Note: Descriptions are shown in the official language in which they were submitted.
HOE 7~/I? 08~
`` ~076~5
;i; This invention relates to novel and valuable unsy,~metri-
. cal 1:2-cobalt complex compounds, to their preparation a~d
.i .
their use as dyestuffs for dyeing natural and synthetic poly-
amide fibers,
It is the object of the present invention to provide un-
symmetrical 1:2-cobalt complex compounds each containing as
dyestuff components an azomethine compound of the formula (1)
an~ a monoazo compound of the formula (2),~and ~ixtures of
. said unsymmetrical 1:2-cobalt complex compound with the symme-
: .10 trical 1:2-cobalt complex compounds of these compounds (1)
and (2)
`i : OH IIO
H035 ~ =CH ~ R2
:'i ' R1 ' :'
.~, ' ' ' .
~: ~H ~O-C
N=N-C (2)
' ' R3
:i . ..
^~: in which ~1 represents a chlorine atom, a lower alkyl group,
.. for example the methyl or ethyl group, preferably the methyl group, or the nitro group,
.~ . R2 represents a hydrogen atom, a lower alkyl group,
~; for example the methyl or ethyl- group, pre*erably
:~ the methyl group, or a lower alkoxy group, for
example the methoxy or ethoxy group, preferably
the methoxy group, ~
;, .
é - 2 - :
'. , ' ' ' ' ' ' ' ;" ', -; ' ': ' '. ', " ' " " " ',' ' ' ' . '' ' ' "' ' ' : . ' ';. ' " ' ' ' ,' , : ' .'
': ' " - ' ', ' ''. '~ "'' '"" '. '.' "' ,' ,.' ~ ' ' " ' `' "," '; ' " ' ' ',', , , "' ' " ', : ' '"" ' ; " ' "
,,: . ', . ~,, ' ~,. ,,, ' .' ,' ' ' ' : ` .' ' .' '`' '' ;' . . ': , ', .' ' ' ' ' '. ' '''.'
': '.. ':' ''.' .. '' ' :' . '' ' ' ` .' " ' ` ' ' , : ' .' ' ': ` ' .... '.... . .; :, ': ' '. '
`` ~07~;1()S ~
.... ; ,,-~ , .
~ . . . . .
R3 represents a hydrogen atom, a chlorine atom, a nitro
J.~ group, or a lower alkyl group, for example the methyl or
ethyl group, preferably the methyl group and
.~ Z stands for a radioal of the formula (3) :-
~ 4 ;~
; _ ~ N=N ~ - S02-X . (3) ~. ~
R : ::
~; 5 :
: or of the formula (4j
NH ~ R7 ~4)
` ~ 6 . ~ :~
in which latter formulae
R~ represents a hydrogen at~om, a lower alkyl or a lower
alkoxy group, for example the methyl, ethyl, methoxy or
ethoxy group, preferably the methyl or methoxy group,
: R~ reprrsents a hydrogen atom, a lower alkyl or a lower
alkoxy ~roup, preferably hydrogen or the methyl, methoxy
or ethoxy group,
: : .
X stands for the hydroxy group, a sulfoalkyl group ha~ing
from 1 to 4 oarbon atoms, ~or example the B-sulf`o-ethyl
- group, or the group of the formula
~,
~ / Rg
:~ -N~ :~
; ~ ~CH -CH -SO H
~ in which
-.: Rg represents a hydrogen atom or a lower alkyl group, for
.. ;~ example the methyl group, and
.,, , ,. . -
.,
~, 3
,~
... . .. ..
.. :. , .
,...... ,~ ,.. .. ........... .. . . . .
: , .... .. .- . . . .. . , . . . ., . .. . ..... ` . .. ... ...
.. . . -. .. . .. . . .. . . . ..... . . .
10761~S Ho~_76/F 082
.
- R6 and R7 which are different from each other represent each
a nitro or a sulfo group,
i~ The novel d~estuffs are preferably used in the form of
their alkali metal or alkaline earth metal salts, for example
as the sodium, pOtaS~iUm or calcium salt, or as ammonium salt.
The unsymmetrical dyestuffs are preferred.
In accordance with the invention, the novel 1:2-cobalt
complex dyestuffs are prepared by metallizing the metal-free
starting compounds of formulae (1) and (2) in a molar pro-
10 portion of 1 : 1 at a temperature of from 60 to 1~5 C, i.e.
at atmospheric pressure at about 60 to 100 -105 C and under
, ~
elevated pressure at about 105 to 145 C, at a pH in the range
of from 5.0 to 10, preferably from 8.0 to 9.5, wheraby the
novel 1:2-cobalt complex dyestuffs are obtained~ The metaïli-
15 zation is preferably carried out in an aqueous medlum.
` According to a preferred embodiment, the azomethine com-
j ~ pound of formula (1) i9 first reacted with a cobalt-yielding
compound, for example in aqueous s~lution at a pH of from 7
to 10, preferably 8.5 to 9.5, at a t~mperature of from 20 to
20 70C, preferably 50 to 60C, and the resulting oompound is
then reacted with the compound of formula (2) at a pH Of from
~ ; 7 to 10, preferably 8.5 to 9.5, at a temperature of from 60
`;~ to 130C, preferably 80 to 105C.
Suitable cobalting agents are cobalt salts of inorganic
25 or organic acids, for example oobalt carbonate, cobalt
'31 ~ ' ` . :.`l hydroxy-carbonate, cobalt acetate and cobalt sulfate.
The metallization can be carried out in the presence Of , ''~
an acid-binding agent, 3uch as a ~alt, oxide or hydroxide of
, r ~ . ,
~ 29 an alkali metal or alkaline earth metal, or Of an allcaline
: ~ :
'~,.;
' '. ''. :''''"'','.' '''. . " "'' .' ' ''~'"'.'; '''''' ''; .' '' ~ '" '
,, , : .. , ,.-,, , : ., ,: . ,. ,, " , ,, , . .:: . ,,. ;, :
. . HOE 7~/~ 082
7~ S .`
.,. .,... , . :~
.~ earth metal and a.lkali metal salt having an alkaline reaction,
for example qodium or potassium acetate, sodium or potassium
-~ carbonate or bicarbonate, sodium or potassium hydroxide, ` .. ;
.~ calcium carbonate, or calcium oxide. ~
~ 5 The cobalt complex dyestuffs obtained in this manner can .:
.. . ...
be isolated frorn their solutions of preparation by salting out
with sodium or potassium chloride or by spray-drying.
A Purther embodiment of this invention is, to hav~ found ~:.;
~ that the novel dyestuffs can be used to dye natural and synthe~
.~. .
10 tic polyamide fibers; for example wool, silk, and synthetic . .
polyamides, such as made from ~-caprolactam, from hexamethyle~e
diamine and adipio acid or from ~-amino-undecylic acid. They
~ are especially suited to dye the aforesaid fiber types in ad-
~~ mixture with other hydrophobic f~bers, for example wool in a
.` 15 mixture of wool with polyester fibers, with excellent resist-
....
`~`, : ibility of the hydrophobic~fibers~
- ~ .The dyestuffs are used for dyeing preferably in the form
of their alkali metal salts, for exampl2 the sodium, potassium
, .
~ ~ or ammonium salts. Alternatively, they Carl be used in ad-
~ 20 mixture wlth other 1:2-cobalt- or -chromium complex dyes con-
taining one or two sulfonic acid groups per dyestuff molecu].e.
Dyeing is performed in known manner under conditions usual
for metal complex dyes. Th~ material is preferably dyed in an
:~ acid or neutral bath, ad~antageously at a pH of from 4.0 to : ~
6.5 and at a temperature in the range of from 90 to 105 C wi.th ;` ~.
~' the addition of the usual dyeing auxiliaries, such as fatty
. ~ . ..
amine or fatty alcohol oxethylation products, and ~sual buffer .:
substances, for example sodium phosphate, sodium acetate,
7,`( ' 29 sodium formate, optionally-in admlxture with the corresponding
.~ _ 5 _. . :.
, ' ' .
i., ", "~ ,"~",""" ,,,~""~,",, .", """",",;,"",,", ,:
~lO~ 76/~` 082
1al76105
, ~ ~
acids to stabilize the pH o~ the dyeing bath. By adding an
acid, for example formic acid or acetic acid or even a mine-
ral acid, to the dyeing bath containing an alkali metal salt
of the formic acid, acetic acid or of another organic acid,
; 5 the pH of the dyeing bath can be optimized with regard to the
dyestuf~ concentration used and to the desired depth of
(color~ shade.
~or local dyeing by printing, pastes are used containing
the usual thickeners and printing auxiliaries and a salt of
~ 10 a weak basq and a strong mineral acid or an organic acid, fo~
`~` example ammonium sulfate or ammonium ta~trate. The printed
. ~: ,. . ~ - .
~` fabrics are dried and treated with hot air or steam for a
~ short period of time.
- ~ The no~el dyestuffs yield thus on natural and synthetic
~ 15 polyamide fibers yellow, golden yellow or yellow brown shades
; ~ ~
having a good to very good fastness to wet processing, fo~
example a fastness to washing at 20 to 60 C,(for example,
40 and 60 C according to DIN 54010 and 54014), fastness to
water (under severe conditions) and fastness to al~aline and
..... . ..
acid perspiration, a good fastness to decatizing and an ex-
cellent fastness to light under the xenotest and daylight
-~' lamps~
The starting compounds of formula (1) (azomethine com-
.. ^. , .
pounds) are obtained by condensing an amine of the formula (5)
O H ~-
) ,:
,:.; ~, ' . '''~ '
R1 ~ i~
., . : :
, .. . . .
,
- 6 -
:
.: . : :.
' ' ' . ' " ' "' ' ' ~, ' ' "" ' ', '' ,; '' ', ' ' . ' ', "" ' , '' , '' '~ ' '' ;'"'' "' '~'", ' ' "' "
., . ,, - , . . .. .. . .
~` . HO~ 76~F 082
107t;i~)~
in which R1 has the aforesaid meaning with an aldehyde o~ the
.~ formula (6) ~-:
~ OH
,,,. 1 . .
C~10 ' - ~ ~
~ ~6) :
:: R2
; in which R2 has the aforeqaid meaning, preferably in aqueous
i solution, at a temperature in the range of from 20 to 80 C,
;~ preferably 50 to 60~, and at a pH of ~rom 80 0 to 9.5, pre- ~
; ferably 8.5 to 9Ø . ~ ~ .
' . The starting compounds of formula (2) are obtained by
coupling an amine,.which has been diazotized in known manner
: and corresponds to the formula (7)
: OH
H2 (7)
-: ~, . - . .......................................... ~
in which R3 has the aforesaid meaning,~with a coupling compo- ~ :
nent of` the formula (8)
-CI~2-CO-NH-z ~8
in which Z has the aforesaid meaning, under the usual known
coupling conditions, for example at a temperature of f`rom
5 C to ~40 C and at a pH of from 6 to 10, prèferably 7 to 8. ~.: .
The sitarting compounds of formula (8) u~ed for the above
reaction in which Z represents a radical of formula (4) above, . .
i.e. 2-nitro~ N-acetoacetylamino-diphenylamino-Z-sulfonic
acid or 4-nltro-4~-N-acetoaoetylamino-diphenylamino-2-sul~onic
~ ~J
~ . ~ 7 ~
.:~ , . ' .
~ . .
H0~ 76~_082
17610S
acid, or the startillg compounds of formula (8) in which Z re-
presents a radical of formula (3), are obtained by reacting a
- compound of the formula (9)
; H N- ~ NH - ~ - R7 (9)
:'' . ~, ' ~
; 6
~; or of the formula (10)
=N - ~ -SO~X ~10)
R
in which R4, R5, R6, ~7 and X have the aforesaid meaning, with
dike$ene, advantageously in aqueous solution, at a temperature
of from 20 to 90C, pre~erably 50 to 60C, and at a pH of from
3 to 9, preferably 5 to 6. ~
The following examples illustrate the invention; the ~-
parts are parts by weight, and the percentages are per cent
by weight.
E X A M P L E 1:
22.4 Parts of 4-chloro-2-aminophenol-6-sulfonic acid
were dissolved in 100 parts of water with the addition of
: ~ ~
12.5 parts o~ an aqueous 33 % sodium hydroxide solution. 1Z.2
Parts of 2-hydroxy-benzaldehyde in 200 parts of water and 34
parts of an aqueous 33 % sodiurn hydroxide solutlon were then
added, and the reaction mixture wa heated to 60 C. A pH of`
9.2 was adjusted with glacial acetic acid, the mixture was
stirred for 1 to 2 hours at 60C and the pH was again adjusted
to a ~alue of 9.2. Next, the reaction mixture was oooled to
-' '
',: . '`,'
~, . . , , . - .-, . . " . , , ~ , " . . ..
.. .. . . . , " ~ . . . , . ., . . ", . . . .... . . . .. .. ... . .. ..
, , , . ,, ,", , : ', ;' , " ", ~, ",. . ~
~ ~10~ 76 ~ 082
.
` ` 1(~76105
25C and 12.5 g of cobalt hydroxy-carbonate were added.
; Stirring was continued for 30 minutes, whereupon the so-
lution of the second azo compound, prepared as follows, was
added.
30.9 Parts of 2-nitro-4~-aminodiphenylamino-4-sulfonic
acid were dissolved at 50 to 60 C at a pH of from 6 to 7 in
100 parts of water and 12.1 parts of an aqueous 33 % sodium
hydroxide solution. 10.1 Parts of diketene were added dropwise
over a period of 30 minutes, stirring of the reaction mixture
-~ 10 was continued for another 2 hours nt 50 to 60 C, whereupoll the
:- mixture was cooled to 20C. - In a separate vessel, 15.4 parts
of 4-nitro-2-aminophenol were dissolved in 150 parts of water
and 25 parts of an aqueous 31 ~ hydrochloric acid, 50 parts
of ice were added and the aminophenol was diazotized by
i 15 adding dropwise 17.3 parts of an aqueous 40 % sodium nitrite
- solution. Stirring was continued for another 30 minutes and
the excess of nitrous acid was decomposed by adding approxi-
mately 0.5 parts of amidosulfonic acid. The afore-described
~ solution of the acetoacetyl coupling component was then added
b~ 20 to the diazo solution obtained, a pH of 8.5 to ~.0 was ad~
justed with sodium carbonate and coupling was c~mpleted at
20 C while stirring for 4 hours.
, . :
The solution of the metal-free azo compound prepared in
this manner was combined with the above solutlon of the
.~ ., .
25 cobalt complex-azomethine compound, and the reaction mixture
was heated for 4 to 6 hours at ggc. The 1:2-cobalt complex
compound formed was precipitated by salting out with sodium
chloride or isolated by spray-drying. In the form of the free
29 acid the dyestuff had the following formula
.. . .
. ` : 9 ~
''','~-~ ' ' . ' , ' ',
, , , , . ' . , ,:
` ', '~ ~` ' ', ~' ' , ' " ' ' ' '
~ IIOE_76/F O~Z
:-~. r~ 10761~)5.
:: .,. ` , ~ . ,
~0~9 ~ ~3 1 :
:~ ,~, I
` . Co .
.. l ~ C - CH ' H(~)
N =`N - C . . ~ 2
NH - ~ ~S03H
,.. " ; N02 C0 ~ NH ~ ~- .
,~ ~ r ' . '
. , D Y E I N G E X A M P L E ~
. ~ " ~. .
.,~ 100 Parts of a woolen fabric were introduced into a
'.`~ dyei~g bath of 40 C, containing 1.0 part o~ the cobalt co~plex .. '.:.
~ dye of Example 1, 0.15 parts of an addition product of 12 mols ~.
','` of ethylene oxide on 1 mol of ste.aryl amine, 2 parts of ammo- '
nium acetate and 2 parts of 60 ~ acetic acid in 3,000 parts .. ',,
of water. The temperature of the dyein~ bath was increased .. ::: .;
within 30 minutes to boil and dyeing was continued for 60 ,: '~
: minutes at 100C. The fabric was then af.ter-treated in usual .
manner. A golden yellow coloration of good egality was ob- ~'
tained having a good to very good *astness to wet processing
~'~ and an excellent fastness to light. ~ ,
,~ When, instead Or the woolen fabric, 100 parts of a fabric
: :. ~ .
~: of polycaprolact,am fibers were dyed, a dyeing is obtained
: which al~o has good to very good fastnesses to use and pro-
ces~.ing and an excellent fastness to light.
' E X A M P L E 2: ~'
. In the preparation of the azo compound according to Example 1 ~':
-- 1 0
,'.. ' , , ' ' , '~'
., . , .. ,. ,:: , .. . . , .;. . .. . . ..
` . HOE 76~ 082
7610~i
the 4-nitro-2-aminophenol was replaced by 14.4 parts of 1~-
. , ,
chloro-2-aminophenyl. With the other conditions remaining the
; same, a 1 : 2-cobalt complex dye was obtained having the
following formula in the form of the free acid.
OJ5 ~ \' = C1 ~
Cl ~ NN ~ S0
~.. ;~ -. :
D Y E I N G E X A M P L E:
,-^ ~ 100 Parts of a fabric of polycaprolac~tam fibers were in- :
troduced into a bath of 40C containing 1.5 parts of the co-
balt complex dye of Example 2, 0.15 parts of an addition pro~
duct of 12 mols of ethylene oxide on 1 mol of stearyl amine~
2,0 parts of ammonium acetate and 2.0 parts of an aqueous 50 %
... ...
acetic acid in 3,000 parts of water. The temperature of the
~ dyeing bath was raised to 98 to 100C within 15 minutes and
- ~ t~e fabric was dyed for 60 minutes at 100 C. After the usual
: . . .~ .completion, a golden yellow dyeing was obtained having good
` to very ~ood fastnesses to wet processing and an excellent
fastness to light.
When the fabric of polycaprolactam fibers was replaced
by 100 parts of wool, the dyeing obtained had likewise good
.: ,
: .
.
,~ . . ,
..
; ~ H0~ 76/F 082
,~ 6~ 1!5
to very good fastnesses to use and processing and an ex-
cellent fastness to light.
E X A M P L E ~:
22.4 Parts of 4-chloro-2-aminophenol-6-sulfonic acid
were dissolved in 100 parts of water with the addition of
.! , :. '
12.5 parts of an aqueous 33 % sodium hydroxide solution. 12.2
Parts of 2-hydroxy-benzaldehyde in 200 parts of water and 34
-- parts of an aqueous 33 % sodium hydroxide solution were then
, . .. .. ~
added and the reaction mixture was heated to 60 C. A pH of -- ;
9.2 was adjusted with glacial acetic acid and the mixture was
stirred for another 1 to 2 hours at 60C at a pH of 9.2. -
Next, the mixture was cooled to 25 C, and 12.5 parts of co
:~ ... .
balt hydroxy-carbonate were added. After 30 minutes, a solu-
tion of a disazo compound,prepared as follows, was added.
27.7 Parts of ~ amino-azobenzene-4~-sulfonic aoid were
: . . ..
dissolved in 200 parts of water and 12.1 parts of an aqueous
33 % sodium hydroxide solution at a pH of 6 to 7 and a tempera-
ture of 50 to 60 C. 10.1 Parts of diketene are then added
~ : .
dropwise over a period of 30 minutes and the reaction mix-
20 ture was stirred for 2 hours at 50 to 60 C, whereupon it was
cooled to 20 C. In a separate vessel, 15.4 parts of` 4-nitro-
2-aminophenol were dissolved in 150 parts of water and 25
parts of 31 % hydrochloric acid, 50 parts of ice were added
::
~ and the phenol was diazotized by slowly adding 17.3 parts of
,i, . . . - .
an aqueous 40 % sodium nitrite solution. After 30 minutes,
about 0.5 parts of amidosulfonic acid were added to decompose
.:; ~ , .
the excess nitrous acid. Next, the solution of the aoetoacetyl
compound described above was added to the diazo solution ob-
-' 29 tained, the pH was adjusted to 8.5 to 9.0 by adding sodium ~ ;
~ - 12 -
: : .
.. , ; ; . . . - . - . . . ., . - . . . .; ... ~ . . ~ . .
~E~.
,~ 76~)5
,
carbonate and coupling was completed at room temperature
, while stirring for 4 hour~.
The solution of the disazo compound obtained was com-
bined with the solution of the cobalt complex azomethine com-
pound described abo~e, and the reaction mixture was heated
at 95 C for 4 to 6 hours. The 1:2-cobalt complex dye obtained
';~ was precipitated by salting out with sodium chloride or iso-
~; lated by spray drying. In the form of the free acid it has
,' the formula
f ~ ( ~
., N = N - C
N=N ~ S03H
N02 C0 - NH ~ \=~ r, .,
: ~
,,~ D Y E I N G_ E X A M P L E:
, ~ Polyamide carpet yarn was padded with an,aqueous padding
'~;; liquor containing 10 parts of the dyestuff of Exan~ple 3,
5 parts of a locust bean flour preparation, 4 parts of an
addition product of 8 mols of ethylene oxide on 1 mol of iso-
b tridecyl alcohol and 10 parts of an aqueous 60 ~p acetic acid
in 1,000 parts of the padding li,quor, to a liquor pickup of
'; 100 %; the yarn was steamed for 6 minutes at 100 to 102 C
, and then rinsed with cold water. The golden yellow dyeing ob- ',
,, ., : ...
. . . . .
. . .
.
io~ ~ :
r - 1~1~7t;105
. i - . `~
tained had good fafitnesses to use and an excellent fastness
- to daylight.
E X A M P L E 4: ;
In the preparation of the disazo dye according to Ex-
ample 3 the 4-amino-azobenzene-4~-sulfonic acid was replaced
by 41.3 parts of 4-amino-6-methyl-3-methoxy-azobenzene-4~
sulfoethyl-sulfone, the other conditions remaining the same.
. .
The 1:2-cobalt complex compound obtained had the following
- formula in the f`orm of th~ free acid.
~1 - , ''`' 1'
H03L ~ -~ N : CN ~
.,~ O ~ / ' ' ' ' ,'
~C ~ . ' : - . "
o 7 ~ ~ C - C113
N ~ N ~ C , CK3 ,
N-N -' ~ S02
C0 - NH ~ CH2
; OC~13~ C~2-S0
.::-, . .
~-~ D Y E I N G E X A M P I, Es
100 Part~ o~ wool flock were introduced into a dyeing
bath of 40C, containing 1.0 part of the cobalt complex dye ~;
.. ..
of Example 4, 0.15 parts of an acldition product of 12 mols of
ethylene oxide on 1 mol of stearyl amine, 2 parts of ammonium
:~ .
~; acetate and 2 parts of an aqueous 60 ~ acetic acid in 3,000
, .:
parts of water. The temperature of the dys bath was raised to
the boil within 30 minutes, and dyeing was continued forj60
.' ,~ .
; ' , ' '
.. . .. . . r ~
~i ~IOE 76~ 082
~i 1~76~5
, . . .
minutes at 100C
After the usual after-treatment and completion, an even
~, golden yellow dyeing was obtained having good to very good
fastnesses to wet processing and an excellent fastness to
light.
When, instead of 100 parts o~ wool flock, the same amount
of woolen yarn in hanks was dyed, a very good and even dyeing
`j having good to very good fastnesses to wet processing and an
~;; excellent fastne-ss to light was likewise obtained.
In the following table are listed further dyestuffs
according to the invention which were prepared under the con- -
ditions specified in the preceding examples. They yielded
golden yeilow dyeings on wool.
E X A_M P L E DYESTU~
.. '
;
',~3
/~ C -- Cii3 ¦ h(
N - N -- C . j~03H . .
~JJ I . 1~ NH ~N0
El co ~ NH ~ \~/ 2
"~
`,:, -
.- -- ~ .
- 15 -
.: ,' : ' ' . .: :
. '-, - ' ". , ,
,, . : ~ . ~ .
',
~ )761S~15 Ho~ 7G~ Q82
:; ' ' :: .
. .. ..
:. CH3 - . . - (--) -
H35J~ N = CH
- \ 0 3 :: .
, . . O ~ ,~ ~ . , :~.
:~ ~Co ~ '
~ . .
6 ~ 11 \o - - -
. '~ . 1 ~ ~c - . C~ i
i,.. ~" , ''11 . , , : ~:
5 ~r- N = N _ C
~; ~ N02 lo - NH ~ N~53
,~ . . ............... .. .
O ' ' ~ . ''
HO~SJ~ N = CH ~
`i, I , ~' ,~==' , .' ,, ": '
O ~ . ` - ' :.
f / ~ C -- CH3
N = N -- C . CE~3
. ¦ ~ N=N~ S0
CH3 C0 - ~H --~,J ~ 1 2 . .
', ' CH2-S3H
.~, .
,:, . _ ~ , .
.j~! ' .
." , , .' ~
` :'
/,', " ' ' .'
.'.,: : l
.~'~ ,...................... . . .' ~ i
-: - 16.-
~: .,
, :
j~=, _ . ,.. ~ .. . . .............. ..... .... . ........... .................
. ., ' ,. ' . ! ' '.' . .. ,: ~ ' ,. '., , ., ' ' ' , ~, . i . ,
~ 1076105 ~-- ~
~ . . . .
,~ , ,
Cl ~ CL~
' C -- CN3 ~ ¦ N ( )
~S~ N = N -- C .
cl ~ lo NH ~ ~3 2 ~ 3 ~;
. ~ , ., . ' ~ CH2,
: SO3H
,,~, ... , ;..... .. .. .- .
:. dO3S~j N =CN
O ~ ~ 3 ~ ¦
~r N= N -- C . ~)CH3
: ~ 1~ I ~ N=N--r\~O -NH
CO NN ~ \~::/ 2 ~ . .
SO3 H
~, ' . ' . ,
- , .
.~,,, ' ' :
`~ ~
,
.'' "
- - 1 7 -
' ', .
'. .' . . ' , '' " ; ' :
' ' .' ~ ' ' , ' '
. ~ , '" '' ' ., .. , ' ' ' ' ' '
' '
. ~ ~
,
~, , . ., ' . ~
_ 08~ ~
0761~S
~' ..... . .
':~.': , . . . . .
. ~ . .
. ÇH3 - . - .
O S~L N = CH
.,' . 'c) ~ ~ '. ''.; '' ' -. , ','',
~~ 10 . Co - . ` - . .
o 7 ~c CH3 . -
N=N~3 50 -N-CII
CH C0 - NH- 2 ~ 3
CH2
503H
'~'Ii ' .
~. .. . ......... . .
. . l ~ . . . . . .
H035 ~-- N = C~ ~ . .
., O ~ ~
0~ \C-C~
N = 1~ -- C . .~)2 :
' ~SO3H . . :
C0 - ~H ~ ~ ~
2~ ~ . .
',"', ' . ' ' ' , ', . . ,: . - ' , '', ',.;, ' ~ ';,
,1 - ~ , . : . ' . ,, :'
.. ~ ~ . . ..
1 B - . :: . .
~10~ 76/~ 082
107~ 5
~, . .
`~; Cl
~303S ~ - ~ = Ch
', ~ . . O \
~ ~2 ~
' :,.'i . /~ - O ' . . ' ' ~ ' ~ .
i ~ f / j C - CH3 H( )
¦ ~ N-N ~ 503U
' CO - NH
E X A_M P L E 13.
32.8-Parts oP the azomethine dyestuff prepared under the
~ condltions oP Example 1 and~55.8 parts of the azo dyestuff
prepared accordin~ to Example 1 were mixed in the form of the
solution or suspension obtained, 1Z.5 parts oP cobalt hydroxy-
carbonate were added and the whole was stirred for 30 minutes
at 20 to 30 C, heated to boil and then refluxed for 4 to 6
hours. After the usual precipitation with sodium chloride or
by spray drying, a dye was obtained containln~, besides the
2-cobalt complex dyestuff Or the azomethine dyestuff and
ths 1:2-cobalt complox dyestuff of the azo compound, the un-
ymmetrical 1:2-cobalt complex dyestuff defined in Example 1
by the formula of the free acid as main component. It had the
same tinctorial properties as the dyestuff of Example 1.
~ E X A M P L E 14:
i ~ 32.8 Parts of the azomethine dyestuff according to
,.. , ~
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.~ _ 1 9
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.; ~ i.. . , . : . . , ,;~
: ~076105 ~lo~ 7~6/~_082
Example 3 and 52.6 parts of a disazo dyestuff according to
Example 3 were mixed in the form of the solution or suspension
obtain0d. 12.5 Parts of cobalt hydroxy-carbonate were added,
the whole was stirred for 30 minutes at 20 to 30C and then
heated to boil. The reaction mixture was then refluxed for 4
to 6 haurs. The dyestuff obtained contained as the main com-
ponent the unsymmetrical 1:2-cobalt complex dyestuff defined
: .
by the formula of Example 3, besides the 1:2-cobalt complex
dyestuff of the azomethine compound and the 1:2-cobalt complex
10 dyestuff of the disazo compound. It had the same good tincto- -
rial properties as the unsymmetrical 1:2-cobalt complex dye- -
stuff of Example 3.
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