CA1064480A - Azo compounds - Google Patents
Azo compoundsInfo
- Publication number
- CA1064480A CA1064480A CA 224262 CA224262A CA1064480A CA 1064480 A CA1064480 A CA 1064480A CA 224262 CA224262 CA 224262 CA 224262 A CA224262 A CA 224262A CA 1064480 A CA1064480 A CA 1064480A
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- Prior art keywords
- formula
- compound
- signifies
- complex
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- Prior art date
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B33/00—Disazo and polyazo dyes of the types A->K<-B, A->B->K<-C, or the like, prepared by diazotising and coupling
- C09B33/02—Disazo dyes
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B33/00—Disazo and polyazo dyes of the types A->K<-B, A->B->K<-C, or the like, prepared by diazotising and coupling
- C09B33/18—Trisazo or higher polyazo dyes
- C09B33/24—Trisazo dyes of the type
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B45/00—Complex metal compounds of azo dyes
- C09B45/02—Preparation from dyes containing in o-position a hydroxy group and in o'-position hydroxy, alkoxy, carboxyl, amino or keto groups
- C09B45/24—Disazo or polyazo compounds
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B45/00—Complex metal compounds of azo dyes
- C09B45/34—Preparation from o-monohydroxy azo compounds having in the o'-position an atom or functional group other than hydroxyl, alkoxy, carboxyl, amino or keto groups
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- Organic Chemistry (AREA)
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Abstract of the Disclosure The present invention relates to azo compounds of formula I, I
in which R1 is hydrogen or nitro, each of R2 and R3, independently. is -OH or R4 is hydrogen, nitro or (C1-4) alkyl, R5 is hydrogen, nitro or (C1-4) alkoxy, R6 is hydrogen, (C1-4) alkyl, (C1-4) alkoxy, -COOM or -SO3M, R7 is hydrogen or -SO3M, R8 is hydrogen or the radical of a diazo component, and M is a hydrogen ion or a non-chromo-phoric cation.
or mixtures thereof in metallized from or unmetallized form, which compounds in metallized form are useful as dyestuffs.
in which R1 is hydrogen or nitro, each of R2 and R3, independently. is -OH or R4 is hydrogen, nitro or (C1-4) alkyl, R5 is hydrogen, nitro or (C1-4) alkoxy, R6 is hydrogen, (C1-4) alkyl, (C1-4) alkoxy, -COOM or -SO3M, R7 is hydrogen or -SO3M, R8 is hydrogen or the radical of a diazo component, and M is a hydrogen ion or a non-chromo-phoric cation.
or mixtures thereof in metallized from or unmetallized form, which compounds in metallized form are useful as dyestuffs.
Description
. Case 150-3607 ; , IMPROVE~ENTS IN OR RELATING TO ORGANIC COMPOUNDS
, ~ The present invention re}ates to metalliz~ble .
. azo compounds, metal complexes thereof, their pro-duct~on and use.
; 5 More particularly the present inventi.on provid~s compounds of formula I, : OH R3 ;~ 3 ~ J~
'4~ ; 1 I ~ :
., ,. . .
in whlch Rl signifies a hydrogen atom or a nitro . ::
. group, ~: ~ each of R2 and R3 , independently, signifies -OH or NH2, 10 R4 signifies a hydrogen atom,a nitro :
group or a (Cl 4~ alkyl radical, .:.
~" .. , ; ~ ~ :R5 signifies a hydrogen atom, a nitro group or a (Cl ~3 alkoxy radical, . R6 s1gnif1es a hydrogen atom, a (Cl 4) ~:
l~ alkyl or (Cl_4) alkoxy radical or :.
t~ a -COOM or -SO3M group, ::
i ~:: t : .
R7 slgnifies a hydrog~n atom or a - :
~ O M gro~p .,. ;.. ,~ .
, .: . ~ . .
. .
~` :
~ 1064480 :
R8 signifies a hydrogen atom or the radical of a diazo component, and M signifies a hydrogen ion or a non-chromophoric cation, ., or mixtures thereof, in metallized or unmentallized form, which metallized ` form comprises a 1:1 metal complex of a compound of formula I, a 1:2 metal i complex of a!formula I or a 1:2 metal complex of a complex of formula I
., ~ j ~;; and a further metallizable compound of formula V, N - N ~ ~ ~R5 ' ~ lO in which each of R2 and R3, independently signify -OH or -NH2, and A signifies a further unsubstituted ; ~ benzene or naphthalene radical or a benzene radical substituted by up to ~'l two further substituents selected from chlorine, nitro and SO3M, the hydroxy group in any such radicals A being in a position ortho to the azo group, R4, R5, R6, R7 and R8 are as defined above. --n is 0 or 1, and m is O, 1 or 2, provided that the sum ; of m ~ n is not more than 2.
The metallized compounds of formula I are 1:1 or 1:2 metal ,.,. . 1 ~ . :
complexes. The 1:2 metal complexes according to the invention are com-plexes of the compounds of formula I or complexes of a compound of formula -I and another metallizable azo compound of formula V as given hereinafter.
The present invention further provides a process for the - .i .. ..
` ! production of compounds of formula I, as defined above, and ~:1 and 1:2 :; a~ ~ - 2 -.~. ~ . .. . .
complexes thereof, as defined above comprising:
a) coupling the diazo derivative of a compound of formula III, :~ R4 ~: ~ NH ~ ~H2 111 :~ R5 :
in which R4 to R7 are as defined above, or a mixture of such compounds and, where required, the diazo derivative as R8, or a mixture of such derivatives, in any desired order, : ',.' :
~' :
... . .
;, ~,, " ' '': ' ' ,: ;:
'' ;'" ;`' :' ~ ':: :
;'`' '" ' ~ :.' . ; :
:. ~
.
,,'. ' ~:.' "", ' ' . ~'~ ' -' .:
' : ' . ~.
' .
- 2a - .
`` '1064480 ~ - 3 - Case~ 150-3607 . , , ~
.
~ , , ~lth a compound of formula II, , OJi~ R3 ,"A~/ ' , R
ln whlch Rl to R3 and M are as def$ned above;
b) reacting a compound of formula I, as deflned above.
or a mlxture of such compounds or a mlxture of a compound -~
of formula I and a further metalllzable compound of formula ~.
V as glven herelnafter wlth a metal donatlng compound to ", obtaln a 1:1 or 1:2 metal c~mplex of a compound of formula I, o) coupling the dlazo aerlvatlvè of a compound of -~-' formula.III, as deflned above, or a mixture of such 10~ - compounds and,~Jhere requlred, th- diazo derlvative as R8, or a ~-`
~ixture of such~derlvatives ln ar.y deslred order, with a l:l or 1:2 metal complex of a compound of formula II, a- deflned above, to obtaln a 1:1 or 1:2 metal ~ complex of a compound of formula I, as deflned above;
d) coupllng the diazo der'vatlve of a compound of - formula III, as deflned above, or a mixture of such compounds,and .
;- where re~uired the dlazo derlvative as ~8~ or a mlxture . - , ,~.
'~ ~'' ' . - ' ' ' . . ~ , . . .
. - . ,.. ~, .
. , " ~,, .
~`` 1064480 - 4 - Ca~e 150-3607 , ::
of ~uch derivatlveis ln any de~lred order, wlth a 1:2 complex of a compound of formula II and a further ~ metalllzable compound of formula V a~ glven herelnafter, , ~ :
e) reactlng a 1:1 metal complex of a compound of formula S I, as deflned above, wlth a further metallizable azo compound of formula V as glven hereinafter - f) coupllng the dlazo derlvatlve as R8 wlth a 1:1 or ls2 complex of a disazo compound of formula I, ~en R8 signifies the radical of a diazo component, the diazonium component which k.as the hisher coupling enera,y le coupled last. Preferably, R8 is à radical of : ,~
diàzo component having higher coupling ener~y than the ~; diazo derivative of formula III, thus the ~ntroduction of~ , , . ' ~
the radiczl R8 is preferably the last coup~lng reaction.
Coupling may be carrled out according to convention- t' ' 5 nl methods. Suitably, the coupling of the dfazo derivatl~e of formula III with a compound of formula II or wi~h a ~ complex containing the compound of formula II is carried -? ~ out at temperatures from 0 to 25C, preferably from 4 to 5C. The reaction is conveniently conducted in aqueous ~edium at a pH value of at least 5.
The coupling of the diazo derlvative as R8 with -- the compound of formula VIIIJ
"~
i, ', . ' . ~ .
: ~j `, .
. . ` ,~' .
,: 1, , , . , ............ . :. . : , .- - : . . .
- 5 - Case 150-3607 ;- ' .. . .
.
~;2 ~ ~R5 Rl VI I I
. ~ ' ~, .
in whi.ch Rl to R7 are as defined above, or a com,plex containing the compound of formula VIII, is suitably carried out at temperatures from 0 to 25C, :, preferably from 4 to 5C. The reaction is preferably , ., conducted in aqueous medium at a pH value from 4 to 9.
A coupling accelerator may also be emPloyed. As exam~l~3s : . of suitable coupling accelerators may be given urea, ~:
. , ~ ~ pyridine and Cellosolve.
.;. ::~ Metal complex formation may be effected by known methods~ For example iron complexes may be formed using . ~ an iron salt. The preferred pH value is from 3.5 to 6, ~:.: more preferably frorn 4 to 4.5. Suitable reaction tempera-, .; 1 ... ,~ .
.'~' .` ,: .
~ i . ,, . ~, .. . . .
.,~ '~
.
.. ~ . .
:. ` . , .
,~ . .
.
~ : .
;, - 6 - Case 150-3607 ' ' . ' '.
` 1~64480 tures are in the range of from 95C to reflux tempexa-- ture or even higher temperatures, for example up to 120C, - when working under pressure. Cobalt, chromium and nickel complexes may be formed under similar temperature conditions. Advantageously, for forming cobalt complexes ;~ the pH value is from 4 to 10, for nickel complexes from 3.5 to 6, and for chomium complexes from 2 to 10. The reaction may be conducted in aqueous, aqueous-organic or organlc medium. Preferred organic solvents are those ~7hich have a boiling point over 100C, are miscible with water and in which the compounds to be complexed and ' their metal salts are soluble. Examples of suitable ;! solvents are alcohols, ether alcohols and amides e.g.
., .
Cellosolve, Methylcellosolve, formamide and dimethyl-;~ 15 formamide. Organic solvents are preferably used in the . 1 . prepaxation of chomium complexes.
, ( Copper complexes may be formed in aqueous medium C~ ` I under neutral to alkaline conditions, preferably at a pH value o rom 7.5 to 10. The reaction is advant-ageously effected in the presence of excess ammonia.
Suitable reactlon temperatures are above 70C, preferably from 80 to 100C, optionally under pressure. The amount of copper compound employed is preferably such that at .. . .
~;~ least one mol of copper is provided per mol azo dyestuf.
; . j:
j.',. :,~ ~ .
s.. l ,~. ., ~ . . ..
. ~ .
... .
,. .. . .
- 7 - case 150-3607 ` 1064480 ~y the term 'excess A~u~nla', lio me~nt ~n amount whlch .
exceeds that whlch 18 coordinately bound by the copper, .li , . . .
and is preferably sufficient so that the copper salt `-- ~8 dlssolved thereln.
~ ,c . .~ , , .. .
S Examples of suitable ~.etal donating compounds ~re ` a~ follows~
- for copper: cuprlc chlor~de, aoetate, formate or ulphate .
for lron: ferrous ~ulphate cr nitrate, ferric sulphate or nltrate or ferrlc chloride for nlckel: nickel ~ormats, acetate or sulphate ;
for chromium: chromlum tr~oxide, chromlc fluoride, ; su'phate, formate or acetate, ammonium or ;~;
~ ~ potassium chromium sulphate, sodium or ~
,, ;j . - - - .~ .
~ potassium chromate or sodium or ~ potassium bichromate P~ for cobilt: ~ cobaltous forr.ate, sulphate, acetate or , ~ " , , - ~ ~-, - chlorlde, cobaltic chlor~de or acetate.
~ In the preparation of 1:2 complexes,advantageously e ;~ 20 ~ ~t l-a~t one mo~,but preferably less than two mols,of metal per two mols of azo compound are employed.
~; ~ It ls advanta~eous when producing asy~etrical 1:2 complexes, especially in the case of 1:2 chromium complexes, to prepare the correspondlng 1:1 metal ~ ~ 25 complexes flrst, and then to react these complexes with a 1: .
1',: -;
: 7 ~ ~
~ 8 - Case 150-3607 . : -:
. ~ . .
~ further metallizable azo dyestuff to form the desired , asymmetrical 1:2 metal complexes.
:- .~ ' . - ' ,, :, .
- Mixtures of metal complexes comprising complexes of different metals are also provided by the present - ;
invention. Such complexes may be formed by reactin~
;~ the azo dyes with different metal donating compounds, preferably by forming the metal complex of one metal and subseauently reacriny any uncomplexed azo compound in - the reaction mixture with a further metal ~onating compound.
Ir. the compounds of formula I, when R8 slgnifies the radical of a diazo component it is preferably of a mono-nuclear aiazo component, more preferably the radical of formula IV, R~ ~ N=N-in which Rg s1gnL~les ~ hydrogen atom, a hydroxy, NH2, (Cl_4) alkyl or (Cl_4) alkoxy `. . i i i ~ ~ ~ .
.: group, 10 signifies a hydrogen atom, a nitro, -COOM or -SO3M group, in whlch M ls as defined above, and Rll sign1fies a h~drogen cr halogen atom, ~ ~ a nitro or a (Cl_4) alkyl group.
,...... . . . .
, -~ .. . .
,~ .
~- ....... . ... . .. ... .
. . .
: ~ ~ :
: - :
~- -- - 9 - 150-3607 /~ 1064480 By halogen ls meant chlorlne, bromlne, fluorlne or lodine, with chlorine being preferred. Preferred amine~ of formula IV are those where at least one, ~ preferably one or two, of Rg, Rlo and Rll slgnifle8 !~ ~ ~ 5 a hydrogen atom.
Examples of R8 are the diazo radlcals of formula IV where all three of Rg, Rlo and R
signlfy hydrogen; where two signlfy hydrogen and the ;1 ~ third slgnlfles nltro, -COQM, or methoxy; where one ':1 :
~1 10 signlfles hydrogen and the other two are the same and 1:
slgnlfy NO2 or CH3; where one slgnlfles hydrogen and ~ the other two are dlfferent and signlfy -SO3M and -OCH3, ; NO2 and -SO3M, NO2 and CH3~ NO2 and Cl, OH and ¢l, OH
and NO2, or OH and SO3M; where all three of Rg, Rlo and Rll have a slgnlflcance other than hydrogen and two signlfy NO2 and the thlrd ~lgnlfles -OH; or where each of Rg, R~o and Rll are diff-rent and slgnlfy OH~ SO3M
and N02, respectlvely; nd the radlcal of formula :.- , . :,. -. ~
-N - N ~ NO2 Whllst any metalllzable compound may be used as -~ 20 the further metalllzable azo compound, those az~
, compounds whlch contaln an aromatlc nucleus on elther side of the azo group substltuted by a metalllzable group, e.g. hydroxy or amlno, ln a position ortho to the azo group are preferred~
" ,:
~ - 10 - 150-3607 The further metalllz~ble azo compounds are compounds of formula V, A-- N ' N~--,N~NEI~) . . V
.. ~ ln whlch each of R2 and R3, lndependently slgnlfy .,~
~ OH or -NH , and :
:~ . 2 A signifies a further unsubsti-~ v tuted benzene or naphthalene :;~ radlc~l or a benzene radical substituted by up to two further t '::' ',: ' ~ substltuents selected from . i . ~
10 ~ chlorlne, nltro and S03M, the ; hydraxy group ln~any ~uch : radlcals A belng in a posltlon ortho to the azo group, a4, i R5~ R6~ R7 and R8 - are as deflned above, lS ~ n ~; 18 0 or l, and m :~ 18 O, l or 2, provlded that the : sum of m I n 18 not more than 2, such compounas,where trlsazo, p~eferably contalnlng at lea~t one sulpho. . ~ -Preferred further metalllzable compounds are -~ .: ~ , .. ....
t ~
. ,,. ' ' ` ~ ~ ':
. . ' : ~, ,..... : ... . :
~ 150-3507 1064480 .~
, .
. compound~ of formula TI, a~ deflned above, or compounds of formulae VI or VIII, .~ ~.
... OH OH
~ Yl ~ N - N ~ VI
v :- 2 OH OH
Yl~N - ~ -- N~ 4 .~ ~n whlch R4 to R8 are as defined above, ................................. Yl slgnlfies a hydrogen or chlorine atom, i~; . . ~ .
. 5 a.-SO3M or nltro group, Y2 slgnlfles a chlorlne atom or a -SO3M
. or nltro group, and R; ~ M ls as deflned above.
~ Thus, a 1:2 complex of a compound of formula I, or k ~ 0.~ a complex of a compound of formula I and a further '6~'~
metallizable azo compound,.can be formed by coupllng.the dlazo derlvatlve of an amlne of formula III, as deflned , ~ .
. above, or a mlxture of such amines, and, where requlred, the dlazo derlvatlve as R8 or a mlxture of such derlva-.~ . .
tlves, wlth a complex of formula IX, ,,:. ,:
:
..
.;
.~. - , :
.'~ '' ' ~''' .
.: , .
, . 11 .,, ~ ..
~ '"' .
.
... .
. i, .. .
~ . ' . ~ ' - ` ~064480 ~ - 12 - Case 150-3607 . .:
,' ~ .
$ N ~- N - ~ 503M
, \ ~ /
Me /
' o ' ~X :.
IX
A-- N -- N ~
H R
. in which each X, independently signifies -NH or -O-Me signifies iron, cobalt, nickel ox ~: . chromium, and ,.,-,, ", . . .
' l' 2 and M are as defined above, ~; 5 employing at least one mol of the diazo derivative of formula III and O, 1, 2 or 3 mols of the diazo derivative as R8 per mol of compound of formula IX, with the proviso that the molar ratio of diazonium compounds to ,' ',i: . ' , ', ,-the compound of formula IX is not more than 4:1. - -:-~ lO As examples of the compounds of formula IX may . . , ~ be given those of formu}a X, .
i~: Z
;.'~ ',~ , : . ...
.,~ . 1 ' , ~ ,, . . ~, ~.
.: .j , . . .
;
` :~` 1064480 : :
. .
.
. '' .
` ` R
R2 ~ ~ SO3M
x~ I /0 ~ e X
,~. .~ . . I
~ ' O l O
1 ~N - N~
''' .. 'j :" : ~
~i , .
`:r'- Rl, R2, X~ Yl, Y2, Me and M sre as ; . deflned above, or, preferably, those formed entirely from a compound ~, .,`, i "~ . ' ; of formula II, especially those of two identlcal compounds of formula II.
- Preferably, the dlazo derlvative of formula ~II, or a mlxture thereof ls coupled w~th a compound of ', ,.,''!:",, ~ formula IX ln a 1:1 to 2:1 molar ratlo and, where required, the dlazo derivative as R8 or a mixture thereof 0 i8 coupled wlth the product ln a 1:1 to 2:1 lar ratlo.
l $
. .
.
.. .
.
. .
- `1064480 - 14 - Case 150-3607 : ' ' ' ' . , ' Preferred compounds of formula I, are those where R8 signifies the radical of a diazo component, more preferably the diazo radical of formula IV, as defined above.
; 5 In the compounds of formula I, any alkyl or ,~ alkoxy radical preferably con~ains 1 or 2 carbon atoms.
Rl preferably signifies a nitro group and ~2 and R3 preferably signify -O~. Each of R4 , R5 and R6 ~ndependantly, preferably signi-1es hydrogen or . ~ ,, .
~ 10 an electron attr~ctinq substituerlt as mentioned above ~ . . . .
as slgnificances for R4, R5 and R6; when anv two of R4, R5 and R signify electron attracting substituents these substituents are preferably in a meta or para .. . .
, position to each other; when all three of R4, R5 and R6 signify electron attracting substituents, they are preferably in positions meta to each other.
; ~en P~7 signifies a -SO3M group this -SO3M
~ group is preferably in position meta to the azo group. -~
'~ Those compounds where at least one of R4~ R5, R6 and R7 has a significance other than hydroyen are preferred.
Compounds and complexes where up to 3 or R4, R5, R6 and . R7 signify hydrogen are especially preferred.
Preferably at most one of R6 and R7 signifies a -SO3M group. The trisazo compounds of formula I preferably ' 25 contaln at most three -SO3M groups, the disazo compounds .. ,,.~ , :
: ., .
:` 14 . ~ . . .
,'~ ~ ,. .
: - i .
~ 1064480 ~ 15 - Case 150-3607 . ~ , ~"
. .j ,.
at most two -SO3M groups. Compounds of formula I which , ~
contain at least two hydrosolubilizing groups are ~ preferred.
- Preferably M signifies hydrogen, an alkali S metal cation or an unsubstituted or substituted a~monium ~ion. Examples of substituted a~moniumi ions are (Cl 3) ;~ alkyl a~monium and h~droxy (C2 3) alkyl ammonium, e~g.
, , triethyl ammoni~m, tetramethyl a~monium, mono-, dl- or tri-ethanol-ammonium and mono-, di- or tri-isopropano~
~` 10an~on~um. Examples of alkali metal cations are . ~ .
lithium, sodium or potassium, sodium and potassium belng the preferred alkali metal cations, particularly the former.
, .. i , .
Preferred compounds of formula I are those ~
- ln which Rl signifies -NO2, ~' ~ 15R2 and R3 both signify -OH, ., ~, .:
., ~
.. . ,.' . .
.
.,, ~ ' , : . , ,, ~
;~ 1064480 - 16 - Case 150-3607 :`. -'.. , ,'.; : ' ;
. each of R4, R5, R6 and R7, independently, . signifies a hydrogen atom or an . electron attracting substituent, R5 and R6 being in ortho or para positions to the amino group, when other than hydrogen,and R7 .~ being in an ortho pOsitiQn to the . ., :: . .
amlno group, R8 slgnifies a diazo component radical, preferably the radical of formula . ~ Iv, as defined above. ;
:~ Especially preferred compounds of formula I, are those of for~ula Ib, OH : :
O~ R~6.;
3 ~ ~=N ~ ~ h ~ R25 Ib H~ ~ H ~ , NO~ ~ '' 7 ~24 in which R8" signifies the diazo co~ponent radical lS ~ of formula I~', as deflned above, ,, ., ~: . . , . ~ .. . .... . ... .. .
~ ~ 16 ... .; . . . . .
.....
i -,A ~ .
- 17 - Case 150-3607 ` elther~ each of R24, R25 ~nd R26 ~lqn - hydrogen atom and R7' slgnlfles or ~ ' signlfies a hydrogen atom, and either, one of R24.and R25 signifles nitro and , - the other signifles -S03M, and R26 ignlfies hydrogen, or ~ach of ~25 and R26 81gnifleS
nltro and R24 slgnlfies -COOM, and - M 18 ~8 defined above.
. . , ' :' Th pref-rr~d metal complexe~ are 1:1 copper and nlckel complexes of the compounds of formula I; 1:2 lron, . .
cobalt and chromium complexes of a compound of formula .
~ I; or 1:2 lron, cobalt and chromlum complexes of a $~
.- ,. . .
~ compound of formula I and a further metallzable compound of , . .
formula V as deflned above, tbe 1:2 complexes of compounds of formula I belng preferred, in particular the iron and cobalt complexes. Furthermore, with regard to mlxed metal , . .
complexe~, those whlch are mlxtures of lron and cobalt complexe~ are preferred.
It wlll be appreciated that when R8 slqnlfles the radlcal of a dlazo component ln a compound of formula I
.., . ..
~ ~ , 1 7 .
.~, . ~.
....
... ... . , .. ... ~ . . ~ ... -. . .. . . . .
.. . . ... . ~ . .. . . . ... . ..
~ 8 - Case 150~3607 , or VII, as defined above, and such compound of formula , . . .
I is co~plexed with another compound of formula I, or a compound of formula VII, any hydroxy or carboxy group ortho to the azo group in the radical as R8 would be available, ~ 5 together with any hydroxy group as R2 to form a metal complex bond. ~
; The negative charge on the metal atom in the 1:2 metal complexes may be compensaied by hydrogen ions or non-chromophoric cations, Suitable such non-chromo-10 phoric cations are those mentioned above for M. The ions ~- which compensate the charge on the metal may be the ;~ same as M or different therefrom, preferably they are the same. Complexes which are in the free acid or a~moni~m salt from are preferred, with the free acid form being r~ 15 especially preferred.
The compounds OI formula III and IV are kno~m or may be produced in conventional manner from available ,. . .
staxting materials.
~` The azo compounds of formula V are known or may ~- 20 be produced in conventional manner from available starting materials. The compounds of formula II are known and may be obtained by coupling the diazo derivative of an amine of formula XI, ..,.
i,i,~
...~ .
., ....................................................................... ~ .
, ....
.: :
,.......... , ~ . . .
' '' :~,.. ', ~, ., " . . ' ., ,.. '. . : , ' ', . . ' , ~ ' ` ~
106448~
-- 19 - Case 150-3bO7 ~ ~H2 R ~ XI
- in which Rl and M are as defined above, ; with a compound of formula XII, ~;. R13 H ~ ~ R2 XII
in which R2 and R3 are as define.d abovf3.
The coupling reaction is carried out in conventionf-~l manner. Suitably,coupling i3 effected in a basic medium, . .f .l; preferah].y aqueous,at pH values of at least 7.5. The .
~ ~ reaction temperature may be in the range of Irom O to 25C, ~: ' : f preferably 4 to 5C. The pH may be adjusted by the addition of alkali metal hydroxides or carbonates or am~onia or amines. It has been found ~hat when R2 and R3 are the same, coupling takes place in the position indicated by the arrow , ~ :
. .~
~-.. ' .
.. ~ ... . .
: 19 - ~:
. , ~ .
, :
,.
.
---~ 1064480 ~ - - 20 - Case 150-3607 . .
- . . .
.,, . -; ~herea~ when R2 and R3 are different a mlxture 18 obtained whlch may be ~epararated in conventlonal manner.
~ Thus, the present lnventlon ~tlll further provldes ;` mixtures of compounds and complexes of formula I, formed .~ .
by employlng a mixture of compounds of formula II. Such mlxtures may be separated lnto the indlvldual CQmponents by known methods, but are preferably employed as such .
~ wlthout separatlon.
. r ~ The metal complexes and mlxtures thereof accordlng to . . ~ ~. . : .
the lnventlon are useful as hydro-soluble dyes. They may be used for dyelng ubstrates whlch are dyeable wlth anlonlc dyes, especlally leather. Any type of leather sultable and lt may be dyed in conventlonal manner.
:,, :
The complexes accordlng to the inventlon have notable dyelng capaclty for leather of weak afflnlty. Dyelngs of deep full brown shades may be obtalned which have notable fa-tness to llght, hard water, washlng, persplratlon, i~( alkall, acld and bufflng.
. .: , :~
r,~
'~ ''i.. , , ., '., . , . , . , , ' ~" ,- ,: , : ,.
.
;`` -~ 1064480 ; - 21 - Case 150-3607 . `,:
( The following Examples serve to further illustxate the invention. In the Examples all parts and per-centag~s are by weight and all temperatures are in .. degrees Centigrade.
~''.
.
.:~, . .
I
. :.
.,.,~
.;' ~, '''~
~'' ~ ~ ' . - ':'.
~ '~ . ' I
. , :,',j~ ' ' ' - ,, ' I ' . . .
- ~ 21 .
;" ~ ' . . .
~...... . .
.
,,1,;, , ~ . , ,, .,, .,,, ........... ~.,. . ,.. ,,". ;.
~ ~ 1064480 ~-~ - 22 - case 1s~-3607 .. , .
,`.,~ EXAMPLE 1 ~ .
. .
~` 2g.5 Parts of the diazo derivative of l-amino-2-hydroxy-4-sulpho-6-nitronaphthalene- (nitro-diazoxide . ~ ~
acid Na-salt) are entered with stirring into a solution of 11 parts of 1,3-dihydroxybenzene in 200 parts of water ; 5 and 35 parts of calc. soda at 0. Coupling is completed after 2 hours. 26.4 Parts of the diazo derivative of 4-~ amino-2-sulpho-diphenylamine is allowed to flow, over r~1 the course of 30 minutes at a pH of 9.5 into the solution of the result~ng monoazo dyestuff and the mixture i5 stirred for~l hour. 13.8 Parts of the diazo derivative of l-amino~4-nitrobenzene is added to the resulting " I
; disazo dyestuff at a pH of 6 over the course of 30 minutes, and the mixture is stirred for 3 hours.
The result mg t~risazo dyestuff is heated to 95, then 13 parts of crystalllsed iron trichloride are added, and the mixture is kept at this temperature for 1 hour at a pH of 4.5. After cooling to 20, the dyestuff is filtered off.
It dries as a black-brown powder and dyes leather ln dark.brown shades which have notable fastness to light, washing, perspiration, hard water, acid and lkali.
, ~ The present invention re}ates to metalliz~ble .
. azo compounds, metal complexes thereof, their pro-duct~on and use.
; 5 More particularly the present inventi.on provid~s compounds of formula I, : OH R3 ;~ 3 ~ J~
'4~ ; 1 I ~ :
., ,. . .
in whlch Rl signifies a hydrogen atom or a nitro . ::
. group, ~: ~ each of R2 and R3 , independently, signifies -OH or NH2, 10 R4 signifies a hydrogen atom,a nitro :
group or a (Cl 4~ alkyl radical, .:.
~" .. , ; ~ ~ :R5 signifies a hydrogen atom, a nitro group or a (Cl ~3 alkoxy radical, . R6 s1gnif1es a hydrogen atom, a (Cl 4) ~:
l~ alkyl or (Cl_4) alkoxy radical or :.
t~ a -COOM or -SO3M group, ::
i ~:: t : .
R7 slgnifies a hydrog~n atom or a - :
~ O M gro~p .,. ;.. ,~ .
, .: . ~ . .
. .
~` :
~ 1064480 :
R8 signifies a hydrogen atom or the radical of a diazo component, and M signifies a hydrogen ion or a non-chromophoric cation, ., or mixtures thereof, in metallized or unmentallized form, which metallized ` form comprises a 1:1 metal complex of a compound of formula I, a 1:2 metal i complex of a!formula I or a 1:2 metal complex of a complex of formula I
., ~ j ~;; and a further metallizable compound of formula V, N - N ~ ~ ~R5 ' ~ lO in which each of R2 and R3, independently signify -OH or -NH2, and A signifies a further unsubstituted ; ~ benzene or naphthalene radical or a benzene radical substituted by up to ~'l two further substituents selected from chlorine, nitro and SO3M, the hydroxy group in any such radicals A being in a position ortho to the azo group, R4, R5, R6, R7 and R8 are as defined above. --n is 0 or 1, and m is O, 1 or 2, provided that the sum ; of m ~ n is not more than 2.
The metallized compounds of formula I are 1:1 or 1:2 metal ,.,. . 1 ~ . :
complexes. The 1:2 metal complexes according to the invention are com-plexes of the compounds of formula I or complexes of a compound of formula -I and another metallizable azo compound of formula V as given hereinafter.
The present invention further provides a process for the - .i .. ..
` ! production of compounds of formula I, as defined above, and ~:1 and 1:2 :; a~ ~ - 2 -.~. ~ . .. . .
complexes thereof, as defined above comprising:
a) coupling the diazo derivative of a compound of formula III, :~ R4 ~: ~ NH ~ ~H2 111 :~ R5 :
in which R4 to R7 are as defined above, or a mixture of such compounds and, where required, the diazo derivative as R8, or a mixture of such derivatives, in any desired order, : ',.' :
~' :
... . .
;, ~,, " ' '': ' ' ,: ;:
'' ;'" ;`' :' ~ ':: :
;'`' '" ' ~ :.' . ; :
:. ~
.
,,'. ' ~:.' "", ' ' . ~'~ ' -' .:
' : ' . ~.
' .
- 2a - .
`` '1064480 ~ - 3 - Case~ 150-3607 . , , ~
.
~ , , ~lth a compound of formula II, , OJi~ R3 ,"A~/ ' , R
ln whlch Rl to R3 and M are as def$ned above;
b) reacting a compound of formula I, as deflned above.
or a mlxture of such compounds or a mlxture of a compound -~
of formula I and a further metalllzable compound of formula ~.
V as glven herelnafter wlth a metal donatlng compound to ", obtaln a 1:1 or 1:2 metal c~mplex of a compound of formula I, o) coupling the dlazo aerlvatlvè of a compound of -~-' formula.III, as deflned above, or a mixture of such 10~ - compounds and,~Jhere requlred, th- diazo derlvative as R8, or a ~-`
~ixture of such~derlvatives ln ar.y deslred order, with a l:l or 1:2 metal complex of a compound of formula II, a- deflned above, to obtaln a 1:1 or 1:2 metal ~ complex of a compound of formula I, as deflned above;
d) coupllng the diazo der'vatlve of a compound of - formula III, as deflned above, or a mixture of such compounds,and .
;- where re~uired the dlazo derlvative as ~8~ or a mlxture . - , ,~.
'~ ~'' ' . - ' ' ' . . ~ , . . .
. - . ,.. ~, .
. , " ~,, .
~`` 1064480 - 4 - Ca~e 150-3607 , ::
of ~uch derivatlveis ln any de~lred order, wlth a 1:2 complex of a compound of formula II and a further ~ metalllzable compound of formula V a~ glven herelnafter, , ~ :
e) reactlng a 1:1 metal complex of a compound of formula S I, as deflned above, wlth a further metallizable azo compound of formula V as glven hereinafter - f) coupllng the dlazo derlvatlve as R8 wlth a 1:1 or ls2 complex of a disazo compound of formula I, ~en R8 signifies the radical of a diazo component, the diazonium component which k.as the hisher coupling enera,y le coupled last. Preferably, R8 is à radical of : ,~
diàzo component having higher coupling ener~y than the ~; diazo derivative of formula III, thus the ~ntroduction of~ , , . ' ~
the radiczl R8 is preferably the last coup~lng reaction.
Coupling may be carrled out according to convention- t' ' 5 nl methods. Suitably, the coupling of the dfazo derivatl~e of formula III with a compound of formula II or wi~h a ~ complex containing the compound of formula II is carried -? ~ out at temperatures from 0 to 25C, preferably from 4 to 5C. The reaction is conveniently conducted in aqueous ~edium at a pH value of at least 5.
The coupling of the diazo derlvative as R8 with -- the compound of formula VIIIJ
"~
i, ', . ' . ~ .
: ~j `, .
. . ` ,~' .
,: 1, , , . , ............ . :. . : , .- - : . . .
- 5 - Case 150-3607 ;- ' .. . .
.
~;2 ~ ~R5 Rl VI I I
. ~ ' ~, .
in whi.ch Rl to R7 are as defined above, or a com,plex containing the compound of formula VIII, is suitably carried out at temperatures from 0 to 25C, :, preferably from 4 to 5C. The reaction is preferably , ., conducted in aqueous medium at a pH value from 4 to 9.
A coupling accelerator may also be emPloyed. As exam~l~3s : . of suitable coupling accelerators may be given urea, ~:
. , ~ ~ pyridine and Cellosolve.
.;. ::~ Metal complex formation may be effected by known methods~ For example iron complexes may be formed using . ~ an iron salt. The preferred pH value is from 3.5 to 6, ~:.: more preferably frorn 4 to 4.5. Suitable reaction tempera-, .; 1 ... ,~ .
.'~' .` ,: .
~ i . ,, . ~, .. . . .
.,~ '~
.
.. ~ . .
:. ` . , .
,~ . .
.
~ : .
;, - 6 - Case 150-3607 ' ' . ' '.
` 1~64480 tures are in the range of from 95C to reflux tempexa-- ture or even higher temperatures, for example up to 120C, - when working under pressure. Cobalt, chromium and nickel complexes may be formed under similar temperature conditions. Advantageously, for forming cobalt complexes ;~ the pH value is from 4 to 10, for nickel complexes from 3.5 to 6, and for chomium complexes from 2 to 10. The reaction may be conducted in aqueous, aqueous-organic or organlc medium. Preferred organic solvents are those ~7hich have a boiling point over 100C, are miscible with water and in which the compounds to be complexed and ' their metal salts are soluble. Examples of suitable ;! solvents are alcohols, ether alcohols and amides e.g.
., .
Cellosolve, Methylcellosolve, formamide and dimethyl-;~ 15 formamide. Organic solvents are preferably used in the . 1 . prepaxation of chomium complexes.
, ( Copper complexes may be formed in aqueous medium C~ ` I under neutral to alkaline conditions, preferably at a pH value o rom 7.5 to 10. The reaction is advant-ageously effected in the presence of excess ammonia.
Suitable reactlon temperatures are above 70C, preferably from 80 to 100C, optionally under pressure. The amount of copper compound employed is preferably such that at .. . .
~;~ least one mol of copper is provided per mol azo dyestuf.
; . j:
j.',. :,~ ~ .
s.. l ,~. ., ~ . . ..
. ~ .
... .
,. .. . .
- 7 - case 150-3607 ` 1064480 ~y the term 'excess A~u~nla', lio me~nt ~n amount whlch .
exceeds that whlch 18 coordinately bound by the copper, .li , . . .
and is preferably sufficient so that the copper salt `-- ~8 dlssolved thereln.
~ ,c . .~ , , .. .
S Examples of suitable ~.etal donating compounds ~re ` a~ follows~
- for copper: cuprlc chlor~de, aoetate, formate or ulphate .
for lron: ferrous ~ulphate cr nitrate, ferric sulphate or nltrate or ferrlc chloride for nlckel: nickel ~ormats, acetate or sulphate ;
for chromium: chromlum tr~oxide, chromlc fluoride, ; su'phate, formate or acetate, ammonium or ;~;
~ ~ potassium chromium sulphate, sodium or ~
,, ;j . - - - .~ .
~ potassium chromate or sodium or ~ potassium bichromate P~ for cobilt: ~ cobaltous forr.ate, sulphate, acetate or , ~ " , , - ~ ~-, - chlorlde, cobaltic chlor~de or acetate.
~ In the preparation of 1:2 complexes,advantageously e ;~ 20 ~ ~t l-a~t one mo~,but preferably less than two mols,of metal per two mols of azo compound are employed.
~; ~ It ls advanta~eous when producing asy~etrical 1:2 complexes, especially in the case of 1:2 chromium complexes, to prepare the correspondlng 1:1 metal ~ ~ 25 complexes flrst, and then to react these complexes with a 1: .
1',: -;
: 7 ~ ~
~ 8 - Case 150-3607 . : -:
. ~ . .
~ further metallizable azo dyestuff to form the desired , asymmetrical 1:2 metal complexes.
:- .~ ' . - ' ,, :, .
- Mixtures of metal complexes comprising complexes of different metals are also provided by the present - ;
invention. Such complexes may be formed by reactin~
;~ the azo dyes with different metal donating compounds, preferably by forming the metal complex of one metal and subseauently reacriny any uncomplexed azo compound in - the reaction mixture with a further metal ~onating compound.
Ir. the compounds of formula I, when R8 slgnifies the radical of a diazo component it is preferably of a mono-nuclear aiazo component, more preferably the radical of formula IV, R~ ~ N=N-in which Rg s1gnL~les ~ hydrogen atom, a hydroxy, NH2, (Cl_4) alkyl or (Cl_4) alkoxy `. . i i i ~ ~ ~ .
.: group, 10 signifies a hydrogen atom, a nitro, -COOM or -SO3M group, in whlch M ls as defined above, and Rll sign1fies a h~drogen cr halogen atom, ~ ~ a nitro or a (Cl_4) alkyl group.
,...... . . . .
, -~ .. . .
,~ .
~- ....... . ... . .. ... .
. . .
: ~ ~ :
: - :
~- -- - 9 - 150-3607 /~ 1064480 By halogen ls meant chlorlne, bromlne, fluorlne or lodine, with chlorine being preferred. Preferred amine~ of formula IV are those where at least one, ~ preferably one or two, of Rg, Rlo and Rll slgnifle8 !~ ~ ~ 5 a hydrogen atom.
Examples of R8 are the diazo radlcals of formula IV where all three of Rg, Rlo and R
signlfy hydrogen; where two signlfy hydrogen and the ;1 ~ third slgnlfles nltro, -COQM, or methoxy; where one ':1 :
~1 10 signlfles hydrogen and the other two are the same and 1:
slgnlfy NO2 or CH3; where one slgnlfles hydrogen and ~ the other two are dlfferent and signlfy -SO3M and -OCH3, ; NO2 and -SO3M, NO2 and CH3~ NO2 and Cl, OH and ¢l, OH
and NO2, or OH and SO3M; where all three of Rg, Rlo and Rll have a slgnlflcance other than hydrogen and two signlfy NO2 and the thlrd ~lgnlfles -OH; or where each of Rg, R~o and Rll are diff-rent and slgnlfy OH~ SO3M
and N02, respectlvely; nd the radlcal of formula :.- , . :,. -. ~
-N - N ~ NO2 Whllst any metalllzable compound may be used as -~ 20 the further metalllzable azo compound, those az~
, compounds whlch contaln an aromatlc nucleus on elther side of the azo group substltuted by a metalllzable group, e.g. hydroxy or amlno, ln a position ortho to the azo group are preferred~
" ,:
~ - 10 - 150-3607 The further metalllz~ble azo compounds are compounds of formula V, A-- N ' N~--,N~NEI~) . . V
.. ~ ln whlch each of R2 and R3, lndependently slgnlfy .,~
~ OH or -NH , and :
:~ . 2 A signifies a further unsubsti-~ v tuted benzene or naphthalene :;~ radlc~l or a benzene radical substituted by up to two further t '::' ',: ' ~ substltuents selected from . i . ~
10 ~ chlorlne, nltro and S03M, the ; hydraxy group ln~any ~uch : radlcals A belng in a posltlon ortho to the azo group, a4, i R5~ R6~ R7 and R8 - are as deflned above, lS ~ n ~; 18 0 or l, and m :~ 18 O, l or 2, provlded that the : sum of m I n 18 not more than 2, such compounas,where trlsazo, p~eferably contalnlng at lea~t one sulpho. . ~ -Preferred further metalllzable compounds are -~ .: ~ , .. ....
t ~
. ,,. ' ' ` ~ ~ ':
. . ' : ~, ,..... : ... . :
~ 150-3507 1064480 .~
, .
. compound~ of formula TI, a~ deflned above, or compounds of formulae VI or VIII, .~ ~.
... OH OH
~ Yl ~ N - N ~ VI
v :- 2 OH OH
Yl~N - ~ -- N~ 4 .~ ~n whlch R4 to R8 are as defined above, ................................. Yl slgnlfies a hydrogen or chlorine atom, i~; . . ~ .
. 5 a.-SO3M or nltro group, Y2 slgnlfles a chlorlne atom or a -SO3M
. or nltro group, and R; ~ M ls as deflned above.
~ Thus, a 1:2 complex of a compound of formula I, or k ~ 0.~ a complex of a compound of formula I and a further '6~'~
metallizable azo compound,.can be formed by coupllng.the dlazo derlvatlve of an amlne of formula III, as deflned , ~ .
. above, or a mlxture of such amines, and, where requlred, the dlazo derlvatlve as R8 or a mlxture of such derlva-.~ . .
tlves, wlth a complex of formula IX, ,,:. ,:
:
..
.;
.~. - , :
.'~ '' ' ~''' .
.: , .
, . 11 .,, ~ ..
~ '"' .
.
... .
. i, .. .
~ . ' . ~ ' - ` ~064480 ~ - 12 - Case 150-3607 . .:
,' ~ .
$ N ~- N - ~ 503M
, \ ~ /
Me /
' o ' ~X :.
IX
A-- N -- N ~
H R
. in which each X, independently signifies -NH or -O-Me signifies iron, cobalt, nickel ox ~: . chromium, and ,.,-,, ", . . .
' l' 2 and M are as defined above, ~; 5 employing at least one mol of the diazo derivative of formula III and O, 1, 2 or 3 mols of the diazo derivative as R8 per mol of compound of formula IX, with the proviso that the molar ratio of diazonium compounds to ,' ',i: . ' , ', ,-the compound of formula IX is not more than 4:1. - -:-~ lO As examples of the compounds of formula IX may . . , ~ be given those of formu}a X, .
i~: Z
;.'~ ',~ , : . ...
.,~ . 1 ' , ~ ,, . . ~, ~.
.: .j , . . .
;
` :~` 1064480 : :
. .
.
. '' .
` ` R
R2 ~ ~ SO3M
x~ I /0 ~ e X
,~. .~ . . I
~ ' O l O
1 ~N - N~
''' .. 'j :" : ~
~i , .
`:r'- Rl, R2, X~ Yl, Y2, Me and M sre as ; . deflned above, or, preferably, those formed entirely from a compound ~, .,`, i "~ . ' ; of formula II, especially those of two identlcal compounds of formula II.
- Preferably, the dlazo derlvative of formula ~II, or a mlxture thereof ls coupled w~th a compound of ', ,.,''!:",, ~ formula IX ln a 1:1 to 2:1 molar ratlo and, where required, the dlazo derivative as R8 or a mixture thereof 0 i8 coupled wlth the product ln a 1:1 to 2:1 lar ratlo.
l $
. .
.
.. .
.
. .
- `1064480 - 14 - Case 150-3607 : ' ' ' ' . , ' Preferred compounds of formula I, are those where R8 signifies the radical of a diazo component, more preferably the diazo radical of formula IV, as defined above.
; 5 In the compounds of formula I, any alkyl or ,~ alkoxy radical preferably con~ains 1 or 2 carbon atoms.
Rl preferably signifies a nitro group and ~2 and R3 preferably signify -O~. Each of R4 , R5 and R6 ~ndependantly, preferably signi-1es hydrogen or . ~ ,, .
~ 10 an electron attr~ctinq substituerlt as mentioned above ~ . . . .
as slgnificances for R4, R5 and R6; when anv two of R4, R5 and R signify electron attracting substituents these substituents are preferably in a meta or para .. . .
, position to each other; when all three of R4, R5 and R6 signify electron attracting substituents, they are preferably in positions meta to each other.
; ~en P~7 signifies a -SO3M group this -SO3M
~ group is preferably in position meta to the azo group. -~
'~ Those compounds where at least one of R4~ R5, R6 and R7 has a significance other than hydroyen are preferred.
Compounds and complexes where up to 3 or R4, R5, R6 and . R7 signify hydrogen are especially preferred.
Preferably at most one of R6 and R7 signifies a -SO3M group. The trisazo compounds of formula I preferably ' 25 contaln at most three -SO3M groups, the disazo compounds .. ,,.~ , :
: ., .
:` 14 . ~ . . .
,'~ ~ ,. .
: - i .
~ 1064480 ~ 15 - Case 150-3607 . ~ , ~"
. .j ,.
at most two -SO3M groups. Compounds of formula I which , ~
contain at least two hydrosolubilizing groups are ~ preferred.
- Preferably M signifies hydrogen, an alkali S metal cation or an unsubstituted or substituted a~monium ~ion. Examples of substituted a~moniumi ions are (Cl 3) ;~ alkyl a~monium and h~droxy (C2 3) alkyl ammonium, e~g.
, , triethyl ammoni~m, tetramethyl a~monium, mono-, dl- or tri-ethanol-ammonium and mono-, di- or tri-isopropano~
~` 10an~on~um. Examples of alkali metal cations are . ~ .
lithium, sodium or potassium, sodium and potassium belng the preferred alkali metal cations, particularly the former.
, .. i , .
Preferred compounds of formula I are those ~
- ln which Rl signifies -NO2, ~' ~ 15R2 and R3 both signify -OH, ., ~, .:
., ~
.. . ,.' . .
.
.,, ~ ' , : . , ,, ~
;~ 1064480 - 16 - Case 150-3607 :`. -'.. , ,'.; : ' ;
. each of R4, R5, R6 and R7, independently, . signifies a hydrogen atom or an . electron attracting substituent, R5 and R6 being in ortho or para positions to the amino group, when other than hydrogen,and R7 .~ being in an ortho pOsitiQn to the . ., :: . .
amlno group, R8 slgnifies a diazo component radical, preferably the radical of formula . ~ Iv, as defined above. ;
:~ Especially preferred compounds of formula I, are those of for~ula Ib, OH : :
O~ R~6.;
3 ~ ~=N ~ ~ h ~ R25 Ib H~ ~ H ~ , NO~ ~ '' 7 ~24 in which R8" signifies the diazo co~ponent radical lS ~ of formula I~', as deflned above, ,, ., ~: . . , . ~ .. . .... . ... .. .
~ ~ 16 ... .; . . . . .
.....
i -,A ~ .
- 17 - Case 150-3607 ` elther~ each of R24, R25 ~nd R26 ~lqn - hydrogen atom and R7' slgnlfles or ~ ' signlfies a hydrogen atom, and either, one of R24.and R25 signifles nitro and , - the other signifles -S03M, and R26 ignlfies hydrogen, or ~ach of ~25 and R26 81gnifleS
nltro and R24 slgnlfies -COOM, and - M 18 ~8 defined above.
. . , ' :' Th pref-rr~d metal complexe~ are 1:1 copper and nlckel complexes of the compounds of formula I; 1:2 lron, . .
cobalt and chromium complexes of a compound of formula .
~ I; or 1:2 lron, cobalt and chromlum complexes of a $~
.- ,. . .
~ compound of formula I and a further metallzable compound of , . .
formula V as deflned above, tbe 1:2 complexes of compounds of formula I belng preferred, in particular the iron and cobalt complexes. Furthermore, with regard to mlxed metal , . .
complexe~, those whlch are mlxtures of lron and cobalt complexe~ are preferred.
It wlll be appreciated that when R8 slqnlfles the radlcal of a dlazo component ln a compound of formula I
.., . ..
~ ~ , 1 7 .
.~, . ~.
....
... ... . , .. ... ~ . . ~ ... -. . .. . . . .
.. . . ... . ~ . .. . . . ... . ..
~ 8 - Case 150~3607 , or VII, as defined above, and such compound of formula , . . .
I is co~plexed with another compound of formula I, or a compound of formula VII, any hydroxy or carboxy group ortho to the azo group in the radical as R8 would be available, ~ 5 together with any hydroxy group as R2 to form a metal complex bond. ~
; The negative charge on the metal atom in the 1:2 metal complexes may be compensaied by hydrogen ions or non-chromophoric cations, Suitable such non-chromo-10 phoric cations are those mentioned above for M. The ions ~- which compensate the charge on the metal may be the ;~ same as M or different therefrom, preferably they are the same. Complexes which are in the free acid or a~moni~m salt from are preferred, with the free acid form being r~ 15 especially preferred.
The compounds OI formula III and IV are kno~m or may be produced in conventional manner from available ,. . .
staxting materials.
~` The azo compounds of formula V are known or may ~- 20 be produced in conventional manner from available starting materials. The compounds of formula II are known and may be obtained by coupling the diazo derivative of an amine of formula XI, ..,.
i,i,~
...~ .
., ....................................................................... ~ .
, ....
.: :
,.......... , ~ . . .
' '' :~,.. ', ~, ., " . . ' ., ,.. '. . : , ' ', . . ' , ~ ' ` ~
106448~
-- 19 - Case 150-3bO7 ~ ~H2 R ~ XI
- in which Rl and M are as defined above, ; with a compound of formula XII, ~;. R13 H ~ ~ R2 XII
in which R2 and R3 are as define.d abovf3.
The coupling reaction is carried out in conventionf-~l manner. Suitably,coupling i3 effected in a basic medium, . .f .l; preferah].y aqueous,at pH values of at least 7.5. The .
~ ~ reaction temperature may be in the range of Irom O to 25C, ~: ' : f preferably 4 to 5C. The pH may be adjusted by the addition of alkali metal hydroxides or carbonates or am~onia or amines. It has been found ~hat when R2 and R3 are the same, coupling takes place in the position indicated by the arrow , ~ :
. .~
~-.. ' .
.. ~ ... . .
: 19 - ~:
. , ~ .
, :
,.
.
---~ 1064480 ~ - - 20 - Case 150-3607 . .
- . . .
.,, . -; ~herea~ when R2 and R3 are different a mlxture 18 obtained whlch may be ~epararated in conventlonal manner.
~ Thus, the present lnventlon ~tlll further provldes ;` mixtures of compounds and complexes of formula I, formed .~ .
by employlng a mixture of compounds of formula II. Such mlxtures may be separated lnto the indlvldual CQmponents by known methods, but are preferably employed as such .
~ wlthout separatlon.
. r ~ The metal complexes and mlxtures thereof accordlng to . . ~ ~. . : .
the lnventlon are useful as hydro-soluble dyes. They may be used for dyelng ubstrates whlch are dyeable wlth anlonlc dyes, especlally leather. Any type of leather sultable and lt may be dyed in conventlonal manner.
:,, :
The complexes accordlng to the inventlon have notable dyelng capaclty for leather of weak afflnlty. Dyelngs of deep full brown shades may be obtalned which have notable fa-tness to llght, hard water, washlng, persplratlon, i~( alkall, acld and bufflng.
. .: , :~
r,~
'~ ''i.. , , ., '., . , . , . , , ' ~" ,- ,: , : ,.
.
;`` -~ 1064480 ; - 21 - Case 150-3607 . `,:
( The following Examples serve to further illustxate the invention. In the Examples all parts and per-centag~s are by weight and all temperatures are in .. degrees Centigrade.
~''.
.
.:~, . .
I
. :.
.,.,~
.;' ~, '''~
~'' ~ ~ ' . - ':'.
~ '~ . ' I
. , :,',j~ ' ' ' - ,, ' I ' . . .
- ~ 21 .
;" ~ ' . . .
~...... . .
.
,,1,;, , ~ . , ,, .,, .,,, ........... ~.,. . ,.. ,,". ;.
~ ~ 1064480 ~-~ - 22 - case 1s~-3607 .. , .
,`.,~ EXAMPLE 1 ~ .
. .
~` 2g.5 Parts of the diazo derivative of l-amino-2-hydroxy-4-sulpho-6-nitronaphthalene- (nitro-diazoxide . ~ ~
acid Na-salt) are entered with stirring into a solution of 11 parts of 1,3-dihydroxybenzene in 200 parts of water ; 5 and 35 parts of calc. soda at 0. Coupling is completed after 2 hours. 26.4 Parts of the diazo derivative of 4-~ amino-2-sulpho-diphenylamine is allowed to flow, over r~1 the course of 30 minutes at a pH of 9.5 into the solution of the result~ng monoazo dyestuff and the mixture i5 stirred for~l hour. 13.8 Parts of the diazo derivative of l-amino~4-nitrobenzene is added to the resulting " I
; disazo dyestuff at a pH of 6 over the course of 30 minutes, and the mixture is stirred for 3 hours.
The result mg t~risazo dyestuff is heated to 95, then 13 parts of crystalllsed iron trichloride are added, and the mixture is kept at this temperature for 1 hour at a pH of 4.5. After cooling to 20, the dyestuff is filtered off.
It dries as a black-brown powder and dyes leather ln dark.brown shades which have notable fastness to light, washing, perspiration, hard water, acid and lkali.
2 2 ~:
.; , . .
, ~,~ ,. . .
., , . . . i . , ` ~ ~
~ ~ 1064480 ~ ~ 23 - Case l50-3607 : ' ., , i: ..................................... .
Replacing the 13 paxts of crystalline iron chloride used in Example l with 14 parts of crystalline cobaltic ;, .
`~; sulphate and carrying out the reaction at a pH of 9, -~ by the addition of sodium hydroxide, a dyestuff is obtained,after salting out, in the form of a sodium salt or by ,: ,'~`
!i,~'~ the addition of free acidj in the form of ree acid, which dyes leather in dark grey-brown shades, which dyeings have `~t'' ~ ~ notable fastness to light, hard water, washing, perspira-~ tion, acid and alkali.
~ ~ ( ~ i~ 10 EXAMPLIS 3 : ,.~,j . .
~-' Replacing the 14 parts of cobaltic sulphate used in ~xample 2 with the corresponding amount of nickel sulphate ,~ , ;l! and using a pH between 3.5 and 5, a dyestuff is obtained which dyes leather in dark brown shades with similar properties.
. ,,, ~:
f . ~
The trisazo dyestuff produced as described in ~i Example 1 is dissolved in formamide, heated to 120 and 25 parts of chrome alum are added. After the complex has been formed, the dyestuff is separated out by pouring it into a 20% common salt solutlon and filtered, it dries as a black-brown powder which dyes leather in deep reddish browm . .,:.. ~, . :
; ,~ shades. The dyestuff may be obtained in the free acid ~ form by separating it out by the addition of acid.
.. . .
- 24 - Case 150-3607 ' ` , ' ' , .. . .
The trlsazo dyestuff produced as descrlbed ln ~xample 1 18 heated to 80 and treated wlth copper for 1 hour at 80 by adding 25 parts of crystallised copper ~-S sulphate ln the pxesence of a slight excess of ammonla. ;;
After coollng to 20, the product is separated out by ;
sprinkling ln common salt, flltered and drled. The product obtalned ls ln the ammonlum salt form and 18 a ~ black powder whlch dyes leather ln dark brown-grey ', 10 shades, whlch dyelngs have notable fastness to light, washlng, persplratlon, hard water, acid and alkall.
In the followlng Table 1 metallizable azo dyestuffs ¦~ of formula ,.................. . , ,,.-_~ N5N~ ~-N ~ N ~ R15 O2N 12 tXIII) , . . - . , -~ ~ aro lS~t-d whlch are oharacterized by the radlcals R12 to ~ ~ IS R16; the 1:2 Co-complex compounds and the l:l-Cu-complex - ` compounds thereof dye leather ln dark grey-brown shades, the ~ . .:
1:2 Fe- and the 1.1 Nl-complex compounds ln dark brown shades and the 1:2-Cr-complex compounds in dark reddlsh brown 6hades. They may be produced ln analagous manner to that ' -I 20 ~ descrlbed in the above Example~.
-- -- - , ..
2 ~ .
~. .
- 2 5 - . Ca se 15 0 - 3 6 0 7 : . 1064480 T A B L E
Exampl~ R12 R
~, ' . _ _~ - ~
; 6 -N=N-~-N2 -H -H -NO2 -SO3H
1 7 ¦-N=N ¦ -503H¦-H ¦-H I -H ¦ , ~I 8 -N=N OC~3 -H -NO2 -NO2 -COOH
1 9 N=N~ ¦ -H ¦-H ¦-NO~ ¦-503H
11 -N=N~ -N2 -H -H -NO2 -SO3H
~.~ . ..
1~ -N=N-~ -COOH -SO3H -H -H -H ;
13 -N=N-~3 -NO2 -SO3H -H -H -H
; 14 -H -H -H -NO2 -SO3H
! 16 -N=N-~3~-COOH -H -H -NO2 -SO3H
-N=N-~ -N02 -SO3H -H -H -H
....,~
, 1 ~
. ~ . .
. . ..
v. . .l ..
...-! . . .__ .
',~;' . " , ., _ _ _ _ _ , 2 ~ `
- 26 ~
.. .`' ' . ' .
:.
EXamP1 13 R19 IR15 16 ~ ,,, _ 17 -H -SO3H E~ -H -H
18 -N=N~-C1 H -NO2 SO3~ -H
19 N N~ CH - SO3 H -H -H -H 1 2 ~-N=N~No2 ~-S H ~-H ~ H
: ~-N=N~O H I-H ~ I H
23 ~N=N~O H ~ H ~ H
:~ 24 ¦ N=N~ ~
j; ~ SO3H -SO3H -H -H -H
t ~ ¦ 25 ¦-NH-3NC~ ¦- 03~ H ¦-H~
~;
~ . 1 :~', - 'I
i ~ 2B
. ~`, .
.
`- 27 - Case 150~36Q7 ' .' ' ' ' '~.`. ' ' ~":
. In the following Table 2 further metallizable azo ~
~ dyestuffs of formula ;:.
., :
: . ' OH 2 \16 ~0~ R13 : 2 12 : (XIV) ~ ` ` , .
.. , . ~ .
.'','~ .
.; are listed which are characterized by the radicals R12 to . Rl6; the 1:2 Co-complex compounds 2nd the 1:1 Cu-complex compounds thereof give dyeings on 1 ather of dark grey-:~ bro~m shades, and the 1:2-Cr-complex compounds o~ dark ~,~ reddish brown shades. They may be produced in analogy with the procedure of the above Examples.
, ~' , . .
. .
i,~
~", , ,,.~
, ~, . ~ . :
~, ~ ,. . .
. -.: , , :
.:
.... .
.
:
- ~ 1064480 - 28 - Case 150-3607 '' ' , .
~ .
;, .~. . .. _ .
EXamP1( 12 -R13--R14 ~ 16 1 . _ _ . .
,~ . 26 -N=N ~ N2 -SO3H -H -H -H
.~. 27 ~ OCH3 -SO3H -H -H -H
28 -N=N ~ -SO3H -H -H -H
i 29 ~O H -SO3H -H -H -H
-N=N ~ -SO3H -s03H -H -H -H
. 31 -N=N ~ ~'2 -H -SO3H -NO2 -H
I 32 -N=N ~ HNO2 -H -SO3H -NO2 -H
"~ 33 OCH3 -H -SO3H -NO2 _y ~ 34 -N=N ~ OCH3 _H -SO3H -NO2 -H
;~ 35 3 -H -SO3H -NO2 -H
36. ~1 -SO3H -H -H -H
¦ 3~N=N~ ~10~ ¦-H ¦ -603 ¦-NO2 ¦--H J
28 `
~ - .
. . -~064480 ~ - 29 - Case 150-3607 - ,;
.: ':
:- .
In the following ~able 3 further metallizable azo -~
: dyestuffs of formula . ~1 :
. OH R
. NH ~6 H035~ R~NH; R13 14 , (XV) ~ :
. . .
. .
: j ~
are listea which are characterized by the radicals R12 to R ; the 1:2 Co-complex compounds and the 1:2-Cu-complex :l: 16 . 1~ 5 compounds the.reof give dyeings on leather of dark grey-, : ;~ brown shades and the 1:2-Cr-complex compounds dark red- ;'1:
~l~ brown shades. They may be produced in analogy with the procedure described in the above Examples.
! ~
~, . . .. .
' .~
!,''. , :
;~., i, .
`:'` ", .:j, ," ,,: , .
' , ,..
~; `" 1064480 _ 30 _ Case 150~3607 ~"
T.~ A B L E 3 ~, . Example R l R l4 ¦ R15 16 j ` 1 : ~ _ _ . _ __ j _ . .
3a -N=N~_No2 -S03H -I-E -H -H
39 -N=N~ - SO3H -El -H - H
. ~ . 40 --N=N~OCH3 --SO3H -H --H -H
; ~ . 42 OCU3 - S03H -EE - H - H
. ~ ~H - SO3 H - H --H --H
. 43 -N-N- ~ -S03H -S03H -H -H -H
l 44 -N-- N~_No2 - ll - S03H -N2 -fl .~; 45 - N-N~No2 - lE -S03EE -N2 -H
4 6 -N=N~OC~E3 -H -SO3H 2 --H
47 -N=N~ -H --SO3H -No2 -H
i 48 -N=N ~ -S03H -H -S03H -N02 -H
;: L~ NC~ ¦-U 1-503U~
`~' ' . ' .
' ' - .
. . _ . .
.; , . .
, ~,~ ,. . .
., , . . . i . , ` ~ ~
~ ~ 1064480 ~ ~ 23 - Case l50-3607 : ' ., , i: ..................................... .
Replacing the 13 paxts of crystalline iron chloride used in Example l with 14 parts of crystalline cobaltic ;, .
`~; sulphate and carrying out the reaction at a pH of 9, -~ by the addition of sodium hydroxide, a dyestuff is obtained,after salting out, in the form of a sodium salt or by ,: ,'~`
!i,~'~ the addition of free acidj in the form of ree acid, which dyes leather in dark grey-brown shades, which dyeings have `~t'' ~ ~ notable fastness to light, hard water, washing, perspira-~ tion, acid and alkali.
~ ~ ( ~ i~ 10 EXAMPLIS 3 : ,.~,j . .
~-' Replacing the 14 parts of cobaltic sulphate used in ~xample 2 with the corresponding amount of nickel sulphate ,~ , ;l! and using a pH between 3.5 and 5, a dyestuff is obtained which dyes leather in dark brown shades with similar properties.
. ,,, ~:
f . ~
The trisazo dyestuff produced as described in ~i Example 1 is dissolved in formamide, heated to 120 and 25 parts of chrome alum are added. After the complex has been formed, the dyestuff is separated out by pouring it into a 20% common salt solutlon and filtered, it dries as a black-brown powder which dyes leather in deep reddish browm . .,:.. ~, . :
; ,~ shades. The dyestuff may be obtained in the free acid ~ form by separating it out by the addition of acid.
.. . .
- 24 - Case 150-3607 ' ` , ' ' , .. . .
The trlsazo dyestuff produced as descrlbed ln ~xample 1 18 heated to 80 and treated wlth copper for 1 hour at 80 by adding 25 parts of crystallised copper ~-S sulphate ln the pxesence of a slight excess of ammonla. ;;
After coollng to 20, the product is separated out by ;
sprinkling ln common salt, flltered and drled. The product obtalned ls ln the ammonlum salt form and 18 a ~ black powder whlch dyes leather ln dark brown-grey ', 10 shades, whlch dyelngs have notable fastness to light, washlng, persplratlon, hard water, acid and alkall.
In the followlng Table 1 metallizable azo dyestuffs ¦~ of formula ,.................. . , ,,.-_~ N5N~ ~-N ~ N ~ R15 O2N 12 tXIII) , . . - . , -~ ~ aro lS~t-d whlch are oharacterized by the radlcals R12 to ~ ~ IS R16; the 1:2 Co-complex compounds and the l:l-Cu-complex - ` compounds thereof dye leather ln dark grey-brown shades, the ~ . .:
1:2 Fe- and the 1.1 Nl-complex compounds ln dark brown shades and the 1:2-Cr-complex compounds in dark reddlsh brown 6hades. They may be produced ln analagous manner to that ' -I 20 ~ descrlbed in the above Example~.
-- -- - , ..
2 ~ .
~. .
- 2 5 - . Ca se 15 0 - 3 6 0 7 : . 1064480 T A B L E
Exampl~ R12 R
~, ' . _ _~ - ~
; 6 -N=N-~-N2 -H -H -NO2 -SO3H
1 7 ¦-N=N ¦ -503H¦-H ¦-H I -H ¦ , ~I 8 -N=N OC~3 -H -NO2 -NO2 -COOH
1 9 N=N~ ¦ -H ¦-H ¦-NO~ ¦-503H
11 -N=N~ -N2 -H -H -NO2 -SO3H
~.~ . ..
1~ -N=N-~ -COOH -SO3H -H -H -H ;
13 -N=N-~3 -NO2 -SO3H -H -H -H
; 14 -H -H -H -NO2 -SO3H
! 16 -N=N-~3~-COOH -H -H -NO2 -SO3H
-N=N-~ -N02 -SO3H -H -H -H
....,~
, 1 ~
. ~ . .
. . ..
v. . .l ..
...-! . . .__ .
',~;' . " , ., _ _ _ _ _ , 2 ~ `
- 26 ~
.. .`' ' . ' .
:.
EXamP1 13 R19 IR15 16 ~ ,,, _ 17 -H -SO3H E~ -H -H
18 -N=N~-C1 H -NO2 SO3~ -H
19 N N~ CH - SO3 H -H -H -H 1 2 ~-N=N~No2 ~-S H ~-H ~ H
: ~-N=N~O H I-H ~ I H
23 ~N=N~O H ~ H ~ H
:~ 24 ¦ N=N~ ~
j; ~ SO3H -SO3H -H -H -H
t ~ ¦ 25 ¦-NH-3NC~ ¦- 03~ H ¦-H~
~;
~ . 1 :~', - 'I
i ~ 2B
. ~`, .
.
`- 27 - Case 150~36Q7 ' .' ' ' ' '~.`. ' ' ~":
. In the following Table 2 further metallizable azo ~
~ dyestuffs of formula ;:.
., :
: . ' OH 2 \16 ~0~ R13 : 2 12 : (XIV) ~ ` ` , .
.. , . ~ .
.'','~ .
.; are listed which are characterized by the radicals R12 to . Rl6; the 1:2 Co-complex compounds 2nd the 1:1 Cu-complex compounds thereof give dyeings on 1 ather of dark grey-:~ bro~m shades, and the 1:2-Cr-complex compounds o~ dark ~,~ reddish brown shades. They may be produced in analogy with the procedure of the above Examples.
, ~' , . .
. .
i,~
~", , ,,.~
, ~, . ~ . :
~, ~ ,. . .
. -.: , , :
.:
.... .
.
:
- ~ 1064480 - 28 - Case 150-3607 '' ' , .
~ .
;, .~. . .. _ .
EXamP1( 12 -R13--R14 ~ 16 1 . _ _ . .
,~ . 26 -N=N ~ N2 -SO3H -H -H -H
.~. 27 ~ OCH3 -SO3H -H -H -H
28 -N=N ~ -SO3H -H -H -H
i 29 ~O H -SO3H -H -H -H
-N=N ~ -SO3H -s03H -H -H -H
. 31 -N=N ~ ~'2 -H -SO3H -NO2 -H
I 32 -N=N ~ HNO2 -H -SO3H -NO2 -H
"~ 33 OCH3 -H -SO3H -NO2 _y ~ 34 -N=N ~ OCH3 _H -SO3H -NO2 -H
;~ 35 3 -H -SO3H -NO2 -H
36. ~1 -SO3H -H -H -H
¦ 3~N=N~ ~10~ ¦-H ¦ -603 ¦-NO2 ¦--H J
28 `
~ - .
. . -~064480 ~ - 29 - Case 150-3607 - ,;
.: ':
:- .
In the following ~able 3 further metallizable azo -~
: dyestuffs of formula . ~1 :
. OH R
. NH ~6 H035~ R~NH; R13 14 , (XV) ~ :
. . .
. .
: j ~
are listea which are characterized by the radicals R12 to R ; the 1:2 Co-complex compounds and the 1:2-Cu-complex :l: 16 . 1~ 5 compounds the.reof give dyeings on leather of dark grey-, : ;~ brown shades and the 1:2-Cr-complex compounds dark red- ;'1:
~l~ brown shades. They may be produced in analogy with the procedure described in the above Examples.
! ~
~, . . .. .
' .~
!,''. , :
;~., i, .
`:'` ", .:j, ," ,,: , .
' , ,..
~; `" 1064480 _ 30 _ Case 150~3607 ~"
T.~ A B L E 3 ~, . Example R l R l4 ¦ R15 16 j ` 1 : ~ _ _ . _ __ j _ . .
3a -N=N~_No2 -S03H -I-E -H -H
39 -N=N~ - SO3H -El -H - H
. ~ . 40 --N=N~OCH3 --SO3H -H --H -H
; ~ . 42 OCU3 - S03H -EE - H - H
. ~ ~H - SO3 H - H --H --H
. 43 -N-N- ~ -S03H -S03H -H -H -H
l 44 -N-- N~_No2 - ll - S03H -N2 -fl .~; 45 - N-N~No2 - lE -S03EE -N2 -H
4 6 -N=N~OC~E3 -H -SO3H 2 --H
47 -N=N~ -H --SO3H -No2 -H
i 48 -N=N ~ -S03H -H -S03H -N02 -H
;: L~ NC~ ¦-U 1-503U~
`~' ' . ' .
' ' - .
. . _ . .
3 0 :, - . . .
,, t ' . , ~ ' , - 31 - Case 150-3607 : :' ~: 1064480 ~;
~' 29.5 Parts of the diazo derivative l-amino-2-hydroxy-~; 4-sulpho-6-nitronaphthalene are entered with stirring '' into a solution of 11 parts of ],3-dihydroxybenzene in `-,~ 5 200 parts of water and 35 parts of calc. soda a~ 0.
, After 2 hours coupling is completed. 26.4 Parts of the diazo derivative of 4-amino-2-s,ulpho-diphenylamine is allowed to flow into the solution of the resulting ; ~i , l monoazo dyestuff at a pH of 9.5 over the course of 30 " , . .
'i' 10 minutes and the mixture is stirred for 1 hour.
: " :
,~ , 12.3 parts of the diazo derivative of 1-amino-2-.j :~ . ,.
j,~; methoxy-benzene is added to the resulting disazo dyestuff at a pH cf 9 and is stirred for 1 hour at 5. After : -: , I .
'~,,'l coupling, the resulting trisazo dyestuff is heated to ,''; lS ~5-100 and 7 parts or crystalline cobaltic sulphate are 'I ~ added,thereto. The pH is adjusted to 9 and the tempera-ture is kept at 95-100 over the course of 1 hour. After ,' ' all the cobalt has been complexed, the p~ of the reaction mixture is adjusted to 4-5, then 6.5 parts of iron chloride are added and the mixture is kept at a temperature of ~ 95-100 for 1 further hour. After cooling, the d~yestuff ;~ is seperated out by employing common salt and dried.
; ' A mixture consisting of 1:2 cobalt and 1:2-ironcomplex of the trisazo dyestuff is obtained which dyes leather in neutral deep brown shades with notable fastnesses.
.~ ,~,, .
, . , :- 3 ~
.
. ', . , . , . . ., ., . . .. -,.. . ...
: ` ~
- 32 - Case 150-3607 .;: .
EXAMPLE Sl ~ ~ -.. . :
NO ~ \
- 1~, N=N ~> SO3H
HO35 ~ N=N~N=N~ NH~>
O ~
~e~'' NO2~ N~N=N~ NN
OH
A N02 ! ~
~e-Fe, Co, Cr.
...
, Dvestuff I
29.5 Parts of the diazo derivatlve of l-amino-2-hydroxy-4-sulpho-6-nltrona~hthalene are entered with stirring lnto a solution of 11 parts of 1,3-dihydroxy-~ benzene dissolved $n 200 parts of water with the addltion - ~ ~ of 35 parts of calclnated soda at 0-15. After 2 hours, coupllng ls completed. 26.4 parts of the diazo derlvatlve of 4-amlno-2-sulpho-diphenylamlne ls allowed to flow lnto the solutlon of the resulting monoazo dyestuff at a pH of 9.5, over the course of 30 mlnutes and the .: .
mlxture 18 stlrred for 1 hour untll the dlazo compound 18 no longer detectable. 12.3 parts of the dlazo ~. . .
derlvatlve of l-amlno-2-methoxy-benzene 18 :~ 32 ~" .
'.~ - , .
~ 33 - Case 150-3607 .' . - .
.' ' .:
allowed to flow into the resulting disazo dyestuff at a pH of 9. Reaction is effected at 0. The mixture ls ~ stlrred for 1 hour. After coupling, the resultlng '`!
triazo dyestuff I ls comblned with ~ S Dvestuff II
"I whlch is produced as follows:
19.9 Parts of the diazo derivatlve of l-amino-2-hydroxy-3, S-dinitrobenzene are coupled at pH 9 and at 0-5 wlth 11 parts of 1,3-dihydroxybenzene; 26.4 parts of the diazo derivative of 4-amino-2-sulpho-diphenylamine are added .
;~ at pH 9 to the resulting monoazo dyestuff and the mixture ls stirred at 0-5 over the course of 2 hours. When coupling 18 completed, dyestuffs I and II are heated . ~ . .
together to 95~ and 27 parts of iron-III-chlorlde (crystalline) are added. The pH is adjusted to 4,5 wlth hydrochlorlc acid and the mlxture ls kept at 95 for 1 p~.. . j : , hour. The product ls separated out by the addition of common salt and filtered. When dry, the dyestuff is a dark brown powder and dyes ieather ln deep reddish brown shades.
: The corresponding Co- and Cr-complexes may ~ be produced by replaclng the lron-II-chloride, used above, ; ~ ~ wlth cobalt, nlckel- and chromlum- donat~ng compounds ~ .
~ employlng the conditions as set out in Examples 1, 2 and .
- ~ c ~
, . . ~, , . . , -. .. ~ .
3 3 ~:
,. , ;, ~ ` , - .
lf~64480 - 34 ~ Case 150-3637 " .
The dyestuff of formula .' ' .
. ~ OH OH
H~C ~503H
N2 N - ~ 3 f~, .
obtained in analogy with the process described in Example 1 may be metallized to form 1:2 cobalt and 1:2 iron complexes in analogy with the procf~dure described in Examples 1 and 2.
, " i ~' f Applic~tion Example A
100 parts of newly tanned and neutralised chromium grain leather are milled in the dyeing vessel for 30 " ~ .
minutes in a liquor consisting of 250 parts of water at .l 55 and 1 part of the dyestuff produced in Example 1, .~. ............. .
~ they are treated for 30 minutes in the same bath With 2 .l parts of an anlonic fat-liquor based on sulphonated train .. oil, and the leathers are dried and finished in the usual , 'f' 15 manner. An evenly dyed leather in a deep grey brown .-~ . ,, : l ~hade i~ obtained.
",'',' _ f.~f'4 ,~,.................................................................... .
. . ' .
': . .
', .
,. . . . . . . .. .
- - 35 - l5Q-3607 :
Appllcatlon Example B
lO0 parts of calf suede leather are mllled for 4 hours in the dyelng vessel wlth 1000 parts of water and , 2 parts of ammonla, and are dyed as follows in a new bath contalnlng 500 parts of water at 55, 2 parts of ammonla and lO parts of the dlssolved dyestuff produced in Example l, for l hour and 30 minutes. In order to exhaust the dye bath, 4 parts of formic acld (85%) are slowly added and dyelng is continued until the dyestuff has been completely fixed. The suede leather whlch ls rinsed, drled and flnished in the usual manner 18 evenly dyed ln a deep brown shade after bufflng the suede slde.
~ `'" ! ".~
.~;~,. , ~i'~"'l' ~, ; ~ APpllcation ExamPle C
lO0 parts of chromlum-vegetable tanned lamb's leather and lO parts of the dyestuff obtalned ln Example l are milled for 45 mlnutes ln the dyeing ve~sel in a liquor conslstlng of lO00 parts of water at 55 and 1.5 parts of an anlonlc sperm oll emulsion and the dyestuff 18 flxed on the leather by slowly adding 5 parts of formlc acld (85%) over the course of 30 mlnutes. After the usual drylng and flnlshlng processes, a ~eather ls : .... .:
~ obtalned whlch 18 dyed ln an even deep grey brown shade.
., .~ .
. ' .~,`~' . ' .
., ~, .
., ,i`.. '~ .
~ . ~
; ,~
, ., -; ;,,, - ~ . . '~ '''" ' ~ ` ' -` 1064480 . .
AP~lication Exam~le D
- ~ A solution of 20 parts of the dyestuff produced ln accordance wlth Example l ln 847 parts of water, lS0 parts ~ of ethyl glycol and 3 parts of formlc acid (85%) is applled ,~ 5 by spraylng, plushing and pouring to the grain slde of a ; buffed, combinat1on-tanned cow-hide. The leather is drled and fini~hed under mild condltlons. A leather dyed in a dark grey-brown shade having notable fastness propertles is obtalned.
Replacing the dyestuff of Example 1 with the same ~- amount of the dyestuffs of Examples 2 to 51 and em~loy-ing the procedure of Examples A to D above, leather ; dyeings with slmllar propertles are obtalned; the shade ; of the dyelngs obtalned 18 lndlcated ln the correspondlng ~ 15 productlon Exampl-s or ln the lntroductlon to the Tables.
,~ ', ~: , ~ .
, ., ' ' '~: , ~, '' '~''~ ~' , ~, :
.,. , ~.. ..
: :, . .
.
`: 36 .
.
.. . . .. . .. .. . .
,, t ' . , ~ ' , - 31 - Case 150-3607 : :' ~: 1064480 ~;
~' 29.5 Parts of the diazo derivative l-amino-2-hydroxy-~; 4-sulpho-6-nitronaphthalene are entered with stirring '' into a solution of 11 parts of ],3-dihydroxybenzene in `-,~ 5 200 parts of water and 35 parts of calc. soda a~ 0.
, After 2 hours coupling is completed. 26.4 Parts of the diazo derivative of 4-amino-2-s,ulpho-diphenylamine is allowed to flow into the solution of the resulting ; ~i , l monoazo dyestuff at a pH of 9.5 over the course of 30 " , . .
'i' 10 minutes and the mixture is stirred for 1 hour.
: " :
,~ , 12.3 parts of the diazo derivative of 1-amino-2-.j :~ . ,.
j,~; methoxy-benzene is added to the resulting disazo dyestuff at a pH cf 9 and is stirred for 1 hour at 5. After : -: , I .
'~,,'l coupling, the resulting trisazo dyestuff is heated to ,''; lS ~5-100 and 7 parts or crystalline cobaltic sulphate are 'I ~ added,thereto. The pH is adjusted to 9 and the tempera-ture is kept at 95-100 over the course of 1 hour. After ,' ' all the cobalt has been complexed, the p~ of the reaction mixture is adjusted to 4-5, then 6.5 parts of iron chloride are added and the mixture is kept at a temperature of ~ 95-100 for 1 further hour. After cooling, the d~yestuff ;~ is seperated out by employing common salt and dried.
; ' A mixture consisting of 1:2 cobalt and 1:2-ironcomplex of the trisazo dyestuff is obtained which dyes leather in neutral deep brown shades with notable fastnesses.
.~ ,~,, .
, . , :- 3 ~
.
. ', . , . , . . ., ., . . .. -,.. . ...
: ` ~
- 32 - Case 150-3607 .;: .
EXAMPLE Sl ~ ~ -.. . :
NO ~ \
- 1~, N=N ~> SO3H
HO35 ~ N=N~N=N~ NH~>
O ~
~e~'' NO2~ N~N=N~ NN
OH
A N02 ! ~
~e-Fe, Co, Cr.
...
, Dvestuff I
29.5 Parts of the diazo derivatlve of l-amino-2-hydroxy-4-sulpho-6-nltrona~hthalene are entered with stirring lnto a solution of 11 parts of 1,3-dihydroxy-~ benzene dissolved $n 200 parts of water with the addltion - ~ ~ of 35 parts of calclnated soda at 0-15. After 2 hours, coupllng ls completed. 26.4 parts of the diazo derlvatlve of 4-amlno-2-sulpho-diphenylamlne ls allowed to flow lnto the solutlon of the resulting monoazo dyestuff at a pH of 9.5, over the course of 30 mlnutes and the .: .
mlxture 18 stlrred for 1 hour untll the dlazo compound 18 no longer detectable. 12.3 parts of the dlazo ~. . .
derlvatlve of l-amlno-2-methoxy-benzene 18 :~ 32 ~" .
'.~ - , .
~ 33 - Case 150-3607 .' . - .
.' ' .:
allowed to flow into the resulting disazo dyestuff at a pH of 9. Reaction is effected at 0. The mixture ls ~ stlrred for 1 hour. After coupling, the resultlng '`!
triazo dyestuff I ls comblned with ~ S Dvestuff II
"I whlch is produced as follows:
19.9 Parts of the diazo derivatlve of l-amino-2-hydroxy-3, S-dinitrobenzene are coupled at pH 9 and at 0-5 wlth 11 parts of 1,3-dihydroxybenzene; 26.4 parts of the diazo derivative of 4-amino-2-sulpho-diphenylamine are added .
;~ at pH 9 to the resulting monoazo dyestuff and the mixture ls stirred at 0-5 over the course of 2 hours. When coupling 18 completed, dyestuffs I and II are heated . ~ . .
together to 95~ and 27 parts of iron-III-chlorlde (crystalline) are added. The pH is adjusted to 4,5 wlth hydrochlorlc acid and the mlxture ls kept at 95 for 1 p~.. . j : , hour. The product ls separated out by the addition of common salt and filtered. When dry, the dyestuff is a dark brown powder and dyes ieather ln deep reddish brown shades.
: The corresponding Co- and Cr-complexes may ~ be produced by replaclng the lron-II-chloride, used above, ; ~ ~ wlth cobalt, nlckel- and chromlum- donat~ng compounds ~ .
~ employlng the conditions as set out in Examples 1, 2 and .
- ~ c ~
, . . ~, , . . , -. .. ~ .
3 3 ~:
,. , ;, ~ ` , - .
lf~64480 - 34 ~ Case 150-3637 " .
The dyestuff of formula .' ' .
. ~ OH OH
H~C ~503H
N2 N - ~ 3 f~, .
obtained in analogy with the process described in Example 1 may be metallized to form 1:2 cobalt and 1:2 iron complexes in analogy with the procf~dure described in Examples 1 and 2.
, " i ~' f Applic~tion Example A
100 parts of newly tanned and neutralised chromium grain leather are milled in the dyeing vessel for 30 " ~ .
minutes in a liquor consisting of 250 parts of water at .l 55 and 1 part of the dyestuff produced in Example 1, .~. ............. .
~ they are treated for 30 minutes in the same bath With 2 .l parts of an anlonic fat-liquor based on sulphonated train .. oil, and the leathers are dried and finished in the usual , 'f' 15 manner. An evenly dyed leather in a deep grey brown .-~ . ,, : l ~hade i~ obtained.
",'',' _ f.~f'4 ,~,.................................................................... .
. . ' .
': . .
', .
,. . . . . . . .. .
- - 35 - l5Q-3607 :
Appllcatlon Example B
lO0 parts of calf suede leather are mllled for 4 hours in the dyelng vessel wlth 1000 parts of water and , 2 parts of ammonla, and are dyed as follows in a new bath contalnlng 500 parts of water at 55, 2 parts of ammonla and lO parts of the dlssolved dyestuff produced in Example l, for l hour and 30 minutes. In order to exhaust the dye bath, 4 parts of formic acld (85%) are slowly added and dyelng is continued until the dyestuff has been completely fixed. The suede leather whlch ls rinsed, drled and flnished in the usual manner 18 evenly dyed ln a deep brown shade after bufflng the suede slde.
~ `'" ! ".~
.~;~,. , ~i'~"'l' ~, ; ~ APpllcation ExamPle C
lO0 parts of chromlum-vegetable tanned lamb's leather and lO parts of the dyestuff obtalned ln Example l are milled for 45 mlnutes ln the dyeing ve~sel in a liquor conslstlng of lO00 parts of water at 55 and 1.5 parts of an anlonlc sperm oll emulsion and the dyestuff 18 flxed on the leather by slowly adding 5 parts of formlc acld (85%) over the course of 30 mlnutes. After the usual drylng and flnlshlng processes, a ~eather ls : .... .:
~ obtalned whlch 18 dyed ln an even deep grey brown shade.
., .~ .
. ' .~,`~' . ' .
., ~, .
., ,i`.. '~ .
~ . ~
; ,~
, ., -; ;,,, - ~ . . '~ '''" ' ~ ` ' -` 1064480 . .
AP~lication Exam~le D
- ~ A solution of 20 parts of the dyestuff produced ln accordance wlth Example l ln 847 parts of water, lS0 parts ~ of ethyl glycol and 3 parts of formlc acid (85%) is applled ,~ 5 by spraylng, plushing and pouring to the grain slde of a ; buffed, combinat1on-tanned cow-hide. The leather is drled and fini~hed under mild condltlons. A leather dyed in a dark grey-brown shade having notable fastness propertles is obtalned.
Replacing the dyestuff of Example 1 with the same ~- amount of the dyestuffs of Examples 2 to 51 and em~loy-ing the procedure of Examples A to D above, leather ; dyeings with slmllar propertles are obtalned; the shade ; of the dyelngs obtalned 18 lndlcated ln the correspondlng ~ 15 productlon Exampl-s or ln the lntroductlon to the Tables.
,~ ', ~: , ~ .
, ., ' ' '~: , ~, '' '~''~ ~' , ~, :
.,. , ~.. ..
: :, . .
.
`: 36 .
.
.. . . .. . .. .. . .
Claims (13)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A compound of formula I, in which R1 signifies a hydrogen atom or a nitro group, each of R2 and R3, independently, signifies -OH or NH2, R4 signifies a hydrogen atom, a nitro group or a (C1-4) alkyl radical, R5 signifies a hydrogen atom, a nitro group or a (C1-4) alkoxy radical, R6 signifies a hydrogen atom, a (C1-4) alkyl or (C1-4) alkoxy radical or a -COOM or -SO3M group, R7 signifies a hydrogen atom or a -SO3M
group, R8 signifies a hydrogen atom or the radical of a diazo component, and M signifies a hydrogen ion or a non-chromophorilc cation, or a mixture thereof, in metallized or unmetalliaed form, which metallized form comprises a 1:1 metal complex of a compound of formula I, a 1:2 metal complex of a formula I or a 1:2 metal complex of a complex of formula I and a further metallizable compound of formula V, V
in which each of R2 and R3, independently signify -OH or -NH2, and A. signifies a further unsubstituted benzene or naphthalene radical or a benzene radical substituted by up to two further substituents selected from chlorine, nitro and SO3M, the hydroxy group in any such radicals A being in a position ortho to the azo group, R4, R5, R6, R7 and R8 are as defined above, n is 0 or 1, and m is 0, 1 or 2, provided that the sum of m + n is not more than 2.
group, R8 signifies a hydrogen atom or the radical of a diazo component, and M signifies a hydrogen ion or a non-chromophorilc cation, or a mixture thereof, in metallized or unmetalliaed form, which metallized form comprises a 1:1 metal complex of a compound of formula I, a 1:2 metal complex of a formula I or a 1:2 metal complex of a complex of formula I and a further metallizable compound of formula V, V
in which each of R2 and R3, independently signify -OH or -NH2, and A. signifies a further unsubstituted benzene or naphthalene radical or a benzene radical substituted by up to two further substituents selected from chlorine, nitro and SO3M, the hydroxy group in any such radicals A being in a position ortho to the azo group, R4, R5, R6, R7 and R8 are as defined above, n is 0 or 1, and m is 0, 1 or 2, provided that the sum of m + n is not more than 2.
2. A compound of formula I, according to Claim 1, in which R8 signifies the radical of a diazo component.
3. A compound of formula I, according to Claim 1, in which R8 signifies the radical of formula IV, IV
in which R9 signifies a hydrogen atom, a hydroxy, NH2-, (C1-4)alkyl or (C1-4)alkoxy group, R10 signifies a hydrogen atom, a nitro, -COOM or -SO3M group, in which M is as defined in Claim 1, and R11 signifies a hydrogen or halogen atom, a nitro or a (C1-4)alkyl group.
in which R9 signifies a hydrogen atom, a hydroxy, NH2-, (C1-4)alkyl or (C1-4)alkoxy group, R10 signifies a hydrogen atom, a nitro, -COOM or -SO3M group, in which M is as defined in Claim 1, and R11 signifies a hydrogen or halogen atom, a nitro or a (C1-4)alkyl group.
4. A compound accordding to Claim 1 in which R1 signifies nitro, each of R2 and R3 signifies hydroxy, R? signifies the radical of formula IV, as defined in Claim 3 and each of R4 to R7 independently, signifies hydrogen or an electron attracting substituent. R4, R5 and R6 being ortho or para to the amino group, when other than hydrogen, and R7 being ortho to the amino group.
5. A compound according to Claim 3, of formula Ib, Ib in which R8" signifies the radical of formula IV, as defined in Claim 3, either, each of R24, R25 and R26 signifies a hydrogen atom and R7' signifies -SO3M, or, R7' signifies a hydrogen atom and either one of R24 and R25 signifies nitro and the other signifies SO3M and R26 signifies hydrogen, or each of R25 and R26 signifies nitro and R24 signifier -COOM, and M is a non-chromophoric cation.
6. A 1:2 metal complex according to Claim 1, in which the further metallizable compound is a compound of formulae II, VI or VII, II
VI
VII
in which R1 to R8 and M are as defined in Claim 1, Y1 signifies a hydrogen or chlorine atom, a -SO3M or nitro group, and Y2 signifies a chlorine atom or a -SO3M
or nitro group.
VI
VII
in which R1 to R8 and M are as defined in Claim 1, Y1 signifies a hydrogen or chlorine atom, a -SO3M or nitro group, and Y2 signifies a chlorine atom or a -SO3M
or nitro group.
7. A complex according to Claim 1, in which the metal of the 1:1 complex is copper or nickel and the metal of the 1:2 complex is selected from the group con-sisting of cobalt, chromium and iron.
8. A 1:2 complex according to Claim 6, in which the metal is iron or cobalt or a mixture thereof.
9. A compound according to Claim 3, of formula, in which M is a hydrogen ion or a non-chromophoric cation, or a 1:2 iron or cobalt complex thereof.
10. A compound according to Claim 3, of formula in which M is a hydrogen ion or a non-chromophoric cation, or a 1:2 iron or cobalt complex thereof.
11. A compound according to Claim 3, of formula in which M is hydrogen ion or a non-chromo-phoric cation, or a 1:2 iron or cobalt complex thereof.
12. A compound according to Claim 3, of formula in which M is a hydrogen ion or a non-chromophoric cation, or a 1:2 iron or cobalt complex thereof.
13. A compound according to Claim 3, of formula in which M is a hydrogen ion or a non-chromophoric cation, or a 1:2 iron or cobalt complex thereof.
14. A mixture of 1:2 iron and 1:2 cobalt complexes according to Claim 3, of a compound of formula in which M is a hydrogen ion or a non-chromophoric cation.
15. A compound according to Claim 3, of formula in which M is hydrogen ion or a non-chromophoric cation, or a 1:2 iron or cobalt complex thereof.
16. A compound according to Claim 1, in which M
signifies a hydrogen ion, an alkali metal cation, ammonium, triethyl ammonium, tetramethyl ammonium, mono-, di- or tri-ethanol-ammonium or mono-; di- or tri-isopropanol-ammonium.
17. A process for the production of a compound of formula I, or a mixture thereof, as defined in Claim 1 in metallized or unmetallized form, comprising a) coupling the diazo derivative of a compound of formula III
III
in which R4 to R7 are as defined in Claim 1, or a mixture of such compounds, and where required, the diazo derivative as R8, or a mixture of such derivatives, in any desired order, with a compound of formula II, II
in which R1 to R3 and M are as defined in Claim 1, b) reacting a compound of formula I, as defined in Claim 1, or a mixture of such compounds or a mixture of a compound of formula I and a further metallizable compound of formula V, as defined in Claim 1, with a metal donating compound to obtain a 1:1 or 1:2 metal complex of a compound of formula 1, c) coupling the diazo derivative of a compound of formula III, as defined in Claim 1, or a mixture of such compounds and, where required, the diazo derivative as R8, or a mixture of such derivatives, in any desired order, with a 1:1 or 1:2 metal complex of a compound of formula II, as defined above, to obtain a 1:1 or 1:2 metal complex of a compound of formula I, as defined in Claim 1, d) coupling the diazo derivative of a compound of formula III, as defined in Claim 1, or a mixture of such compounds, and where required the diazo derivative as R8, or a mixture of such derivatives, in any desired order, with a 1:2 complex of a compound of formula II and a further metallizable compound of formula V, as defined in Claim 1, e) reacting a 1:1 metal complex of a compound of formula I, as defined above, with a further metallizable azo compound of formula V, as defined in Claim 1, to obtain a 1:2 metal complex of a compound of formula I and further metallizable azo compound, f) coupling the diazo derivative as R8 with the 1:1 or 1:2 complex of a diazo compound of formula I?
18. A process for dyeing substrates dyeable with anionic dyes, comprising employing a compound of formula I or a mixture of compounds of formula I, as defined in Claim 1, in metallized form as dyeing agent.
13. A compound according to Claim 3, of formula in which M is a hydrogen ion or a non-chromophoric cation, or a 1:2 iron or cobalt complex thereof.
14. A mixture of 1:2 iron and 1:2 cobalt complexes according to Claim 3, of a compound of formula in which M is a hydrogen ion or a non-chromophoric cation.
15. A compound according to Claim 3, of formula in which M is hydrogen ion or a non-chromophoric cation, or a 1:2 iron or cobalt complex thereof.
16. A compound according to Claim 1, in which M
signifies a hydrogen ion, an alkali metal cation, ammonium, triethyl ammonium, tetramethyl ammonium, mono-, di- or tri-ethanol-ammonium or mono-; di- or tri-isopropanol-ammonium.
17. A process for the production of a compound of formula I, or a mixture thereof, as defined in Claim 1 in metallized or unmetallized form, comprising a) coupling the diazo derivative of a compound of formula III
III
in which R4 to R7 are as defined in Claim 1, or a mixture of such compounds, and where required, the diazo derivative as R8, or a mixture of such derivatives, in any desired order, with a compound of formula II, II
in which R1 to R3 and M are as defined in Claim 1, b) reacting a compound of formula I, as defined in Claim 1, or a mixture of such compounds or a mixture of a compound of formula I and a further metallizable compound of formula V, as defined in Claim 1, with a metal donating compound to obtain a 1:1 or 1:2 metal complex of a compound of formula 1, c) coupling the diazo derivative of a compound of formula III, as defined in Claim 1, or a mixture of such compounds and, where required, the diazo derivative as R8, or a mixture of such derivatives, in any desired order, with a 1:1 or 1:2 metal complex of a compound of formula II, as defined above, to obtain a 1:1 or 1:2 metal complex of a compound of formula I, as defined in Claim 1, d) coupling the diazo derivative of a compound of formula III, as defined in Claim 1, or a mixture of such compounds, and where required the diazo derivative as R8, or a mixture of such derivatives, in any desired order, with a 1:2 complex of a compound of formula II and a further metallizable compound of formula V, as defined in Claim 1, e) reacting a 1:1 metal complex of a compound of formula I, as defined above, with a further metallizable azo compound of formula V, as defined in Claim 1, to obtain a 1:2 metal complex of a compound of formula I and further metallizable azo compound, f) coupling the diazo derivative as R8 with the 1:1 or 1:2 complex of a diazo compound of formula I?
18. A process for dyeing substrates dyeable with anionic dyes, comprising employing a compound of formula I or a mixture of compounds of formula I, as defined in Claim 1, in metallized form as dyeing agent.
13. A process according to Claim 18, in which the substrate is leather.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CH506674A CH606323A5 (en) | 1974-04-10 | 1974-04-10 | Metallisable dis-and trisazo cpds. |
| CH1518674A CH609719A5 (en) | 1974-04-10 | 1974-11-14 | Process for the preparation of metal complex compounds |
| CH1562174A CH610001A5 (en) | 1974-04-10 | 1974-11-25 | Process for the preparation of metal complex compounds |
| CH1562074A CH610003A5 (en) | 1974-04-10 | 1974-11-25 | Metallisable dis-and trisazo cpds. |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1064480A true CA1064480A (en) | 1979-10-16 |
Family
ID=27428853
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA 224262 Expired CA1064480A (en) | 1974-04-10 | 1975-04-09 | Azo compounds |
Country Status (11)
| Country | Link |
|---|---|
| JP (1) | JPS6020420B2 (en) |
| AR (1) | AR205925A1 (en) |
| BE (1) | BE827700A (en) |
| CA (1) | CA1064480A (en) |
| DD (2) | DD122077A5 (en) |
| DE (1) | DE2514008C2 (en) |
| ES (1) | ES436393A1 (en) |
| FR (1) | FR2267349B1 (en) |
| GB (1) | GB1499745A (en) |
| IT (1) | IT1034983B (en) |
| NL (1) | NL7504020A (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5298736A (en) * | 1976-02-17 | 1977-08-18 | Sandoz Ag | Azo compounds and metal complex salt thereof |
| DE3124172A1 (en) * | 1981-06-19 | 1982-12-30 | Basf Ag, 6700 Ludwigshafen | Dyes containing sulphonic acid groups |
| DE3142608A1 (en) * | 1981-10-28 | 1983-05-05 | Basf Ag, 6700 Ludwigshafen | POLYAZO DYES |
| DE3263035D1 (en) * | 1981-12-15 | 1985-05-15 | Ciba Geigy Ag | Chromium complexes of polyazo dyestuffs |
| DE3428836A1 (en) * | 1983-08-09 | 1985-02-21 | Basf Ag, 6700 Ludwigshafen | AZO CONNECTIONS |
| US4996302A (en) * | 1987-12-16 | 1991-02-26 | Ciba-Geigy Corporation | Process for the preparation of polyazo dyes |
| DE3932829C1 (en) * | 1989-09-30 | 1991-05-02 | Ciba-Geigy Ag, Basel, Ch |
Family Cites Families (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2045090A (en) * | 1933-05-03 | 1936-06-23 | Gen Aniline Works Inc | Cupriferous polyazo dyes and their production |
| US2200445A (en) * | 1933-11-25 | 1940-05-14 | Gen Aniline & Film Corp | Azo dyestuffs containing a heavy metal in a complex form |
| DE675558C (en) * | 1933-11-26 | 1939-05-23 | I G Farbenindustrie Akt Ges | Process for the production of complex metal compounds of polyazo dyes |
| DE670935C (en) * | 1933-11-26 | 1939-01-28 | I G Farbenindustrie Akt Ges | Process for the production of complex copper compounds from polyazo dyes |
| DE707225C (en) * | 1933-11-26 | 1941-06-16 | I G Farbenindustrie Akt Ges | Process for the production of complex chromium compounds from polyazo dyes |
| DE855142C (en) * | 1941-08-29 | 1952-11-10 | Bayer Ag | Process for the preparation of complex chromium compounds of disazo dyes |
| DE855141C (en) * | 1941-08-29 | 1952-11-10 | Bayer Ag | Process for the preparation of complex chromium compounds of disazo dyes |
| CH444996A (en) * | 1964-04-22 | 1967-10-15 | Sandoz Ag | Process for the preparation of trisazo dyes |
| CH531032A (en) * | 1969-05-23 | 1972-11-30 | Sandoz Ag | Process for the production of polyazo compounds and their metal complex compounds |
| CH529200A (en) * | 1969-08-21 | 1972-10-15 | Sandoz Ag | Process for the preparation of polyazo compounds |
-
1975
- 1975-03-29 DE DE19752514008 patent/DE2514008C2/en not_active Expired
- 1975-04-04 NL NL7504020A patent/NL7504020A/en not_active Application Discontinuation
- 1975-04-08 DD DD18530575A patent/DD122077A5/xx unknown
- 1975-04-08 GB GB1425975A patent/GB1499745A/en not_active Expired
- 1975-04-08 ES ES436393A patent/ES436393A1/en not_active Expired
- 1975-04-08 DD DD19517175A patent/DD126920A5/xx unknown
- 1975-04-08 BE BE155204A patent/BE827700A/en unknown
- 1975-04-08 AR AR25832475A patent/AR205925A1/en active
- 1975-04-08 JP JP4194575A patent/JPS6020420B2/en not_active Expired
- 1975-04-09 IT IT2217175A patent/IT1034983B/en active
- 1975-04-09 CA CA 224262 patent/CA1064480A/en not_active Expired
- 1975-04-10 FR FR7511212A patent/FR2267349B1/fr not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| ES436393A1 (en) | 1977-04-01 |
| JPS50136318A (en) | 1975-10-29 |
| AR205925A1 (en) | 1976-06-15 |
| FR2267349A1 (en) | 1975-11-07 |
| GB1499745A (en) | 1978-02-01 |
| FR2267349B1 (en) | 1980-05-09 |
| JPS6020420B2 (en) | 1985-05-22 |
| DE2514008A1 (en) | 1975-10-23 |
| BE827700A (en) | 1975-10-08 |
| DD126920A5 (en) | 1977-08-24 |
| NL7504020A (en) | 1975-10-14 |
| DD122077A5 (en) | 1976-09-12 |
| IT1034983B (en) | 1979-10-10 |
| DE2514008C2 (en) | 1984-03-08 |
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