CA1072083A

CA1072083A - Azo dyestuffs

Info

Publication number: CA1072083A
Application number: CA257,593A
Authority: CA
Inventors: Jacky Dore
Original assignee: Sandoz AG
Current assignee: Sandoz AG
Priority date: 1975-07-25
Filing date: 1976-07-22
Publication date: 1980-02-19
Also published as: CH616444A5; MY8200239A; KE3193A; DE2631830A1; FR2318907B1; AR210505A1; FR2318907A1; IT1066028B; JPS604850B2; AU1625376A; DE2631830C2; JPS5215523A; BR7604810A; AU501133B2; ES450120A1; GB1550208A; HK8082A; BE844481A

Abstract

Abstract of the disclosure The present invention relates to pure asymmetric 1:2 cobalt complexes and mixtures thereof, I
in which X is hydrogen or nitro, either, R1 and R2, independently, are hydrogen, (C1-4)-alkyl, (C1-4) alkoxy, chlorine, bromine or nitro or R1 is hydrogen, chlorine or nitro, and R2 is -SO2NR3R4, in which the groups R1 and R2 occupy the 4- and 5-positions, either R3 is hydrogen, unsubstituted or substituted (C1-4) alkyl, and R4 is hydrogen, unsubstituted or substituted (C1-4) alkyl, (C5-7) cycloalkyl or phenyl, or , R3 and R4, together with the nitrogen atom to which they are bound, form a non-aromatic 5- or 6- membered heterocyclic ring which contains one or two hetero atoms, B is a divalent radical of a coupling component of the 1- or 2-hydroxynaphthalene series which is coupled in the 2- or 1-position ortho to the hydroxy group and is bound to the cobalt atom through the oxygen atom, D is a divalent radical of a coupling component of the 2-naphthylamine series which is coupled in the 1- position ortho to the amine group, or a divalent radical of the 5-amino pyrazole series which is coupled to the carbon atom next to that carrying the amino group, whereby the divalent radical D is bound to the cobalt atom through the amino group, and M is hydrogen or an equivalent of a non-chromophoric cation, with the provisos that the molecule (i) contains a single sulpho group, which sulpho group is in salt form, (ii) contains at maximum a single sulphonamide group, which group is in radical D or is R2, and (iii) is free from

Description

iO~Z083 Case 150-3778 AZO DYESTUF~S
-.'. ', .
- The present lnventlon relates to pure asymmetric 1~2 cobalt comp1exos and mixtures o~ such pure as~mmetrlc complexe~, thelr production and use. ~ ~:
More particularly, the present lnventlon provides pure asymme~r~c 1:2 cobalt complexes o formula I, ~Y~ U/

N e N

R2 ,.

ln whlch X is hydrogen or nitro, elther, Rl and R2, independently, are hydro~en, (Cl_4)-alkyl, tCl 43alkoxy, chlorine, ~romina or nitro or Rl ls hydrogent chlorine or ni~ro, and ~:~
R2 is -SO2NR3R4, in which ¢ase the groups R
and R2 occupy the 4- and 5-positions, .... .
elther R3 i8 hydrogen, ~Cl_4)alkyl unsubstltuted or .; `
~ubstituted by up to two ~ubstltue~ts selected ~rom halogen~ hydroxy, cyano, ~Cl_~)alkoxy and phenyl, and ;
R4 ~ ~ydrogen, (Cl_~)alkyl un~ubstituted or substitu~ed by up to two substituents ~,~
diiP
~ .

~ 3 \ .

- 2 - 150-3778 .
selected from halogen, hydroxy, cyano, (Cl_4)alkoxy and phenyl, (C5 7)cycloalkyl unsubstituted or substi~uted by up to three methyl groups,phenyl unsubstituted or substltute~ by a total of up to three substltuents selected from halogen ~max.
)alkyl, ~Cl_4)alkoxy a~d n1tro (max. 2 of each of those).

. . , . ~
or,R3 and R4, to~ether with the nitrogen atom to which they are bound,form a non-aromatic ~ -~ 5- or 6- membered heterocyclic rin~ which ; - contains one or two hetero atoms, ' B is a divalent radical of a couplin~
component of the l- or 2-hydroxyna~hthalene eries which is coupled in the 2- or 1-position ortho to the hydroxy group and 1s bound to the cobalt atom through the oxygen atom, D is a divalent radlcal of a coupling component of the 2-naphthylamine series which is ~ coupled in the 1- position ortho to the amine : group, or a d~valent radical of the 5-amino pyrazole. series which is coupled to the carbon atom next to that carrying the amino group, whereby the divalent radical D is ound to the cobalt a~om through the amlno group, and M ls hydrogen or an equiva~ent of a non-.chromophor~c cat~Qn, :~ .
,. ...... . .

Z~3

- 3 - 150-3778 ~ith the provisos that the molecule ~1) contain6 a - single sulpho group, which sulpho group is in salt form, (il) contains at maximum a single sulphonamide group whlch.grvup ls in the radical D or is R2, and ~iti~ is free from -N-C-O- groups, and mixtuxes of such pure asymmetric complexes~
. . . ~ . , .
When Rl and /.or ~2 ls alkyl, such alkyl is preferably ~.
methyl or eth~l, w1th methyl being especially preferred.
When ~1 and/or R2 is alkoxy, preferably such alkoxy is methoxy or ethoxy.
When R3 and/or R4 is an unsubstituted alkyl group, such alkyl group is straight-chain or branched and prefe~ably contains 1 to 3 carbon atoms, with methyl, ethyl and isopropyl being especially preferred.
When R3 and/or R4 is a substituted alkyl group, such 81Xyl group la straight chain or branched. Preferably any halogen substituent on an alkyl group as R3 and/or R4 is chlorine or bromine and preferably any alkoxy substituent is methoxy or ethoxy. Preferred substituents are hydroxy, methoxy . .
and ethoxy. More preerably, any substituted alkyl group as R3 and/or R~ ls monosubstituted. ^
When R4 is an unsubstituted or substituted cycloalkyl preferably such cycloalkyl contains 5- or 6-ring carbon atoms, with cyclohexyl being most preferredO
When R4 is substituted phenyl, preferably such phenyl ls mono~ubstltut~d by - ~ ~ 150-3778 chlorine, nitro, methyl, methoxy or ethoxy or di~substituted by two methyl, two methoxy or two ethoxy groups. Most preferably any phenyl radical as R4 is unsubstituted.
When R3 and R4~together with the nitrogen atom to which they are bound,form a heterocyclic ring, such hetero-cyclic ring is preferably a pyrrolidine, piperidine or morpholine ring.
By halogen is meant chlorine, bromine or fluorinP with chlorine and bromine being preferred.
R3 is preferahly R3/where R3 is hydrogen, tCl 3)alkyl or ~-or ~-hydroxy (C2_3)alkyl. Most preferably, R3 is hydrogen.
R4 is preferably R4, where R4 is hydrogen; (Cl 3)alky~;
~3 or ~-hydroxy(C2 3)alkyl;Rllo-(CH2)n-,where Rll is methyl or-ethyl and n is 2, 3 or 4, preferably 2 or 3; phenyl; phenyl monosubstituted by chlorine, nitro, methyl, methoxy or ethoxy; or phenyl disubstituted by two methyl, two methoxy or two etho~y groups. More preferably R4 is R4, where R4 is methyl, ethyl, isopropyl, 2-hydroxyethyl, -CE12-CH(OH)-CH3,~(CH2)3-OCH3 or phenyl. Even more preferably R~ is R41 , where R4'is methyl, -~CH2)3-OCH3 or phenyl.
Preerably Rl is R1, where Rl is hydrogen, methyl, chlorine or nitro. More preferably, Rl is Rl, where Rl is hydrogen~
chlorine or nitro.
R2 is~preferably R2, where R2 is chlorine, nitro or -SO~NHR4 prefexably -SO2NHR4' with the proviso that when R2 is -SO2NHR4 or -SO2NHR4', Rl is hydrogen.
More preferably, Rl and R2, independently, are chlorine or nitro. When one of Rl and R2 is hydrogen and the other has a significance other than hydrogen, the substituent is preferably in the 4- or 5- position. When both of Rl and R2 have a signlflcance other than hydrogen, the substituents are,preferably in the 4~ and 6-positions, wlth the exception that when R2 is -S02NR3R4 the suhstituents Rl and R2 are in the 4- and 5-positions.

The group B is preferably a group of formula (a), (b), (c) or (d), \O ' O \O Cl O

~a) (b) (c) (d) ' in which Yl is hydrogen, (Cl 2)alkyl (preferably methyl), :(Cl_2)alkoxy :(preferably methoxy)~chloxine or bromine;

: preferably Yl ls Yl, where Yl is hydrogen, methyl or ; - ~ methoxy. :`

More preferably B is B', where B' is a group of formula (a~, (c), (d), or (b) in which Yl is Yl.

The group D is preferably a group of formula (e) or (f), ~? ~ N ~ R
.s, ~ Y2 C = N

Rl 2 (e~ (f) 7Z~1!33 .: - 6 - 150-3778 in which R5 is hydrogen, (Cl 4)alkyl or a group of formula ~g) or (h), 6 ~8\

Rg :
( ~ (h) in whlch one of R6 and R7 is hydrogen and the other is hydrogen, chlorine, bromine, ~:
(Cl_2)alkyl (prefexably methyl), (Cl 2)alkoxyt (preferably methoxy) or trifluoromethyl, R8 is hydrogen or methyl, and R9 is methyl, chlorine or bromine with the pxoviso that when Rg is chlorine or bromine R8 1s hydro~en, Y2 is hydroyen or ~SO2NHRlo in the 5-: or 6- position,in which Rlo is hydrogen, :~
(Cl 4)alkyl'or hydroxy~C2 4)alkyl, ~' Rl~ is hydrogen; (C~ ~), preferably (Cl 2) alkyl, more preferably methyl; (Cl_2) alkoxy, preferably methoxy; or phenyl, R13 is hydrogen; (C1 ~)alkyl, preferably ~(Cl_2)alkyli phenyl(cl-4)alkyL
preferably phenyl (Cl_2)alkyl;
; cyclohexyl or a radical ~.
of formula (i) -;

q2~3 :~

~' ~

in which either Zl is hydrogen and Z2 is hydrogen; fluorine; chlorine;
bromine; ~Cl_4)alkyl,~preferably (Cl_2)alkyl; (Cl_2)alkoxy, nitrojor . 5 trifluoromethyl, ; or Zl and Z2 are the same and are both chlorine, bromine, methyl or methoxy, with the provisos that:
when both Zl and Z2 are ahloxine, the chlorine atoms are in the 2,3-, 2,4-, 2,5-, 2, 6-, or 3,4 positions, when both Zl and Z2 are bromine, the bromine atoms axe in : the 2,~- or 3,5-positions, .:
when both Zl and Z2 are methyl, the methyl groups are in : 15 ~he 2,3-, 2,4-, 2,5-, 2,6~ or 3,5- pos~tions, :and when both Zl and Z2 are methoxy, the methoxy groups ar~
in the 3,4-pos$tions, or Zl and Z2 are different and signify 3-chloro-2-~ethyl, 4~chloro~2-methyl, 5-chloro-2-metl-1yl, ~-bromo-2-methyl or 5-chloro-2-methoxyJ
Preferably Zl and Z2 are Zl and Z2~ where Zl and Z2 are, independently, hydrogen, chlorine or methyl.
When R5 is alkyl it 1~ preerably methyl or ethyl.
: When R5 is a radicaI o formula (g), preferably one of R6 and R7 is hydrogen and the other is hydroyen, chlorine, methyl or methoxy, more preferably hydrogen, chlorine or methyl ' ~2V8~

- - 8 - 15~-3778 When R5 is a radical of formula (h), Rg is preferably - Rg, where Rg is methyl or chlorine.
Preferably R5 is R5 where R5 is hydrogen, phenyl, 2,3~ or 4-chlorophenyl, 2- or 4-methyl~henyl or 2,6-dimethyl-phenyl~ ~ore preferably, R5 is R5 whexe R5 is hydrogen or phenyl, with phenyl being especially pxeferred.
When Rlo is aLkyl, such alkyl is preferably methyl or ethyl, more pxeferably methyl. When R1o is hydroxyalkyl~such hydroxyalkyl is preferably ~- or ~hydroxy(C2 3)alkyl with ~-hydroxyalkyl being preferred.
Prefer~bly Rlo is Rlo~ where Rlo is hydrogen, me~hyl or ~-hydroxy(C2 3)alkyl.
Y2 is pxeferably hydrogen or -S02NHRlo, hydrogen being preferred ~Ihen R5 is other than hydrogen~and -S02NHRlo bein~
preferred when R5 is hydrogen Most preferably Y2 is hydrogen.
Preferably, in the radical of formula (e), R5 is R5 and Y2 is hydrogen or -S02NHRlo. Most preferably (e) is a radical of formula ~e)', N -'~.
- '' '.
(e)' In the radical of formula (f), R12 is preferably methyl and R13 is preferably a radical of formula (i).
Preferably (f) is a radical of formula (f)l, ` 11~17~0~3 ~ _ 9 - 150-~778 - C ¦ ~ Z~ , ~
C = N

wherein Zl and Z2 are as defined above~
Preferably each of Zl and Z2 are zl and æ2.
D is pre~erably a radical of formula (e), wherein R5 ;~
is R5 and ~2 is hydrogen or -S02NHRlo or a radical of formula S (f)'. Most preferably D is a xadical of formula (e)'.
Preferably M signifies an alkali metal cation, an unsub stituted or substituted ammonium ion or a ~uarternary amine.
As examples o~ alkali metal cations may be given sodium, lithium and potassium, with sodium being preferred. Suita~le substituted ammonium ions are (Cl 3)alkyl ammonium and hydroxy (C2_4)alkylammonium, for example triethyl ammonium, mono-, di-and triethanol ammonium and mono-, di- and tri-isopropanol ammoniumJ Suitable quarterniæed ~mines include N-ethyl-N-hexylamine, cyclohexyla~ine, N,N-dicyclohexylamine or cyclic amines such as morpholine in quarternary form. When M is a quarternary amine, the water solubility of the 1:2 complexes is reduced such that they are scarcely soluble or only soluble in the presence of organic solvents.
The 1:2 complexes in which M is hydrogen may, in certain cases, be scarcely soluble in water.

~. , .
The salt form of the sulpho group m~y correspond to any - of the above~mentioned cations for M. The salt orm cation .
may be the same as or different from M.
Representative asymmetric 1:2 cobal~ complexes of form~la I are those of formula Ia, ~ ~035 ~ ~ N I,-~ ~

> Co ¦ b~ Ia ~ N D

R2 ' ~:

in which Rl, R2, X, B, D and M are as defined above, with the proviso that when D is a ra~ical of formula (e) R5 is only hydrogen when Y2 is -S02NHRlo or B is a radical of formula (b), (c) or ~d).
Of the complexes of formula Ia, those in which R5 is R5 and Y2 is hydrogen or ~SO2NHRlo are preferred.
Preferred complexes of formula I are those of ormula Ib a~d Ic, `` ~07~83 ~ 150-377 I X ._ ~, ¦ N035~ N - N - S' M~

~ / ~ ~ N ~r R7 ~ Ib R2 ~ .

M~

R~ ~ C ~ ¦ { ~ Ic in which R1 is hydrogen, methyl, chlorine or nitro, with hydrogen, chlorine and nitro being preferred, . iO~ZO~

; ,.;~
R~ is chlorlne, nitro or -SO2NHR4, ~preferably -SO2NHR~'), with the proviso :
that R2 is only -SO2NHR4 or -SO2NHR4' when Rl is hydrogen, -.
~ is a radical of formula (a), (b), (c) or ~d), with the proviso that when B is a xadical of formula (b), Yl is Yi, and X, Zl~ Z2~ M, R6 and R7 are as defined above.
Especially preferred complexes of formula Ib are those wherein one of R6 and R7 is hydrogen and the other is hydrogen, ch~orine, methyl or methoxy, more preferably hydrogen, chlorine -~ , ox methyl.
Espec1ally preferred complexes of formula Ic are those in which each of Zl and Z2 are Zl and Z2- ~.

lS The present invention also provides a process for the ;production of complexes or mixtures of complexes of formula I~ comprising a) reacting a compound of formula II, in free acid or salt form, ONO L L
\ ~1 ~ 2 Co ~ T\ II
HO3S ~ N=N - B
~0~
.~ . . .

' ~

~2~

in which Ll and L2 are monodentate Ligands and ~-X and B are as defined above, or a mixture of compounds of formula II, w1th a compound of formula III, OH H
N - N ~ D III
~Y~, ' '.
H

in which Rl, R2 and D are as defined above, ox a mixture of compounds of formula III, or b) reacting a corresponding nitrite-containing cobalt complex of a compound of ~ormula III, or a mixture thereof, with a compound of formula IV, in free acid or salt form, H03S ~ _ N = N----B IV
.

X
in which X and B are as defined above, or a mixture thereof, any sulpho in the free acid form beiny converted into salt form.
The reaction is suitably carried out by employing the reactants in stoichiometxic amounts. Suitable monodentate ligands are colourless inorganic or organic molecules which contain an oxygen or nitrogen group with electron donating properties, in particular water molecules. The reaction may be carried out in aqueous, aqueous/oryanic or organic medium.
Examples of organic solvents include low mo]ecular weight 20 carboxylic acid amides such as formamide or an alkylated derivative~
thereo~, glycols such as ethylene glycol, di- or triethylene-glycol or ether derivatives thereo~ The reactions are suitably ~7~83 ~ 150-3778 conducted in neutral or alkaline medium and is completed after all the 1 1 complex has been reacted~ The product obtained may be isolated in conventional manner, for example by salting out or weakly acidifying,and after ~ashing with S a concentrated salt solutlon may be collected and dried.
Process a) is preferred.
The obtalned asymme-tric complexes are pure asymmetric complexes, that is, the complexes contain less than 10% of the possible symmetric complexes.
The 1:1 cobalt complex - starting materials may be produced by reacting a compound of formulae III or IV, as the case may be, with a cobalt-donating compound in the form of a cobalt(II) salt in the presence of an inorganlc nitrite Suitably the compound of formula III or IV is reacted with the cobalt-donating compound in a 1:1 molar ratio. Preferably 2 to 6 moles of nitrite per gram atom cobalt are used. The metallization may be conducted in conventional manner.
Depending on the reaction and isolation conditions (e.y.
addition oi base to obtain an alkaline pH or the salt used to salt-out the product) a complex of formula I is obtained in which M is preferably an alkali metal cation, such as lithium, sod$um or potassium, or an ammonium ion and in which the salt form of the sulpho group is the same as or di~ferent than M.
When a weak acid is used a complex is obtained in which M is hydrogen and the sulpho group is in salt form. The hydrogen ion may be replaced by an alkali metal cation or quaternary ammonium lon by the additon of alkali metal hydroxides or organic amines. ~t will be appreciated that the cation of the sulpho yroup may also be replaced at the same time.
The compounds of formula II, III and IV ~re known or may be prepared in conventional manner rom known starting materials.

0~3 - 15 - 150~3778 l'he complexes of formula I and mixtures thereof are useful for dyeing and prlnting nitrogen~containing organic substrates. Examples of suitable substrates are those which consist of or comprise natural or synthetic polyamides such as wool, silk or nylon, or polyurethane or leather.
The dyeings obtained exhibit notable light and wet fastness~
They also exhibit notable rubbin~ fastness and resistance to car~onization,ironing, wool chlorination andithe action of acids and alkalis.
The dyestuffs build up fxom a nautral medium on poly amide fibres, the build-up being tone~in-tone due to thelr pure asymmetric character. The dyestuffs also build-up equally on wool and nylon when dyed together. The dyestuffs are suitable for use in combination with other 1:2 metal complexes. The complexes may be formed into stable printing pastes which build-up well on all types of polyamides~
The complexes o formula I which are well soluble in water, i.e. those in which M ls other than hydrogen or an amine such as N-ethyl-N-hexylamine, cyclohexylamlne, N,N-dicyclohexylamine or cyclic amines such as morpholine in quaternary form are also useful for dyeing metals, espe-cially anodized aluminium.
The compounds of formula I in which M is a quaternary 2S amine as given above may also be used in the preparation of printing laquers and ball-point pen inks.

. . . . . - ~

- 16 - 150-377~

The dyes according to the invention may be employed as such or in the form of liquid or solid preparations.
Preferably water-soluble organic solvents optionally mixed with water are used for the liquid preparations which ~ ', are in the form of stable concentrated stock solutions;
conventional additives such as dissolving agents (e.g. urea ~, or alkali reacting organic or inorganic,substances) may be added thereto. The stock solutions may he diluted with water.
Such preparations may be made, for example, in accordance with the procedure described in German Patent No. 1,619,470 or in ~;
German Patent Application No. 2,033,989. Also concentrated stable aqueous preparation which contain the conventional additives may be used.
Solid preparatlons which are in powder or granulate orm with an average particle slze of at least 20 }l can be ''' used, which preparations contain conventional additives such as standardization agent~. 5uch solid preparations may be made for example in accordance with the procedure described in British Patent 1,370,845. The solid preparations are well soluble in water whereby the exact quantity of dye preparation needed in the dyebath may be added thereto.
The following Examples further serve to illustrate the invention. In the Examples the temperatures are in degrees Centigrade and the parts are by weight.

`\ :
:: ~ 17 - 15Q-3778 EXAMPLi-3 1 45 Parts of the dyestuff obtained by the acid coupling of diazotised 2~amino-1-hydroxy-4,6-dinitxobenzene with 2~(3' chlorophenyl)-aminonaphthalene and the paste of the l:l-cobalt complex obtained from 44 parts of the monoazo dyestuffof 1-amino-2-hydroxy-6-nitronaphthalene-4-sulphonic acid ~ 2-hydroxynaphthalene are stirred into 600 parts of water and 300 parts of ethanol ! and this is set at a pH o~
11.0 - 11.5 by adding sodium hydroxide solution. The reaction mixture is heated to 30 and stirred at this temperature for 24 hours. If any starting material remains ater this time the temperature is raised to 80C and stirring is continued until the disappearance of both starting materials. 'rhe pH
is kept to 11-11,5 during th~ whole reaction. The chromato-graph of the asymmetrical 1:2-cobalt compleY thus formed must show no more or very little traces of the metal-free dyestuf and none o~ oobalt complex. The dyestuf is salted out by adding sodium chloride, it is filtered, washed with a 5%
sodium chloride solutlon and dried. It corresponds to formula N2 , NdO3S~N

¦ N~

¦0;!1-- ~N = --" .
,, . ' i 1~7Z~83 ~ 150-3778 and has a very high degree of purity (in all at most 5%
of symmetrical complexes). The dyestuff is well soluble in water and dyes natural and synthetic polyamlde fi~res such as wool and nylon in a grey or hlack shade, the dyestuff being absorbed from a neutral bath in an even manner.
The dyeing has good all-round wet fastness and notable ,~
light fastness, as well as notable fastness to rubbing. The cobalt complex used as the starting material may be produced as follows:
1028 parts of cobalt-(II)-sulphate.7H2O and 28 parts o sodium !~
nitrite are dissolved in a beaker in 500 parts of water. Then, ; ~
44 parts of the monoazo dyestuff 1-amino-2-hydroxy-6-nitro-naphthalene-4-sulphonic acid- - ~ 2-hy~roxynaphthalene are entexed with good stirring. The pH value is set at S.5 - 6.0 duriny and after addition of the monoazo dyestuff, and is kept in this range for about 20 hours until the initial dyestuff h~s been completely converted into the l:l-cobalt complex, During metallisation, the temperature must be maintained at between 20 and 30. The l:l-cobalt complex is preaipitated by salting out with sodium chloride solution until the iltra~e is free from co~alt. The paste of the l:L-cobalt complex obtained may be used directly for the xeaction to orm the asymmetrical 1:2-cobalt complex.
In the ollowing Table the structural formulae of further dyestuffs ~1hich may be prepared in analogy with the procedure described in ExampLe 1, are given. The dyestuffs in -~2~3 - 19 ~ 150~377~ :

in the ~able glve dyeings on polyamide which have similar properties to the dyeing obtained with the dyestuff of Example 1. ~he dye shade obtalned in each case is indicated by the letters a to i given in column I, whereby ~;
a is black b is reddish black c is greenish black d is bluish black e is brown f is red-brown g is bordeaux h is red-bordeaux, and i is rubine - 20 ~ 150-3778 ~_ ~xam le No Con~pound o~ formula IV Compound of formula III I
P . in the form o~ 1:1 Co-complex in Metal free form _ . _ ~ ~ . ' ,:
2 1-amino-2-hydroxy-6-nitro- 2-amino-4-chloro-l-hydroxy- a -:
naphthalene-4-sulphonic acid 6-nitrobenzene ~ 2-~2-hydroxynaphthalene phenylamino-naphthalene 3 do.~ 2-amino-4,6-dinitro-1- a hydroxybenzene--~ 2-aminonaphthalene

4 do. 2-amino-4,6-dinitro-1-hydroxy- a benzene-~ 2-phenylamino-. naphthalene S do. 2-amino-1-hydroxybenzene e - ---t 2-phenylamino-naphthalene - 6 do. 2-amino-1-hydroxy-4-methyl- a 6-ni~robenzene-----~ 2-(4'-chlorophenyl)aminonaphthalene 7 do. 2-amino-1-hydroxy-~-me~hoxy~- a benzene ~ 2-phenylamino-naphthalene 8 do. 2-amino-l-hydroxyben7,ene-4- b sulphonic acid amide 2-(2'~6'-dimethylphenyl) aminonaphthalene 9 do. 2 amino-1-hydroxybenzene-4~N- b ~3 7 -methoxypropyl)sulphonic acid amide -----~ 2-phenyl-aminonaphthalene `~
do. 2-amino-1-hydroxybenæene-~-N- b phenyl sulphonic acid amide . t 2-phenylaminonaphthalen 11 do. 2-amino-1-hydroxybenzene-5-N- a methyl sulphonic acid amide -- ~ 2-(4'-methylphenyl)-l aminonaphthalene , 12 do. 2-amino~l-hydroxyben~ene-4~N- b (2'-hydroxypropyl)sulphonic acid amide - ~ 2-phenyl-aminonaphthalene 13 do. 2-amino-4-chloro-1-hydroxy- a benzene-5-sulphonic acid amid -~ -t 2-phenylaminonaph-thalene . ~, __ _ _ -0~ 2~ 8 3 .. _ __ _ _~ __~_ Compound of formula IY Compound of formula III I
Example No in the form of 1:1 Co-complex in metal free form ___7__ __ ~ ~ __ _ 14 l~amino--2-hydroxy-6-nitro- 2-amino-4,6-dinitro-1-hydroxy- a naphthalene-4-sulphonic benzene ~ ~2-aminonaphthalene-acid ~ 2-hydroxynaph- 6-N-(2'-hydroxypropyl)sulphonic thalene acid amide lS do. 2-amino-4,6-dinitro-1-hydroxy- a ben~ene --~2-ethylamino- -naphthalene 16 do. 2-amino-1-hydroxy-5-nitro- e ¦ benæene ~ 3-methyl-1-phenyl-I 5-aminopyrazole 17 do. 2-amino-4,6-dinitro-1-hydroxy-benzene ~ ----~ 3-methyl-1-phenyl-5~aminopyrazole fl-amino-2-hydroxy-6-nitro- ~ . . .-naphthalene-4-sulphonic acid~
\ - ~2-hydroxynaphthalene J 2-amino-4,6-dinitro-1-hydroxy- a 18 ~ and ~ benzene ~2-(3t-chloro-l-amino-2-hydroxynaphthalene-~ phenyl)aminonaphthalene 4-sulphonic acid ~2- J
hydroxynaphthalene 19 1-amino-2-hydroxynaphthalene- do. `~
4-sulphonic acid ~ 2-hydroxynaphthalene f~ ;~
2-amino-4,6-dichloro-1-hydrox~
benzene _ ~2 phenylaminonaph-thalene . 20 do. 5 and ~ a 2-am;no-4~6-dichloro-1-hydroxy-benzene ~2-phenylaminonaph-~ ~thalene ~
21 do. 2-amino-4,6-dinitro-1-hydroxy- d benzene~ 2-aminonaphthalene 22 do. 2-amino-4,6-dinitro-1-hydroxy- a benzene- ~2-phenylamino-naphthalene 23 do, 2-amino-1-hydroxybenzene-4-N- b phenylsulphonic acid amide 2-phenylaminonaphthalene 24 do. 2-amino-1-hydroxy-5-nitrobenzene g -73 methyl-1-~2',s~_di_ chlorophenyl)-5-aminopyrazole :' do. 2-amino 4,6--dinitro-1-hydroxy- i . benzene - ~3-methyl-1-phenyl-

5-aminopyrazole ---- :
~' .

1~2~83 ~ 22 - 150-3778 , _ _ ____~ _ ~ .~.
Compound of formula IV Compound of formula III I
Example No. in the for~ of l:l Co-complex in metal free form , _ _~
26 1-amino~2-hydroxy-6-nitro- 2-amino-4,6 dinitro-l-hydroxy- c naphthalene-4-sulphonic acid benzene - ~ 2-phenylamino-- - ~ l-hydroxy-~-methoxy- naphthalene .
naphthalene 27 1-amino-2-hydroxy-6-nitro- 2-smino-1-hydroxybenæene-4- a naphtllalene-4-sulphonic acid sulphonic acid morpholine ~ l-hydroxy-4-methyl- -~ 2-phenylaminonaph-naphthalene thalene 28 do. 2-amino-1-hydroxybenzene~4- g N-phenylsulphonic acid amide ~ 3-methyl-l-phenyl-5-aminopyrazole 29 1-amino-2-hydroxynaphthalene- 2-amino-4,6-dinitro^-1-hydroxy- a .
4-sulphonic acid ~ hydroxy- benzene-~ 2-phenylamino-4-methoxynaphthalene naphthalene 1-amino-2-hydroxynaphalene-4- 2-amino-6-chloro-4-nitro-1- a sulphonic aicd~ l-hydroxy~ hydroxybenzene - t 2 phenyl .
4-methylnaphthalene aminonaphthalene 31 1-amino-2-hydroxynaphthalelle- 2-amino-4,6-dinitro-1-hydroxy- a 4-sulphonic acid~ l-hydroxy- benzene ~ 2 phenylamino-S-chloronaphthalene naphthalene 32 1-amino-2~hydroxynaphthalene-4- 2-amino-4,6-dinitro-1-hydroxy- a sulphonic acid ~ -hydroxy- benæene --~2-ethylamino-5,8-dichloronaphthalene naphthalene 33 do. 2-amino-1-hydroxybenzene-4-N,N- b . diethyl sulphonic acid amide . ~-~ 2-phenylaminonaphthalene 34 do. 2-amino-4-chloro-6-nitro-1- e . . hydroxybenzene- ->3-methyl- .
. 1-(4'-methylphenyl)-5-amino . . pyraæole 1-amino-2-hydroxy-6-nitro- 2-amino-4,6-dichloro-1-hydroxy b naphthalene-4~sulphonic acid benzene ~ 2-phenylamino-- )l-hydroxy-5,8-dichloro- naphthalene naphthalene . .
36 do. 2-amino-4,6-dinitro-1-hydroxy- a ben~ene----~2-(3'-chloro-phenyl)aminonaphthalene 37 do. 2-amino-4,6-dichloro-1-hydroxy f benzene------~3-~ethyl-1-(3'-L chlorophenyl)-5-aminopyrazole _ .
____ __ ___ __. _ 072~8~

-~ 23 ~ L50-3778 AI?PLICATION l',XAMPLE A
0.03 g (to obtain a grey shade~ or 0.15 g (to obtain a black shade) of the dyestuff obtained in Example 1 is dissolved in 300 parts of water, and 0.2 g of ammonium sulphate is added. Subsequently, the moistened material (5 ~ of wool gabardine or 5 g of nylon satin) is entered into the bath and is heated to boiling temperature over the course `~
of 30 minutes. The water which is evaporated during the 30 minutes boiling is replaced and dyeing is completed at boiling temperature for another 30 minutes, with subsequent rinsing. After drying, a grey or black dyeing with notable wet and light fastness is obtained.

The clyestuffs of Examples 2 to 37 may be used for dyeing in analagous manner to that described above.

~ . . _ Polyamide is printed with a printing paste containing the following:

50 parts dyestuff of Example 4 50 parts urea 50 paxts dissolving agent, for example thiodiethylglycol 300 parts water 500 parts suitable thickening agent, for example based on locus bean gum ~;

60 paxts acid acceptor for example, ammonium tartrate and 60 parts thiourea The printed goods are steamed for 40 minutes at lOZ

(saturated steam), then rinsed with cold water, washed for -~

~83 - 24 - 150-377~

5 minutes at 60 with a dilute solution of a conventional detergent and then rinsed again. A black print with good wet- and liyht-fàstness is ohtained.
In analogous manner printing pastes may be made using ~:
the dyestuffs of Examples 1 to 3 and 5 to 37.
' :~

-: ', .
~ . , ~: :
' ~ `:

Claims

THE EMBODIMENTS OF THE INVENTION IN WHICH AN EXCLUSIVE
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:

1. A pure asymmetric 1-2 cobalt complex of formula I, I
in which X is hydrogen or nitro, either, R1 and R2, independently, are hydrogen, (C1-4)-alkyl, (C1-4)alkoxy, chlorine, bromine or nitro or R1 is hydrogen, chlorine or nitro, and R2 is -SO2NR3R4, in which the groups R1 and R2 occupy the 4- and 5-positions, either R3 is hydrogen, (C1-4)alkyl unsubstituted or substituted by up to two substituents selected from halogen, hydroxy, cyano, (C1-4)alkoxy and phenyl, and R4 is hydrogen, (C1-4)alkyl unsubstituted or substituted by up to two substituents selected from halogen, hydroxy, cyano, (C1-4)alkoxy and phenyl, (C5-7)cycloalkyl unsubstituted or substituted by up to three methyl groups, phenyl unsubstituted or substituted by a total of up to three substituents selected from halogen (max. three) (C1-4)alkyl, (C1-4)alkoxy and nitro (max. 2 of each of those), or, R3 and R4, together with the nitrogen atom to which they are bound, from a non-aromatic 5- or 6-membered heterocyclic ring which contains one ox two hetero atoms.
B is a divalent radical of a coupling component of the 1- or 2-hydroxypaphthalene series which is coupled in the 2- or 1-position ortho to the hydroxy group and is bound to the cobalt atom through the oxygen atom, D is a divalent radical of a coupling component of the 2-naphthylamine series which is coupled in the 1- position crtho to the amine group, or a divalent radical of the 5-amino pyrazole series which is coupled to the carbon atom next to that carrying the amino group, whereby the divalent radical D is bound to the cobalt atom through the amino group, and M is hydrogen or an equivalent: of a non-chromophoric cation, with the provisos that the molecule (1) contains a single sulpho group, which sulpho group is in salt form, (ii) contains at maximum a single sulphonamide group, which group is in radical D or is R2, and(iii) is free from groups, and mixtures of such pure asymmetric complexes.

2. A 1:2 cobalt complex or mixture according to Claim 1, an which B is a radical of formula (a), (b), (c) or (d) (a) (b) (c) (d) in which Y2 is hydrogen, (C1-2)alkyl, (C1-2)alkoxy, chlorine or bromine, and D is a group of formula (e) or (f), (e) (f) in which R5 is hydrogen, (C1-4)alkyl or a group of formula (g) or (h), (g) (h) in which one of R6 and R7 is hydrogen and the other is hydrogen, chlorine, bromine, (C1-2)alkyl, (C1-2)alkoxy, or trifluoromethyl, R8 is hydrogen or methyl, and R9 is methyl, chlorine or bromine with the proviso that when R9 is chlorine or bromine R8 is hydrogen, Y2 is hydrogen or -SO2NHR10 in the 5-or 6-position, in which R10 is hydrogen (C1-4)alkyl or hydroxy(C2-4)alkyl, R12 is hydrogen; (C1-4)alkyl; (C1-2) alkoxy or phenyl, R13 is hydrogen; (C1-4)alkyl, phenyl(C1-4)-alkyl, ; cyclohexyl or a radical of formula (i), (i) in which either Z1 is hydrogen and Z2 is hydrogen; fluorine; chlorine;
bromine; (C1-4)alkyl, (C1-2)alkoxy;
nitro; or trifluoromethyl, or Z1 and Z2 are the same and are both chlorine; bromine; methyl or methoxy, with the provisos that:

when both Z1 and Z2 are chlorine, the chlorine atoms are in the 2,3-, 2,4-, 2,5-, 2, 6-, or 3,4-positions, when both Z1 and Z2 are bromine, the bromine atoms are in the 2,4- or 3,5-positions, when both Z1 and Z2 are methyl, the methyl groups are in the 2,3-, 2,4-, 2,5-, 2,6- or 3,5- positions, and when both Z1 and Z2 axe methoxy, the methoxy groups are in the 3,4-positions, or Z1 and Z2 are different and signify 3-chloro-2-methyl, 4-chloro-2-methyl, 5-chloro-2-methyl, 4-bromo-2-methyl or 5-chloro-2-methoxy.

3. A 1:2 cobalt complex or mixture according to Claim 1, of formula Ia, Ia in which X and M are as defined in Claim 1, either R1 and R2, independently, are hydrogen, (C1-4)-alkyl, (C1-4)alkoxy, chlorine, bromine or nitro, or R1 is hydrogen, chlorine or nitro, and R2 is -SO2NR3R4, in which the groups R1 and R2 occupy the 4- and 5-positions, either R3 is hydrogen, unsubstituted (C1-4)alkyl or (C1-4)alkyl substituted by up to two substituents selected from halogen, hydroxy, cyano, (C1-4)alkoxy and phenyl, and R4 is hydrogen; unsubstituted(C1-4)alkyl;

(C1-4)alkyl substituted by up to two substituents selected from halogen, hydroxy, cyano, (C1-4)alkoxy and phenyl;
unsubstituted (C5-7)cycloalkyl; (C5-7)cyclo-alkyl substituted by up to three methyl groups; unsubstituted phenyl; phenyl substi-tuted by up to three substituents selected from up to three halogen, (C1-4)alkyl, (C1-4)-alkoxy groups and nitro (maximum of two nitro ), or R3 and R4 together with the nitrogen atom to which they are bound, form a non-aromatic 5- or 6-membered heterocyclic ring which contains one or two hetero atoms, B is a radical of formula (a), (b), (c) or (d) (a) (b) (c) (d) in which Y1 is hydrogen, (C1-2)alkyl, (C1-2) alkoxy, chlorine or bromine, and D is a group of formula (e) or (f), (e) (f) in which R5 is hydrogen, (C1-4)alkyl or a group of formula (g) or (h), (g) (h) in which one of R6 and R7 is hydrogen and the other is hydrogen, chlorine, bromine, (C1-2)alkyl, (C1-2)alkoxy, or trifluoromethyl, R8 is hydrogen or methyl, and R9 is methyl, chlorine or bromine with the proviso that when R9 is chlorine or bromine R8 is hydrogen, Y2 is hydrogen or -SO2NHR10 in the 5-or 6-position, in which R10 is hydrogen (C1-4)alkyl or hydroxy(C2-4)alkyl, R12 is hydrogen; (C1-4)alkyl; (C1-2) alkoxy or phenyl, R13 is hydrogen; (C1-4)alkyl, phenyl(C1-4)-alkyl, ; cyclohexyl or a radical of formula (i), (i) in which either Z1 is hydrogen and Z2 is hydrogen; fluorine; chlorine;
bromine; (C1-4)alkyl, (C1-2)alkoxy nitro; or trifluoromethyl, or Z1 and Z2 are the same and are both chlorine; bromine; methyl or methoxy, whereby:
when both Z1 and Z2 are chlorine, the chlorine atoms are in the 2,3-, 2,4-, 2,5-, 2, 6-, or 3,4-positions, when both Z1 and Z2 are bromine, the bromine atoms are in the 2,4- or 3,5-positions, when both Z1 and Z2 are methyl, the methyl groups are in the 2,3-, 2,4-, 2,5-, 2,6- or 3,5- positions, and when both Z1 and Z2 are methoxy, the methoxy groups are in the 3,4-positions, or Z1 and Z2 are different and signify 3-chloro-2-methyl, 4-chloro-2-methyl, 5-chloro-2-methyl, 4-bromo-2-methyl or 5-chloro-2-methoxy, with the proviso that when D is a radical of formula (e), R5 is only hydrogen when Y2 is -SO2NHR10 or B is a radical of formula (b), (c) or (d).

4. A 1:2 cobalt complex or a mixture according to Claim 3, in which R5 is R?, where R? is hydrogen, phenyl, 2,3, of 4-chlorophenyl, 2- or 4-methylphenyl or 2,6-dimethylphenyl and Y2 is hydrogen or -SO2NHR?0 in which R?0 is hydrogen, methyl or .beta.-hydroxy(C2-3)alkyl.

5. A 1:2 cobalt complex or mixture according to Claim 3, of formula Ib, Ib in which R? is hydrogen, methyl, chlorine or nitro, R? is chlorine, nitro or -SO2NHR?, where R?
methyl, ethyl, isopropyl, 2-hydroxyethyl, -CH2-CH(OH)-CH3,-(CH2)3-OCH3 or phenyl, with the proviso that R? is only -SO2NHR?
when R1 is hydrogen, B' is a radical of formula (a), (b), (c) or (d), with the proviso that when B' is a radical of formula (b). Y1 is Y?, where Y?
is hydrogen, methyl or methoxy, and X, M, R6 and R7 are as defined in Claim 3.

6. A 1:2 cobalt complex ox mixture, according to Claim 3, of formula Ic, Ic in which R? is hydrogen, methyl, chlorine or nitro, R? is chlorine, nitro or -SO2NHR?, when R?
is methyl, ethyl, isopropyl, 2-hydroxyethyl, -CH2-CH(OH)-CH3, -(CH2)3-OCH3 or phenyl, with the proviso that R? is only -SO2NHR?
when R1 is hydrogen, B' is a radical of formula (a), (b), (c) or (d), with the proviso that when B' is a radical of formula (b), Y1 is Y?, where Y?
is hydrogen, methyl or methoxy, and X, Z1, Z2 and M are as defined in Claim 3.

7. A 1:2 cobalt complex according to Claim 5, in which R? is hydrogen, chlorine or nitro and R? is methyl, -(CH2)3 -OCH3 or phenyl.

8. A 1:2 cobalt complex according to Claim 6, in which R? is hydrogen, chlorine or nitro and R? is methyl, -(CH2)3 -OCH3 or phenyl.

9. A 1.2 cobalt complex according to Claim 5 of formula in which M is hydrogen or an equivalent of a non-chromophoric cation, and M1is an equivalent of a non-chromophoric cation.

10. A 1:2 cobalt complex according to Claim 5, of formula, in which M is hydrogen or an equivalent of a non-chromophoric cation, and M1is an equivalent of a non-chromophoric cation.

11. A 1: 2 cobalt complex according to Claim 5, of formula, in which M is hydrogen or an equivalent of a non-chromophoric cation, and M1 is an equivalent of a non-chromophoric cation.

12. A 1:2 cobalt complex according to Claim 6 of formula, in which M is hydrogen or an equivalent of a non-chromophoric cation, and M1is an equivalent of a non-chromophoric cation.

13. A 1:2 cobalt complex according to Claim 5 of formula, in which M is hydrogen or an equivalent of a non-chromophoric cation, and M1is an equivalent of a non-chromophoric cation.

14. A 1:2 cobalt complex according to Claim 5, of formula, in which M is hydrogen or an equivalent of a non-chromophoric cation, and M1 is an equivalent of a non-chromophoric cation.

15. A process for the production of a 1:2 cobalt complex of formula I, as defined in Claim 1, or a mixture thereof, comprising a) reacting a compound of formula II, in free acid form, II

in which L1 and L2 are monodentate ligands and X and B are as defined in Claim 1, or a mixture of compounds of formula II, with a compound of formula III, III

in which R1, R2 and D are as defined in Claim 1, or a mixture of compounds of formula III, or b) reacting a corresponding nitrite-containing cobalt complex of a compound of formula III, or a mixture thereof, with a compound of formula IV, IV

in which X and B are as defined in Claim 1, or a mixture thereof.

16. A process for dyeing or printing nitrogen-containing organic substrates comprising employing a complex or mixture according to Claim 1, as dyeing or printing agent.