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Патент USA US2408962

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Patented Oct. 8, 1946
2,408,961
-'
UNITED .STATES' PATENT OFFICE
2,408,961
TRISAZO METALLIZABLE DYESTUFFS
.Fritz Straub, Kaiseraugshnear Base1,-:and Jakob
Brassel and. Hans Mayer,.Basel, Switzerland,
assignors to the ?rm SocietyVof Chemical In
dustry in Basic, Basel, Switzerland
No Drawing. Application September 10, 1943,
Serial No.. 501,868. In Switzerland September
.12.,1942
'6 Claims.
1
2
'7
.
_
diazo components, 1. e., para-nitraniline,- ll-ami
The present invention is concerned with. azo
dyestuffs containing at least two .azo groups.
no-‘l'—nitrodiphenylamino-2'-sulfonic acid,» sul
fanilic acid, metanilic acid, and the‘halogen sub
stitution products thereof, aminophenols such as
More particularly it provides valuable new dye
stuffs of the type capable. of forming complex
5-nitro-2-amino-l-phenol, 4-nitro-, ~4-methyl
and 4—chloro-2-amino-1-phenol-6-sulfonic acid,
metal compounds. Further objects will appearas =
.the speci?cation proceeds.
6-nitro- .or
It is well known in-the art that resorcinol (i. e.
6-chloro~2-amino-1-phenol-ll-sul
fonic acid, Z-amino-1-phenol-6-carboxylic acid
Ll-sulfonic acid,A-nitro-Z-amino-l-benzoic acid,
4.: G-dinitro-Z-amino- l-phenol, v4--methyl-2-ami
1:3-dihydroxybenzene) is capable of coupling
more than once, in View of the two hydroxyl
,groups. present, in thebenzene nucleus. .A con-:
siderable number of azo-dyestuffs has been. pre
pared in which resorcinol is used as a twice-cou
no-l-phenol-B-sulfonic ~ acid, .3 : 6-.dichloro-2-ami
. nod-phenol-li-sulfonic acid, l-amino-Z-hydroxy
i cheap. product because it is easily ‘obtainable on
. medium, e. g. alkaline with bicarbonates, car
:naphthalene-4<-sulfonic acid and the-1 substitution
pling azo component, comprising direct dyeing
Coupling with .an 1:3-dihy
_ products thereof.
(substantive), mordant dyeing, and acid wool
dyestu?s etc. Resor'cinol is r a comparatively $15 ,droxynaphthalene maybe effected in an alkaline
bonatesor in a‘caustic alkaline medium. ‘If de
sired two-molecular proportions of diazo com
. an industrial scale, and therefore there .is noth
ing to prevent its use in the manufacture of ‘dye
- stuffs.
1In J contradistin'ction , to " this,
1‘: 3-dihydroxy
_ ponents may be-combined in one step or succes
20 sively in .two steps - with 1:3-dihydroxynaph
0t‘ so ' easily obtainable'and has
industrial use‘aslfar as is known.
" It was to be expected ‘that-the 'fused-on‘benzene
ring in > ‘the 1:3-dihydroxynaphth‘alene (:536
. thalenes.
naphthalene is
' not found an
benzo-lz3edihydroxy benzene) :would render cou
pling reactions substantially more’ difficult than
with resorcinol and it could-"not-be expected o?
wheniusing twov identical or different diazo
. components of the saidkind, ‘among which only
one needs to possess .a lake-forming group, a
25' great number of very valuable disazo dyestuffs
hand that 1:3-dihydroxynaphthalene ‘would be
> capable at all of coupling twice. *MOI'GOVBI' there
~wasv nothing to induce any expert-to try 1:3
dihydroxybenzene in the manufacture of disazo
and polyazo dyestuiis as component coupling
twice. Contrary to every expectation, applicants
have found it worth while doing so, because the‘
dyestuffs thus obtained have unexpected superior
are obtained.
'
In many instances there are preferably used
dia-zo» components containing azo groups which
are ‘obtainable; for-instance by couplingxa diazo
compound with a middle component. ‘Particu
larly valuable dyestuffs are in many cases ob
tained by using diazo compounds which are ob
tained by a one sided coupling of tetrazotized
diamines, particularly of the benzidine series,
with coupling components. In this case particu
larly" also such coupling components come into
properties in many respects.
'
It has now been found that valuable disazo ' ' ' consideration which possess lake-forming groups
and polyazo dyestuffs, and particularly trisazo
such, as, the salicylic acid grouping, e. g., salicylic
dyestuffs to which the appended claims are di
acid and its substitution products capable of
rected, may be obtained if for their synthesis 1:3-dihydroxy-naphthalene is used as twice cou
coupling.
pling azo component and if agents yielding metal
‘~ are-causedto. react with the dyestuffs thus; ob
=tained, if desired.
For the synthesis of ‘the dyestuffs the-known ‘
diazo components maybe used according‘ to the
present’ process;’ for- instance such of the benzene,
naphthalene and. particularly also of the benzi
dine series. ' In‘ many cases also such diazo com
pounds maybe used with advantage which possess r
lake-forming groupsjforexample, a 'hydroxyl
group, a carboxyl group, an alkoxy' group or an
alkoxy-carboxy groupin ortho-position to the
A series of particularly valuble trisazo dyestuffs
is-obtained ~if~a 1:3-dihydroxynaphthalene is
coupled on the one hand with a diazotized amine
of the aryl series containing in ortho-position to
the diazo group a lake-forming group and on
the‘ other :hand with a diazoazo compound, which
is obtained byv one sided coupling of a tetrazo
tized benzidine with an ortho-hydroXy-aryl car
boxylic acid capable of coupling. The coupling
may be conducted with advantage in ‘the said
sequence or also in areverse order. In this
manner there is obtained a series of predomi
nantly brown 'dyestuiis of good fastness proper
diazo group. Thus for example, benzidine and its
55 ties.
substitution products come into consideration as
2,408,961
4
The dyestu?’s obtainable according to the
1/2 hour at 4-6“ C. to a solution of 8.5 parts of 1:3
present process may be used for dyeing and printdihydroxynaphthalene, 8 parts of sodium carbon
ing the most various animal and in particular
ate and 5 parts by volume of caustic soda solution
cellulosic ?bers. Many of the disazo dyestuffs
of 30 per cent. strength in 50 parts of water.
produced according to the present process are 5 After stirring for 1 hour at 5-8° C. coupling is
for example suitable for W001, silk and particucomplete. The dyestu?’ of the formula
on
on
H
OOH
'
SOgNHg
larly leather, whereas, when using substantive
components, disazo and principally polyazo dye-
is separated by addition of 30 parts of sodium
chloride and ?ltered oif. It is introduced in the
stu?s are obtained, which are predominantly
form of a paste into the suspension of the diazo
useful for cotton, linen, rayon and staple ?bers 15 azo compound prepared according to the ?rst
from regenerated cellulose.
paragraph. The whole is coupled for one hour
If by a suitable choice of the components care
at 11-12° C. and for 50 hours at 18-20° C., where
has been taken that the dyestu? contains lakeupon the temperature is raised to 90° C. and the
forming groups in the molecule, these dyestuffs
trisazo dyestu? formed ?ltered from the hot re
can be converted in substance, in the dye-bath 20 action mixture. When dry it is a dark powder
or on the fiber into complex metal compounds.
which dissolves in water and sodium carbonate
In this case, for example, chromium, cobalt, iron
solution to a yellow-brown, in dilute caustic
and particularly copper are coming into consideralkalies to a brown-red and in concentrated
ation as suitable metals. The conversion into
sulfuric acid to a violet solution. Cotton is dyed
such metal complex compounds may appro- 25 havana brown shades which are fast to washing
priately be conducted in substance if the dyewhen dyed and coppered according to the one
stu?, due to the presence of a su?icient number
bath process.
of groups promoting solubility, e. g. sulfonic acid
Example 2
groups, possesses also in the metallized state
still a su?lcient solubility. Many of the metal- 30 11-2, PM,“ "I f1‘°h1°r°'Z‘a‘mM'I'PheMI'G‘
merous dyestuffs thus obtained are remarkably
sulfomc acid are diaaotized in the usual manner
suitable for the dyeing of leather. Those dyewith hydrqchloric acld and sodium mtnte' The
stu?s, the complex metal compounds of which
dlazo solufmon is added within 1/2 hour at 4*60 C‘
are sparingly soluble to insoluble may with ad-
to 3' 5011mm of 8'5 pains of lza'dlhydroxynaph'
vantage be dyed according to a known after_ 35 thalene, 8 parts or sodium carbonate and 2 parts
metallizing process, for example the after-copof S°diPm .hydroxlde m 50 parts of water‘ The
pering method. Advantageous use, particularly
in the dyeing oi’ cellulosic ?bers, may be made in
whole is stirred for one hour at 5-8° C. and for
4 hours at 15400 C‘ The (.iyestu? is separated
this case of the one-bath after-coppering process
Py adding ,40 parts of sodmm chloride‘ It is
known by the U. 5 Patent 2,148,659 (on also 40 introduced in the form of a paste into the diazo
French patent'gog?gg), m which process dyeing
azo compound from benzidine and salicylic acid
followed by coppering is eil’ected in the same
Prepared according to Example 1' The whOle
bath. In this case complex copper tartrates or
is coupled for 1 hour at 10—12° C. and for 50 hours
similar metal compounds, stable towards alkalies,
at 18-2? 0-, heated after diluting the Coupling
are used with advantage in a weakly alkaline 45 mixture with 100 parts of water to 85° C. and the
medium.
formed trisazo dyestu?' of the formula
on
OH
H
OOH
01
The following examples illustrate the inven“on, the Parts being by weight unless otherwise
stated:
Example 1
is then ?ltered off. When dry it is a dark powder
which dissolves in water to a red brown, in dilute
alkalies to a brown and in concentrated sulfuric
acid to a violet solution, from which vegetable
9.2 parts of benzidine are tetrazotized as usual
?bers 9're dye (1 fast b r o wn shad es’ when dyed
_
_
with hydrochloric acid and sodium nitrite. The
and coppered accordin
to the one bath
rocess.
A Similar dyestu? 1: obtained if in $1,115 ex
clear tetrazo solution is then combined during 1
am
0
_
_
ple the 11.2 parts of 4-chloro-2-aminophenol
hour “.545 C- Wlth *1 Solution Pf 8 Parts Of Sall6-sulfonic acid are replaced by 11.7 parts of 4
cylic acid and 20 parts of sodium carbonate in 70 nitm_2_a,mino_1_pheno1_6_su1fonic acid or by
80 parts of water. A brown-orange suspension of
9 5
'
- _
- ‘
the diazoazo compound is thus obtained.
'4 parts of 2 ammo l phenol 4 sulfomc acid’
_9.4 parts of 2-amino-phenol-4-solfamide are
diazotized with hydrochloric acid and sodium
Example 3
13.8 parts of 1:3;6-trichloro-2-aminobenzene
nitrite and the drama suspension added Within 75 4-sulfonic acid are diazotized in the usual man
ner with hydrochloric-- acid and. sodium nitrite.
x170. 85°. C. after diluting the. coupling mixture with
Thesuspension of the vvdiazo compound is caused
to react with 20 parts of crystallized sodium ace-
.100 parts of water and the‘ formed .trisazodye
stuff of the formula
tateand the whole is stirred at. ordinary .temper- 15 is ‘then ?ltered o?. When dry it .isa.,_da'rk_ pow
ature until the chlorine atom in one-position is
replaced by the hydroxyl group, which generally
is the case after afew hours. The thus dissolved
ortho-hydroxy-diazo compound is added Within
der which dissolves in water and in dilute sodi
um carbonate solution to a Bordeaux red, in di
lute caustic alkalies to a violet brown and in
concentrated sulfuric acid to a blue-red solution,
20 from which vegetable ?bers are dyed fast brown
' shades,~when dyed and copperedv according to
‘the one ‘path process.
If 3:3'-dichloro-4:4'-diaminodiphenyl is used
instead of benzidine in preparing the d'iazoazo
:5 compound mentionedabove, a similar rdyestuif is
= Obtained
I 1/2 hour at 5-8° C. to a solution of 8 parts of 1:3dihydroxynaphthalene, 18 parts of sodium car-
bonate and 5 parts of caustic soda solution of 30
per cent. strength in 100 parts of water. The
whole is stirred for 1 hour at 5—10° C-, then f0!‘ 20
hoursat 15-2090. and the monoazo dyestufiw thus
vformed is separated by additionofisodium'chloride. It is, introduced,~while. still moist,‘into the
v Example 5
suspension of the‘diazo compound from benzidine
and salicylic acid, obtained according to Example
@15 parts _of zfammoil'phfenol'§'ca'rboxync
1‘ The Whole is coupled fol-one hour at mama 1L ac1d-4-suliomc acid are vdiazotized in a hydro
C. and then for 24v hours at 13_20° ‘(1 heated to ’ chloric acid medium in the usual manner with
90° C. and the trisazo dyestu?' thus formed of
the formula
Sodium nitrite at 15-20° C. The diazo compound
is added within 1A2 hour at 4—6° C‘. to a solution
0H ‘i’H
y,
‘
E
‘('30011
01
soan
?ltered from the hot reaction mixture after ad-
of 8.5 parts of li3-dihydl‘oxynaphthalene_, 8
dition of sodium chloride. When dry it is a dark
part5 0_f Sodium Carbonate and 2 Parts Of SOdHIIfI
powder, which dissolves in Water and dilute alka- i5‘ hlfdroxlde m 50 parts of Water- The whole is
lies to a brown, in concentrated sulfuricacid-to
a violet solution and dyes vegetable ?bers brown
Stlrred for 1 hour at 5'3 C- and for 14 hours at
10~15° C. and the monoazo dyestu?‘is separated
.
h.
n 1.
vi‘ h n
shades Whlch are fast to was mg a d lght w e
by addition of 60 parts of sodium ‘chloride. ~It is
‘ introduced in the form of a paste .into the diazo
dyed and coppered according to the one ‘bath
azo compound, prepared according to Example‘ 1.
process‘
E
Z
4
’ L .The whole is coupled for one hour .at 10-12° C.
.and for 50 hours at 18-22’ 0., heated to 85°C.
“mp 6'
11.7 parts of 6-nit-ro-'2'-aminophenol-liesulfonic
; after diluting the coupling mixture with 100 parts
acid’ are diazotized as usual at 10-15° "(L-'With
of water, and the formed trisazo'dyestuff of the
hydrochloric acid' and, sodium nitrite. The di- 55‘ formula
, (‘m
coon
SOaH
azo solution is added within 1/; hounat 4-6“,C.
to a solution of 8.5 parts of 1:3-dihydroxynaphthalene, 8 parts of sodium carbonate andi2 parts
of sodium hydroxide in 50 parts of water. The
. is ?ltered on. »When ‘dry it is a dark powder,
which dissolves inwater to ‘an orangeebrown,
in dilute sodium carbonate solution toayellow
brown, in‘ dilute caustic alkalies to a‘ brown red
whole is stirred for one hour at 5—8° C. and the
and in concentrated sulfuric acid to a violet so
monoazo dyestuff separated by addition of 60 7O lution, Which dyes vegetable ?bers fast brown
parts of sodium chloride. It is introducedin the
shades; Whendyed and coppered according to the
form of a paste into the diazoazo compound from
"one ‘bath process'
benzidine and salicylic acid prepared according
‘Emamplab‘
_
to Example 1. The whole is coupledforv 1' hour
v7.7 parts of 5-nitro-2-amino-l-phenol are diaz
' at 10-120 C. and ior>50hours at ‘18--22° C'.'heated 75~otized as usualwithhydrochloric acid and sodium
‘2,408,961
8
nitrite. The suspension of the diazo compound
which vegetable ?bers are dyed fast yellow brown
is added within 1/2 hour at 4-6“ C. to a solution
shades when treated and coppered according to
of 8.5 parts of 1:3-dihydroxynaphthalene, 8 parts
the one bath process.
of sodium carbonate and 2 parts of sodium hyExample 8
droxide in 50 parts of water. The whole is stirred 5
for one hour at 5—8° C. and the monoazo dyestu?
22.7 Parts Of a Paste Containing 55 Per cent of
is separated by addition of 40 parts of sodium
chloride. It is introduced in the form of a paste
diazotized 1-amino-2-hYd1'0Xynaphtha1ene-4—Su1
ionic acid (corresponding to 11-9 parts of 1
into the diazoazo compound, prepared according
amin0—2—hyd1‘0XynaDhtha1ene - 4 - sulfonic acid)
to Example 1. The whole is coupled for 1 hour 10 are introduced in the course of 1A» hour at 4—6°
at 10-12° C. and for 24 hours at 18-22° C., heated
0. into a solution of 8.5 parts of 1:3-dihydroxy
to 95° C. after diluting the coupling mixture with
100 parts of water and the formed trisazo dyestuff
of the formula
naphthalene, 8 parts of sodium carbonate and 2
parts of sodium hydroxide in 100 parts of water.
The whole is stirred for one hour at 5-8” C., 10
COOH
NO:
is filtered off. When dry it is a dark powder
' parts of sodium chloride are added and stirring
which dissolves in water and sodium carbonate 25 is continued for one hour at 10-15" C. The formed
solution to a red brown, in dilute caustic alkalies
monoazo dyestllif iS ?ltered off and introduced in
to a violet brown and in concentrated sulfuric
the form of a paste into the diazoazo compound
acid to a violet solution from which vegetable
from benzidine and salicylic acid, prepared ac
?bers are dyed fast brown shades when dyed and 30 cording to Example 1. The whole is coupled for
coppered according to the one bath process.
1 hour at 1042’ C. and for 48 hours at 18-22° C.,
heated to 80° C. after diluting the coupling mix
ture with 100 parts of water and the trisazo dye
stuff of the formula
Example 7
9.1 parts of 4-nitro-2-amino-l-benzoic acid are
on
Q
on
0011
H0
|
SOIH
diazotized in a hydrochloric acid medium in the
is separated by addition of 20 parts of sodium
usual manner with sodium nitrite. The suspenchloride. When dry it is a dark powder, which
$1011 of the diaZO Compound is added within 1/2
dissolves in water and sodium carbonate solution
hour at 4-6° C. to a solution of 8.5 parts of 1:3to a brown,'in dilute caustic alkalies to an orange
dihydroxynaphthalene, 13 Parts Of Sodium Car- 50 brown and in concentrated sulfuric acid to a
bonate and 2 Parts Of Sodium hydroxide in 80
blue red solution, from which vegetable ?bers are
Parts Of Water-
The Whole is Stirred during 1
dyed fast orange brown tints, when dyed and
coppered according to the one bath prgcesg
110111‘ at 5—8° C. and the formed 1110110310 dyestuff
is ?ltered oil.
It is introduced in the form of a
_
paste into the diazoazo compound, prepared ac- 65
cording to Example 1. The whole is coupled for
'
Example 9
25.5 parts of a paste containing 58 per cent of
1 hour at 5-8° C. and for 24 hours at Ill-22° C.,
6-nitro-l-diazo-Z-hydroxy-naphthalene - 4 - sul
heated to 95° C. after diluting with 100 parts of
water and the formed trisazo dyestuff of the
ionic acid (corresponding to 14.2 parts of 6-nitro
1-amino-2-naphthol-4-sulfonic acid) are intro
formula
_duced within 1/2 hour at 4—6° C. into a solution of
V
_
'
coon
OH
H00
COOH
I
r“
H
\
No,
is filtered o?.
When dry it is a dark powder
8.5 parts of 1:B-dihydroxynaphthalene, 18 parts
which dissolves in water and dilute sodium carbonate solution a yellow brown, in dilute caustic
of sodium carbonate and 2 parts of sodium hy
droxide in 100 parts of water. The whole is
alkalies to an orange brown and in concentrated
stirred for 1 hour at 5—8° C. 10 parts of common
sulfuric acid to a Bordeaux red solution, from 75 salt are added and stirring is continued for 1
hour’at 10-15“ C. The formed monoazo dyestu?‘
is ?ltered off andfintroduced in the form‘of 'a»
is'-?ltered"from--the =rot~ reaction mixture after ‘
addition'ofcommon-salt: When ‘dry it is a dark‘
paste into the diazoazo compound prepared 'ac-
powdereewhic'h'dissolves-inwaterand diluteso
cording to- Example 1. The mixture is coupled
dium canbonate solutionto a brown,- iii-dilute
for 1 hour at 10-12° C. and for 48 hours at 18-22° 5_ caustic alkalies "to a»v brown red- and in‘ concene
(3., heated to 75° C. and the trisazo dyestuff 0f
the formula
trated sulfuric acid to a'violet-solution'from-which‘
vegetables ?bers are “dyed brown'shade's :fast" to
COOH
N03
|
303K
is separated by the addition of 20 parts of com- 20 washing and to light when dyed and coppered ac
mon salt. When dry it is a dark powder which
cordingito the one bath process;
dissolves in water and sodium carbonate solution
to a brown, in dilute caustic alkalies to a, red
Ewam_ple 11
tinged brown and in concentrated sulfuric acid
10-15 parts of 2—am1n0-4-methy1-l-hydroxy
to a violet solution from which vegetable ?bers 25 benzene Sulfonic acid (Obtained by boiling 2-111
are dyed fast orange brown shades, when dyed
1'10-4=-me'0hy1-l-hydl‘oxybenzene With bisulfliie411+v
and coppered according to the one bath process_
‘
known manner) are "diazotized in ahydroohloric.
acid medium in the-‘usual manner with sodiunr
Example 10
nitrite. The .diazo compoundqobtained iStintI'O-g
9.2 parts of benzidine are vtetrazotized in the 30 duced in the course of l/z-hOLll‘ at 4-69‘ Cuint'oau
usual manner with hydrochloric acid and sodium
Solution of 8 parts of .1I3-dihydroxynaphthalene;..
nitrite. The clear tetrazo solution is mixed dur8 parts of anhydrous-sodium. carbonate ,-and <51,
ing 1 hour at 4-6“ C. with a solution of 8 parts of
parts by volume ‘of - caustic soda solution. of; 30...
salicylic acid and 20 'parts‘of anhydrous sodium
per cent. strength in ,50. parts of water. The:
carbonate in 30 parts of water; There is -0b_ 35 whole is stirred for 1 hour .at 5-10? C.,.then:for.-1
tained a brown orange suspension of the intere
hour at 10—15° C. and'theeformed. monoazodyeev
mediate compound benZidjne—>sa,1icy1ic acid,
stu? isseparated by ?ltration after addition of
11.65 parts of 6-nitro-2-amino-l-phenol-é-sulcommon salt- It is introduced in the form-of a».
famide are diazotized in'a hydrochloric acid me- '
paste into the suspension Of the diaZoaZo com
dium‘ in the usual manner with sodium nitrite. 40 pound from benzidine and salicylic acid. The
The diazo compound obtained is introduced‘withmixture ‘is coupled 'for -1 hour‘at 10-12“ C. and for
in 1/2 hour at 4-6" C. into ‘a solution vof 8.0 parts
2O1hours at'18—20° C., heated-to ‘YO-80°C.v andthe
of 1:3-dihydroxy-naphthalene,‘ 3 parts of anhye
formedv'triazo-dyestuif'of the formula
H04
N—NNF_NP; vi,
liq-N
OOH
drous sodium carbonate and 5 parts by volume of :
caustic soda solution of 30 per cent. strength in '55
50 parts of water. The whole is stirred for 2 hours
at 5-10° C., then for 15 hours at 15-20° C. and the
formed monazo- dyestu? is separated by ?ltration,
is ?ltered‘ from the hot reaction" mixture-‘after
addition of ‘commonsalt.’ When‘dry‘it’is a dark"
powder ‘which dissolves-in water ‘and ‘dilute’ see
dium carbonate solution to a‘ yellow-"brown; in"
dilute’ alkalies-toca ' red brown‘ and“ in concen
if necessary after addition of common salt., It is
trated ‘sulfuric’ acid ‘ to a violet ' solution from‘
introduced in the form of a paste into the sus- 60 which vegetable ?bers are dyed ‘brown shades >
pension of the diazoazo compound from benzifast to washing and light, when dyed‘ and icop
dine and salicylic acid, prepared as described
pered according to theone bath-process.
above. The mixture is coupled for 1 hour at
Emm Z__12,_
10-120 0. and for 24 hours at 1s_20° 0., heated to.
p6
90° C. and the. formed triazo. dyestui’fv of the 65
9-45 parts of 2-amino-1-pheno1-4-sulfonic acid
formula
are diazotized with hydrochloric acid. and sodium
NO:
801N111.
2,408,961‘
11
12
nitrite and the diazo suspension is introducedin
aminoazobenzene sulfonic acid orv 4'-nitro-4-'
the course of 1/2 hour at 4—6° C. into a solution of
amino-diphenylamine-Z'-sulfonic acid, there are
obtained dark brown to black brown dyeing prod
ucts. The dyestuff obtained when using the
8.0 parts of 1:3-dihydroxynaphthalene, 8 parts of
anhydrous sodium carbonate and 5 parts by vol
ume of caustic soda solution of 30 per cent. 5 last named diazo component has the formula
strength in 50 parts of water. The whole is stirred
for 2 hours at 510° C., then for 15 hours at 15-20°
C. and the formed monoazo dyestu? is separated
by addition of common salt and dilute acetic acid.
OH
OH
It is introduced in the form of a paste into the i0
OH
suspension of the diazoazo compound from benzi
dine and salicyclic acid obtained as described in
Example 10. The mixture is coupled for 1 hour at
l0-12° C. and then for 24 hours at 18-20° 0.,
heated to 90° C. and the formed trisazo dyest
of the formula
N=N
——Fl
SOSH
N01
-
When replacing part of the iron by other metals,
OH
OH
|
COOH
$0111
is ?ltered from the rot reaction mixture after
for example copper, the shade of the dyestu?f
is displaced to red tinged dark brown to reddish
black brown. The order of succession of the
diazo components to be used can also be reversed
addition of common salt. When dry it is a dark
powder which dissolves in water and dilute so
dium carbonate solution to a brown, in dilute
caustic alkalies to a brown red and in concen 30 and similar dyestuffs are then obtained.
¢ trated sulfuric acid to a violet solution from which
Example 14
vegetable ?bers are dyed brown shades fast to
washing and light, when dyed and coppered ac
If 3 : 3’-dimethyl-4 :4'-diaminodiphenyl or 3 :3’ -
A mixture consisting of 11.7 parts of 4-nitro
Z-amino-l-phenol—6-sulfonic acid and 15.5 parts
dimethoxy-4:4'-diaminodiphenyl is used instead
of benzidine in preparing the diazoazo compound,
acid is diazotized in usual manner and coupled
cordinglto the one bath process.
of 4'- intro-4-aminodiphenylamine - 2’- sulfonic
in the presence of 2.1 parts of freshly precipi
tated iron-(IID-hydroxide and 0.6 part of cop
per hydroxide with 8.0 parts of 1:3-dihydr0xy
naphthalene in a medium alkaline with sodium
carbonate. When the dyestu? formation is com
plete, the whole is heated for some time to 60-70°
C. and the formed metal compound of the for
mula
similar dyestuffs are obtained.
'
Example 13
23.4 parts of 4-nitro-2-amino-l-phenol-B-sul
fonic acid are diazotized in usual manner and
coupled with 16 partsof 1:3-dihydroxynaphtha
lene in a solution alkaline with sodium carbonate
and in the presence of 5.5 parts of freshly pre
cipitated iron-(III) -hydr0xide. When coupling
is complete, the whole is heated for some time
to 60-80° C. and the formed iron compound sep
HOI
SOzH
arated in a‘neutral medium and dried; ' It dyes
vegetable tanned and chrome tanned leather
50
brown violet shades.
22 parts of the above iron compound (of the
dyestuff from diazotized 4-nitro-2-amino-1-phe
nol-?-sulfonic acid and 1:3-dihydroxynaphtha
lene) are dissolved. in 200 parts of water and 15
NO:
SOIH
parts of caustic soda solution of 30 per cent. 55 '
strength, mixed with 15 parts of anhydrous so
is then precipitated in usual manner and dried.
dium carbonate and coupled with the diazo com
A product is obtained which dyes leather power
pound from 6.9 parts of para-nitraniline pre
ful black brown shades.
pared in the usual manner. The disazo dyestu?
of the formula
60
Example 15
The dyestuif obtained from 29.5 parts of 6
nitro-l-diazo-2-hydroxynaphthalene- 4 -sulfonic
5 acid and 16 parts of 1:3-dihydroxynaphthalene
is heated to the boil in 800 parts of water and
' boiled for 24 hours in a re?ux apparatus with
a quantity of chromium sulfate corresponding
to‘10 parts of CI‘zOa. The whole is then ?ltered
‘7 70 to remove the precipitated chromium compound
NO:
is precipitated in the usual manner and dried.
It dyes leather olive-tinged, brown shades.
When using instead of para-nitraniline for
example
which-is then dried at a moderate temperature.
The dyestu? dyes leather red tinged blue shades.
50.7 parts of the above chromium compound
are coupled in a solution alkaline with sodium
1-aminonaphthalene-4-sulfonic' acid, 75 carbonate with the diazo compound from 20.7
231683361?
133
‘7.6 parts Eofgfreshly precipitated chromium: hya
parts, of 4 -chloro-1-aminobenzene-3=sulfonic'~
droxide; 15v partsof ‘tartaric acid and 2'7 parts ofv
caustic soda solution-of. 30.per:cent. strength;
The dyestu?f- is salted out, ?ltered and dried. The;
chromium compound dyes vegetable tanned-and-Z
chrome tanned leather deep blue shades. The "
leather is dyed with a good penetration.
acid. A- product isthus obtained of .theiormula
_
SOsH
OH
ClON=N
_Y, HUN 1..
19 parts of the above chromium compound are
coupled in‘ a medium alkaline/with. sodium car
V. 10 bonate with the diazo compound from 8.7 parts of
——G:
In?”
I
‘-—OH
4-aminobenzenesulfonic acid. . The dyestuff ob
tained of the formula
-
NO
155
S0313?-~
HO'aSON-éN
‘
0H
_
whichfdyes leath'ergrey, tinged blue shades.- It
the disazo dyestu?is?rst produced and subse-1
quently coupled, thereis obtained a similar dyea 20.
stu?. By replacing. 4-chloro-l-aminobenZene-3sulfonic acid. by é-nitro-l-aminobenzene-izesul
is freely soluble in water and dyes leather green
ionic acid, 2? -nitr0-4-aminodiphenylamine-4' --v
tinged blue shades. By replacing "the sulfanilic
sulfonic acid or 4’-nitro-ll-aminodiphenylamine- ~
acid for example‘by aniline-2:5;disulfonic acid; a“
2’-sulfonic acid, dyestu?s are obtained which dye, ’ similar dyestu? is obtained.v
leather green tingedgrey blue or black o-r-olive
blackshades.
Example 18
Other metals, foriexample iron
or manganese, lead to violet brown to dark brown .
shades.
'
from diazotized 4-nitro-“2‘-amino-l-phenol" and i
'
Example 16-‘
19.9 parts of 4:6-dinitro-2eamino-l-phenol are
diazotized in usual manner and coupled in a me
dium alkaline with bicarbonate with 16 parts of
l:3-dihydroxynaphthalene.
ls-partsof the iron compound ‘of theidyestuffi
30 1:3-dihydroxynaphthalene are‘coupled- in a me-'‘
dium alkaline with sodium carbonatewith the-4
diazo-i compound from' 11.7 parts of-‘ll-nitro-Z-l
amino-‘l-phenol'-6-sulfonicI acid.’ When the for:
mat-ion ' of dyestuff ‘is » complete; the " solution“ is
35 neutralized at 60° C. and treated for‘some-timea
with a mixturev of '4 parts of copper sulfate and’
The monoazo-dye
stuii is precipitated in crystalline form, then ?l
1.3 parts ‘of iron-(IID-chloride. The dyestu? of}
tered and Washed. .
18.5 parts of this dyestu? are suspended in 200
the‘ formula
parts of water and 15 parts of calcined sodium
carbonate and mixed with the diazo compound 40
from 15.4- parts of 2' - nitro- d-aminodiphenyl
amine-4'-sulfonic acid. When coupling is com
plete, the disazo-dyestu? is separated in usual
manner.
34.5 parts of thedisazo dyestu? are dissolved
in .water and. heated for some timeat v70—90° C.
with 12.5 parts of copper sulfate and 14' parts of "
sodium acetate. The copper compound is then
separated with common salt anddried at a mod
‘
.
.V
then‘ filtered-and vdried at ‘a moderate tempera-‘
ture. There is obtained a'brown black‘ powder‘v
55 5 which dissolves in water and dilute sodium car:
bonate solution‘ to a deep'brown'solution and
N02
N=N
/
N02
isprecipitated by addition" of sodium‘ chloride,
on
NO
P
1 H018
erate temperature. A dyestuff is thus obtained
of the formula
‘
--0
u
dyes leather ‘powerful red tinged dark‘ brown"
shades.
When replacing the copper sulfate'by'nickel"
sulfate,
a slightly more yellow dyestuffds *ob
60
tained.
N02 1
which dyes leather brown violet shades. When
using as second diazo component l-aminonaph
thalene-ll-sulfonic acid andinstead of the. cop
per sulia'tea mixture of manganese and nickel
sulfate,there is obtained a red brown dyestuff.
Example 17
The dyestuff obtained from 15.4.- parts of diazo
tized 5-nitro-2'-amino-1-phenol and 16 parts of
1:3-dihydroxynaphthalene in a medium alkaline
with sodium carbonate is suspended in 500 parts
of Water and boiled for 15 hours in a re?ux ap
paratus with a ‘chromium solution consisting of
When'using'the corresponding quantityof 4:6‘
dinitro-2-amino-1-phenol instead "of the ,4-‘nitro-"
aminophenol; a blackish violet brown dyestu?'ls
obtained; '
Example v19
22 'parts 'of the iron compound of thevdyestuff'
from’ diazotized 6-nitro-2-amino-l-phenol;4=
sulfonic acid and 1:3-dihydroxynaphthalene are
coupled in a medium alkaline with sodium car
bonate with the diazo compound from 9.9 ‘parts
of 4 : 6-dinitro-2-aminoel-hydroxybenzene. The
whole is mixed with a solution consisting of ‘4.5
parts- I of iron»v (III) ‘chloride;- 2‘ lparts :aof" tartaric
2,408,961
15..
acid and 16 parts of caustic soda solution of 30
per cent. strength and heated for some hours to
60—'IO° C. After neutralizing, ?ltering and drying
there is obtained a black powder which dyes
leather black brown shades. The dyestu? has 5
the formula
r"
(IJH.
NO
.
16
compound from 6.9 parts or para-nitraniline.
When the formation of dyestu?f is complete, the
solution is worked up in the usual manner. There
is obtained a product which dyes leather power
ful, medium brown shades.
When using the 4'-nitro-4-aminodiphenyl
amine-2'-sulfonic acid instead of the para
"
nitraniline, there is obtained a disazo dyestu?
which dyes leather powerful red tinged dark
N=N
OH
brown shades.
Example 23
NO;
OH
HO
—-F6
100 parts of cotton are introduced at 50° C. into
a dye-bath which contains in 2500 parts 01' water
15 2 parts of sodium chloride and 1.5 parts of the
dyestuff prepared according to Example 3, and
the temperature of the bath is gradually raised
to 90-95" C. 30 parts or Glaubers salt are added
after M; hour and dyeing is continued for 3/4 hour
20 at this temperature. The bath is then cooled to
_
0.11
J
about 70° C., the necessary quantity or a solution
Example 20
made feebly alkaline with sodium carbonate of
A mixture consisting of 23.4 parts of 4-nitro-2
complex copper tartrate is added and the mate
amlno-l-phenol-S-sulfonic acid and 22.3 parts of
rial is coppered at 80-90° C. for 1/2 hour. The
4-chloro-2-amino-l-phenol-?-sulfonic acid is di 25 cotton is thoroughly rinsed and soaped for a short
N0
N=N
azotized in usual manner and coupled with a so
time, if necessary. It is dyed fast brown shades.
lution alkaline with sodium carbonate of 16 parts
The expression “benzene series” in the follow
of 1:3-dihydroxynaphthalene. When the forma
ing
claims will be understood to encompass the
tion of dyestuff is complete, the solution is neu
tralized with hydrochloric acid, the reaction solu 30 benzidine series.
What We claim is:
tion heated to 80° C. and mixed with iron-(III) -
chloride solution corresponding to 5.6 parts of
iron, and 30 parts of crystallized sodium acetate.
1. Trisazo dyestu?s of the general formula
The whole is boiled for some time in a reflux ap
paratus. After salting out, ?ltering and drying 35
there is obtained a metal complex which dyes
leather olive tinged black brown shades.
When replacing a part, for example half of the
iron by copper, there is obtained a red tinged
dark. brown shade.
40
Example 21
29.5 parts of 6-nitro-l-diazo-2-hydroxynaph
HO
Iii-N=N
wherein R3 stands for the radical of a coupling
component containing the salicyclic acid group
ing and R2 stands for the radical of a diazo com
ponent containing a, member selected from the
thalene-‘l-sulfonic acid are coupled with 16 parts
of 1:3-dihydroxynaphthalene in a feebly alkaline 45 group consisting of OH and COOH in ortho posi
tion to the diazonium group, the said diazo com
medium. 13.3 parts of caustic soda solution and
ponents being selected from group consisting of
a neutralized diazo solution from 14.35 parts of
4-chl0ro-2-amino-l-phenol are then added.
When coupling is complete, the whole is heated
to 50° C. and the disazo dyestuif is separated in
diazo components oi.’ the benzene and naphtha
lene series.
2. Trisazo dyestu?s of the general formula
usual manner.
30.5 parts of the dyestu? are mixed in 500 parts
of water with a quantity or basic chromium sul
fate corresponding to ‘7.6 parts of CrzO: and heat
ed to boiling in a re?ux apparatus for 24 hours.v
After this time the formed chromium compound
is salted out, ?ltered and dried. A blue black
HO
Iii-N=N
powder is obtained which dyes leather red tinged
blue grey shades.
wherein R3 stands for the radical of an ortho
When using instead of the 4-chloro-2-amino-l
hydroxy benzoic acid and R2 stands for the radi
phenol as second diazo component for example
cal of a diazo component of the benzene series
containing a hydroxyl group in ortho-position to
the diazonium group.
4-chloroaminonaphthol-6-sulfonic acid, 4-nitro
aminophenol-G-sulfonic acid, sulfoanthram'lic
acid, G-nitro-1-amino-2-hydroxynaphthalene-4
‘ 3. The trisazo dyestu?? oi the formula
sulfonic acid, or instead of the chromium a mix 65
ture of chromium and iron, there are obtained
products which dye leather navy blue to blue
black shades. When using iron instead of chro
mium there are obtained dark brown to black
brown dyestu?s.
70
Example 22
24 parts of the dyestu? from diazotized 4’-nitro
4-aminodiphenylamine-2’-sulfonic acid and 1:3
dihydroxynaphthalene are coupled in a solution
alkaline with sodium carbonate with the diazo 75
0 OH
OH
IHO
HOOC
N=N
2,408,961
17
ther with one molecular proportion of the diazo
azo compound obtained by one-sided coupling of
tetrazotizccl benzidine and salicylic acid.
6. Process for the manufacture of trisazo dye
OH
c0011
‘
OH
|
18
tized 2-amino-LhyrlroxyA-sulfamide and fur‘
4. The trisazo dyestu? of the formula
><\
\
stu?s, comprising coupling 1:3-dihydroxynaph
E0
thalene with one molecular proportion of diazo
tized Z-amino-l-hydroxybenzene-B-carboxylic-4
-N:N
sulfonic acid and further with one molecular
10 proportion of the diazoazo compound obtained by
one-sided coupling of tetrazotized benzidine and
SO2NH2
salicylic acid.
5. Process for the manufacture of trisazo dye
stuffs, comprising coupling 1:3-dihydroxynaph
thalene with one molecular proportion of (ham
15
‘‘
FRITZ STRAUB.
JAKOB BRASSEL.
HANS MAYER.
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