucleus, for example the ben
I. ing complexlmetal, compounds unless ‘coupling
zene nucleus, may carry substituents such as for
,components are used .whichrare by themselves
(i. e. without the aid-10f, a complex form-in'ggroup
25 example a sulfamide, nitro or amino group, as
vwell as the salicylic acid grouping.
in the diazo component) capable of forming com
plex metal compounds, such as salicylic acid or
ortho: ortho'-dihydroxy-azo-dyestufis capable of
coupling, etc. Thereby the choicé‘of coupling
components is obviously very restricted; The
methoxy groups in ortho-position to the azo
groups in the dianisidine dyestuffs act, it is true,
as complex forming groups, but the complex metal
compounds obtained vwith “these dyestuffs’ are
I j
_, be‘ present in the pyrazolones, such as in the,
,
‘
case
of
1-(3'-carboxy-4'-hydroxyphenyl)-3
methyl-5-pyrazolone.“
.
-
,_
. In his manner a great number of’ very [valu
able disazo dyestuffs may be obtained according
to the. present invention. For the production of
rather unstable and often do not withstand even
mild soaping.
.
Particularly valuable dyestuffs are in many
I_'cases'obtained if as at least one azo component
.such, a component is used which-contains the
salicylic acid grouping. This grouping may ‘also
,
. trisazo and polyazo dyestuffs there are‘advanf
Furthermore, it is well known in the art that
many valuable acid wool dyestuffs are obtained
. tageously used azo components which contain? an
' ries.?_As far as we are aware, nothing was known
Further also such azo ‘components. may be used
which are capable of repeated coupling, 'or also
such components which lend themselves to other
amino group capable of further diazotization
with coupling components of the pyrazolone se-;v;4 0. orva substituent convertible into such. a, group.
prior to the present invention which would in
dicate a bene?cial effect to be expected in using
pyrazolone coupling components in the manu
facture of-substantive azo ‘dyestuffs of‘uthev said
kind.
'>
"
an
connecting ‘reactions leading to the synthesis of
polyazo dyestuffs, “such as urea formation, reduc
tive connection of two nitro groups, etc. ‘As ex
-'. ‘i
amples there are mentioned 1-(3'-aminophenyl)-_
It has been found that ‘valuable disazoiand
polyazo. dyestuffs may be obtained by coupling
3-methyl-5-pyrazolone, 2-amino-5-hydroxynaph;
tetrazo compoundsrwith azo components, if de
thalene-7-sulfonic acid, resorcinol and 5:5'-di
-- sired ‘by using further couplingor connectingre-q 5 0 hydroxy-2i2'-dinaphthylamino - 7:7’ - disulfonic
I actions, if as a tetrazo compoundgtetrazotized 3
hydroxy-4:4’-diaminodiphenyl, and, as at least
one, azo component a; pyrazolone are used and,
acid. ' The dyestuffs thus obtained may then be
_ converted in known manner into trisazo or poly
ago dyestu?s. Furthermore, trisazo and polyazo
dyestuffs are of course obtained by using coupling
if desired, causing agents yielding metal toreact
, with; the dyestuffs thus ,obtained.', . 7.
Oi
components containing azo groups in at leastone
2,404,198
,
,
3
V
stirred for 1 hour at 10-12° C. and for 20 hours
; place, for example azo dyestuffs containing a car
at 15-20" C. The dyestu?' is precipitated‘ by the
bon atom capable of coupling in a benzene ring‘
addition of common salt.
I (such as mono-coupled resorc'inol dyestu?s) or
When dry, it is a dark
‘ r=powderof they-formula
in a naphthalene ring-(such asYaZodyestu?sirOm
'
‘a
‘anyx-diazolcompounds and am'inoenaphtholsul
j fonic acids coupled in an acid medium), etc. '
It is to be remarked that the two diazonimnj
groups in tetrazotized‘ 3-hydroxyz-4 :AV'H-liiaminQ-H
3 diphenyl possess a rather differentcouplinggen-i.
‘ ergy, in that the 4'-diazonium group couples ?rst"
‘ andthe 4-diazonium groupe‘cin lort'ho position :to'
coon‘
‘ the 3-hydroxyl group) afterwards. jmlfreiieforegitf; '
‘ is well possible, and in many iins'tancesipi-‘e?‘er'abile; '
l to unite the said tetrazo compounds with two dif
:15
‘1 ferent
component
coupling
may becomponents;
selected tocontaina
jllhusp -:the
grouping
.
#1 wfh'ich?ii'issolves
capable of forming complex metal compounds by I
; itself, whereas the second coupling component
‘ brings about a complex forming group "by a; sim
water to an orange-brown, in
dilute alkalies-‘It‘o'1an orange-red and in concen
trated sulfuric acid to a ruby-red solution and
dyes vegetable ?bers red tints which are fast to
Ivple coupling inorth'o-position vto a hydroxyl 20é>washing and light on'f'beingdyed and coppered
group; in
jofithe *hydr'ox-yl - group standing in
T'ortho position tQTthe diazoniu‘m sgroup in~'the=di
V
‘"azo‘compon
p fl‘hedyes‘tfui‘fs
v . 1obtained according
_
' tiavvlthepres
~
V ‘ jjen‘t'inyention are'suitable fordyeingand‘pziinting
‘£13119 Vfll'lUSlJ various animai and particular-1y ce‘llue
% *lc‘s'ici?bers, such as wodL'silk/leather,randlespeé
j cially cotton2 linen, rayonga‘nd staplef‘?bersfrom ‘
;' ‘regenerated ‘cellulose; every ya'luablered; shades, Q
n
= 130] "
7 ‘among other shades, are ' also obtained.
‘ I 556' partsrllo‘f;'?ihydroxybenriidme are tetrazo
Favorable results are ‘obtained if ' “g
i‘. tifzed "with sodiuml'nitrite-in v‘the- us‘ual ‘manner '
' and in _i- thepresence bfr'li'lhydi‘o‘éhlb?c ac'idf ‘I ‘The
‘clear, solution Fof ‘the ‘tetrazocompound is added
‘351 *at 51-01-15" "C: 'to‘ ya solution" “alkalinewith ‘sodium
ii'?iéreiiroims' lending ‘solubility; t0 5 ‘
,
“ ‘particuiarlysulfonicfacid groups isiconst'ituted
'in~ surch*a_;__i'nanner that alsoits complex-'metal ‘
I carbonate Yo‘f- “7173, parts-of ‘the dyestuff prepared
'j ‘by’_ vcoupling ' l moL-?o'f “diazotized fZ-am'ino-“I
' phenol-4e‘su-l'famide'with ‘il-mol'.‘ "6f resorcinol in
'- “a ‘medium
‘I
V ‘alkaline ‘with sodium carbonate. _'1 ‘The
v I
1:; compounds produced ' in ‘substance, -_' for "instance 4Qiwhcle is stirred for ‘1" hour atv 10-42“ ‘C: and a’ .l
gccmplexfccpper compounds, are soluble, the lat
c 5 \ter‘may be ‘produced known-‘manner and used
ifjfor fdyein'g. _ Dyeings'of‘ particularly good “fast
i Jjl'one is 'added- to the-coupling mixture} igtniringis/
"IE-118°C. and couplin‘g'is
If ne'ss to'rwet treatments are ‘obtained inmany in- ‘ ' "continued “for ‘l'hourfa't
V
‘ stances with such dyestuffs, Iobtainaible according :45’ ‘completed by heating‘ the mixture i-"foi *2'?é3'05h011rs
to the presentjinvention;whose v‘complex metal
f to 35440" c. The trisazo'e'dyestiiil’ crtnerdimun
j 'compounds- are ‘sparingly soluble to'insolume.
use is made ‘oijsuch dyestuffs itj-is "of advantage
' after-coppering process, or’m'or'esimplyaccordé
‘~ ing to the ‘dyeing ‘process-known ‘for-example from
1. ‘the U. ‘S; ‘Patent "No; 1148;6759 _ *(see also. Fren‘c'h
‘ Patent No. 809,893) according to‘whichidyein‘g is
;" conductediin' ‘the; same ‘bath as‘ltheafteir-treat- ‘
1,_ vmien-t- withiagents “yielding ‘meta-l, particularly ‘
agentsj yielding copper. , Such agents ‘yielding
icopper‘mainly come into consideration ‘which ‘are
‘ stable ‘towards ‘alkal'ie's, such
complex copper
I"tartrates,
[The following
H
,examples
,7
V 'illu'strateithe
'
inven
j Iti'o'n; ‘thepartsbeingby weight‘:
‘
'
‘
Example‘ 1
‘
~
A
“ tized with sodium nitrite :in-ft-he usua’ljmanner
‘ andjinj'thejpresence-10f hydrochloric; acid. v"The
solution
"
“theltet'razoicompound is mixed at157° "C.
"and“dilu‘te So'cl?umY-carbOIIate sermon: tore} Jbor
'"th a ‘solution iofjf3.5 ‘parts of salicylic acid-and
A‘. jpalrts of vsodium ‘hydroxide in E'Oparts'o'f water,
j ‘and‘the vinixtrlr'e 'iisistirred ‘for hour at ‘445° 'C.
"d'eaux »red,‘*in “dilute causticifalkalies to a; brown
70 > red- and i in concentrated hydrochloric acid
a
" ‘After jthis ‘time thefmonoazo-dyestuff ; is. formed.
1; ‘dichrdic 'redi-blue -¢so‘luti_on~wliich" ‘dyes vegetable
f Afsolution;‘of“5;8‘5*parts of 1-‘(4'-hydroxy-f3"=car
fboxyplrenyli j-v3-methyl-‘5 epyrazolone and '12- parts
~~washmg onsbeing ' ‘dyed'? and-coppered according
1-‘0'1’s0di‘unrlmdrogtidein‘50 parts of water-are now,
_
v and hydrochloric acid. When dry, it is a-igre‘en
' powder‘o'f bronze l-us'tre,-' whlch-édiss'olves?in water
‘ ' ‘aidd'edto'the ‘coupling mixture;
?bers ' iiiole‘t -" *‘brown- ‘shades ‘*Wl?'?h lare'l 'T‘fast’ ito
" to‘the one‘bath'process;
The mixture ‘is l 75
"
"
_'
'_
Similar dyestuffs ‘having ‘it-he same-'11 ifastness
‘incomes
‘I5
'
.
-
properties? can- be obtained by replacingthe 2
amino-1-phenol-4-sulfamide v.used in this exam
-1‘.~ Azo dyestuffs ofthe general formula , j 4 ~,
ple by other ortho-aminophenols,‘for-example by
the equivalent quantity of 4-nitro-2-a'mino-1
phenol.
'
,
2...
*5
Example 3
5 parts of 3-hydroxybenzidine are tetrazotized
,wherein R" stands fontlie', radical of a" coupling
with sodium nitrite in usual manner and in the
presence of hydrochloric acid. The solution of
the tetrazo. compound isadded at 5° C. to a solu
the radical of a pyrazolone coupling component.
component selected-fromthose belonging ‘to the‘
benzene and naphthalene series and Rastandsfor
.2 AZO dyestuffs 0i the genera! female.
.. 1 .
tion of- 3.46 parts of‘salicylicacid and-6,.p'arts of,
sodium hydroxide in. 40 parts of'water. The
whole lisv stirred for 1/2 hour. at .4-.6° ‘Cs; a solu
tion 'of 4.73 parts of .,1-'(3'-aminophenyl)-.3- “15
wherein R stands for the radical of a coupling
component selected from those belonging to. the ,
methyl-‘5-pyrazolone and‘ 2 parts of sodium hy- "
droxide ‘in 50 parts of water is added and stirring
is continued for~1 hour. at:10-12.° C..: and 20-25
hours at:I5-20° C. ‘I "After-neutralizing with hydro-I
chlorlc acid the disazo-dyestu?'is ?ltered-janddis- Q0
benzene and naphthalene series, and P2 stands
for the radical of a pyrazolone coupling3..com.
ponent, at least one of the said coupling ‘com
solved by the addition of 1.2 parts of sodium hy- ‘ ‘
ponents containing a grouping capable of form;
droxide in 400 parts of water.‘ 25 parts byvol
ing
' 3. complex
Azo dyestuffs,
metalcompounds.
of the generalbyformula
itself.’ . ~
ume of N-sodium nitrite solution are added to
the dyestuffsolutioncand themixture is cooled
to 5° C. 60 parts by volume’ of.E21\I.-hydrochloric__n
acid are :poured to the.solution=-while stirring‘~‘
OH
well. " The te'mperatureis maintained for 15-20
wherein
stands for the radical of a coupling
‘component selected from those belonging to the
hours at 10-‘15" C; and the diazodisazo-dyestu?is
?ltered; This is introduced,“ in the- form-of a
moist'paste, into a solution of‘ 5.85 parts of§1~-‘ ,_,
benzene and naphthalene series, and Pa stands
(4’-hydroxy-3'-carboxyphenyl) .-'3-‘methyl-5-'pyr
for the radical of a pyrazolone coupling com
ponent, at least one of the said coupling compo
nents containing a salicyclic acid grouping.
azolone and '6 parts of sodium hydroxide .in 90
parts of water.v ‘Stirring is continued for. 1 hour
at 10-12° C; and coupling is completed‘at 18'—20°;C.
4- AZOF dyestuffs of lthevrgeneralaformula; > _., ‘
wherein R'?stands: for the radical of a’cOupIing
component, selected from those belonging to the
benzene and , naphthalene series, containing a
grouping capable of forming complex metal com
pounds by itself, and Pa stands for a pyrazolone
coupling component.
5.‘ A20 dyestuffs of the general formula
a
-
'
OH
The trisa'zoidyestu‘ff of the formula is precipi-e-gp wherein R stands for the“ radical of a coupling
tated and dried. It is a dark powder of rue
component, selected from those belonging to the
tallic lustre which dissolves in water to an or
benzene and naphthalene series, containing a
ange brown, in dilute alkalies to a red brown and
grouping capable of forming complex metal com
in concentrated sulfuric acid to a bordeaux red
pounds by itself, and P2 stands for a pyrazolone
solution and dyes vegetable ?bers red tints of 55 coupling component ‘also containing a grouping
very good fastness to light and washing on being
capable of forming complex metal compounds by
dyed and coppered according to the one bath ' itself.
process.
6. Am dyestuffs of the general formula
Example 4
100 parts of cotton are introduced at 50° G. into 60
a dyebath containing in 2500 parts of water 2
parts of sodium carbonate and 1.5 parts of the
dyestuff prepared according to Example 1, ?rst
paragraph, and the temperature is slowly raised,
to 90-95° C. 30 parts of Glauber’s salt are added
wherein R stands for the radical of a coupling
1‘ component, selected from those belonging to the
' benzene and naphthalene series, containing a
grouping capable of forming complex metal com
pounds by itself, Pz stands for the radical of a
after 1/4, hour and-dyeing is continued at this
temperature for a further 3/1 hour. The bath is
then cooled to about 70° C., the necessary quan
=pyrazolone coupling component, and wherein at
least one of the components R and Pa contains
tity of a solution of complex copper tartrate» made
.
feebly alkaline with sodium carbonate is added 70 at least one azo group.
7. Azo dyestuffs of the general formula
and the material is coppered at 80-90“ C‘. for 1/2
hour. It is then thoroughly rinsed and soalped for
' a short time, if necessary.
fast red tints.
What we claim is:
The cotton is dyed
75'
I
coon
v
\on
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